Compound, polymerizable composition, polymer, holographic image recording medium, optical material, and optical component

Abstract

The present invention is a compound represented by formula (1). # imgabs0 # [In the formula, A represents a polymerizable group. And n represents an integer of 1-3. L represents a branching (n + 1)-valent linking group. Z represents an oxygen atom or an optionally substituted nitrogen atom. And m represents 0 or 1. X represents a single bond, an oxygen atom, a sulfur atom, an optionally substituted carbon atom, or an optionally substituted nitrogen atom. And p represents an integer of 0-2. When p is 2, the two X may be the same as or different from each other. Y1 and Y2 are each independently a benzene ring, a naphthalene ring or a phenanthrene ring. When Y1 or Y2 is a benzene ring, a or b corresponding to Y1 or Y2 is an integer of 0-4. When Y1 or Y2 is a naphthalene ring, a or b corresponding to Y1 or Y2 is an integer of 0-6. When Y1 or Y2 is a phenanthrene ring, a or b corresponding to Y1 or Y2 is an integer of 0-8. And R1 and R2 each independently represent an optionally substituted aromatic ring group. When a and b are 2 or more, the plurality of R1 and R2 may be the same as or different from each other. In the formula, Y1 and Y2 are both benzene rings, and a and b are both 0.

Description

Technical Field

[0001] The present invention relates to a compound having a high refractive index, high transparency and excellent chemical stability, and also to a holographic image recording medium, an optical material and an optical component using a polymerizable composition containing the compound or a polymer thereof. Background Art

[0002] Previously, glass was mostly used as an optical material. For example, in the case of an optical lens, even if the lens has the same focal length, if a high refractive index material is used to manufacture it, the lens can be made thinner, thereby having the advantages of being lightweight and increasing the degree of freedom in the design of the optical path. In addition, a high refractive index optical lens is also effective for miniaturization, high resolution, and wide angle of an optical camera device.

[0003] In recent years, plastics with high transparency have attracted attention as optical materials to replace glass. Plastic materials have the following advantages over glass, such as easy weight reduction, easy improvement of mechanical strength, and easy processing and forming. With the development of peripheral technologies, there is also a constant demand to improve the performance of plastic optical materials. For example, for materials used in optical lenses, it is required to be easy to polymerize (easy polymerization), harden or chemically stable, especially good thermal stability, and the refractive index of the polymer is high.

[0004] Prior to this, various 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, but the refractive index of the monomer is about 1.62, which is not sufficiently high (Patent Document 1). In order to increase the refractive index, in addition to introducing an aromatic ring, it is also effective to introduce a sulfur atom into the molecule. For example, Patent Document 2 describes a diacrylate monomer having a pentaerythritol skeleton with 1 to 2 naphthylthio groups in one molecule. The refractive index in this case is 1.62 to 1.65. Patent Document 3 describes an acrylate compound having a glycerol skeleton with two benzothiazole rings in one molecule. In this case, the refractive index is also 1.63. These are insufficient for applications requiring ultra-high refractive indices greater than 1.65.

[0005] Patent Documents 4 and 5 describe ultra-high refractive index acrylate compounds having dibenzofuran or dibenzocarbazole and a refractive index greater than 1.7. However, these compounds may change color due to heating in air, long-term storage, light irradiation, etc., and cannot be considered as highly stable materials. Previous technical literature Patent Literature

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 6-220131 [Patent Document 2] Japanese Patent Publication No. 2008-527413 [Patent Document 3] Japanese Patent Application Publication No. 2005-133071 [Patent Document 4] International Publication No. 2021 / 006011 [Patent Document 5] International Publication No. 2021 / 006012 Summary of the invention Technical issues to be solved by the invention

[0007] An object of the present invention is to provide a compound having high refractive index, high transparency and chemical stability which can be used as an optical material or an optical component. [Technical means to solve the problem]

[0008] The present inventors have successfully improved the high refractive index, high transparency, and chemical stability of polymerizable compositions and polymers, thereby completing the present technology.

[0009] That is, the gist of the present invention is as follows.

[0010] [1] A compound represented by the following formula (1).

[0011] [Chemistry 1]

[0012] [In the formula, A represents a polymerizable group. n represents an integer of 1 to 3. L represents a branched or unbranched (n+1)-valent linking group. Z represents an oxygen atom or a nitrogen atom which may have a substituent. m represents 0 or 1. X represents a single bond, an oxygen atom, a sulfur atom, a carbon atom which may have a substituent, or a nitrogen atom which may have a substituent. p represents an integer of 0 to 2. When p is 2, two Xs are the same or different from each other. Y 1 and Y 2 are independently a benzene ring, a naphthalene ring or a phenanthrene ring. 1 or Y 2 When it is a benzene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 4. 1 or Y 2 When it is a naphthalene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 6. 1 or Y 2 When it is a phenanthrene ring, it corresponds to Y 1 or Y2 a or b is an integer from 0 to 8. R 1 , R 2 Each independently represents an aromatic ring group which may have a substituent. When a and b are 2 or more, a plurality of R 1 , R 2 Same as or different from each other. In the formula, there is no Y 1 With Y 2 are all benzene rings and a and b are both 0].

[0013] [2] The compound according to [1], wherein p is 0 or 1.

[0014] [3] The compound according to [1] or [2], wherein A is an oxirane group, a vinyl group, an isopropenyl group, an allyl group, or a (meth)acryloyl group.

[0015] [4] The compound according to [3], wherein A is a (meth)acryloyl group. [5] The compound according to any one of [1] to [4], wherein Z is a nitrogen atom which may have a substituent. [6] The compound according to any one of [1] to [5], wherein R 1 and / or R 2 It is a condensed aromatic ring group which may have a substituent, or a monocyclic aromatic group substituted with an aromatic ring group. [7] The compound according to any one of [1] to [6], wherein Y 1 and / or Y 2 It is a benzene ring or a naphthalene ring. [8] The compound according to [7], wherein the above Y 1 and Y 2 It is a benzene ring. [9] A polymerizable composition comprising the compound according to any one of [1] to [8] and a polymerization initiator.

[10] A holographic image recording medium comprising the polymerizable composition described in [9].

[11] A polymer obtained by polymerizing the polymerizable composition described in [9].

[12] An optical material comprising the polymer described in

[11] .

[13] An optical component comprising the polymer described in

[11] .

[14] A large-capacity storage device comprising the holographic image recording medium described in

[10] .

[15] An optical element obtained by recording a holographic image on the holographic image recording medium described in

[10] .

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

[15] . [Effects of the Invention]

[0016] According to the present invention, a high refractive index compound having both high transparency and chemical stability such as thermal stability, which can be used as an optical material, is provided. The compound of the present invention is particularly useful as a reactive compound used in a hard coat layer of an optical lens or an optical member or in a holographic image recording medium. By using the compound of the present invention, it is possible to realize an optical material or optical component having high diffraction efficiency, high light transmittance, and high chemical stability.

Simple explanation of the diagram

[0017] Figure 1 This is a schematic diagram showing the outline of the structure of an apparatus used for holographic image recording. [Implementation Method]

[0018] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof.

[0019] In the present invention, "(meth)acrylate" is a general term for acrylate and methacrylate. "(meth)acryloyl" is a general term for acryloyl and methacryloyl. The same applies to "(meth)acrylic acid". In the present invention, “may have a substituent” means that the compound may have one or more substituents.

[0020] 1. About the compounds of the present invention The compound of the present invention is represented by the following formula (1). Hereinafter, the compound represented by the following formula (1) may be referred to as "compound (1)".

[0021] [Chemistry 2]

[0022] [In the formula, A represents a polymerizable group. n represents an integer of 1 to 3. L represents a branchable (n+1)-valent linking group. Z represents an oxygen atom or a nitrogen atom which may have a substituent. m represents 0 or 1. X represents a single bond, an oxygen atom, a sulfur atom, a carbon atom which may have a substituent, or a nitrogen atom which may have a substituent. p represents an integer of 0 to 2. When p is 2, two Xs may be the same or different from each other. Y 1 and Y2 are independently a benzene ring, a naphthalene ring or a phenanthrene ring. 1 or Y 2 In the case of a benzene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 4. 1 or Y 2 In the case of a naphthalene ring, Y 1 or Y 2 a or b is an integer from 0 to 6. 1 or Y 2 In the case of a phenanthrene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 8. R 1 , R 2 Each independently represents an aromatic ring group which may have a substituent. When a and b are 2 or more, a plurality of R 1 , R 2 They can be the same or different from each other. In the formula, there is no Y 1 With Y 2 are all benzene rings and a and b are both 0].

[0023] 1-1. About compound (1) The compound (1) is characterized by a structure in which a linking group having a polymerizable group and an aromatic amine group exhibiting a high refractive index are bonded via a carbonyl bond.

[0024] In optical materials, aromatic amine compounds such as carbazoles are sometimes used as free radical polymerization initiators that generate free radical species by light irradiation. However, in order to improve the chemical stability to heating, light irradiation or oxidation, which is the subject of the present invention, it is strictly prohibited to generate or decompose reactive species represented by free radical species from the aromatic amine structure.

[0025] In compound (1), by bonding the carbonyl group, which is an electron-withdrawing group, to an aromatic amine group, which is rich in electrons and highly reactive, i.e., lowering the HOMO, chemical stability can be imparted, thereby suppressing decomposition or coloration due to heat or light irradiation, oxidation, etc. In addition, by bonding a flexible linking group having a polymerizable group to an aromatic amine skeleton, which is easily rigid and exhibits a high refractive index, the solubility and polymerizability of compound (1) in various media can be improved.

[0026] If in formula (1), Y 1 With Y 2If all of them are benzene rings and a and b are both 0, the proportion of aromatic amine in the whole compound (1) is small, the refractive index of the compound (1) is reduced, and it cannot be said that it is sufficient for the purpose of requiring an ultra-high refractive index greater than 1.65. Therefore, in formula (1), there is no Y 1 With Y 2 The case where both are benzene rings and both a and b are 0.

[0027] 1-2. Regarding A in formula (1) A is a polymerizable group, and its structure is not particularly limited. Examples of polymerizable groups include: (meth)acryloyl, allyl, vinyl, isopropenyl, vinyl-substituted phenyl, isopropenyl-substituted phenyl, vinyl-substituted naphthyl, isopropenyl-substituted naphthyl, oxirane, 2-methyloxirane, oxetane, etc., and a group suitable for the target polymerization method can be selected. In the photopolymerization using a photopolymerization initiator, preferably, an oxirane, vinyl, allyl, (meth)acryloyl group. Among them, based on the consideration of higher reactivity, preferably (meth)acryloyl group.

[0028] 1-3. About n in formula (1) n represents an integer of 1 to 3. This n can be appropriately selected. For example, n=2 or 3 can be selected from the viewpoint of the easiness of polymerizing the compound (1). On the other hand, from the viewpoint of the tendency to achieve a higher refractive index, the compound (1) preferably has a smaller number of polymerizable groups A, and is more preferably a monofunctional compound having 1 polymerizable group A. That is, from the viewpoint of a higher refractive index, n=1 or 2 is preferred, and n=1 is more preferred.

[0029] 1-4. About L in formula (1) L represents a branchable (n+1)-valent linking group. L may have an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.

[0030] As the linking group constituting L, from the viewpoint of its ease of synthesis and ease of acquisition, an aliphatic hydrocarbon group which may have a substituent is preferred. The carbon number of the aliphatic hydrocarbon group (excluding the carbon number of the substituent) is preferably 1 to 8. If the carbon number of the aliphatic hydrocarbon group is 8 or less, the refractive index of the compound (1) is not easily reduced, and the viscosity is reduced due to the small molecular weight, thereby the processability tends to be improved. As the aliphatic hydrocarbon group constituting L, it can be any of a cyclic aliphatic hydrocarbon group and a chain aliphatic hydrocarbon group, and these structures can also be combined. From the viewpoint of alleviating the steric hindrance around the polymerizable group A, a chain aliphatic hydrocarbon group is preferred.

[0031] As the chain aliphatic hydrocarbon group constituting L, when n=1, an alkyl group having 1 to 8 carbon atoms may be mentioned. When n=2 or 3, L may be a combination of two or more alkyl groups having 1 to 8 carbon atoms.

[0032] From the viewpoint of imparting high solubility to the compound (1) in various media, L is preferably an aliphatic hydrocarbon group having an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent. The aliphatic hydrocarbon group may also have a substituent. The carbon number of the aliphatic hydrocarbon group (excluding the carbon number of the substituent) is preferably 1 to 8. If the carbon number of the aliphatic hydrocarbon group is 8 or less, the refractive index of the compound (1) is not easily reduced, and the viscosity is reduced due to the small molecular weight, thereby tending to improve processability. The aliphatic hydrocarbon group constituting L may be any of a cyclic aliphatic hydrocarbon group and a chain aliphatic hydrocarbon group, and these structures may also be combined. From the viewpoint of alleviating the steric hindrance around the polymerizable group A, a chain aliphatic hydrocarbon group is preferred.

[0033] As the chain aliphatic hydrocarbon group having an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent constituting L, the following may be mentioned. When n=1, examples include: oxymethylene, oxyethylene, oxypropylene, 2-oxypropylene, oxybutylene, oxypentylene, oxyhexylene, oxyheptylene, oxyoctylene, -CH2CH2OCH2CH2-, -CH2CH2OCH2CH2O-, -CH2CH2OCH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2O-, -CH2CH2OCH2CH2OCH2CH2O-, -CH2CH2OCH2CH2NH-, -CH2CH2OCH2CH2OCH2CH2NH-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2O-, etc. L may be a combination of two or more of these groups. When n=2 or 3, L may be -C(CH3)(CH2O)2-, or a linking group in which any hydrogen atom in the above-mentioned chain aliphatic hydrocarbon group is replaced with a bond to the polymerizable group. In this case, the group may be bonded to the polymerizable group via a branched structure.

[0034] From the viewpoint of high refractive index, L preferably contains a cyclic group, and the ring contained in the cyclic group constituting L may be a monocyclic structure or a condensed ring structure. The number of rings contained in L is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 to 2. The ring contained in L does not necessarily need to be aromatic, but in order to keep the size occupied in the entire molecule small while maintaining a high refractive index, an aromatic hydrocarbon ring is preferably used. Examples of the aromatic hydrocarbon ring constituting L include a benzene ring, an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, an acenaphthene ring, an anthracene ring, a phenanthrene ring and a pyrene ring.

[0035] The linking group L may have a substituent. Examples of the substituent that L may have include a halogen atom (chlorine atom, bromine atom, iodine atom), a hydroxyl group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a 2,4,6-trimethylphenyl group, a tolyl group, a naphthyl group, a cyano group, an acetoxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, an amide sulfonyl group, an alkylamide sulfonyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetamide group, a dialkylaminoethyl group to which an alkyl group having 1 to 4 carbon atoms is bonded, a trifluoromethyl group, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, and a nitro group.

[0036] 1-5. About Y in Formula (1) 1 , Y 2 , a, b Y 1 , Y 2 Each of them is independently a benzene ring, a naphthalene ring, or a phenanthrene ring. In Y 1 or Y 2 In the case of a benzene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 4. In Y 1 or Y 2 In the case of a naphthalene ring, Y 1 or Y 2 a or b is an integer from 0 to 6. In Y 1 or Y 2 In the case of a phenanthrene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 8.

[0037] Based on the consideration of ease of synthesis and availability of raw materials, Y 1 , Y 2 A benzene ring or a naphthalene ring is preferably each independently selected, and a benzene ring is more preferably selected from the viewpoints of chemical stability and low coloring.

[0038] 1-6. About R in Formula (1) 1 , R 2 R 1 , R 2 It represents an aromatic ring group which may have a substituent. The aromatic ring group is roughly divided into an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

[0039] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, biphenylene ring, trimethylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.

[0040] Examples of the aromatic heterocyclic ring include: an aromatic heterocyclic ring containing one heteroatom such as a furan ring, a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a naphthothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, a pyrrole ring, an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, and an isoquinoline ring; an aromatic heterocyclic ring containing two or more heteroatoms such as an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a thiazole ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a thiadiazole ring; a benzoxazole ring, a thieno[pi]azole ring, a The oxazole ring, thiazolophiazole ring, oxazolooxazole ring, oxazoloimidazole ring, oxazolopyridine ring, oxazolopyridazine ring, oxazolopyrimidine ring, oxazolopyrazine ring, naphthooxazole ring, quinolineoxazole ring, dioxazolopyrazine ring, phenoxazine ring, benzothiazole ring, fluorothiazole ring, thienothiazole ring, thiazolothiazole ring, thiazolophiazole ring, thiazolophiazole ring, thiazolophiazide ring, thiazolophiadiazole ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiazolopyrazine ring, naphthothiazole ring, quinolinethiazole ring, thianthium ring, and phenothiazine ring include a ring formed by the condensation of two or three aromatic heterocyclic rings containing two or more hetero atoms.

[0041] As a component of R 1 , R 2 The aromatic hydrocarbon ring of is preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a biphenylene ring, or a fluorene ring, from the viewpoint of the ease of synthesis and availability. 1 , R 2 The aromatic hydrocarbon rings are more preferably each independently a benzene ring, a naphthalene ring, a biphenylene ring or a fluorene ring.

[0042] As a component of R 1 , R 2 The aromatic heterocycle of is preferably a sulfur-containing aromatic heterocycle, based on the tendency to increase the refractive index of the compound (1). The sulfur-containing aromatic heterocycle has at least a sulfur atom as a hetero atom constituting the aromatic heterocycle. As a hetero atom, in addition to the sulfur atom, it may also have an oxygen atom, may also have a nitrogen atom, or may have an oxygen atom and a nitrogen atom. From the perspective of avoiding coloration and ensuring solubility, the number of hetero atoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, and more preferably 1 to 2.

[0043] Examples of the sulfur-containing aromatic heterocycle include an aromatic heterocycle containing one sulfur atom, such as a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, a thiopyran ring, a naphthothiophene ring, a dinaphthothiophene ring, and a dibenzothiopyran ring; an aromatic heterocycle containing two or more sulfur atoms, such as a thiophene ring; and an aromatic heterocycle containing two or more heteroatoms, such as a thiazole ring, an isothiazole ring, a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazolimidazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a dioxazolopyrazine ring, a thiazolopyrazine ring, a thiazolopyrazine ring, a thiazolooxazole ring, a dibenzobenzothiophene ring, a thienooxazole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring.

[0044] The sulfur-containing aromatic heterocyclic ring may be a single ring or a condensed ring. From the viewpoint of increasing the refractive index, a condensed ring is preferred. The number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5 from the viewpoint of easy access to raw materials or easy synthesis.

[0045] In particular, from the viewpoint of increasing the refractive index and reducing the coloring property, the sulfur-containing aromatic heterocyclic ring is preferably a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, or a thione ring.

[0046] As a component of R 1 , R 2 The aromatic heterocycle may be a nitrogen-containing aromatic heterocycle from the viewpoint of its ease of synthesis. The nitrogen-containing aromatic heterocycle has at least a nitrogen atom as a heteroatom constituting the aromatic heterocycle. As heteroatoms, in addition to nitrogen atoms, oxygen atoms, sulfur atoms, or both oxygen atoms and sulfur atoms may be present. From the perspective of avoiding coloration, the number of heteroatoms constituting the nitrogen-containing aromatic heterocycle is preferably 1 to 3, and more preferably 1 to 2.

[0047] Examples of the nitrogen-containing aromatic heterocyclic ring include an aromatic heterocyclic ring containing one nitrogen atom, such as a pyrrole ring, an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a naphthooxazole ring, a benzothiazole ring, a naphthothiazole ring, a phenoxazine ring, a phenothiazine ring, a thienooxazole ring, a thiazolooxazole ring, an oxazolooxazole ring, a fluorothiazole ring, a thienothiazole ring, and a thiazolothiazole ring; and an aromatic heterocyclic ring containing one nitrogen atom, such as an imidazole ring, a triazole ring, Aromatic heterocyclic rings containing two or more nitrogen atoms such as a tetrazole ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiadiazole ring, a benzimidazole ring, an oxazolidinimide ring, an oxazolopyridine ring, an oxazolopyridazine ring, an oxazolopyrimidine ring, an oxazolopyrazine ring, a hydroxyquinolineoxazole ring, a dioxazolopyrazine ring, a thiazolimidazole ring, a thienothiadiazole ring, a thiazolinothiadiazole ring, a thiazolinothiadiazole ring, a thiazolinotpyridine ring, a thiazolinotpyridazine ring, a thiazolinotpyrimidine ring, a thiazolinotpyrazine ring, and a quinolinethiazole ring.

[0048] The nitrogen-containing aromatic heterocyclic ring may be a monocyclic ring or a condensed ring. From the viewpoint of increasing the refractive index, a condensed ring is preferred. The number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5 from the viewpoint of easy access to raw materials or easy synthesis.

[0049] In particular, based on the considerations of high refractive index and low coloration, the nitrogen-containing aromatic heterocycle is preferably a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, or a thiadiazole ring, and more preferably a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, or a thiadiazole ring.

[0050] As a component of R 1 , R 2 The aromatic heterocycle may be an oxygen-containing aromatic heterocycle. The oxygen-containing aromatic heterocycle tends to improve the heat resistance or weather resistance of the polymer produced using compound (1) as a raw material. The oxygen-containing aromatic heterocycle has at least an oxygen atom as a heteroatom constituting the aromatic heterocycle. As heteroatoms, in addition to oxygen atoms, nitrogen atoms, sulfur atoms, or nitrogen and sulfur atoms may be present. In view 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.

[0051] Examples of the oxygen-containing aromatic heterocycle include: an aromatic heterocycle containing one oxygen atom, such as a furan ring, a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a phenoxazine ring, an oxazole ring, an isoxazole ring, a benzoxazole ring, a benzisoxazole ring, a naphthoxazole ring, a thienoxazole ring, a thiazoloxazole ring, an oxazolidinazole ring, and a fluorothiazole ring; and an aromatic heterocycle containing two or more oxygen atoms, such as a dibenzodioxine ring, an oxazoloxazole ring, and a dioxazolopyrazine ring.

[0052] The oxygen-containing aromatic heterocyclic ring may be a monocyclic ring or a condensed ring. From the viewpoint of increasing the refractive index, a condensed ring is preferred. The number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5 from the viewpoint of easy access to raw materials or easy synthesis.

[0053] In particular, from the perspective of high refractive index and low coloring, the oxygen-containing aromatic heterocycle is preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, an oxazole ring, an isoxazole ring, a benzoxazole ring, a benzisoxazole ring, or a naphthoxazole ring, and more preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, or a benzoxazole ring.

[0054] These constitute R 1 , R 2The aromatic ring may have a substituent. Examples of the substituent include halogen atoms such as chlorine, bromine, and iodine; alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkynyl groups having 2 to 8 carbon atoms, alkoxy groups, cyano groups, acetoxy groups, alkylcarbonyloxy groups having 2 to 9 carbon atoms, alkoxycarbonyl groups having 2 to 9 carbon atoms, sulfonyl groups, alkylsulfonyl groups having 2 to 9 carbon atoms, alkylcarbonyl groups having 2 to 9 carbon atoms, phenethyl groups, hydroxyethyl groups, acetamide groups, dialkylaminoethyl groups formed by bonding alkyl groups having 1 to 4 carbon atoms, trifluoromethyl groups, alkylthio groups having 1 to 8 carbon atoms, aromatic ring thio groups having 6 to 10 carbon atoms, and nitro groups. Among them, preferred examples include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, a cyano group, an acetoxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, an amide sulfonyl group, an alkylamide sulfonyl group having 2 to 9 carbon atoms, and a nitro group.

[0055] About these components R 1 , R 2 The aromatic ring of the compound (1) is preferably further substituted with a group containing an aromatic ring from the viewpoint of increasing the refractive index of the compound (1). 1 , R 2 The aromatic rings contained in these substituents may be at any position with the aromatic rings constituting R 1 , R 2 The aromatic ring of R may be directly bonded to the aromatic ring, or may be bonded to the aromatic ring of R through an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent. 1 The aromatic ring of R 1 The substituent is more preferably directly bonded to the aromatic ring constituting R 1 , R 2 Aromatic ring.

[0056] In addition, when the aromatic ring contained in the substituent is a sulfur-containing aromatic heterocyclic ring, the refractive index of the compound (1) tends to be higher. The definition of the sulfur-containing aromatic heterocyclic ring is the same as R 1 , R 2 The sulfur-containing aromatic heterocyclic ring in is synonymous with the sulfur-containing aromatic heterocyclic ring. As the sulfur-containing aromatic heterocyclic ring, a condensed ring is more preferred, and a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, or a thienyl ring is particularly preferred.

[0057] R 1 , R 2 The number of aromatic rings as a substituent is not particularly limited, but is preferably 1 to 4, more preferably 1 to 2, from the viewpoint of ease of synthesis and solubility.

[0058] About the composition R 1 , R 2The aromatic rings are preferably independently fused aromatic rings which may have substituents, or monocyclic aromatic rings substituted with aromatic ring groups, based on the viewpoint of taking into account both high refractive index and high solubility in various media, and more preferably fused aromatic heterocycles which may have substituents, or aromatic hydrocarbon rings having aromatic heterocycles as substituents.

[0059] Composition R 1 , R 2 The aromatic ring of may have two or more selected from the above-mentioned sulfur-containing aromatic heterocyclic rings, nitrogen-containing aromatic heterocyclic rings, and oxygen-containing aromatic heterocyclic rings.

[0060] 1-7. About Z in Formula (1) Z represents an oxygen atom, or a nitrogen atom which may have a substituent, that is, a nitrogen atom which does not have a substituent or a nitrogen atom which has a substituent.

[0061] When the nitrogen atom of Z has a substituent, examples of the substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a phenyl group, a 1,3,5-trimethylphenyl group, a tolyl group, a naphthyl group, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetamido group, a trifluoromethyl group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 20 carbon atoms.

[0062] As Z, based on the viewpoint of solubility in various media, an oxygen atom is preferably used. In addition, based on the viewpoint of ease of obtaining raw materials, as Z, a nitrogen atom that may have a substituent is preferably used. In particular, based on the viewpoint of ease of synthesis and the high refractive index of the polymer that can be expected by utilizing intermolecular hydrogen bonds, as Z, a nitrogen atom that does not have a substituent is more preferably used.

[0063] 1-8. About m in formula (1) m represents 0 or 1. This m can be appropriately selected. For example, from the viewpoint of improving the solubility of the compound (1) in various media, m=1 is preferred. On the other hand, from the viewpoint of the chemical stability of the compound (1), m=0 is preferred.

[0064] 1-9. About X in formula (1) X represents a single bond, an oxygen atom, a sulfur atom, a carbon atom which may have a substituent, or a nitrogen atom which may have a substituent.

[0065] X is preferably a single bond because it tends to achieve a high refractive index of the compound (1). When X=single bond, the compound (1) is preferably a carbazole compound because of ease of synthesis.

[0066] From the perspective of the tendency to improve the solubility of compound (1) in various media, X is preferably an oxygen atom, a sulfur atom, a carbon atom which may have a substituent, or a nitrogen atom which may have a substituent. In particular, from the perspective of the tendency to achieve a high refractive index, X is more preferably a sulfur atom. On the other hand, from the perspective of being able to adjust the physical properties of the medium used, a carbon atom which may have a substituent, or a nitrogen atom which may have a substituent is more preferably used.

[0067] Examples of the substituent that the carbon atom constituting X may have include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a 1,3,5-trimethylphenyl group, a tolyl group, a naphthyl group, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, a trifluoromethyl group, an alkylthio group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, an aromatic cyclic thio group having 6 to 10 carbon atoms, and a nitro group.

[0068] Examples of the substituent that the nitrogen atom constituting X may have include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a phenyl group, a 1,3,5-trimethylphenyl group, a tolyl group, a naphthyl group, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetamido group, a trifluoromethyl group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 20 carbon atoms.

[0069] 1-10. Regarding p in formula (1) p represents an integer of 0 to 2. This p can be appropriately selected. For example, from the viewpoint that the refractive index of the compound (1) tends to be high, p is preferably an integer of 1 to 2. On the other hand, from the viewpoint of improving the solubility of compound (1) in various media, p=0 is preferred. From the viewpoint of increasing the refractive index and solubility, p is preferably 0 or 1.

[0070] 1-11. Suitable compounds of compound (1) From the viewpoint of increasing the refractive index and easiness of synthesis, the compound (1) is preferably a compound in which X in the above formula (1) is a single bond, and is preferably a compound represented by the following formula (2).

[0071] [Chemistry 3]

[0072] In the above formula (2), A, n, L, Z, m, Y 1 , Y 2 , R 1 , R 2 , a, and b have the same meanings as in the above formula (1), and preferred ones are also the same.

[0073] 1-12. Molecular weight From the viewpoint of suppressing the viscosity to be low and maintaining good processability, the molecular weight of the compound (1) is preferably 2000 or less, more preferably 1500 or less, and further preferably 1200 or less. From the viewpoint of reducing the shrinkage during polymerization, the molecular weight of the compound (1) is preferably 400 or more, more preferably 450 or more, and further preferably 500 or more.

[0074] 1-13. Relationship between molecular structure and physical properties Compound (1) has the following effect: by bonding a flexible linking group containing a polymerizable group to a nitrogen atom of a highly planar aromatic amine compound such as a carbazole compound, a benzocarbazole compound, a dibenzocarbazole compound, a phenothiazine compound, a phenoxazine compound, acridine compound, an iminostilbene compound, etc. through a carbonyl bond, the HOMO of the aromatic amine compound is lowered. This can simultaneously achieve the improvement of the stability of the compound against heating, light irradiation, oxidation, etc., the assurance of the solubility of the monomer in various media, and the adjustment of the compatibility between the polymer after the polymerization reaction and the medium.

[0075] Generally speaking, by introducing a carbonyl bond into the aromatic ring of an aromatic amine compound, the effect of reducing the HOMO of the aromatic amine compound can also be expected. However, in this case, there is a tendency that the energy difference between HOMO and LUMO is smaller than that of compound (1), and there is a concern that the compound will develop color. Therefore, in the use of optical materials that are colorless and transparent in the visible light range, it is preferred to introduce a carbonyl bond into the nitrogen atom as in formula (1). In addition, in the compound (1) having R 1 , R 2 In the case of 1 or R 2 The molecular twisting that makes the dihedral angle of the linking part with the aromatic amine skeleton 0 degrees or more is appropriately introduced into the monomer and the polymer. This can further improve the solubility in various media and can be used as a polymerizable monomer with an ultra-high refractive index.

[0076] 1-14.Exemplary compounds Specific examples of the compound (1) are shown below, but the compound (1) of the present invention is not limited thereto unless it exceeds the scope of the present invention.

[0077] [Chemistry 4]

[0078] [Chemistry 5]

[0079] [Chemistry 6]

[0080] 1-15. Synthesis method Compound (1) can be synthesized by combining various known methods, for example, by reacting a compound represented by the following formula (3) (hereinafter sometimes referred to as "compound (3)") with a carbonylating agent such as isocyanate having a polymerizable group.

[0081] [Chemistry 7]

[0082] [Where X, p, Y 1 , Y 2 , R 1 , R 2 a, b have the same meanings as those in the above formula (1)]

[0083] One example of the synthesis of compound (1) is described below.

[0084] [Chemistry 8]

[0085] [In the above reaction formula, Z, m, L, A, and n have the same meanings as those in the above formula (1). 6 In the following reaction formula, the same symbols as those in formula (1) also represent the same ones]

[0086] For example, compound (1) can be produced by reacting the amine group of compound (3) with a carbonylating agent compound having a polymerizable group represented by formula (i) (hereinafter sometimes referred to as carbonylating agent (i)). When Z has a nitrogen atom without a substituent, the compound (1) can also be produced using isocyanates represented by the above formula (ii) (hereinafter sometimes referred to as "isocyanates (ii)").

[0087] Examples of the carbonylating agent (i) include acid chlorides such as 4-vinylbenzoyl chloride and chloroformates such as allyl chloroformate.

[0088] Examples of the isocyanates (ii) include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethoxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0089] The reaction of the active hydrogen of the amino group in formula (3) with the carbonylating agent (i) or the isocyanate (ii) can be carried out by a known method. For example, compound (3) is reacted with isocyanate (ii) in the presence of a basic compound to obtain compound (1).

[0090] The basic compound may be one or more organic basic compounds (triethylamine, diisopropylethylamine, 1,1,3,3-tetramethylguanidine, diazabicycloundecene, diazabicyclononene, pyridine, imidazole, etc.), or one or more inorganic basic compounds (sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, potassium tert-butoxide, etc.). One or more organic basic compounds and one or more inorganic basic compounds may be combined.

[0091] In the reaction of compound (3) with carbonylating agent (i) or isocyanate (ii), it is preferred to use an organic solvent. Examples of the organic solvent include dichloromethane, tetrahydrofuran (THF), dimethoxyethane, toluene, N,N-dimethylformamide (DMF), etc. The organic solvent may be one kind or two or more kinds may be used in combination.

[0092] In the manufacture of compound (1), it is preferred to purify the reactant (crude product) obtained in the synthesis reaction. Low coloring can be achieved by removing impurities through purification. As a purification method, known techniques can be applied. For example, purification can be performed by extraction, column chromatography, recrystallization, distillation, etc. These purification methods can be implemented by only one method or in combination.

[0093] When the compound (1) is solid at room temperature, it is preferred to use a recrystallization method from the viewpoint of facilitating high degree of removal of coloring matter.

[0094] Examples of the recrystallization solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and mesitylene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, tert-butyl methyl ether, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, 2-methoxyethanol, 2-butoxyethanol, and propylene glycol monomethyl ether; glycols such as ethylene glycol and diethylene glycol; water, etc. These solvents may be used alone or in combination of two or more.

[0095] [Chemistry 9]

[0096] [In the above reaction formula, X 3 , X 4 , X 5 represents a leaving group such as a halogen atom. Z' and A' represent chemical species that are precursors of Z and A]

[0097] Compound (1) can also be produced by reacting compound (3) with a carbonylating agent represented by the above formula (iii) represented by phosgene or triphosgene or carbonyldiimidazole (hereinafter sometimes referred to as "carbonylating agent (iii)") to obtain a compound represented by the above formula (4) as an intermediate (hereinafter sometimes referred to as "intermediate (4)"), and then reacting the obtained compound with a reagent represented by the above formula (iv) having a polymerizable group (hereinafter sometimes referred to as "reagent (iv)").

[0098] Furthermore, compound (1) can also be produced by reacting compound (3) with a carbonylating agent (iii) or a compound having a linking group represented by formula (v) (hereinafter sometimes referred to as "compound (5)") with a polymerizable group precursor represented by formula (vi), or by subjecting compound (5) to a polymerizable group forming reaction such as an oxidation reaction or a cyclization reaction.

[0099] Compound (3) which is a starting material of Compound (1) can be produced by combining various known methods.

[0100] [Chemistry 10]

[0101] For example, the aromatic group R can be linked to the aromatic halide represented by the above formula (6) by a coupling reaction with the organic reagent represented by the above formula (vii) and formula (viii). 1 , R 2 The compounds (3) can be synthesized by combining them simultaneously or sequentially.

[0102] 2. Regarding the polymerizable composition of the present invention The polymerizable composition of the present invention contains the compound (1) and a polymerization initiator. The polymerizable functional group A of the compound (1) undergoes a polymerization reaction with a polymerization initiator, thereby obtaining the polymer of the present invention.

[0103] 2-1. Polymerization initiator The type of the polymerization initiator is not particularly limited, and may be appropriately selected from known polymerization initiators depending on the polymerization method. The polymerization method is not limited, and polymerization can be carried out by a known method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, partial polymerization, or the like.

[0104] Examples of the polymerization initiator contained 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 cations as active species upon light irradiation may also be used. The following examples of polymerization initiators also include those generally called polymerization catalysts.

[0105] 2-1-1. Radical polymerization initiator <Photopolymerization initiator> As for the photopolymerization initiator that assists the polymerization of the polymerizable composition of the present invention, any one can be used as long as it is a known photoradical polymerization initiator. For example, 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, aminoformic acid derivatives, sulfonamides, triarylcarbinols, oxime esters, etc. can be used. Among them, as the photopolymerization initiator, benzophenones, acylphosphine oxide compounds, oxime ester compounds, etc. are preferred from the viewpoints of compatibility and ease of acquisition.

[0106] Specific examples of the photopolymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, tert-butyl anthraquinone, 2-ethyl anthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligomeric {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl)phenyl]propanone, and the like. phenyl)-butanone-1, diethyl thioxanthone, isopropyl thioxanthone, 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-methylpropane-1-one and methyl benzoylformate, 1-[4-(phenylthio)-2-(O-benzoyl oxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime)ethanone, etc.

[0107] These photopolymerization initiators may be used alone or in combination of two or more in any combination and ratio.

[0108] Regarding the content of the photopolymerization initiator in the polymerizable composition of the present invention, when the total of all compounds capable of free radical polymerization in the polymerizable composition is set to 100 parts by mass, it 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. Its 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 the content of the photopolymerization initiator is too much, there is a concern that the polymerization proceeds violently, not only increasing the birefringence of the cured body, but also deteriorating the hue. On the other hand, if the amount of the photopolymerization initiator added is too little, there is a concern that the polymerizable composition is not fully polymerized.

[0109] <Thermal polymerization initiator> As a thermal polymerization initiator that assists the polymerization of the polymerizable composition of the present invention, any known thermal free radical polymerization initiator may be used. Examples thereof include organic peroxides and azo compounds. Among them, organic peroxides are preferred from the viewpoint that bubbles are not easily generated in the polymer obtained in the polymerization reaction.

[0110] Specific examples of organic peroxides include: ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, and 1,1-di(tert-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; diisopropylbenzene peroxide, Dialkyl peroxides such as di-tert-butyl peroxide; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-tert-butylcyclohexyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate; and peroxyesters such as tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl perbenzoate, and 1,1,3,3-tetramethylbutyl-2-ethylhexanoate.

[0111] Specific examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, 2,2'-azobisisobutyric acid dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane) dihydrochloride.

[0112] These thermal polymerization initiators may be used alone or in combination of two or more in any combination and ratio.

[0113] Regarding the content of the thermal polymerization initiator in the polymerizable composition of the present invention, when the total of all free radical polymerizable compounds in the polymerizable composition is set to 100 parts by mass, it 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. Its 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 the content of the thermal polymerization initiator is too much, there is a concern that the polymerization proceeds rapidly, not only damaging the optical uniformity of the obtained polymer, but also deteriorating the hue. On the other hand, if the content of the thermal polymerization initiator is too little, there is a concern that the thermal polymerization is not sufficiently carried out.

[0114] When a photopolymerization initiator and a thermal polymerization initiator are used together, the mass ratio thereof is generally "100:1" to "1:100" ("photopolymerization initiator: thermal polymerization initiator", the same shall apply in this paragraph below), preferably "10:1" to "1:10". If the thermal polymerization initiator is too little, polymerization may be insufficient, and if the thermal polymerization initiator is too much, there is a concern of coloration.

[0115] 2-1-2. Redox polymerization initiator The redox polymerization initiator is a free radical initiator that utilizes a redox reaction by combining a peroxide and a reducing agent. It can generate free radicals even at low temperatures and is generally used in emulsion polymerization and the like.

[0116] Specific examples of redox polymerization initiators include: a combination of dibenzoyl peroxide as a peroxide and aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine as a reducing agent; a combination of hydrogen peroxide as a peroxide and metal soaps as a reducing agent; a combination of hydrogen peroxide as a peroxide and thioureas as a reducing agent, etc. Regarding the water-soluble redox polymerization initiator, a peroxide such as persulfate, hydrogen peroxide, or hydroperoxide is mixed with a water-soluble inorganic reducing agent (Fe 2+ Or NaHSO3, etc.) or an organic reducing agent (alcohol, polyamine, etc.) are used in combination.

[0117] The preferred range of the content of the redox polymerization initiator in the polymerizable composition of the present invention is the same as that of the thermal polymerization initiator.

[0118] 2-1-3. Anionic polymerization initiator Examples of the anionic polymerization initiator used in the polymerizable composition of the present invention include alkali metals, n-butyl lithium, sodium amide, sodium naphthalenide, Grignard reagents, lithium alkoxides, alkali metal ketyl benzophenones, etc. These may be used alone or in combination of two or more in any combination and ratio.

[0119] 2-1-4. Cationic polymerization initiator Examples of the cationic polymerization initiator used in the polymerizable composition of the present invention include: Brunst acids such as perchloric acid, sulfuric acid, and trichloroacetic acid; Lewis acids such as boron trifluoride, aluminum trichloride, aluminum tribromide, and tin tetrachloride; iodine, chlorotriphenylmethane, etc. These may be used alone or in combination of two or more in any combination and ratio.

[0120] The amount of the anionic polymerization initiator or cationic polymerization agent in the polymerizable composition of the present invention is generally 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more, relative to a total of 100 parts by mass of all compounds capable of anionic or cationic polymerization in the polymerizable composition. The upper limit is generally 5 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less. If the anionic or cationic polymerization initiator is less than 0.001 parts by mass, a sufficient reaction is not caused. If the amount is greater than 5 parts by mass, it is difficult to take into account both the application time and the polymerization rate.

[0121] 2-1-5. Photocationic polymerization initiator The photocationic polymerization initiator in the present invention is an initiator that generates cationic species by light. As the photocationic polymerization initiator, there is no particular limitation, as long as it is a compound that generates cationic species by light irradiation, and onium salts are generally known. As onium salts, diazonium salts of Lewis acid, iodonium salts of Lewis acid, sulfonium salts of Lewis acid, etc. can be cited. Specifically, phenyldiazonium salts of boron tetrafluoride, diphenyliodonium salts of phosphorus hexafluoride, diphenyliodonium salts of antimony hexafluoride, tri-4-methylphenylsulfonium salts of arsenic hexafluoride, tri-4-methylphenylsulfonium salts of antimony tetrafluoride, etc. can be cited. Aromatic sulfonium salts can be preferably used.

[0122] Specific examples of the photocationic polymerization initiator include: S,S,S',S'-tetraphenyl-S,S'-(4,4'-thiodiphenyl)disulfonium bishexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluoroantimonate, and the like. Examples include: UVI-6992 manufactured by Dow Chemical, CPI-100P manufactured by SAN-APRO, CPI-101A manufactured by SAN-APRO, CPI-200K manufactured by SAN-APRO, Omnicat 270 manufactured by IGM Resins, and the like.

[0123] These photocationic polymerization initiators may be used alone or in combination of two or more in any combination and ratio.

[0124] The content of the photocationic polymerization initiator in the polymerizable composition of the present invention is preferably 0.02 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total of all the compounds capable of photocationic polymerization in the polymerizable composition. If the photocationic polymerization initiator is less than 0.02 parts by mass, a sufficient reaction will not occur, and if it is more than 20 parts by mass, it will be difficult to achieve a balance between the pot life and the polymerization rate.

[0125] In the process of using the photocationic polymerization initiator, the above-mentioned cationic polymerization initiator may also be used in combination. In this 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, relative to 100 parts by mass of the cationic polymerizable compound in the polymerizable composition. If the amount of the cationic polymerization initiator used is too small, there is a concern that the polymerization rate will slow down. On the other hand, if the amount of the cationic polymerization initiator used is too large, there is a concern that the physical properties of the obtained polymer will be reduced.

[0126] In addition, during the use of the photocationic polymerization initiator, a photocationic polymerization sensitizer may also be used. The so-called photocationic polymerization sensitizer is a formula that efficiently transfers the energy of the irradiated light to the photocationic polymerization initiator when the irradiated light of the light source used for photocationic polymerization does not match the absorption wavelength of the photocationic polymerization initiator, and the photocationic polymerization sensitizer is used. Phenolic compounds such as methoxyphenol (Japanese Patent Laid-Open No. 5-230189), thioxanthone compounds (Japanese Patent Laid-Open No. 2000-204284), and dialkoxy anthracene compounds (Japanese Patent Laid-Open No. 2000-119306) are known.

[0127] The photocationic polymerization sensitizer is used in an amount of usually 0.2 to 5 parts by mass, preferably 0.5 to 1 part by mass, relative to 1 part by mass of the photocationic polymerization initiator. If the amount of the photocationic polymerization sensitizer is too small, the sensitizing effect may not be easily exhibited. On the other hand, if the amount of the photocationic polymerization sensitizer is too large, the physical properties of the polymer may be reduced.

[0128] 2-2. About polymerizable compounds The polymerizable compound contained in the polymerizable composition of the present invention may be any one of the compounds of the present invention represented by formula (1) alone, or may be contained in any combination and ratio of two or more.

[0129] The polymerizable composition of the present invention may contain other polymerizable compounds in addition to the compound (1).

[0130] The content of the compound (1) of the present invention in the polymerizable composition of the present invention is 1% by mass or more and 99% by mass or less, preferably 5% by mass or more and 95% by mass or less, based on 100% by mass of the total solid content of the polymerizable composition of the present invention. If the content of the compound (1) of the present invention is less than 1% by mass, the effect of using the compound (1) tends not to be fully exerted, while if the content of the compound (1) exceeds 99% by mass, the curability tends to decrease.

[0131] Examples of other polymerizable compounds other than compound (1) include cationic polymerizable monomers, anionic polymerizable monomers, free radical polymerizable monomers, etc. These polymerizable compounds may be used alone, or two or more may be used in any combination and ratio. In addition, polymerizable compounds having two or more polymerizable functional groups in one molecule (sometimes referred to as multifunctional monomers) may also be used. When a multifunctional monomer is used, since a cross-linked structure is formed inside the polymer, thermal stability, weather resistance, and solvent resistance may also be improved.

[0132] When the polymerizable composition of the present invention contains other polymerizable compounds other than compound (1), the content thereof is preferably 0.1% by mass or more and 10% by mass or less, and particularly preferably 0.3% by mass or more and 5% by mass or less, based on 100% by mass of the total solid content of the polymerizable composition of the present invention. If the content of the other polymerizable compounds is less than 0.1% by mass, the property-imparting effect due to the addition of the other polymerizable compounds tends not to be fully exerted, while if it is more than 5% by mass, problems such as loss of optical properties and strength tend to occur.

[0133] <Cationically polymerizable monomer> Examples of the cationically polymerizable monomer include compounds having an oxirane ring, styrene and derivatives thereof, vinylnaphthalene and derivatives thereof, vinyl ethers, N-vinyl compounds, compounds having an oxetane ring, and the like. Among them, it is preferable to use a compound having at least an oxirane ring, and it is more preferable to use a compound having an oxetane ring and a compound having an oxirane ring in combination.

[0134] The compound having an ethylene oxide ring may, for example, be a polymerizable monomer containing two or more ethylene oxide rings in one molecule. Examples of such polymerizable monomers include alicyclic polyepoxides, polyglycidyl esters of polyacids, polyglycidyl ethers of polyols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxides, and epoxidized polybutadienes.

[0135] Examples of styrene and derivatives thereof include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, and divinylbenzene.

[0136] Examples of vinylnaphthalene and derivatives thereof include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, and 4-methoxy-1-vinylnaphthalene.

[0137] Examples of the vinyl ethers include isobutyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether, and the like.

[0138] Examples of the N-vinyl compound include N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, and N-vinylphenothiazine.

[0139] Examples of the compound having an oxetane ring include various known oxetane compounds described in JP-A-2001-220526 and JP-A-2001-310937.

[0140] These cationically polymerizable monomers may be used alone or in combination of two or more in any combination and ratio.

[0141] <Anionic polymerizable monomer> Examples of the anionic polymerizable monomer include hydrocarbon monomers and polar monomers.

[0142] Examples of the hydrocarbon monomer include styrene, α-methylstyrene, butadiene, isoprene, vinylpyridine, vinylanthracene, and derivatives thereof.

[0143] Examples of polar monomers include: methacrylates (e.g., methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, etc.); acrylates (e.g., methyl acrylate, ethyl acrylate, etc.); vinyl ketones (e.g., methyl vinyl ketone, isopropyl vinyl ketone, cyclohexyl vinyl ketone, phenyl vinyl ketone, etc.); isopropenyl ketones (e.g., methyl isopropenyl ketone, phenyl isopropenyl ketone, etc.); other polar monomers (e.g., acrylonitrile, acrylamide, nitroethylene, methylene malonate, cyanoacrylate, dicyandiamide, etc.), etc.

[0144] These anionic polymerizable monomers may be used alone or in combination of two or more in any combination and ratio.

[0145] <Free radical polymerizable monomer> Examples of the radical polymerizable monomers are compounds having one or more ethylenically unsaturated double bonds in one molecule, such as (meth)acrylates, (meth)acrylamides, vinyl esters, and styrenes.

[0146] Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (n- or iso-)propyl (meth)acrylate, (n-, iso-, primary- or tert-)butyl (meth)acrylate, pentyl (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, 2-(Hydroxyphenylcarbonyloxy)ethyl (meth)acrylate, phenol EO-modified (meth)acrylate, phenylphenol EO-modified (meth)acrylate, p-isopropylphenylphenol EO-modified (meth)acrylate, nonylphenol EO-modified (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, bisphenol F EO modified diacrylate, bisphenol A EO modified diacrylate, dibromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl acrylate, tricyclodecane dimethylol di(meth)acrylate, bisphenoxyethanol fluorene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Here, "EO" means "ethylene oxide".

[0147] 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-(sulfamoylphenyl)(meth)acrylamide, N-(phenylsulfonyl)(meth)acrylamide, N-(tolylsulfonyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, and N-hydroxyethyl-N-methyl(meth)acrylamide.

[0148] Examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoate, vinyl tert-butyl benzoate, vinyl chlorobenzoate, 4-ethoxy vinyl benzoate, 4-ethyl vinyl benzoate, 4-methyl vinyl benzoate, 3-methyl vinyl benzoate, 2-methyl vinyl benzoate, 4-phenyl vinyl benzoate, and vinyl pivalate.

[0149] Examples of styrenes include styrene, p-acetyl styrene, p-benzoyl styrene, 2-butoxymethyl styrene, 4-butyl styrene, 4-sec-butyl styrene, 4-tert-butyl styrene, 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.

[0150] These radical polymerizable monomers may be used alone or in combination of two or more in any combination and ratio.

[0151] Any of the cationically polymerizable monomers, anionic polymerizable monomers, and radical polymerizable monomers exemplified above may be used, and two or more of them may be used in combination. For example, when used for a high refractive index optical lens or a hologram recording medium, it is preferable to use a radical polymerizable monomer as the other polymerizable compound used in combination with the compound (1) because it is less likely to inhibit the reaction of forming the resin matrix.

[0152] 2-3. Other added ingredients The polymerizable composition of the present invention may contain other components within a range not impairing the effects of the present invention.

[0153] Examples of other components include various additives such as solvents, antioxidants, plasticizers, ultraviolet absorbers, sensitizers, chain transfer agents, defoamers, polymerization inhibitors, any fillers including organic or inorganic substances, diffusing agents, pigments, and wavelength conversion materials such as phosphors.

[0154] The polymerizable composition of the present invention may contain a solvent to adjust the viscosity.

[0155] Specific examples of the solvent include, depending on the physical properties of the polymerizable composition, alcohols such as ethanol, propanol, isopropanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as hexane, pentane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; chain ethers such as dimethyl ether and diethyl ether; cyclic ethers such as dioxane and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and ethyl butyrate; acetone, methyl ethyl ketone, and methyl isobutyl ketone. , cyclohexanone and other ketones; methyl cellosolve, ethyl cellosolve, butyl cellosolve and other cellosolves; methyl carbitol, ethyl carbitol, butyl carbitol and other carbitols; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and other glycol ether esters; N,N-dimethylformamide, N,N-dimethylacetamide, etc.), sulfoxides (amides such as dimethyl sulfoxide; nitriles such as acetonitrile, benzonitrile and other organic solvents such as N-methylpyrrolidone.

[0156] These solvents may be used alone or as a mixed solvent. In addition, water may be used depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.). When a solvent (or dispersion medium) is used, the amount thereof is not particularly limited, and may be adjusted and used so as to obtain a polymerizable composition having an appropriate viscosity according to the polymerization method, processing method, and application.

[0157] In the present invention, in order to improve the heat yellowing resistance or weather resistance of the obtained polymer, it is preferred to mix an antioxidant or a light stabilizer as an additive in the polymerizable composition.

[0158] Specific examples of antioxidants include phenolic antioxidants such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate]methane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], and 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; and triphenyl phosphite, triisodecyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, tetra(C12-C1 Phosphorus-based antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tris(tridecyl)phosphite, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexane-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocene, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di-octadec-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and tris(2,4-di-tert-butylphenyl)phosphite. These may be used alone or in combination of two or more.

[0159] As the antioxidant, it is preferred to use a phenolic antioxidant and a phosphorus antioxidant in combination. As a preferred combination of a phenolic antioxidant and a phosphorus antioxidant, there can be mentioned: a combination of at least one selected from tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane and 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate n-octadecyl ester as a phenolic antioxidant and tris(2,4-di-tert-butylphenyl) phosphite as a phosphorus antioxidant.

[0160] The amount of the 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 the polymerizable composition, from the viewpoint of improving the heat yellowing resistance of the obtained polymer.

[0161] As the light stabilizer, a hindered amine light stabilizer (HALS) is preferably used. Specific examples of HALS include: 2,2,6,6-tetramethyl-4-piperidyl 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-undecyloxypiperidin-4-yl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Adekastab LA-68 (manufactured by ADEKA Co., Ltd.), Adekastab LA-63P (manufactured by ADEKA Co., Ltd.), butane-1,2,3,4-tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)ester, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidyl)ester, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 249, TINUVIN 292, TINUVIN 5100 (all manufactured by BASF), etc. These may be used alone or in combination of two or more.

[0162] From the viewpoint of improving the heat yellowing resistance or weather resistance of the obtained polymer, the amount of the 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, relative to 100 parts by mass of the total amount of the polymerizable composition.

[0163] The antioxidant and the light stabilizer may be used alone or in combination of two or more.

[0164] 2-4. Method for producing polymerizable composition The polymerizable composition of the present invention may be produced by mixing the components, or may be produced by preliminarily mixing the components other than the polymerization initiator and then adding the polymerization initiator immediately before the polymerization reaction.

[0165] 3. Polymerization method of the polymerizable composition of the present invention The polymerization method of the polymerizable composition of the present invention is not particularly limited, and there are a method of polymerizing by irradiating active energy rays and a method of polymerizing by heating.

[0166] 3-1. Polymerization initiation method (active energy beam) When the polymerizable composition of the present invention is subjected to photoradical polymerization, the polymerization is carried out by irradiating active energy rays. As the active energy line used, preferably an electron beam or light in the wavelength range from ultraviolet to infrared. As the light source, for example, if the active energy line is ultraviolet light, an ultrahigh 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 light, a halogen light source can be used. In addition, light sources such as lasers and LEDs can also be used.

[0167] The irradiation amount of the active energy ray is appropriately set according to the type of light source, the film thickness of the coating film, etc., and is preferably appropriately set so that the total reaction rate of the polymerizable functional groups of the compound (1) and other polymerizable compounds reaches 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 based on the infrared absorption spectrum. After polymerization is carried out by irradiation with active energy rays, a heating treatment or an annealing treatment may be carried out as necessary to further advance the polymerization. The heating temperature at this time is preferably in the range of 80 to 200° C. The heating time is preferably in the range of 10 to 60 minutes.

[0168] 3-2. Polymerization initiation method (heating) When the polymerizable composition of the present invention is subjected to heat treatment in order to polymerize, the heating temperature is preferably in the range of 80 to 200° C., 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 prolonged, which tends to be less economical, and if the heating temperature is higher than 200° C., energy costs are incurred, and heating temperature rise time and temperature drop time are required, which tends to be less economical.

[0169] 4. Polymer Hereinafter, the polymer of the present invention obtained by polymerizing the polymerizable composition of the present invention will be described.

[0170] 4-1. Refractive index Generally speaking, the overall density is increased by the polymerization reaction, so the refractive index of the polymer is often higher than that of the monomer before polymerization as its precursor. By using a monomer with a high refractive index to fully carry out the polymerization reaction, the refractive index of the obtained polymer can be increased, so it is considered important to increase the refractive index of the polymer by designing the molecular structure of the monomer. Regarding the refractive index, if it is evaluated with short-wavelength irradiation light, a larger value is shown, but a sample that shows a relatively large refractive index at a short wavelength also shows a relatively large refractive index at a long wavelength, and this relationship is not reversed. Therefore, by evaluating the refractive index at a fixed wavelength and comparing them, the magnitude of the intrinsic refractive index of the material can be compared. In the present invention, the value of the irradiation light wavelength of 587nm is used as a reference.

[0171] The refractive index of the compound and polymer of the present invention is preferably 1.55 or more, more preferably 1.60 or more, particularly preferably 1.63 or more, and most preferably 1.65 or more. The upper limit of the refractive index of the compound and polymer of the present invention is not particularly limited, but is usually 2.0 or less. When using the compound of the present invention and the polymer of the present invention as an optical material of a lens, if the refractive index is less than 1.55, the central portion of the optical lens, etc., sometimes becomes thicker, which damages the lightness characteristic of the plastic, so it is not preferred. In addition, in the development of precision optical components such as lenses, it is also important to achieve optical properties suitable for components by combining a variety of optical materials with a refractive index. Based on this viewpoint, monomers and polymers having a refractive index greater than 1.63 can be said to be particularly useful materials suitable for optical components.

[0172] When the compound of the present invention and the polymer of the present invention are used as recording layer materials of holographic image recording media, the refractive index of the compound of the present invention and 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 not sufficient. In addition, if the refractive index is greater than 1.78, the difference between the refractive index and the matrix resin becomes too large, resulting in increased scattering, so the transmittance is reduced, and more energy is required during recording or regeneration.

[0173] 4-2. Glass transition temperature The glass transition temperature of the polymer of the present invention is preferably 90°C or more, more preferably 100°C or more, further preferably 110°C or more, particularly preferably 120°C or more, and preferably 250°C or less, more preferably 220°C or less, and further preferably 200°C or less. If it is lower than this range, there is a concern that the optical properties deviate from the designed values ​​under the use environment, and the heat resistance required for practical use may not be satisfied. In addition, if it is higher than this range, the processability of the polymer may be reduced, and a molded body with good appearance or high dimensional accuracy may not be obtained. In addition, there is a concern that the polymer becomes brittle and the mechanical strength is reduced, thereby deteriorating the operability of the molded body.

[0174] 5. Optical materials and optical parts The compound, polymerizable composition, and polymer of the present invention can be applied to various optical materials and optical parts because of their high refractive index, easy processability, high chemical stability, and other properties.

[0175] Examples of the optical material include optical overcoats, hard coating agents, adhesives for optical members, resins for optical fibers, and acrylic resin modifiers. As optical parts, for example, there can be mentioned: lenses, filters, diffraction gratings, prisms, optical waveguide elements, cover glass for display devices, optical sensors, optical switches, LEDs, light-emitting elements, optical waveguides, optical splitters, optical fiber adhesives, substrates for display elements, substrates for color filters, substrates for touch panels, polarizing plates, display backlight devices, light guide plates, anti-reflection films, viewing angle expansion films, optical recording, optical shaping, optical embossing, etc. Moreover, it can also be used as these layers. For example, a display protective film etc. are mentioned.

[0176] Among them, the compounds and polymers of the present invention can be preferably applied to plastic lenses based on their high refractive index characteristics. Examples of lenses include imaging lenses, lenses, beam focusing lenses, light diffusion lenses, etc. for cameras (car cameras, digital cameras, PC cameras, mobile phone cameras, surveillance cameras, etc.). Lenses using the compounds and polymers of the present invention may be subjected to physical or chemical treatments such as surface grinding, antistatic treatment, hard coating, non-reflective coating, dyeing, etc., as needed, to improve, for example, anti-reflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting anti-fogging properties, or imparting fashionability.

[0177] 6. Holographic image recording medium The polymerizable composition of the present invention can be suitably used in the recording layer of a holographic image recording medium. In this case, the polymerizable composition of the present invention is preferably a photoreactive composition containing a matrix resin, a photopolymerization initiator, a radical scavenger, and other additives in addition to the compound of the present invention. The details of the use of the polymerizable composition as a material suitable for a holographic image recording medium are described below.

[0178] 6-1. About 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 image recording medium is an organic substance that does not chemically and physically change due to light irradiation, and mainly contains a polymer of an organic compound.

[0179] Since the matrix resin constitutes the polymerizable composition of the present invention together with the above-mentioned polymerizable compound or the photopolymerization initiator described below, it is strongly required to have excellent compatibility with the polymerizable compound or the photopolymerization initiator. If the compatibility of the matrix resin and the above-mentioned other components is low, an interface is formed between the materials, and light is refracted or reflected at the interface, causing light to leak to unnecessary parts, so the interference fringes may be distorted or cut and recorded in inappropriate parts, thereby causing information degradation. Regarding the compatibility of the matrix resin with the above-mentioned other components, as described in, for example, Japanese Patent Gazette No. 3737306, for the sample, the scattered light intensity is obtained by setting a detector in a direction different from the transmitted light, etc. for evaluation.

[0180] The matrix resin of the polymerizable composition of the present invention includes a variety of materials that can be dissolved in a solvent in the polymerizable composition. Resins that are three-dimensionally cross-linked after being formed into a use state can also be used, for example, thermoplastic resins, thermosetting resins, and photocurable resins described below.

[0181] The three-dimensionally cross-linked resin is a reaction solidified product of a polymerizable compound that is liquid at room temperature and a compound that is reactive with the polymerizable compound. The three-dimensionally cross-linked resin acts as a physical barrier, thereby suppressing the volume change during recording. That is, in the recording layer after recording, the bright part often expands and the dark part shrinks, resulting in unevenness on the surface of the holographic image recording medium. In order to suppress this volume change, the recording layer is more preferably a polymerizable composition containing a three-dimensionally cross-linked resin matrix. Among them, from the viewpoint of adhesion to the support, the matrix resin is preferably a thermosetting resin. The resin material that can be used as the matrix resin is described in detail below.

[0182] 6-1-1. Thermoplastic resin Specific examples of the thermoplastic resin include chlorinated polyethylene, polymethyl methacrylate resin (PMMA), copolymers of methyl methacrylate and other alkyl acrylates, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate resin (PVAC), polyvinyl alcohol, polyvinyl formal, polyvinyl pyrrolidone, cellulose resins such as ethyl cellulose and nitrocellulose, polystyrene resins, polycarbonate resins, etc. These may be used alone or in combination of two or more.

[0183] The solvent for these thermoplastic resins is not particularly limited as long as it can dissolve them, and examples thereof 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; amides such as N,N-dimethylacetamide and N-methylpyrrolidone, etc. These may be used alone or in combination of two or more.

[0184] 6-1-2. Thermosetting resin When a thermosetting resin is used as the matrix resin, the curing temperature varies depending on the type of the cross-linking agent or catalyst. Representative examples of functional group combinations that cure at room temperature include epoxy resin and amine, epoxy resin and thiol, isocyanate and amine. In addition, representative examples of using a catalyst include epoxy resin and phenol, epoxy resin and acid anhydride, isocyanate and polyol.

[0185] The former reacts immediately after mixing, so it is relatively simple, but it is difficult to adjust when there is a process such as forming a holographic image recording medium because there is no time. On the other hand, the latter can freely select the curing temperature or curing time by appropriately selecting the type and amount of the catalyst, so it is more suitable when curing is accompanied by the formation of a holographic image recording medium. These various resin raw materials from low molecular weight to high molecular weight are commercially available, so the compatibility with the polymerizable reactive compound or photoinitiator or the adhesion with the substrate can be maintained and selected. Hereinafter, each raw material will be described, but all raw materials may be used alone or in combination of two or more.

[0186] <Epoxide> Examples of the epoxide include polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerol; alicyclic epoxy compounds having a 4- to 7-membered cyclic aliphatic group such as 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexanemethyl ester 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.

[0187] The epoxide preferably has two or more epoxy groups in one molecule, and its type is not particularly limited. If the number of epoxy groups is small, the hardness required as a matrix may not be obtained. The upper limit of the number of epoxy groups in one molecule is not particularly limited, but is preferably usually 8 or less, especially 4 or less. If the number of epoxy groups is too large, it may take more time to consume the epoxy groups, thereby forming a matrix resin that is too time-consuming.

[0188] <Amine> As the amine, a primary or secondary amine group may be used. Examples of such amines include aliphatic polyamines such as ethylenediamine, diethylenetriamine or derivatives thereof; alicyclic polyamines such as isophoronediamine, menthanediamine, N-aminoethylpiperidine or derivatives thereof; aromatic polyamines such as meta-xylylenediamine, diaminodiphenylmethane or derivatives thereof; polyamides such as condensates of dicarboxylic acids such as dimer acid and the above polyamines; imidazole compounds such as 2-methylimidazole or derivatives thereof; and other compounds such as dicyandiamide and adipic acid dihydrazide.

[0189] <Mercaptan> Examples of the thiol 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; and thiol compounds such as polythiols such as polysulfide rubber (manufactured by TORAYFINE CHEMICALS) and jER Cure QX40 (manufactured by Mitsubishi Chemical Co., Ltd.). Among them, commercially available fast-curing polythiols such as jER Cure QX40 are preferably used.

[0190] <Phenol> As the phenol, bisphenol A, novolac-type phenol resins, resol-type phenol resins, etc. may be mentioned.

[0191] <Acid anhydride> Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride or derivatives thereof as monofunctional acid anhydrides; and pyromellitic dianhydride, benzophenonetetracarboxylic anhydride or derivatives thereof as difunctional acid anhydrides.

[0192] <Amount of amine, thiol, phenol, and acid anhydride used> The amount of amine, thiol, phenol, or acid anhydride used is preferably in the range of usually 0.1 equivalent or more, especially 0.7 equivalent or more, and usually 2.0 equivalent or less, especially 1.5 equivalent or less, based on the ratio to the molar number of the epoxy group. If the amount of amine, thiol, phenol, or acid anhydride used is too small or too large, there may be a large number of unreacted functional groups, which may impair storage stability.

[0193] <Polymerization initiator for thermosetting resin> As a catalyst for curing the thermosetting resin, an anionic polymerization initiator and a cationic polymerization initiator can be used depending on the curing temperature and the curing time.

[0194] Anionic polymerization initiators are those that generate anions by irradiation with heat or active energy rays, and examples thereof 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 alone or in combination depending on the curing temperature or curing time.

[0195] Cationic polymerization initiators are those that generate cations by irradiation with heat or active energy rays, and as examples, aromatic onium salts and the like can be cited. As specific examples, compounds containing anionic components such as SbF6-, BF4-, AsF6-, PF6-, CF3SO3-, B(C6F5)4-, and aromatic cationic components containing atoms such as iodine, sulfur, nitrogen, and phosphorus can be cited. Among them, diaryl iodonium salts, triaryl sulfonium salts, and the like are preferred. These can be used in one or more types depending on the curing temperature or curing time.

[0196] The usage amount of these thermosetting resin polymerization initiators is preferably usually more than 0.001 mass %, especially more than 0.01 mass % and usually less than 50 mass %, especially less than 10 mass % relative to the matrix resin. If the usage amount of these thermosetting resin polymerization initiators is too small, the concentration of the thermosetting resin polymerization initiator is too low, so sometimes the polymerization reaction is too time-consuming. On the other hand, if the usage amount of the thermosetting resin polymerization initiator is too much, then sometimes no continuous ring-opening reaction as the polymerization reaction is produced.

[0197] <Isocyanate> As isocyanate, it is preferred that there are two or more isocyanate groups in one molecule, and its type is not particularly limited. If the number of isocyanate groups in one molecule is small, the hardness required as the matrix resin cannot be obtained sometimes. The upper limit of the number of isocyanate groups in one molecule is not particularly limited, and is preferably usually 8 or less, especially 4 or less. If the number of isocyanate groups in one molecule is too much, it sometimes takes more time to consume the isocyanate groups, so that the formation of the matrix resin is too time-consuming. The upper limit of the number of isocyanate groups in one molecule is not particularly limited, and is usually about 20 or less.

[0198] 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 toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and naphthalene-1,5'-diisocyanate; and polymers thereof, among which tri- to heptamers are preferred.

[0199] In addition to these, water, reaction products of polyols such as trimethylolethane and trimethylolpropane with the above-mentioned isocyanates, polymers of hexamethylene diisocyanate, and derivatives thereof may also be mentioned. The molecular weight of isocyanate is in the number average molecular weight, preferably more than 100 and less than 50000, more preferably more than 150 and less than 10000, and then preferably more than 150 and less than 5000. If the number average molecular weight is too small, then the cross-linking density is promoted, so the hardness of the matrix resin becomes too high, and may cause the recording speed to reduce. In addition, if the number average molecular weight is too large, then the compatibility with other components is reduced or the cross-linking density is reduced, so the hardness of the matrix resin becomes too low and sometimes the recorded content can disappear.

[0200] <Polyol> Examples of the polyol include polypropylene polyol, polycaprolactone polyol, polyester polyol and polycarbonate polyol.

[0201] (Polypropylene polyol) Polypropylene polyol is obtained by the reaction of propylene oxide with a diol or a polyol. Examples of the diol or polyol 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, polytetramethylene glycol, etc. Commercially available polypropylene polyols include SANNIX GP-400, GP-1000 (both manufactured by Sanyo Chemical Co., Ltd., trade names), ADEKApolyether G400, G700, G1500 (all manufactured by ADEKA Co., Ltd., trade names), etc.

[0202] (Polycaprolactone polyol) Polycaprolactone polyols are obtained by reacting lactones with diols or polyols. Examples of lactones include α-caprolactone, β-caprolactone, γ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, and β-methyl-ε-caprolactone.

[0203] Examples of the diol or polyol 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.

[0204] Commercially available polycaprolactone polyols obtained by reaction of ε-caprolactone include PLACCEL 205, PLACCEL 205H, PLACCEL 205U, PLACCEL 205UT, PLACCEL 210, PLACCEL 210N, PLACCEL 210CP, PLACCEL 220, PLACCEL 230, PLACCEL 230N, PLACCEL 240, PLACCEL 220EB, PLACCEL 220EC, PLACCEL 303, PLACCEL 305, PLACCEL 308, PLACCEL 309, PLACCEL 312, PLACCEL 320, PLACCEL 401, PLACCEL L205AL, PLACCEL L212AL, PLACCEL L220AL, PLACCEL L320AL, PLACCEL T2103, PLACCEL T2205, PLACCEL P3403, PLACCEL 410 (all manufactured by Daicel Corporation, trade names), etc.

[0205] (Polyester polyol) The polyester polyol may be a polyester polyol obtained by polycondensing a dicarboxylic acid or an acid anhydride thereof with a polyol.

[0206] As a dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, maleic anhydride, isophthalic acid, terephthalic acid, trimellitic acid etc. are mentioned, for example.

[0207] Examples of the polyol 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.

[0208] Examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, etc. Commercially available polyester polyols include Adeka New Ace F series, Adeka New Ace Y series, Adeka New Ace NS series (manufactured by ADEKA Co., Ltd., trade names), KURARAY POLYOL N-2010, P-4011, P-1020 (all manufactured by Kuraray Co., Ltd., trade names), etc.

[0209] (Polycarbonate polyol) Examples of the polycarbonate polyol include those obtained by a dealcoholization condensation reaction of a diol and a dialkyl carbonate (e.g., dimethyl carbonate, diethyl carbonate, etc.), those obtained by a dephenolization condensation reaction of a diol and a diphenyl carbonate, and those obtained by a deglycolization condensation reaction of a diol and a carbonate (e.g., ethylene carbonate, diethyl carbonate, etc.).

[0210] Examples of the diols include aliphatic diols such as 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol and neopentyl glycol; and alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol.

[0211] Examples of the polycarbonate polyol include poly(hexamethylene carbonate) polyol obtained by a condensation reaction of 1,6-hexanediol and diethyl carbonate, poly(pentylene carbonate) obtained by a condensation reaction of pentylene glycol and diethyl carbonate, and poly(butylene carbonate) obtained by a condensation reaction of 1,4-butanediol and diethyl carbonate.

[0212] Commercially available polycarbonate polyols include PLACCEL CD CD205, PLACCEL CD CD210, PLACCEL CD CD220 (all manufactured by DAICEL CORPORATION, trade names), DURANOL T5651, DURANOL T5652, DURANOL T5650J (all manufactured by Asahi Kasei Corporation, trade names), and the like.

[0213] (Molecular weight of polyol) The molecular weight of the polyol described above is preferably 100 or more and 50000 or less, more preferably 150 or more and 10000 or less, and then preferably 150 or more and 5000 or less in terms of number average molecular weight. If the number average molecular weight is too small, the cross-linking density is promoted, so the hardness of the matrix resin becomes too high, and may cause the recording speed to reduce. In addition, if the number average molecular weight is too large, the compatibility with other components is reduced or the cross-linking density is reduced, so the hardness of the matrix resin becomes too low, and sometimes the recorded content disappears.

[0214] <Other ingredients> The matrix resin in the present embodiment may contain other components in addition to the above-mentioned components as long as it does not violate the spirit of the present invention.

[0215] Examples of such other components include compounds having a hydroxyl group, 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 for the purpose of changing the physical properties of the matrix resin.

[0216] <Urethane polymerization catalyst> In order to promote the reaction between isocyanate and polyol, an appropriate urethane polymerization catalyst may be contained. Examples of the carbamate polymerization catalyst include onium salts such as bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonic acid, bis(4-tert-butylphenyl)iodonium p-toluenesulfonic acid, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonic acid, (4-bromophenyl)diphenylsulfonium trifluoromethanesulfonate, (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyliodonium perfluoro-1-butanesulfonic acid, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium trifluoromethanesulfonic acid, and bis(alkylphenyl)iodonium hexafluorosulfonic acid; Lewis acid catalysts such as zinc chloride, tin chloride, ferric chloride, aluminum chloride, and BF3; Catalysts with acid as the main component; protonic 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 trimellitate; bases such as sodium hydroxide, potassium hydroxide, and potassium carbonate; tin catalysts such as dibutyltin laurate, dioctyltin laurate, and dibutyltin octoate; bismuth catalysts such as tri(2-ethylhexanoate) bismuth and tribenzoyloxybismuth; zirconium catalysts such as tetrakis(ethylacetoacetate), 1,1'-isopropyldichlorozirconocene, and tetrakis(2,4-pentanedionate).

[0217] Among them, in order to improve storage stability, bismuth catalysts and zirconium catalysts are preferred.

[0218] The bismuth-based catalyst is a catalyst containing a bismuth element and is not particularly limited as long as it is a compound that promotes the reaction of isocyanate and polyol. Examples of bismuth-based catalysts include bismuth tris(2-ethylhexanoate), bismuth tribenzoyloxy, bismuth triacetate, bismuth tris(dimethyldithiocarbamate), bismuth hydroxide, triphenylbismuth(V)bis(trichloroacetate), tris(4-methylphenyl)oxybismuth(V), and triphenylbis(3-chlorobenzoyloxy)bismuth(V).

[0219] Among them, based on the consideration of catalyst activity, a trivalent bismuth compound is preferred, and a bismuth carboxylate, represented by the general formula Bi(OCOR)3 (R is a linear or branched alkyl, cycloalkyl, or substituted or unsubstituted aromatic group) is more preferred. The above bismuth-based catalysts may be used alone or in combination of two or more in any combination and ratio.

[0220] The zirconium-based catalyst is a catalyst containing a zirconium element and is not particularly limited as long as it is a compound that promotes the reaction of isocyanate and polyol. Examples thereof include cyclopentadienyl zirconium trichloride, decamethyl zirconocene dichloride, 1,1'-dibutyl zirconocene dichloride, 1,1'-isopropylidene zirconocene dichloride, zirconium tetrakis(2,4-pentanedionate), zirconium tetrakis(trifluoro-2,4-pentanedionate), zirconium tetrakis(hexafluoro-2,4-pentanedionate), zirconium butoxide, zirconium tert-butoxide, zirconium propoxide, zirconium isopropoxide, zirconium ethoxide, dibutoxy zirconium bis(ethylacetoacetate), zirconium tetrakis(ethylacetoacetate), zirconium oxide, barium zirconium oxide, calcium oxide, zirconium bromide, zirconium chloride, zirconium fluoride, (indenyl) zirconium dichloride, and zirconium carbonate.

[0221] Among them, based on the compatibility with other components, compounds having organic ligands are preferred, and alkoxides or compounds having acetylacetonate (2,4-pentanedione) structures are more preferred. The above zirconium compounds may be used alone or in combination of two or more in any combination and ratio.

[0222] The bismuth-based catalyst and the zirconium-based catalyst may be used alone or in combination.

[0223] The usage amount of the carbamate polymerization catalyst is preferably in a range of usually 0.0001 mass %, especially 0.001 mass % or more and usually 10 mass %, especially 5 mass % or less, based on the ratio of the matrix resin. If the usage amount of the carbamate polymerization catalyst is too small, curing is sometimes too time-consuming. On the other hand, if the usage amount of the carbamate polymerization catalyst is too much, it is sometimes difficult to control the curing reaction.

[0224] The curing can be performed at room temperature by using a urethane polymerization catalyst, but the curing can also be performed at an elevated temperature, preferably at a temperature between 40°C and 90°C.

[0225] 6-1-3. Photocurable resin When using a photocurable resin as the matrix resin, it is necessary to use a matrix resin photoinitiator that matches the wavelength used for curing. Since curing during light irradiation will cause obstacles to molding or bonding, it is more ideal to have a stable curing reaction near room temperature, which is the main operating temperature. Based on this situation, the catalyst curing using the matrix resin photoinitiator is an ideal choice.

[0226] Generally, when irradiated with light, a reactive matrix such as a cation or anion is generated from a photoinitiator for a matrix resin. Therefore, it is considered that a matrix resin can be prepared by curing the reactive matrix selected from these reactive matrixes.

[0227] As functional groups that react with cations such as protons, epoxy groups and oxetane groups can be cited. As compounds having these, specifically, as compounds having epoxy groups, polyglycidyl ether compounds of polyhydric alcohols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerol, alicyclic epoxy compounds having 4-7-membered cyclic aliphatic groups such as 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester 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, phenol or cresol novolac type epoxy compounds, etc. can be cited. Examples of the oxetane group include 2-ethyl-2-oxetane ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetaneoxy)hexane. (In addition, the description of "(poly)ethylene glycol" and the like herein refers to both "ethylene glycol" and its polymer "polyethylene glycol")

[0228] Examples of the functional group that reacts with anions include epoxy groups and epithio groups. Specific examples of compounds having an epithio group include phenyl episulfide and dithiomethyl ether of bisphenol A.

[0229] The amount of the matrix resin photoinitiator used when the matrix resin is photocured is preferably in a range of usually 0.01% by mass or more, especially 0.1% by mass or more, and usually 1% by mass or less, especially 0.5% by mass or less, based on the ratio to the polymerizable compound. If the amount of the matrix resin photoinitiator used is too small, curing may take too long. On the other hand, if the amount of the matrix resin photoinitiator used is too large, it may be difficult to control the curing reaction.

[0230] In addition, especially when used as a holographic image recording material, since light is also irradiated during recording, it is important that the wavelength during curing is different from the wavelength during recording, and the wavelength difference is at least 10nm, preferably 30nm. The selection of the photoinitiator for the matrix resin can be roughly predicted based on the absorption wavelength of the initiator.

[0231] 6-2. Photopolymerization initiator As long as the photopolymerization initiator assisting the polymerization of the compound of the present invention is a known photo-radical polymerization initiator, any one can be used. As an example, 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, aminoformic acid derivatives, sulfonamides, triarylcarbinols, oxime esters, etc. can be used. Among them, as a photopolymerization initiator, based on the reason that the polymerization reaction is generated by light in the visible light range, it is preferably a titanocene compound, an acylphosphine oxide compound, an oxime ester compound, etc.

[0232] 6-2-1. Titanocene compounds When a titanocene compound is used as the photopolymerization initiator, the type thereof is not particularly limited, and the initiator may be appropriately selected from various titanocene compounds described in, for example, JP-A-59-152396 and JP-A-61-151197.

[0233] Specific examples of the titanocene compound include: bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium bisphenyl, bis(cyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(cyclopentadienyl)titanium bis(2,3,5,6-pentafluorophenyl-1-yl)titanium, bis(cyclopentadienyl)titanium bis(2,4,6-trifluorophenyl-1-yl)titanium, bis(cyclopentadienyl)titanium bis(2,6-di-fluorophenyl-1-yl)titanium , bis(cyclopentadienyl)bis(2,4-di-fluorobenzene-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,5,6-pentafluorobenzene-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorobenzene-1-yl)titanium, bis(cyclopentadienyl)bis(2,6-difluoro-3-(pyridin-1-yl)-benzene-1-yl)titanium, etc.

[0234] 6-2-2. Acylphosphine oxide compounds Specific examples of the acylphosphine oxide compound include a monofunctional initiator having only one photodecomposition point in one molecule and a bifunctional initiator having two photodecomposition points in one molecule.

[0235] Examples of the monofunctional initiator include triphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2,6-dichlorobenzoyldiphenylphosphine oxide.

[0236] Examples of the bifunctional initiator 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.

[0237] 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]-1-(O-acetyloxime)ethanone,

[0063] methyl 1-(9-ethyl-6-cyclohexanoyl-9H-carbazol-3-yl)-1-(O-acetyloximo)glutaric acid, methyl 1-(9-ethyl-9H-carbazol-3-yl)-1-(O-acetyloximo)glutarate, methyl 1-(9-ethyl-9H-carbazol-3-yl)-1-(O-acetyloximo)glutarate, 1-(O-acetyloximo)-3-methyl-butyric acid 1-(9-ethyl-9H-carbazol-3-yl) ester, and the like.

[0238] 6-2-4. Amount of photopolymerization initiator used The above-mentioned various photopolymerization initiators may be used alone or in combination of two or more in any combination and ratio.

[0239] The content of the photopolymerization initiator in the polymerizable composition of the present invention is preferably 0.5 μmol / g or more, based on the molar amount per unit weight of the polymerizable composition. It is more preferably 1 μmol / g or more. In addition, the content of the photopolymerization initiator in the polymerizable composition of the present invention is preferably 100 μmol / g or less, based on the molar amount per unit weight of the polymerizable composition. It is more preferably 50 μmol / g or less.

[0240] If the content of the photopolymerization initiator is too low, the amount of free radicals generated decreases, so the speed of photopolymerization sometimes slows down, resulting in a lower recording sensitivity of the holographic image recording medium. On the other hand, if the content of the photopolymerization initiator is too high, the free radicals generated by light irradiation re-bond with each other or become uneven, so sometimes the help for photopolymerization becomes less, still resulting in a lower recording sensitivity of the holographic image recording medium. When two or more photopolymerization initiators are used in combination, it is preferred that the total amount of these initiators meets the above range.

[0241] 6-3. Free radical scavengers In the holographic image recording, a free radical scavenger may also be added to fix the interference light intensity pattern with good accuracy as the polymer distribution in the holographic image recording medium. The free radical scavenger preferably has both a functional group for capturing free radicals and a reactive group fixed to the matrix resin by a covalent bond. As the functional group for capturing free radicals, a stable nitroxyl radical may be cited.

[0242] 6-3-1. Types of free radical scavengers Examples of the reactive group fixed to the matrix resin by covalent bonds include hydroxyl groups, amine groups, isocyanate groups, and thiol groups. Examples of such radical scavengers include 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical (TEMPOL), 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxyl radical, 3-hydroxy-8-azabicyclo[3.2.1]octane N-oxyl radical, and 5-HO-AZADO: 5-hydroxy-2-azatricyclo[3.3.1.13,7]decane N-oxyl radical.

[0243] 6-3-2. Content of free radical scavenger The above-mentioned various radical scavengers may be used alone 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, more preferably 1 μmol / g or more, in terms of molar amount per unit weight of the polymerizable composition. In addition, the content of the radical scavenger in the polymerizable composition of the present invention is preferably 100 μmol / g or less, more preferably 50 μmol / g or less.

[0244] If the content of the radical scavenger is too low, the efficiency of catching radicals tends to be low, the polymer with low polymerization degree diffuses, and the components that do not contribute to the signal increase. On the other hand, if the content of the radical scavenger is too high, the polymerization efficiency of the polymer tends to decrease, and signal recording cannot be performed. When two or more radical scavengers are used in combination, it is preferred that the total amount thereof satisfy the above range.

[0245] 6-4. Other ingredients The polymerizable composition of the present invention may contain other components in addition to the above-mentioned components, unless it violates the spirit of the present invention.

[0246] As other components, solvents, plasticizers, dispersants, leveling agents, defoamers, adhesion promoters, etc. used to prepare polymerizable compositions may be cited. In particular, when used for holographic image recording media, chain transfer agents, polymerization terminators, compatibilizers, reaction aids, sensitizers, etc. used to control the recording reaction may be cited. In addition, as examples of other additives that may be required for improving properties, preservatives, stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, etc. may be cited. Any of these components may be used alone, or two or more of them may be used in any combination and ratio.

[0247] <Sensitizer> A compound that controls the excitation of the photopolymerization initiator may be added to the polymerizable composition of the present invention. Examples of such a compound include a sensitizer and a sensitizing auxiliary.

[0248] As a sensitizer, any one of various known sensitizers can be selected for use. As a general sensitizer, colored compounds such as pigments are mostly used to absorb visible light and ultraviolet laser light. When used in a holographic image recording medium, although it depends 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 Laid-Open No. 5-241338, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 2-55446, etc. In the case of a system using a blue laser, compounds described in Japanese Patent Laid-Open No. 2000-10277, Japanese Patent Laid-Open No. 2004-198446, etc. can be cited. Any of these sensitizers can be used alone, or two or more can be used in any combination and ratio.

[0249] When the obtained holographic image recording medium needs to be colorless and transparent, it is preferred to use a cyanine pigment as a sensitizer. Cyanine pigments are generally easily decomposed by light, so by post-exposure, that is, placing the holographic image recording medium under room light or sunlight for several hours to several days, the cyanine pigment in the holographic image recording medium is decomposed and no longer absorbs in the visible light range, so that a colorless and transparent holographic image recording medium can be obtained.

[0250] The amount of the sensitizer needs to be increased or decreased according to the thickness of the recording layer to be formed, and is preferably set to a range of usually 0.01 mass %, especially 0.1 mass % or more and usually 10 mass %, especially 5 mass % or less, relative to the ratio of the above-mentioned 6-2. photopolymerization initiator. If the amount of the sensitizer used is too small, the initial efficiency is sometimes reduced, and a lot of time is required for recording. On the other hand, if the amount of the sensitizer used is too much, the absorption of the light used for recording or regeneration is sometimes increased, making it difficult for the light to reach the depth direction. When using two or more sensitizers in combination, the total amount of the sensitizers is set to meet the above range.

[0251] <Plasticizer> The polymerizable composition of the present invention may contain a plasticizer in order to improve the reaction efficiency and adjust the physical properties of the recording layer of the hologram recording medium.

[0252] Examples of plasticizers include: phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and diundecyl phthalate; adipic acid esters such as bis(2-ethylhexyl) adipate, diisononyl adipate, and di-n-butyl adipate; sebacic acid esters such as dioctyl sebacate and dibutyl sebacate; phosphate esters such as tricresyl phosphate; citrate esters such as acetyl tributyl citrate; trimellitic acid esters such as trioctyl trimellitic acid; alkoxylated (poly) alkylene glycol esters such as epoxidized soybean oil, chlorinated paraffin, and acetoxymethoxypropane; terminal alkoxylated polyalkylene glycols such as dimethoxypolyethylene glycol, etc.

[0253] A plasticizer containing fluorine as exemplified in Japanese Patent No. 6069294 may also be used. Examples of plasticizer containing fluorine include 2,2,2-trifluoroethyl butyl carbamate, bis(2,2,2-trifluoroethyl)-(2,2,4-trimethylhexane-1,6-diyl)biscarbamate, [4-({[(2,2,2-trifluoroethoxy)carbonyl]amino}-methyl)octane-1,8-diyl]biscarbamate bis(2,2,2-trifluoroethyl) ester, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecanoylbutyl carbamate, and 2,2,2-trifluoroethylphenyl carbamate.

[0254] These plasticizers are used in an amount of usually 0.01% by mass to 50% by mass, preferably 0.05% by mass to 20% by mass, relative to the total solid content of the polymerizable composition. If the content of the plasticizer is less than the above range, the effect of improving the reaction efficiency or adjusting the physical properties is not exerted, and if the content of the plasticizer is more than the above range, the transparency of the recording layer is reduced or the oozing of the plasticizer becomes significant.

[0255] <Leveling agent> A leveling agent may be used in the polymerizable composition of the present invention. Examples of the leveling agent include polycarboxylic acid sodium salts, polycarboxylic acid ammonium salts, polycarboxylic acid amine salts, silicon-based leveling agents, acrylic acid-based leveling agents, ester compounds, ketone compounds, fluorine compounds, and the like. Any of these may be used alone, or two or more of them may be used in any combination and ratio.

[0256] <Chain transfer agent> A chain transfer agent can be used in the polymerizable composition of the present invention. Examples of the chain transfer agent include: phosphites such as sodium phosphite and sodium hypophosphite; thiols such as thioglycolic acid, mercaptopropionic acid, 2-propanethiol, 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, 1,4-heptadiene, 1,4-hexadiene, and 2-methyl-1,4-pentadiene. , 3,6-nonadien-1-ol, 9,12-octadecadienol and other non-conjugated dienes; linolenic acid, γ-linolenic acid, methyl linolenic acid, ethyl linolenic acid, isopropyl linolenic acid, linolenic anhydride and other linolenic acids; linolenic acid, methyl linolenic acid, ethyl linolenic acid, isopropyl linolenic acid, linolenic anhydride and other linolenic acids; eicosapentaenoic acid, eicosapentaenoic acid ethyl ester and other eicosapentaenoic acids; docosahexaenoic acid, docosahexaenoic acid ethyl ester and other docosahexaenoic acids, etc.

[0257] The amount of these additives used is preferably in the range of usually 0.001% by mass or more, especially 0.01% by mass or more, and usually 30% by mass or less, especially 10% by mass or less, based on the total solid content of the polymerizable composition of the present embodiment. When two or more additives are used in combination, the total amount thereof is within the above range.

[0258] 6-5. Composition ratio of each component in the polymerizable composition The content of each component in the polymerizable composition of the present invention is arbitrary as long as it does not violate the purpose of the present invention. The ratio of each component shown below is preferably in the following range based on the molar amount per unit mass of the polymerizable composition.

[0259] The content of the polymerizable compound including the compound of the present invention is preferably 5 μmol / g or more, more preferably 10 μmol / g or more, and further preferably 100 μmol / g or more. In addition, the content of the polymerizable compound is preferably 1000 μmol / g or less, more preferably 500 μmol / g or less, and further preferably 300 μmol / g or less. By making the content of the polymerizable compound greater than the above lower limit, sufficient diffraction efficiency can be obtained in the holographic image recording medium, and by making the content of the polymerizable compound less than the above upper limit, compatibility with the resin matrix in the recording layer is often ensured, thereby keeping the shrinkage of the recording layer caused by recording low.

[0260] When isocyanate and polyol are used as the matrix resin in the polymerizable composition of the present invention, the total content of these 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 the content to be above the lower limit, it is easy to form a recording layer.

[0261] In this case, the ratio of the number of isocyanate-reactive functional groups of the polyol to the number of isocyanate groups of the isocyanate is preferably 0.1 or more, more preferably 0.5 or more and usually 10.0 or less, preferably 2.0 or less. By making this ratio within the above range, the number of unreacted functional groups is reduced and the storage stability is improved.

[0262] In addition, the content of the urethane polymerization catalyst in the polymerizable composition is preferably determined in consideration of the reaction rate of the isocyanate and the polyol, and is preferably 5% by mass or less, further preferably 4% by mass or less, and more preferably 1% by mass or less. In addition, it is preferably used at 0.003% by mass or more.

[0263] The total amount of the components other than the above components may be 30% by mass or less, preferably 15% by mass or less, and more preferably 5% by mass.

[0264] 6-6. Method for producing polymerizable composition In the present invention, the method for producing the polymerizable composition comprising the polymerizable compound, the matrix resin and the photopolymerization initiator is not particularly limited, and the order of mixing can be appropriately adjusted. In addition, when the polymerizable composition comprises components other than those described above, the components can be mixed in any combination and order.

[0265] When isocyanate and polyol are used as the matrix resin, the polymerizable composition can be obtained, for example, by the following method, but the present invention is not limited thereto. In addition to the polymerizable compound and the photopolymerization initiator, all components except the isocyanate and the urethane polymerization catalyst are mixed to prepare a photoreactive composition (liquid A). The mixture of the isocyanate and the urethane polymerization catalyst is referred to as liquid B. Alternatively, all components except isocyanate may be mixed with the polymerizable compound and the photopolymerization initiator to prepare a photoreactive composition (liquid A).

[0266] Each liquid is preferably dehydrated and degassed. If the dehydration and degassing are insufficient, bubbles may be generated during the preparation of the holographic image recording medium, and a uniform recording layer cannot be obtained. During the dehydration and degassing, heating and decompression may also be performed as long as the components are not damaged.

[0267] When manufacturing the polymerizable composition of the mixture of liquid A and liquid B, it is preferably carried out before the holographic image recording medium is formed. At this time, the mixing technology based on the previous method can also be used. In addition, when the liquid A and liquid B are mixed, degassing can be performed as needed to remove residual gas. Furthermore, liquid A and liquid B are preferably filtered separately or after mixing to remove foreign matter and impurities, and it is more preferable to filter each liquid separately.

[0268] In addition, an isocyanate functional prepolymer obtained by reacting an isocyanate having an excess of isocyanate groups with a polyol as an isocyanate may be used as the matrix resin. Furthermore, an isocyanate reactive prepolymer obtained by reacting a polyol having an excess of isocyanate reactive functional groups with an isocyanate as a polyol may be used as the matrix resin.

[0269] 6-7. Hologram Recording Medium of the Present Invention The holographic image recording medium of the present invention using the polymerizable composition of the present invention has a recording layer and, if necessary, further has a support or other layers. Generally, the holographic image recording medium has a support, and the recording layer or other layers are stacked on the support to constitute the holographic image recording medium. However, in the case where the recording layer or other layers have the strength or durability required for the medium, the holographic image recording medium may not have a support. Examples of other layers include: a protective layer, a reflective layer, an anti-reflective layer (anti-reflective film), etc.

[0270] 6-7-1. Recording layer The recording layer of the holographic image recording medium of the present invention is a layer formed of the polymerizable composition of the present invention, and is a layer for recording information. The information is usually recorded in the form of a holographic image. As described in the recording method below, a part of the polymerizable compound (hereinafter referred to as polymerizable monomer) contained in the recording layer undergoes chemical changes such as polymerization due to holographic image recording, etc. Therefore, in the holographic image recording medium after recording, a part of the polymerizable monomer is consumed and exists in the form of a reacted compound such as a polymer.

[0271] The thickness of the recording layer is not particularly limited, and can be appropriately determined in consideration of the recording method, etc., and is preferably 1 μm or more, more preferably 10 μm or more, and preferably 1 cm or less, and more preferably 3 mm or less. By setting the thickness of the recording layer to be above the above lower limit, the selectivity of each holographic image can often be improved during multiple recording of the holographic image recording medium, and the degree of multiple recording can be improved. By setting the thickness of the recording layer to be below the above upper limit, the entire recording layer can often be uniformly formed, and multiple recording can be performed with uniform diffraction efficiency of each holographic image and relatively high S / N.

[0272] The shrinkage rate of the recording layer due to exposure during recording and reproduction of information is preferably 0.25% or less in view of recording reproducibility.

[0273] 6-7-2. Support The details of the support are not particularly limited, and any support can be used as long as it has the strength and durability required for the hologram recording medium. The shape of the support is not limited, but is usually formed into a flat plate or a film. The material constituting the support is also not limited, and may be transparent or opaque.

[0274] When transparent materials are cited as materials for the support, organic materials such as acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polystyrene, polycycloolefin, and cellulose acetate, and inorganic materials such as glass, silicon, and quartz can be cited. Among them, polycarbonate, acrylic resin, polyester, amorphous polyolefin, and glass are preferred, and polycarbonate, acrylic resin, amorphous polyolefin, polycycloolefin, and glass are particularly preferred.

[0275] When an opaque material is cited as the material of the support, examples thereof include metals such as aluminum, and a material obtained by coating the above-mentioned transparent support with metals such as gold, silver, and aluminum, or a dielectric such as magnesium fluoride and zirconium oxide.

[0276] The thickness of the support is also not particularly limited, but is preferably set to a range of 0.05 mm to 1 mm. If the thickness of the support is above the lower limit, the mechanical strength of the holographic image recording medium can be obtained, and the substrate can be prevented from bending. If the thickness of the support is below the upper limit, the following advantages can be obtained, such as an increase in the amount of light transmitted, a reduction in the weight or cost of the holographic image recording medium, etc.

[0277] The surface of the support may also be subjected to a surface treatment. This surface treatment is usually used to improve the adhesion between the support and the recording layer. Examples of surface treatment include: subjecting the support to a corona discharge treatment, or pre-forming an undercoat layer on the support. Examples of the composition of the undercoat layer include: halogenated phenols, or partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, and the like.

[0278] The surface treatment of the support may be performed for purposes other than improving adhesion. Examples thereof include: reflective coating treatment for forming a reflective coating layer made of metal such as gold, silver, and aluminum; dielectric coating treatment for forming a dielectric layer such as magnesium fluoride or zirconium oxide. These layers may be formed as a single layer or may be formed as two or more layers.

[0279] These surface treatments may also be provided for the purpose of controlling the gas or water permeability of the substrate. For example, by making the support sandwiching the recording layer also have the function of suppressing the gas or water permeability, the reliability of the holographic image recording medium can be improved.

[0280] The support may be provided only on either the upper side or the lower side of the recording layer of the holographic image recording medium of the present invention, or may be provided on both the upper and lower sides. However, when the support is provided on both the upper and lower sides of the recording layer, at least one of the supports is transparent so that the active energy rays (excitation light, reference light, reproduction light, etc.) can pass therethrough.

[0281] In the case of a holographic recording medium having a support on one or both sides of the recording layer, a transmissive or reflective holographic image can be recorded. In addition, in the case of using a support having a reflective property on one side of the recording layer, a reflective holographic image can be recorded.

[0282] The support may be patterned for data addresses. The patterning method in this case is not limited, and for example, the support itself may be provided with unevenness, or a pattern may be formed on the reflective layer described below, or a combination of these methods may be used.

[0283] 6-7-3. Protective layer The protective layer is a layer for preventing the recording and reproducing characteristics of the recording layer from deteriorating. The specific composition of the protective layer is not limited, and any known one can be applied. For example, a layer containing a water-soluble polymer, an organic / inorganic material, etc. can be formed as the protective layer.

[0284] The protective layer may be formed at any position without particular limitation, and may be formed, for example, 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.

[0285] 6-7-4. Reflection layer The reflective layer is formed when the holographic image recording medium is configured as a reflective type. In the case of a reflective holographic image recording medium, the reflective layer can be formed between the support and the recording layer, or on the outer side of the support, and is usually preferably formed between the support and the recording layer. As the reflective layer, any known reflective layer can be used, and for example, a metal thin film or the like can be used.

[0286] 6-7-5. Anti-reflection film For any type of holographic recording medium, whether transmissive or reflective, an anti-reflection film may be provided on the side where the information light, reference light, and reproduction light enter or exit, or between the recording layer and the support. The anti-reflection film has the function of improving the efficiency of light utilization and suppressing noise generation. As the antireflection film, any known antireflection film can be used.

[0287] 6-7-6. Method for manufacturing holographic image recording medium The method for producing the holographic image recording medium of the present invention is not limited. For example, the holographic image recording medium can be produced by coating the polymerizable composition of the present invention on a support without a solvent to form a recording layer. In this case, any coating method can be used. Specific examples include spraying, spin coating, wire bar coating, dipping, air knife coating, roll coating, blade coating, and blade roll coating.

[0288] When forming a recording layer, especially when forming a thick recording layer, a method of placing in a mold for molding or a method of applying on a release film and punching the mold can also be used. In addition, the polymerizable composition of the present invention can be mixed with a solvent or an additive to prepare a coating liquid, and the coating liquid can be applied on a support and dried to form a recording layer. In this case, any method can be used as a coating method, for example, the same method as described above can be used.

[0289] The solvent used for the coating liquid is not limited. It is usually preferred to use a solvent that has sufficient solubility for the used components, can provide good film coating properties, and will not immerse in supports such as resin substrates. One solvent can be used alone, or two or more solvents can be used in any combination and ratio. In addition, the amount of solvent used is not limited. Among them, based on the coating efficiency and operability, it is preferred to prepare a coating liquid with a solid content concentration of about 1 to 100% by mass.

[0290] Examples of the solvent 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 furan methanol; 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 ethyl Ester solvents such as ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, methyl 3-methoxypropionate, etc.; perfluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, hexafluorobutanol, etc.; high polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc.; chain hydrocarbon solvents such as n-hexane and n-octane; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, tert-butylcyclohexane, cyclooctane, etc.; or mixed solvents thereof, etc.

[0291] As a method for manufacturing a holographic image recording medium, for example, the following methods can be cited: a method in which a polymerizable composition melted by heat is applied to a support, cooled and solidified to form a recording layer to manufacture the medium; a method in which a liquid polymerizable composition is applied to a support, solidified by thermal polymerization to form a recording layer to manufacture the medium; a method in which a liquid polymerizable composition is applied to a support, solidified by photopolymerization to form a recording layer to manufacture the medium.

[0292] The holographic image recording medium manufactured in this way can be in the form of a vertical flat plate or disc, and can be used in three-dimensional image display devices, diffractive optical elements, large-capacity storage, and other uses. In particular, the holographic image recording medium of the present invention using the polymerizable composition of the present invention has a high refractive index modulation and can also be used as a light guide plate of AR glasses (AR glasses).

[0293] 6-7-7. Application of holographic image recording medium <Mass storage applications> The writing (recording) and reading (reproduction) of information on the hologram recording medium of the present invention are both performed by light irradiation.

[0294] When recording information, light that can cause a chemical change in a polymerizable monomer, that is, can cause it to polymerize and change its concentration, is used as object light (also called recording light).

[0295] For example, when information is recorded in the form of a volume hologram, the recording layer is irradiated with object light and reference light at the same time, and the object light and reference light are caused to interfere in the recording layer. Thereby, the interference light polymerizes the polymerizable monomer in the recording layer and changes the concentration. As a result, interference fringes cause a refractive index difference in the recording layer, and the interference fringes recorded in the recording layer are recorded in the form of a hologram in the recording layer.

[0296] When reproducing the volume hologram recorded on the recording layer, a predetermined reproducing light (usually a reference light) is irradiated on the recording layer. The irradiated reproducing light is diffracted according to the interference fringes. The diffracted light contains the same information as the recording layer, so the information recorded on the recording layer can be reproduced by reading the diffracted light using an appropriate detection mechanism.

[0297] The wavelength range of the object light, the reproduction light, and the reference light can be arbitrary according to their respective uses, and can be in the visible light range or in the ultraviolet range. Among these lights, suitable ones 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; lasers with excellent monochromaticity and directivity such as dye lasers with pigments, etc.

[0298] There is no restriction on the irradiation amount of the object light, the regeneration light and the reference light. As long as it is within the range that can record and reproduce, the irradiation amount can be arbitrary. When the irradiation amount is extremely small, the chemical change of the polymerizable monomer may be too incomplete to fully demonstrate the heat resistance and mechanical properties of the recording layer. On the contrary, when the irradiation amount is extremely large, it may cause the components of the recording layer (components of the polymerizable composition of the present invention) to deteriorate. Therefore, the object light, the regeneration light and the reference light are usually 0.1 J / cm according to the composition of the polymerizable composition of the present invention used to form the recording layer, the type of photopolymerization initiator, and the amount of the photopolymerization initiator. 2 Above and 20J / cm 2 The following ranges are irradiated.

[0299] As holographic image recording methods, there are polarization collinear holographic image recording methods, reference light incident angle multiplexed holographic image recording methods, etc. When the holographic image recording medium of the present invention is used as a recording medium, any recording method can provide good recording quality.

[0300] <Application of light guide plates for AR glasses> The hologram recording medium of the present invention records a volume hologram in the same manner as in the above-mentioned large-capacity storage application.

[0301] For the volume hologram recorded on the recording layer, the recording layer is irradiated with a prescribed regeneration light. The irradiated regeneration light is diffracted according to the above-mentioned interference fringes. At this time, even if the wavelength of the regeneration light is inconsistent with the wavelength of the recording light, diffraction will occur as long as the Bragg condition is established with the above-mentioned interference fringes. Therefore, if the corresponding interference fringes are pre-recorded according to the wavelength and incident angle of the regeneration light to be diffracted, the regeneration light in a wide wavelength region can be diffracted, and the display color gamut of the AR glasses can be expanded.

[0302] If interference fringes corresponding to the wavelength and diffraction angle of the regenerated light are pre-recorded, the regenerated light incident from the outside of the holographic image recording medium can be waveguided to the inside of the holographic image recording medium, or the regenerated light waveguided inside the holographic image recording medium can be reflected, split, expanded, or shrunk, so that the regenerated light waveguided inside the holographic image recording medium can be emitted to the outside of the holographic image recording medium, thereby expanding the viewing angle of the AR glasses.

[0303] The wavelength region of the object light and the regeneration light can be arbitrary according to their respective uses, and can be the visible light region or the ultraviolet region. Among these lights, as suitable ones, the above-mentioned lasers can be exemplified. As the regeneration light, it is not limited to lasers, etc., and display devices such as liquid crystal displays (LCDs) and organic electroluminescent displays (OLEDs) are also suitable.

[0304] There is no restriction on the irradiation amount of the object light, the regeneration light and the reference light. As long as it is within the range that can record and reproduce, the irradiation amount can be arbitrary. When the irradiation amount is too small, the chemical change of the polymerizable monomer may be too incomplete to fully demonstrate the heat resistance and mechanical properties of the recording layer. When the irradiation amount is too large, the components of the recording layer (components of the polymerizable composition of the present invention) may deteriorate. Therefore, the object light, the regeneration light and the reference light are usually 0.1 J / cm according to the composition of the polymerizable composition of the present invention used in the formation of the recording layer, the type of photopolymerization initiator, and the formulation amount. 2 Above and 20J / cm 2 The following ranges are irradiated.

[0305] 6-8. Performance indicators for holographic image recording media The performance of the holographic recording medium is measured by the total Δn calculated by summing the diffraction efficiencies of the multiple recordings. In the case of a transmission holographic image, the diffraction efficiency of the holographic image is given by the ratio of the intensity of the diffracted light to the sum of the intensity of the transmitted light and the intensity of the diffracted light. Δn is calculated from the obtained diffraction efficiency using the following formula based on Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the total sum of the multiple recordings is taken as the total Δn.

[0306] [Number 1] totalΔn=∑Δn

[0307] Here, η is the diffraction efficiency, T is the thickness of the medium, λ is the wavelength of the reference light, and θ is the incident angle of the reference light.

[0308] In the case of large-capacity storage, a higher total Δn means that more information can be recorded per unit volume, which is preferred. In addition, in the case of AR glasses, a higher total Δn means that the projected image of the projector can be clearly transmitted to the eyes, or power consumption can be suppressed, or the viewing angle can be expanded, which is preferred. [Example]

[0309] The present invention will be described in further detail below by way of Examples and Synthesis Examples, but the present invention is not limited to the following Examples unless it departs from the gist of the present invention.

[0310] [Raw materials used] The composition raw materials used in Examples and Comparative Examples are as follows.

[0311] <Isocyanate> ·Donaide (registered trademark) TSS-100: Hexamethylene diisocyanate-based polyisocyanate (NCO 17.6%) (manufactured by Asahi Kasei Corporation)

[0312] <Polyol> PLACCELPCL-205U: Polycaprolactone diol (molecular weight 530) (manufactured by Daicel Corporation) PLACCEL PCL-305: Polycaprolactone triol (molecular weight 550) (manufactured by Daicel Corporation)

[0313] <Photopolymerization initiator> HLI02: 1-(9-ethyl-6-cyclohexanoyl-9H-carbazole-3-yl)-1-(O-acetyloxime)glutaric acid methyl ester

[0314] <Free Radical Scavenger> TEMPOL: 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0315] <Light stabilizer> ·Adekastab LA-63P (manufactured by ADEKA Co., Ltd.)

[0316] <Urethane polymerization catalyst> · Octanoic acid solution of tri(2-ethylhexanoate) bismuth (active ingredient: 56% by mass)

[0317] [Example 1] <Production of Compound M-1> Compound M-1 was produced by the following synthesis method.

[0318] [Chemistry 11]

[0319] 3,6-dibromocarbazole (8.2 g), dibenzothiophene-4-boric acid (12.1 g), and potassium phosphate (16.1 g) were suspended in 100 mL of toluene, 100 mL of ethanol, and 50 mL of water, and degassed by passing nitrogen through the liquid. 2 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen was passed through the liquid for 5 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred at reflux for 3 hours. After cooling to room temperature, the generated solid was separated by filtration, and the obtained solid was washed with toluene. The solid was dried using a vacuum dryer to obtain 12.8 g of compound S-1.

[0320] The NMR measurement data of compound S-1 are shown below. 1 H-NMR(400MHz, CDCl3, δ, ppm)8.52-8.49(Ar,2H),8.29(brs,NH,1H),8.22-8.19(Ar, 2H),8.18-8.15(Ar,2H),7.88-7.81(Ar,4H),7.64-7.56(Ar,6H),7.50-7.42(Ar,4H)

[0321] Compound S-1 (9.0 g), 2-(2-methacryloyloxyethoxy)ethyl isocyanate (5.0 g) and tetrahydrofuran (THF) (90 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was poured into 50 mL of an aqueous ammonium chloride solution, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was washed with a mixed solvent of hexane / ethyl acetate to obtain 10.0 g of compound M-1.

[0322] The NMR measurement data of compound M-1 are shown below. 1 H NMR (400MHz, CDCl3, δ, ppm)8.47(brd,Ar,2H),8.25-8.15(Ar,6H),7.90(dd,Ar,2H),7.83(Ar,2H),7.60(Ar,4H),7.47( Ar,4H),6.32(brs,NH,1H),6.00(brs,C=CH2,1H),5.40(dt,C=CH2,1H),4.37(CH2,2H),3.86(CH2,6H),1.81(brs,Me,3H)

[0323] <Production of holographic image recording media> Liquid A was prepared by dissolving 0.239 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 in 2.53 g of Dornade (registered trademark) TSS-100. Separately, 1.73 g of PLACCEL PCL-205U and 0.74 g of PLACCEL PCL-305 were mixed (PLACCEL PCL-205U:PLACCEL PCL-305=70:30 (mass ratio)), and 0.2 mg of an octanoic acid solution of bismuth tri(2-ethylhexanoate) was dissolved therein to prepare a liquid B.

[0324] After degassing liquid A and liquid B at room temperature or 45° C. for 2 hours under reduced pressure, 2.39 g of liquid A and 2.11 g of liquid B were stirred and mixed, and further degassed under vacuum for several minutes. Next, the vacuum degassed mixed solution was poured onto a glass slide with 0.5 mm thick spacers placed at two opposing end edges, a glass slide was placed thereon, the periphery was fixed with a clamp, and heated at 80° C. for 24 hours to prepare a holographic image recording medium as an evaluation sample. The evaluation sample had a 0.5 mm thick recording layer formed between the glass slides as covers.

[0325] The holographic image recording medium was prepared with a ratio of isocyanate groups in liquid A to isocyanate reactive groups in liquid B of 1.0, with 58.3 μmol / g of polymerizable monomer, 3.05 μmol / g of photopolymerization initiator, and 3.05 μmol / g of free radical scavenger.

[0326] <Holographic image recording and evaluation> Using the hologram recording medium prepared as the evaluation sample, hologram recording and evaluation of the hologram recording performance of the hologram recording medium were carried out in the following procedure.

[0327] Holographic image recording is done using a semiconductor laser with a wavelength of 405nm. Figure 1 The exposure device shown in the figure has an exposure power density of 10.2 mW / cm 2 Perform holographic image recording of two-beam plane waves. Rotate the medium from -22.5° to 22.5° and perform angle multiplexing recording at the same location. Measure the diffraction efficiency during each multiplexing recording. Calculate Δn from the obtained diffraction efficiency, and set the total Δn in the entire multiplexing recording. This will be described in detail below.

[0328] (Holographic image recording) Figure 1 This is a diagram showing the outline of a device used for holographic image recording. Figure 1 In the figure, S is a sample of the holographic image recording medium, M1 to M3 all represent mirrors, PBS represents a polarization beam splitter, and L1 represents a laser light source for recording light that emits light of wavelength 405 nm (a single-mode laser manufactured by TOPTICA Photonics that can obtain light of wavelength near 405 nm). Figure 1 1 is a LED unit.

[0329] like Figure 1 As shown, the light of wavelength 405nm is split by a polarization beam splitter ("PBS" in the figure), and the two beams are made to cross on the recording surface in such a way that the angle formed by the two beams reaches 59.3°. At this time, the bisector of the angle formed by the two beams is made perpendicular to the recording surface, and the vibration plane of the electric field vector of the two beams obtained by splitting is made perpendicular to the plane containing the two crossed beams for irradiation.

[0330] After the holographic image is recorded, a light having a wavelength of 633 nm using a He-Ne laser (V05-LHP151 manufactured by Melles Griot: "L2" in the figure) is used to irradiate the holographic image recording medium at an angle of 50.7°, and the diffracted light is detected using a photodiode and a light sensor amplifier (S2281, C9329 manufactured by Hamamatsu Photonics: "PD1" in the figure) to determine whether the holographic image recording was performed correctly.

[0331] (Determination of diffraction efficiency) The angle of the sample relative to the optical axis (the two beams, i.e. Figure 1 The angle between the internal angle bisector at the intersection of the incident light incident on the mirrors M1 and M2 and the sample normal) was moved from -22.5° to 22.5° in a manner of 0.3° each time, and multiple recordings were performed 151 times.

[0332] After multiple recording, the LED unit (1 in the figure, central wavelength 405nm) is lit for a certain period of time to consume the remaining initiator and monomer. This step is called post-exposure. The power of the LED is set to 100mW / cm 2 With a cumulative energy of 12 J / cm 2 way of irradiation.

[0333] The diffraction efficiency of a holographic image is given by the ratio of the diffracted light intensity to the sum of the transmitted light intensity and the diffracted light intensity. Figure 1 The light (wavelength 405nm) from the mirror M1 was measured to measure the diffraction efficiency from -23° to 23°. The following formula based on Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947) was used to calculate Δn from the obtained diffraction efficiency, and the total of the multiple recording was set as the total Δn.

[0334] [Number 2] totalΔn=∑Δn

[0335] Here, η is the diffraction efficiency, T is the medium thickness, λ is the wavelength of the reference light, and θ is the incident angle of the reference light (29.65°).

[0336] Using a variety of prepared samples, multiple evaluations were performed by changing the irradiation energy conditions, such as increasing or decreasing the irradiation energy at the beginning of recording, increasing or decreasing the total irradiation energy, etc., to find the conditions that consume the polymerizable monomer (the total Δn reaches a roughly balanced state during multiple recordings) and maximize the total Δn. The maximum value obtained was then set as the total Δn of the medium.

[0337] (Preparation of samples for ΔE and absorption coefficient measurement) Prepare to use a 405nm central wavelength LED manufactured by THORLAB at 36J / cm 2 The hologram recording medium obtained after exposure to energy of was used for the measurement of ΔE and absorption coefficient.

[0338] (Determination of ΔE) For the prepared holographic image recording medium, as a long-term performance stability test, before heating and after heating at 75°C for 100 hours in dry air, the color index ΔE(00) of the holographic image recording medium exposed to the entire surface under a 10-degree field of view was measured using an SE7700 spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. based on JIS: Z8722: 2009. As a reference, one sheet of EAGLE XG glass produced by Corning was used.

[0339] These evaluation results are shown in Table 1 below.

[0340] [Example 2] Compound M-2 was produced by the following synthesis method.

[0341] [Chemistry 12]

[0342] 3,6-dibromocarbazole (4.5 g), 1-naphthylboronic acid (5.2 g), potassium phosphate (8.8 g) were suspended in 50 mL of toluene, 50 mL of ethanol, and 25 mL of water, and degassed by passing nitrogen through the liquid. 10 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen was passed through the liquid for 5 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred at reflux for 3 hours. The generated solid was separated by filtration, and the obtained solid was washed with water and ethanol. The solid was dried using a vacuum dryer to obtain 5.0 g of compound S-2.

[0343] The NMR measurement data of compound S-2 are shown below. 1 H-NMR(400MHz,CDCl3,δ,ppm)8.25(brs,NH,1H),8.19(brs,Ar,2H),8.00(brd,Ar,2H),7.91(brd,A r,2H),7.89-7.83(Ar,2H),7.59(brs,Ar,4H),7.57-7.51(Ar,4H),7.48(dd,Ar,2H),7.41(ddd,Ar)

[0344] Compound S-2 (1.0 g), 2-isocyanatoethyl acrylate (0.4 g) and THF (10 mL) were mixed, and diazabicycloundecene (0.01 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was poured into 50 mL of aqueous ammonium chloride solution, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was washed with a mixed solvent of hexane / ethyl acetate to obtain 0.7 g of compound M-2.

[0345] The NMR measurement data of compound M-2 are shown below. 1 H NMR(400MHz, CDCl3, δ, ppm)8.19-8.10(Ar,4H),7.97-7.82(Ar,6H),7.62(dd,Ar,2H),7.55-7.43(Ar,6H),7.39(Ar,2H),6 .48(dd,CH=CH2,1H),6.28(drt,NH,1H),6.18(dd,CH=CH2,1H),5.87(dd,CH=CH2,1H),4.53(t,CH2,2H),3.93(dt,CH2,2H)

[0346] A hologram recording medium was prepared and evaluated in the same manner as in Example 1 except that the compound M-2 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0347] [Example 3] Compound M-3 was produced by the following synthesis method.

[0348] [Chemistry 13]

[0349] Compound S-1 (4.7 g), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (2.6 g), and THF (15 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.04 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was poured into 50 mL of aqueous ammonium chloride solution, extracted with 150 mL of ethyl acetate, washed with 20 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was purified by silica gel column chromatography to obtain 3.3 g of compound M-3.

[0350] The NMR measurement data of compound M-3 are shown below. 1 H NMR (400MHz, CDCl3, δ, ppm)8.38(brd,Ar,2H),8.17-8.09(Ar,6H),7.84(dd,Ar,2H),7.76(Ar,2H),7.57-7.49(Ar,4H),7.46-7.38(Ar,4H ),6.48(dd,CH=CH2,2H),6.35(s,NH,1H),6.19(dd,CH=CH2,2H),5.89(dd,CH=CH2,2H),4.69(d,CH2,2H),4.63(d,CH2,2H),1.76(s,Me,3H)

[0351] A hologram recording medium was prepared and evaluated in the same manner as in Example 1 except that the compound M-3 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0352] [Synthesis example 1] Compound M-4 was produced by the following synthesis method.

[0353] [Chemistry 14]

[0354] 3,6-dibromocarbazole (3.5 g), 4-dibenzofuran boronic acid (5.0 g), potassium phosphate (6.9 g) were suspended in 50 mL of toluene, 50 mL of ethanol, and 25 mL of water, and degassed by passing nitrogen through the liquid. 2 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen was passed through the liquid for 5 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred at reflux for 3 hours. The generated solid was separated by filtration, and the obtained solid was washed with water and ethanol. The solid was dried using a vacuum dryer to obtain 5.0 g of compound S-3.

[0355] The NMR measurement data of compound S-3 are shown below. 1 H-NMR(400MHz, CDCl3, δ, ppm)8.69(brd,Ar,2H),8.26(brs,NH,1H),8.04(dd,Ar,2H),8.02(ddd,Ar, 2H),7.95(dd,Ar,2H),7.76-7.72(Ar,2H),7.66-7.61(Ar,4H),7.50-7.44(Ar,4H),7.37(ddd,Ar,2H)

[0356] Under a nitrogen atmosphere, compound S-3 (2.0 g), 2-isocyanatoethyl acrylate (0.6 g), and THF (10 mL) were mixed, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was poured into 50 mL of aqueous ammonium chloride solution, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was washed with a mixed solvent of hexane / ethyl acetate to obtain 1.2 g of compound M-4.

[0357] The NMR measurement data of compound M-4 are shown below. 1 H NMR(400MHz,CDCl3,δ,ppm)8.65(brd,Ar,2H),8.22(d,Ar,2H),8.08(dd,Ar,2H),8.02(brd,Ar,2H),7.97(dd,Ar,2H),7.73(dd,Ar,2H),7.63(d,Ar,2H),7.51- 7.44(Ar,4H),7.38(ddd,Ar,2H),6.52(dd,CH=CH2,1H),6.24(brt,NH,1H),6.22 (dd,CH=CH2,1H),5.93(dd,CH=CH2,1H),4.57(brt,CH2,2H),3.98(brq,CH2,2H)

[0358] [Synthesis example 2] Compound M-5 was produced by the following synthesis method.

[0359] [Chemistry 15]

[0360] 3,6-dibromocarbazole (3.5 g), 9-phenanthrene boronic acid (5.3 g), and potassium phosphate (6.9 g) were suspended in 50 mL of toluene, 25 mL of ethanol, 25 mL of tetrahydrofuran, and 25 mL of water, and degassed by passing nitrogen through the liquid. 2 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen was passed through the liquid for 5 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred at reflux for 3 hours. After cooling to room temperature, 50 mL of 1N sodium hydroxide aqueous solution and 100 mL of ethyl acetate were added to perform a liquid separation operation. After the obtained organic layer was dried with magnesium sulfate, the solvent was distilled off. The generated solid was separated by filtration, and the obtained solid was washed with hexane. The solid was dried using a vacuum dryer to obtain 4.2 g of compound S-4.

[0361] The NMR measurement data of compound S-4 are shown below. 1 H-NMR(400MHz, CDCl3, δ, ppm)8.79(brd,Ar,2H),8.73(brd,Ar,2H),8.29(brs,NH,1H),8.27(brs, Ar,2H),8.03(dd,Ar,2H),7.90(dd,Ar,2H),7.79(brs,Ar,2H),7.69-7.58(Ar,10H),7.53(Ar,2H)

[0362] Under a nitrogen atmosphere, compound S-4 (1.0 g), 2-(2-methacryloyloxyethoxy)ethyl isocyanate (0.75 g) and THF (10 mL) were mixed, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was poured into 50 mL of aqueous ammonium chloride solution, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained mixture was purified by column chromatography to obtain 1.1 g of compound M-5.

[0363] The NMR measurement data of compound M-5 are shown below. 1 H NMR(400MHz, CDCl3, δ, ppm)8.75(d,Ar,2H),8.69(d,Ar,2H),8.22(d,Ar,2H),8. 20(brs,Ar,2H),7.97(d,Ar,2H),7.87(d,Ar,2H),7.75(s,Ar,2H),7.71-7.54(Ar ,8H),7.51(dd,Ar,2H),6.38(drt,NH,1H),6.01(s,C=CH2,1H),5.39(brs,C=CH2, 1H),4.34(dd,CH2,2H),3.84(brs,CH2,4H),3.81(dd,CH2,2H),1.80(brs,Me,3H)

[0364] [Synthesis example 3] Compound M-6 was produced by the following synthesis method.

[0365] [Chemistry 16]

[0366] 3,6-dibromocarbazole (4.5 g), 2-naphthylboronic acid (5.2 g), potassium phosphate (8.8 g) were suspended in 50 mL of toluene, 50 mL of ethanol, and 25 mL of water, and degassed by passing nitrogen through the liquid. 10 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen was passed through the liquid for 5 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred at reflux for 3 hours. The generated solid was separated by filtration, and the obtained solid was washed with water and ethanol. The solid was dried using a vacuum dryer to obtain 5.8 g of compound S-5.

[0367] The NMR measurement data of compound S-5 are shown below. 1 H-NMR(400MHz,CDCl3,δ,ppm)8.51(brs,Ar,2H),8.21(brs,NH,1H),8.16(brs,Ar ,2H),7.97-7.86(Ar,8H),7.83(dd,Ar,2H),7.56(brd,Ar,2H),7.54-7.46(Ar,4H)

[0368] Under a nitrogen atmosphere, compound S-5 (1.0 g), 2-(2-methacryloyloxyethoxy)ethyl isocyanate (0.7 g) and THF (5 mL) were mixed, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was injected into 50 mL of an aqueous solution of ammonium chloride, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was washed with a mixed solvent of hexane / ethyl acetate to obtain 1.2 g of compound M-6.

[0369] The NMR measurement data of compound M-6 are shown below. 1 H NMR(400MHz,CDCl3,δ,ppm)8.23(brd,Ar,2H),8.05(brs,Ar,2H),7.99(d,Ar,2H),7.89-7.80(Ar,6H),7.78(dd,Ar,2H),7.72(dd,Ar,2H),7.5 0-7.42(Ar,4H),6.28(brs,NH,1H),5.99(brt,C=CH2,1H),5.37(brt,C=CH2,1H),4.33-4.29(CH2,2H),3.78-3.70(CH2,6H),1.79(brs,Me,3H)

[0370] [Synthesis Example 4] Compound M-7 was prepared by the following synthesis method.

[0371] [Chemistry 17]

[0372] 1.3 g of 7H-dibenzo[c,g]carbazole, 2-isocyanatoethyl acrylate (1.0 g), and THF (10 mL) were mixed, and diazabicycloundecene (0.01 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was injected into 50 mL of an aqueous solution of ammonium chloride, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was washed with a mixed solvent of hexane / ethyl acetate to obtain 1.3 g of compound M-7.

[0373] The NMR measurement data of compound M-7 are shown below. 1 H NMR(400MHz,CDCl3,δ,ppm)9.09(d,Ar,2H),8.21(d,Ar,2H),8.04(brd,Ar,2H),7.93(d,Ar,2H),7.68(ddd,Ar,2H),7.57(dd,Ar ,2H),6.50(dd,CH=CH2,1H),6.24(drt,NH,1H),6.19(dd,CH=CH2,1H),5.92(dd,CH=CH2,1H),4.55(t,CH2,2H),3.97(dt,CH2,2H)

[0374] [Synthesis example 5] Compound M-8 was produced by the following synthesis method.

[0375] [Chemistry 18]

[0376] Compound S-2 (2.0 g), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (1.4 g), and THF (5 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.04 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was poured into 50 mL of aqueous ammonium chloride solution, extracted with 100 mL of ethyl acetate, washed with 20 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was purified by silica gel column chromatography to obtain 1.2 g of compound M-8.

[0377] The NMR measurement data of compound M-8 are shown below. 1 H NMR (400MHz, CDCl3, δ, ppm)8.17-8.13(Ar,4H),7.96-7.86(Ar,6H),7.63(dd,Ar,2H),7.58-7.47(Ar,6H),7.45-7.40(Ar,2H),6.49 (dd,CH=CH2,2H),6.25(s,NH,1H),6.20(dd,CH=CH2,2H),5.91(dd,CH=CH2,2H),4.70(d,CH2,2H),4.64(d,CH2,2H),1.78(s,Me,3H)

[0378] [Synthesis example 6] Compound M-9 was produced by the following synthesis method.

[0379] [Chemistry 19]

[0380] 5.0 g of carbazole was dissolved in 50 mL of dimethylformamide and cooled to 0 degrees. 17 g of N-bromosuccinimide was slowly added thereto, stirred for 30 minutes at 0 degrees, and then placed at room temperature overnight. The reaction mixture was injected into 200 mL of water, and the generated solid was filtered and separated, and washed with water. After the obtained crude purified product was suspended and washed with dichloromethane, the solid obtained by filtering was washed with dichloromethane, and 10 g of compound S-7 was obtained.

[0381] The NMR measurement data of compound S-6 are shown below. 1 H NMR (400MHz, CDCl3, δ, ppm)8.28(brs,NH,1H),8.12(d,Ar,1H),8.08(d,Ar,1H),7.72(d,Ar,1H),7.57(dd,Ar,1H),7.38(d,Ar,1H)

[0382] Compound S-6 (3g), dibenzothiophene-4-boric acid (5.6g), potassium phosphate (7.9g) were suspended in 25mL of toluene, 25mL of ethanol, and 15mL of water, and degassed by passing nitrogen through the liquid. 53mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen was passed through the liquid for 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred at 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, 0.4g of activated carbon was added to the obtained organic layer, and stirred for 30 minutes. After filtration with diatomaceous earth, the organic layer was concentrated to obtain 4.6g of a crude product of compound S-7.

[0383] The NMR measurement data of compound S-7 are shown below. 1 H NMR(400MHz, CDCl3, δ, ppm)8.62(brd,Ar,1H),8.56(brs,Ar,1H),8.32-8.25(Ar,3H),8.23-8.18(Ar,2H),8.18-8 .14(Ar,2H),8.09(d,Ar,1H),7.87-7.77(Ar,NH,4H),7.72-7.67(Ar,2H),7.64-7.56(Ar,3H),7.55-7.41(Ar,7H)

[0384] Compound S-7 (4.3 g), 2-(2-methacryloyloxyethoxy)ethyl isocyanate (1.8 g) and THF (6 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.04 g) was added thereto, followed by stirring for 3 hours. After the reaction, the reaction solution was poured into 50 mL of aqueous ammonium chloride solution, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was washed with a mixed solvent of hexane / ethyl acetate to obtain 3.7 g of compound M-9.

[0385] The NMR measurement data of compound M-9 are shown below. 1H NMR(400MHz, CDCl3, δ, ppm)8.64(d,Ar,1H),8.54(d,Ar,1H),8.26-8.14(Ar,7H),8.11(d,Ar, 1H),7.91(dd,Ar,1H),7.87-7.83(Ar,3H),7.72-7.58(Ar,6H),7.54-7.43(Ar,6H),5.94(brs, C=CH2,1H),5.56(t,NH,1H),5.41(C=CH2,1H),4.04-3.99(CH2,2H),3.24(brs,CH2,1H),3.15- 3.04(CH2,2H),2.96(brs,CH2,1H),2.67(brs,CH2,1H),2.35(brs,CH2,1H),1.79(brt,Me,3H)

[0386] [Comparative Example 1] Compound R-1 was produced by the following synthesis method.

[0387] [Chemistry 20]

[0388] 9H-carbazole (1.4 g), bis(bromomethyl)oxetane (1.0 g), sodium hydroxide (0.66 g), and benzyltrimethylammonium bromide (20 mg) 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 generated white solid was filtered and separated, washed with methanol, and dried under reduced pressure to obtain 1.3 g of compound L-1.

[0389] The NMR measurement data of compound L-1 are shown below. 1 H NMR(400MHz,CDCl3,δ,ppm)8.13(brd,4H),7.43(Ar,4H),7.27(Ar,8H),4.69(s,4H),4.64(s,4H)

[0390] Compound L-1 (5.3 g), 2-mercaptobenzothiazole (2.1 g), and toluenesulfonic acid monohydrate (100 mg) were suspended in 30 mL of toluene. The reaction solution was heated to 120° C. under a nitrogen atmosphere and stirred at reflux for 1 hour. After the mixture was cooled to room temperature, it was extracted with ethyl acetate and washed with a 1M aqueous sodium hydroxide solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layer was concentrated. The crude product obtained was washed with a small amount of methanol to obtain 6.9 g of compound L-2.

[0391] The NMR measurement data of compound L-2 are shown below. 1 H NMR(400MHz,CDCl3,δ,ppm),8.11(brd,4H),7.82(d,1H),7.61(d,1H),7.44(Ar,9H) ,7.25(Ar,5H),5.20(t,OH,1H),4.88(d,2H),4.50(d,2H),4.18(d,2H),3.89(s,2H)

[0392] Compound L-2 (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 the solution and reacted at room temperature. After 48 hours, a saturated aqueous sodium bicarbonate solution was added to the reaction solution and extracted with 50 mL of chloroform. The obtained organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by the above concentration was purified using a silica gel column (hexane / ethyl acetate) to obtain 3.4 g of compound R-1.

[0393] The NMR measurement data of compound R-1 are shown below. 1 H NMR(400MHz, CDCl3, δ, ppm)8.08(d,4H),7.80(d,1H),7.72(d,1H),7.39(Ar,9H),7.29(Ar,1H),7.23(Ar,4H),6.42(d,1H),6.13( dd,1H),5.86(d,1H),4.73(d,2H),4.68(d,2H),4.43(s,2H),4.40(t,OH,1H),4.06(t,2H),3.99(s,2H),3.75(m,2H),3.24(m,2H)

[0394] A hologram recording medium was prepared and evaluated in the same manner as in Example 1 except that the compound R-1 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0395] [Comparative Example 2] Compound R-2 was produced by the following synthesis method.

[0396] [Chemistry 21]

[0397] 3-Bromo-9H-carbazole (5.1 g), bis(bromomethyl)oxetane (2.5 g), potassium carbonate (2.9 g), and benzyltrimethylammonium bromide (0.1 g) 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 generated solid was separated by filtration, washed with a mixed solvent of ethyl acetate / hexane, and dried under reduced pressure to obtain 5.2 g of compound L-3.

[0398] The NMR measurement data of compound L-3 are shown below. 1 H NMR(400MHz,CDCl3,δ,ppm)8.23(d,2H),8.07(d,2H),7.50(dd,2H),7.45(Ar,2H),7.29(d,2H),7.26(d,2H),7.14(d,2H),4.63(s,4H),4.58(s,4H)

[0399] Compound L-3 (3.5 g), dibenzothiophene-4-boric acid (2.8 g), and potassium phosphate (5.2 g) were suspended in 60 mL of toluene, 30 mL of ethanol, and 30 mL of water, and degassed by passing nitrogen through the liquid. 31 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen was passed through the liquid for 10 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred at reflux for 6 hours. After cooling to room temperature, it was extracted with ethyl acetate and washed with water. The aqueous layer was extracted twice with ethyl acetate, and 0.4 g of activated carbon was added to the obtained organic layer, and stirred for 30 minutes. After diatomaceous earth filtration, the crude product obtained by concentration was purified using a silica gel column (hexane / ethyl acetate) to obtain 4.3 g (90% yield) of compound L-4.

[0400] The NMR measurement data of compound L-4 are shown below. 1 H NMR(400MHz,CDCl3,δ,ppm)8.51(d,2H),8.19(Ar,6H),7.83(Ar,4H),7.59(d,4H),7.47(Ar,8H),7.38(d,2H),7.32(t,2H),4.81(s,4H),4.77(s,4H)

[0401] Compound L-4 (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 was cooled to room temperature, it was extracted with ethyl acetate and washed with 1M sodium hydroxide aqueous solution. The aqueous layer was extracted again with ethyl acetate, and the combined organic layer was concentrated. The crude product was purified using a silica gel column (hexane / ethyl acetate) to obtain 3.8 g (65% yield) of compound L-5.

[0402] The NMR measurement data of compound L-5 are shown below. 1 H NMR(400MHz, CDCl3, δ, ppm)8.49(d,2H),8.19(Ar,6H),7.85(Ar,2H),7.80(Ar,2H),7.66(Ar,2H ),7.58(Ar,7H),7.46(Ar,9H),7.29(t,2H),4.98(d,2H),4.62(d,2H),4.27(s,2H),3.99(s,2H)

[0403] Compound L-5 (3.8 g) was dissolved in 30 mL of tetrahydrofuran and dibutyltin diacetate (60 mg) was added. 2-isocyanatoethyl acrylate (0.9 g) was added to the solution and reacted at room temperature. After 48 hours, a saturated aqueous sodium bicarbonate solution was added to the reaction solution and extracted with 50 mL of chloroform. The obtained organic layer was dried with magnesium sulfate and concentrated at a temperature below 30°C. The crude product obtained by the above concentration was purified using a silica gel column (hexane / ethyl acetate) to obtain 3.4 g (78% yield) of compound R-2.

[0404] The NMR measurement data of compound R-2 are shown below. 1 H NMR(400MHz, CDCl3, δ, ppm)8.47(d,2H),8.17(Ar,6H),7.82(Ar,4H),7.73(Ar,2H),7.58(Ar,6H),7.44(Ar,10H),7.29 (t,2H),6.36(d,1H),6.08(dd,1H),5.74(d,1H),4.82(s,4H),4.61(brt,NH,1H),4.55(s,2H),4.11(m,4H),3.32(m,2H)

[0405] A hologram recording medium was prepared and evaluated in the same manner as in Example 1 except that the compound R-2 was used as the polymerizable monomer. The results are shown in Table 1 below.

[0406] [Table 1]

[0407] When preparing the hologram recording medium, the molar concentrations of the polymerizable monomer, the photopolymerization initiator, and the additives were set to their own values, and only the type of the polymerizable monomer was changed to prepare the hologram recording medium, and the evaluation was performed (Table 1). As shown in Table 1, in Comparative Examples 1 to 2 in which the polymerizable monomer used had an aromatic amine group not bonded by a carbonyl bond, the coloration index ΔE after heating at 75°C for 100 hours was 3.8 or more. On the other hand, in Examples 1 to 3 in which the polymerizable monomer having a carbonyl group bonded to the nitrogen atom of the aromatic amine compound was used, the coloration index ΔE after heating at 75°C for 100 hours was 3.0 or less.

[0408] In the use of optical elements of AR glasses light guide plates, if the total Δn of the holographic image recording medium is high, the projected image can be bright and the viewing angle can be expanded. In addition, in storage applications, the increase in total Δn can increase the recording capacity. On the other hand, holographic image recording media with higher colorability, especially in the use of AR glasses waveguide plates, will absorb waveguide light, thereby reducing light utilization efficiency and aesthetics. In addition, if the color tone of the waveguide plate changes over time, the absorption intensity of the waveguide light also changes, resulting in reduced performance stability of the waveguide plate. Therefore, by using the compound of the present invention having both high total Δn and low colorability and low color variability, it is possible to produce an AR glasses light guide plate with excellent light utilization efficiency and long-term performance stability. Based on the above, the compounds of the present invention used in the examples can be said to be superior to the compounds of the comparative examples.

[0409] [Measurement of refractive index] The refractive index of the polymerizable monomers produced in Examples and Comparative Examples was measured by the following method. The sample was dissolved in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate at a mass ratio of 4:1 to prepare a test solution. 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 by a Kalnew precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-2000). The temperature of the test solution was set to 23°C, and the measurement wavelength was set to helium lamp d-ray (587.6nm). Based on the measurement results, a calibration curve showing the correlation between sample concentration and refractive index was prepared, and the refractive index when the sample concentration was 100% by mass was obtained from the obtained calibration curve as the refractive index of the sample.

[0410] [Table 2] Polymerizable monomer Refractive Index Example 1 M-1 1.703 Example 2 M-2 1.685 Example 3 M-3 1.688 Comparative Example 1 R-1 1.664 Comparative Example 2 R-2 1.701

[0411] As shown in Table 2, the refractive index of the compounds of the examples is a value of 1.65 or more, and these compounds have a sufficient refractive index as a high refractive index monomer. The compounds of the examples have a refractive index equal to or higher than that of the compounds of the comparative examples, so it can be seen that the compounds of the examples have improved colorability when heated while maintaining a high refractive index, and are excellent high refractive index materials with high compound stability compared to the compounds of the comparative examples.

[0412] While the present invention has been described in detail using specific aspects, it will be apparent to one skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2022-106252 filed on June 30, 2022, and the entirety of the patent application is incorporated herein by reference.

Explanation of symbols

[0413] S: Holographic image recording medium M1,M2,M3:Mirror L1: Semiconductor laser light source for recording light L2: Laser light source for regeneration light PD1, PD2, PD3: Light detector PBS: Polarization Beam Splitter 1:LED unit.

Claims

1. A compound represented by the following formula (1): In the formula, A represents a polymerizable group, and n represents an integer of 1 to 3. L represents a branched or unbranched (n+1)-valent linking group, Z represents an oxygen atom or a nitrogen atom which may have a substituent, m represents 0 or 1, X represents a single bond, an oxygen atom, a sulfur atom, a carbon atom which may have a substituent, or a nitrogen atom which may have a substituent, p represents an integer of 0 to 2, and when p is 2, two Xs are the same or different from each other, Y 1 and Y 2 are independently a benzene ring, a naphthalene ring or a phenanthrene ring, and Y 1 or Y 2 In the case of a benzene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 4. 1 or Y 2 In the case of a naphthalene ring, Y 1 or Y 2 a or b is an integer from 0 to 6. 1 or Y 2 In the case of a phenanthrene ring, the corresponding Y 1 or Y 2 a or b is an integer from 0 to 8, R 1 , R 2 Each independently represents an aromatic ring group which may have a substituent, and when a and b are 2 or more, a plurality of R 1 , R 2 Same or different from each other, in, There is no Y in the formula 1 With Y 2 The case where both are benzene rings and both a and b are 0.

2. The compound according to claim 1, wherein The p is 0 or 1.

3. A compound according to claim 1 or 2, wherein The A is an oxirane group, a vinyl group, an isopropenyl group, an allyl group, or a (meth)acryloyl group.

4. A compound according to claim 3, wherein The A is a (meth)acryloyl group.

5. A compound according to claim 1 or 2, wherein The above-mentioned Z is a nitrogen atom which may have a substituent.

6. A compound according to claim 1 or 2, wherein The R 1 and / or R 2 It is a condensed aromatic ring group or a monocyclic aromatic group substituted with an aromatic ring group.

7. A compound according to claim 1 or 2, wherein The Y 1 and / or Y 2 It is a benzene ring or a naphthalene ring.

8. A compound according to claim 7, wherein The Y 1 and Y 2 It is a benzene ring. 9 . A polymerizable composition comprising the compound according to claim 1 or 2 and a polymerization initiator. 10 . A holographic image recording medium comprising the polymerizable composition according to claim 9 .

11. A polymer obtained by polymerizing the polymerizable composition according to claim 9.

12. An optical material comprising the polymer according to claim 11.

13. An optical part comprising the polymer according to claim 11.

14. A large-capacity storage device comprising the holographic image recording medium according to claim 10.

15. An optical element obtained by recording a hologram on the hologram recording medium according to claim 10. AR glasses comprising the optical element according to claim 15 .

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