Compound, polymerizable composition, polymer, holographic recording medium, optical material, and optical member

Abstract

The present invention provides a compound represented by formula (1). [In the formula, n represents an integer of 1-3. And L1 represents a branching (n + 1)-valent linking group (excluding a chain saturated aliphatic hydrocarbon group). And X represents an oxygen atom or an optionally substituted nitrogen atom. And R1-1 represents an optionally substituted aromatic ring group. M is an integer of 3-5, and a plurality of R1-1 may be the same or different. Wherein, in the formula, the total number of carbon atoms of a plurality of R1-1 represented by-(R1-1) m is 25 to 70. In the formula, the benzene ring having R1-1 may further have a substituent in addition to R1-1. And R2 represents a hydrogen atom or a methyl group. ]. # imgabs0 #

Description

Technical Field

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

[0002] In the past, 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 it is manufactured using a material with a higher refractive index, the lens can be thinned, which has the advantages of being lightweight and having an increased 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, highly transparent plastics have attracted attention as optical materials to replace glass.

[0004] Compared with glass, plastic materials have the advantages of being easy to lighten, easy to improve mechanical strength, and easy to process and shape. With the development of peripheral technologies, the demand for improving the performance of plastic optical materials has also increased. For example, in the materials used for optical lenses, it is required to be easy to polymerize (polymerizability), have good curability or solubility in various solvents, and have a high refractive index of the polymer.

[0005] To date, a large number of resins have been developed to increase the refractive index.

[0006] In order to increase the refractive index, it is effective to introduce an aromatic ring. For example, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene is frequently used as a high-refractive-index acrylate. However, the refractive index of this compound is about 1.62, which is not high enough (Patent Document 1).

[0007] Patent Documents 2 and 3 describe that a holographic recording medium with high diffraction efficiency and light transmittance can be obtained by using a high-refractive-index aromatic acrylate compound substituted with a large number of aromatic rings. However, it is generally known that the high molecular weight produced by the introduction of aromatic substituents and the solubility in various media are in a trade-off relationship, and if the number of aromatic substituents is increased, the solubility is significantly reduced. Even the polymerizable compounds of the examples of Patent Documents 2 and 3 do not have sufficient solubility in solvents to exhibit holographic recording performance that can withstand actual use.

[0008] Patent Document 4 describes that the solubility is improved by introducing an alkylene linker into a phenol substituted with a large number of aromatic rings. However, due to the trade-off between the increase in molecular weight and the decrease in solubility caused by the introduction of aromatic rings, this example is limited to disubstituted phenols.

[0009] Similarly, in Patent Document 5 regarding an acrylate monomer for holograms having polyaromatic substituted phenol and aniline, the total number of carbon atoms of the aromatic substituents showing a high refractive index is limited to 24 or less.

[0010] In addition to introducing an aromatic ring, introducing a sulfur atom into a molecule is also effective for increasing the refractive index of a compound. For example, Patent Document 6 describes an acrylate compound having a glycerol skeleton with two benzothiazole rings in one molecule, and its refractive index is 1.63.

[0011] Patent Document 7 describes a diacrylate monomer having a pentaerythritol skeleton with 1 to 2 naphthylthio groups in one molecule. The refractive index of this compound is also 1.62 to 1.65.

[0012] It cannot be said that these are materials having a refractive index sufficient for applications requiring an ultra-high refractive index exceeding 1.65.

[0013] Patent Documents 8 and 9 describe monomers having a dibenzothiophenethio group and a refractive index exceeding 1.65. Patent Documents 10 and 11 describe ultra-high refractive index acrylate compounds having a dibenzocarbazolyl group and a refractive index exceeding 1.7. However, these compounds have alkylthio groups or alkylcarbazolyl groups that are easily oxidized by oxygen, and therefore there is a concern that they may discolor or change in hue due to heating in air, long-term storage, light irradiation, etc., and cannot be considered as materials with high chemical stability.

[0014] Prior art literature

[0015] Patent Literature

[0016] Patent Document 1: Japanese Patent Application Laid-Open No. 6-220131

[0017] Patent Document 2: International Publication No. 2009 / 151061

[0018] Patent Document 3: Japanese Patent No. 5664707

[0019] Patent Document 4: Japanese Patent No. 6089867

[0020] Patent Document 5: European Patent Application Publication No. 2354845

[0021] Patent Document 6: Japanese Patent Application Publication No. 2005-133071

[0022] Patent Document 7: Japanese Patent Application No. 2008-527413

[0023] Patent Document 8: Japanese Patent No. 6458645

[0024] Patent Document 9: International Publication No. 2021 / 100654

[0025] Patent Document 10: International Publication No. 2021 / 006011

[0026] Patent Document 11: International Publication No. 2021 / 006012 Summary of the invention

[0027] An object of the present invention is to provide a compound having a high refractive index, high transparency, easy polymerizability, chemical stability, high solubility in various solvents, and storage stability of a solution thereof, which is useful as an optical material or an optical component.

[0028] The present inventors have found that by bonding a polymerizable group to a high refractive index structure in which three or more aromatic substituents are introduced into one benzene ring in a manner that leads to a high molecular weight, via a linking group, it is possible to break the trade-off relationship between the high molecular weight caused by the introduction of a large number of aromatic substituents and the reduction in solubility in various media. As a result, a compound that solves the problem of the present invention can be obtained, in which the polymerizable composition and the polymer have high refractive index, high transparency, easy polymerization, and chemical stability, and the solvent solubility is improved.

[0029] Specifically, the inventors have found that a high-performance hologram recording medium having high diffraction efficiency can be obtained by using a compound represented by the following formula (1) or a compound represented by the following formula (2), thereby completing the present invention.

[0030] That is, the gist of the present invention lies in the following aspects.

[0031] [1] A compound represented by the following formula (1).

[0032]

[0033] [In the formula, n represents an integer of 1 to 3.

[0034] L 1 It represents a branchable (n+1)-valent linking group (excluding chain-like saturated aliphatic hydrocarbon groups).

[0035] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0036] R1-1 It represents an aromatic ring group which may have a substituent.

[0037] m is an integer from 3 to 5, and multiple R 1-1 It can be the same or different.

[0038] Among them, in the formula, the composition-(R 1-1 )m shown in multiple R 1-1 The total number of carbon atoms is 25-70.

[0039] In addition, the formula with R 1-1 The benzene ring is R 1-1 In addition, it may further have a substituent.

[0040] R 2 represents a hydrogen atom or a methyl group.]

[0041] [2] A compound represented by the following formula (2).

[0042]

[0043] [In the formula, n represents an integer of 1 to 3.

[0044] L represents a (n+1)-valent chain saturated aliphatic hydrocarbon group which may have a substituent.

[0045] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0046] R 1-2 It represents an aromatic ring group represented by the following formula (2-1).

[0047] m is an integer from 3 to 5, and multiple R 1-2 It can be the same or different.

[0048] Among them, in the formula, the composition-(R 1-2 )m shown in multiple R 1-2 The total number of carbon atoms is 25-70.

[0049] In addition, the formula with R 1-2 The benzene ring is R 1-2 In addition, it may further have a substituent.

[0050] R 2 represents a hydrogen atom or a methyl group.]

[0051]

[0052] [In formula (2-1), R 3 represents a substituent.

[0053] In formula (2-1), there are multiple R3 In the case of , they may be bonded to each other to form a ring condensed with the naphthalene ring in formula (2-1), and the condensed ring may further have a substituent.

[0054] p represents 0 or an integer whose upper limit is the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1).

[0055] * represents the bonding site to the benzene ring in formula (2).]

[0056] [3] The compound according to [1] or [2], wherein m is 3 or 5.

[0057] [4] The compound according to [1] or [3], wherein R 1-1 It is a condensed aromatic ring group which may have a substituent or a monocyclic aromatic ring group substituted with an aromatic ring group.

[0058] [5] The compound according to [2] or [3], wherein R 1-2 It is a condensed aromatic ring group which may have a substituent or a monocyclic aromatic ring group substituted with an aromatic ring group.

[0059] [6] The compound according to any one of [1] to [5], wherein X is an oxygen atom.

[0060] [7] The compound according to any one of [1] to [5], wherein X is a nitrogen atom which may have a substituent.

[0061] [8] The compound according to any one of [1] to [7], wherein m is 3.

[0062] [9] A polymerizable composition comprising the compound according to any one of [1] to [8] and a polymerization initiator.

[0063]

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

[0064]

[11] An optical material comprising the polymerizable composition described in [9].

[0065]

[12] An optical component comprising the polymerizable composition described in [9].

[0066]

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

[10] .

[0067]

[14] An optical element obtained by performing holographic recording on the holographic recording medium described in

[10] .

[0068]

[15] An AR light guide plate comprising the optical element described in

[14] .

[0069]

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

[14] .

[0070]

[17] A polymer comprising a structure represented by the following formula (P1-1) or the following formula (P1-2).

[0071]

[0072] [In the formula (P1-1), n ​​represents an integer of 1 to 3.

[0073] L 1 It represents a branchable (n+1)-valent linking group (excluding chain-like saturated aliphatic hydrocarbon groups).

[0074] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0075] R 1-1 It represents an aromatic ring group which may have a substituent.

[0076] m is an integer from 3 to 5, and multiple R 1-1 It can be the same or different.

[0077] Among them, in the formula, the composition-(R 1-1 )m shown in multiple R 1-1 The total number of carbon atoms is 25-70.

[0078] In addition, the formula with R 1-1 The benzene ring is R 1-1 In addition, it may further have a substituent.

[0079] R 2 represents a hydrogen atom or a methyl group.

[0080] In the formula (P1-2), n represents an integer of 1 to 3.

[0081] L represents a (n+1)-valent chain saturated aliphatic hydrocarbon group which may have a substituent.

[0082] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0083] R 1-2 It represents an aromatic ring group represented by the following formula (2-1).

[0084] m is an integer from 3 to 5, and multiple R 1-2 It can be the same or different.

[0085] Among them, in the formula, the composition-(R 1-2 )m shown in multiple R 1-2 The total number of carbon atoms is 25-70.

[0086] In addition, the formula with R 1-2 The benzene ring is R 1-2 In addition, it may further have a substituent.

[0087] R 2 represents a hydrogen atom or a methyl group.

[0088] q represents the number of repetitions of the structure represented by formula (P1-1) or formula (P1-2).]

[0089]

[0090] [In formula (2-1), R 3 represents a substituent.

[0091] In formula (2-1), there are multiple R 3 In the case of , they may be bonded to each other to form a ring condensed with the naphthalene ring in formula (2-1), and the condensed ring may further have a substituent.

[0092] p represents 0 or an integer whose upper limit is the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1).

[0093] * represents the bonding site to the benzene ring in formula (2).]

[0094]

[18] A holographic recording medium comprising the polymer described in

[17] .

[0095]

[19] An optical material comprising the polymer described in

[17] .

[0096]

[20] An optical component comprising the polymer described in

[17] .

[0097]

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

[18] .

[0098]

[22] An optical element obtained by performing holographic recording on the holographic recording medium described in

[18] .

[0099]

[23] An AR light guide plate comprising the optical element described in

[22] .

[0100]

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

[22] .

[0101] According to the present invention, a high refractive index compound which is useful as an optical material and has high refractive index, high transparency, easy polymerizability, chemical stability, high solubility, and storage stability of a solution can be provided.

[0102] The compound of the present invention is particularly useful as a reactive compound used in a hard coat layer of an optical lens or optical component, or a holographic recording medium. By using the compound of the present invention, an optical material or optical component having high diffraction efficiency, high light transmittance, high chemical stability, and excellent processability can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0103] Figure 1 This is a schematic diagram showing an outline of the configuration of an apparatus used for holographic recording. DETAILED DESCRIPTION

[0104] 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.

[0105] 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".

[0106] In the present invention, “may have a substituent” means that the compound may have one or more substituents.

[0107] 1. About the compounds of the present invention

[0108] The compound according to one embodiment 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)".

[0109]

[0110] [In the formula, n represents an integer of 1 to 3.

[0111] L 1 It represents a branchable (n+1)-valent linking group (excluding chain-like saturated aliphatic hydrocarbon groups).

[0112] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0113] R 1-1 It represents an aromatic ring group which may have a substituent.

[0114] m is an integer from 3 to 5, and multiple R 1-1 It can be the same or different.

[0115] Among them, in the formula, the composition-(R 1-1 )m shown in multiple R 1-1 The total number of carbon atoms is 25-70.

[0116] In addition, the formula with R 1-1 The benzene ring is R1-1 In addition, it may further have a substituent.

[0117] R 2 represents a hydrogen atom or a methyl group.]

[0118] The compound according to another embodiment of the present invention is represented by the following formula (2). Hereinafter, the compound represented by the following formula (2) may be referred to as "compound (2)".

[0119]

[0120] [In the formula, n represents an integer of 1 to 3.

[0121] L represents a (n+1)-valent chain saturated aliphatic hydrocarbon group which may have a substituent.

[0122] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0123] R 1-2 It represents an aromatic ring group represented by the following formula (2-1).

[0124] m is an integer from 3 to 5, and multiple R 1-2 It can be the same or different.

[0125] Among them, in the formula, the composition-(R 1-2 )m shown in multiple R 1-2 The total number of carbon atoms is 25-70.

[0126] In addition, the formula with R 1-2 The benzene ring is R 1-2 In addition, it may further have a substituent.

[0127] R 2 represents a hydrogen atom or a methyl group.]

[0128]

[0129] [In formula (2-1), R 3 represents a substituent.

[0130] In formula (2-1), there are multiple R 3 In the case of , they may be bonded to each other to form a ring condensed with the naphthalene ring in formula (2-1), and the condensed ring may further have a substituent.

[0131] p represents 0 or an integer whose upper limit is the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1).

[0132] * represents the bonding site to the benzene ring in formula (2).]

[0133] Hereinafter, "Compound (1)" and "Compound (2)" are collectively referred to as "compounds of the present invention".

[0134] 1-1. Structure of the Compound of the Present Invention

[0135] The compound of the present invention is characterized in that it is connected via a specific linking group L 1 Or a structure in which L has a polymerizable group bonded to a high molecular weight phenol compound or aniline compound having 3 or more aromatic ring groups (aromatic substituents) and a total of 25 to 70 carbon atoms in the 3 or more aromatic ring groups.

[0136] In optical materials, in order to improve the refractive index, organic compounds with aromatic ring groups are sometimes used. However, organic compounds with high planar aromatic ring groups generally have insufficient solubility in various solvents, so it is difficult to use them in the form of high-concentration solutions with high refractive index. In addition, even if high-concentration solutions can be prepared, due to the high crystallinity of the organic compounds, there is also a problem of being easily separated out from the preservation solution over time. In particular, the aromatic organic compounds used in optical materials with a refractive index exceeding 1.65 have multiple aromatic rings as substituents, and there is a trend of reduced solubility in various solvents as their molecular weight increases.

[0137] The compound of the present invention has a phenol skeleton or an aniline skeleton densely containing a large number of aromatic ring groups, thereby causing molecular distortion between the substituents, which can reduce the crystallinity of the compound of the present invention. 1-1 or R 1-2 The higher the molecular weight, the higher the refractive index and molecular weight of the compound of the present invention. However, the symmetry and planarity of the molecule as a whole tend to decrease, and high solubility in solvents can be achieved. 2 Since the (meth)acrylic group concentration of -C(=CH2)-C(=O)-O- is relatively low, it is very useful as an optical material with little shrinkage during curing.

[0138] In addition, through the specific linking group L 1 or L, so that the polymerizable group is bonded to an appropriate position away from the high refractive index site with large steric hindrance via the linking group, thereby greatly improving the flexibility of the compound of the present invention, and showing high polymerizability as a (meth)acrylate monomer, which can achieve a high refractive index of the polymer and improve chemical stability.

[0139] 1-2. About L in Formula (1) 1

[0140] L 1represents a branchable (n+1)-valent linking group other than the chain-like saturated aliphatic hydrocarbon group as L in the following formula (2). 1 It may also have an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.

[0141] As a component of L 1 The linking group other than the chain saturated aliphatic hydrocarbon group is preferably an unsaturated aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group which may have a substituent from the viewpoint of ease of synthesis and availability. The number of carbon atoms of the unsaturated aliphatic hydrocarbon group or the cyclic aliphatic hydrocarbon group (excluding the number of carbon atoms of the substituent) is preferably 1 to 8. If the number of carbon atoms of the unsaturated aliphatic hydrocarbon group or the cyclic aliphatic hydrocarbon group is 8 or less, the refractive index of the compound (1) is not easily reduced, and the viscosity tends to be reduced and the processability tends to be improved due to the small molecular weight. As a constituent of L 1 The unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group may be any one of a cyclic aliphatic hydrocarbon group and a chain unsaturated aliphatic hydrocarbon group, or these structures may be combined. 2 From the viewpoint of steric hindrance around -C(=CH2)-C(=O)-O-, a chain unsaturated aliphatic hydrocarbon group is preferred.

[0142] As a component of L 1 In the case of n=1, the chain unsaturated aliphatic hydrocarbon group may be an alkynylene group or an alkenylene group having 2 to 8 carbon atoms. In the case of n=2 or 3, L 1 The group may be a group formed by combining two or more alkynylene groups or alkenylene groups having 2 to 8 carbon atoms, or a group formed by combining an alkynylene group or alkenylene group having 2 to 8 carbon atoms and an alkylene group.

[0143] From the viewpoint of imparting high solubility to the compound (1) in various media, L 1 Preferably, the (n+1)-valent linking group has an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent. These linking groups may also have a substituent, and the number of carbon atoms (excluding the number of carbon atoms of the substituent) is preferably 1 to 8. If the number of carbon atoms of the (n+1)-valent linking group is 8 or less, the refractive index of the compound (1) is not easily reduced, and the viscosity tends to be reduced and the processability tends to be improved due to the small molecular weight. 1 The (n+1)-valent linking group may be a cyclic linking group or a chain linking group, or a combination of these structures. From the viewpoint of alleviating steric hindrance around the polymerizable (meth)acrylate, a chain linking group is preferred.

[0144] As a component of L 1The (n+1)-valent chain linking group having an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent, when n=1, includes -CH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2(CO)-, -CH2CH2CH2(CO)-, -CH2CH2CH2CH2(CO)-, -CH2CH2CH2CH2(CO)-, -CH2CH2OCH2CH2(CO)-, -CH2CH2NH(CO)-, -CH2CH2CH2NH(CO)-, -CH2CH2CH2CH2NH(CO)-, -CH2CH2OCH2CH2NH(CO)-, etc. 1 A group formed by combining two or more of these groups may also be used. 1 , examples include -(CH2)2C(CH3)-, -(CH2)2C(CH3)(CO)-, -(CH2)2C(CH2CH3)(CO)-, -(CH2)3C(CO)-, -(CH2)2C(CH3)NH(CO)- or any hydrogen atom in the above chain linking group is substituted with a bonding site with a polymerizable group. In this case, it is also possible to bond to the polymerizable group via a branched structure.

[0145] From the perspective of high refractive index, L 1 Preferably, it contains a cyclic group, constituting L 1 The ring contained in the cyclic group may be a monocyclic structure or a condensed ring structure. 1 The number of rings contained in is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 to 2. 1 The ring contained in L does not necessarily need to be aromatic, but in order to keep the size of the entire molecule small and maintain a high refractive index, an aromatic hydrocarbon ring is preferably used. 1 Examples of the aromatic hydrocarbon ring include a benzene ring, an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, an acenaphthene ring, anthracene ring, a phenanthrene ring and a pyrene ring.

[0146] Linking group L 1 It may also have a substituent. 1The substituent which may be possessed includes a halogen atom (a chlorine atom, a bromine atom, an 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 mesityl 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, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide 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.

[0147] 1-3. R in Formula (1) 1-1

[0148] R 1-1 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.

[0149] 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, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

[0150] 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; and examples thereof include an aromatic heterocyclic ring containing one heteroatom such as an imidazole ring, a triazole ring, a tetrazole ring, Aromatic heterocyclic rings containing two or more heteroatoms, such as azole rings, thiazole rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, and thiadiazole rings; benzo[pi] Azole ring, thieno Azole, thiazole Azole ring, Oxazo Azole ring, Azolimidazole ring, Azolopyridine ring, Oxalopyridazine ring, Azolopyrimidine ring, Azolopyrazine ring, naphtho Azole, quinoline Azole ring, di Azopyrazine ring, phen The invention also includes a ring formed by condensing two or three aromatic heterocyclic rings containing two or more hetero atoms, such as an oxazine ring, a benzothiazole ring, a furothiazole ring, a thienothiazole ring, a thiazolothiazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a thiazolidazole ring, a naphthothiazole ring, a quinolinethiazole ring, a thianthracene ring, and a phenothiazine ring.

[0151] As a component of R 1-1 The aromatic hydrocarbon ring of R 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 ease of synthesis and availability. 1 The aromatic hydrocarbon ring of R is more preferably a benzene ring, a naphthalene ring, a phenanthrene ring, a biphenylene ring, or a fluorene ring. 1-1 The aromatic hydrocarbon ring is more preferably a 1-naphthalene ring, a 9-phenanthrene ring or a 9-anthracene ring.

[0152] As a component of R 1-1 The aromatic heterocycle of is preferably a sulfur-containing aromatic heterocycle from the aspect of having a 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 heteroatoms, in addition to sulfur atoms, it may have an oxygen atom, may have a nitrogen atom, or may have an oxygen atom and a nitrogen atom. From the aspect of avoiding coloration and ensuring solubility, the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, and more preferably 1 to 2.

[0153] 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 thianthracene ring; a thiazole ring, an isothiazole ring, a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazolidazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a dithiopyrimidine ring, and a dithiopyrimidine ring. Azolopyrazine ring, thiazolopyrazine ring, thiazolopyrazine ring Azole ring, dibenzobenzothiophene ring, thieno An aromatic heterocyclic ring containing two or more hetero atoms, such as an azole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring.

[0154] The sulfur-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 availability of raw materials and easy synthesis.

[0155] In particular, from the viewpoint of increasing the refractive index and reducing coloration, 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 thianthrene ring.

[0156] As a component of R 1-1 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 hetero atom 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.

[0157] Examples of the nitrogen-containing aromatic heterocyclic ring include a pyrrole ring, an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, Azole ring, thiazole ring, benzo Azole, naphtho Azole ring, benzothiazole ring, naphthiazole ring, phen Azine ring, phenothiazine ring, thieno Azole, thiazole Azole ring, Oxazo an aromatic heterocyclic ring containing one nitrogen atom, such as an azole ring, a furanothiazole ring, a thienothiazole ring, a thiazolothiazole ring, etc.; an imidazole ring, a triazole ring, a tetrazole ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiadiazole ring, a benzimidazole ring, Azolimidazole ring, Azolopyridine ring, Oxalopyridazine ring, Azolopyrimidine ring, Azopyrazine ring, quinoline Azole ring, di An aromatic heterocyclic ring containing two or more nitrogen atoms such as an oxazolopyrazine ring, a thiazolimidazole ring, a thienothiadiazole ring, a thiazolothiadiazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a thiazolopyrazine ring, and a quinolinothiazole ring.

[0158] The nitrogen-containing aromatic heterocyclic ring may be a monocyclic ring or a condensed ring. From the viewpoint of high 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 perspective of easy availability of raw materials and easy synthesis.

[0159] In particular, from the viewpoint of high refractive index and low coloring, the nitrogen-containing aromatic heterocyclic ring is preferably a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a benzo azole ring, benzothiazole ring, benzimidazole ring, thiadiazole ring, more preferably carbazole ring, benzocarbazole ring, dibenzocarbazole ring, benzo Azole ring, benzothiazole ring, benzimidazole ring, thiadiazole ring.

[0160] As a component of R 1-1 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 using compound (1) as a raw material. The oxygen-containing aromatic heterocycle has at least an oxygen atom as a hetero atom constituting the aromatic heterocycle. As heteroatoms, in addition to oxygen atoms, it may also have a nitrogen atom, a sulfur atom, or a nitrogen atom and a sulfur atom. From the perspective 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.

[0161] Examples of the oxygen-containing aromatic heterocyclic ring include a furan ring, a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a phenanthrofuran ring, Oxazine ring, Azole ring, iso Azole ring, benzo Azole ring, benzyl isocyanate Azole, naphtho Azole ring, thieno Azole, thiazole Azole ring, Aromatic heterocyclic rings containing one oxygen atom, such as oxadiazole rings and furanthiazole rings; dibenzodiphenylamine rings British Ring, Oxazo Azole ring, di An aromatic heterocyclic ring containing two or more oxygen atoms, such as an oxazolopyrazine ring.

[0162] 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 perspective of easy availability of raw materials and easy synthesis.

[0163] In particular, from the viewpoint of high refractive index and low coloring, the oxygen-containing aromatic heterocyclic ring is preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, Azole ring, iso Azole ring, benzo Azole ring, benzyl isocyanate Azole, naphtho The azole ring is more preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a benzo Azole ring.

[0164] These R1-1 The aromatic ring may have a substituent. Examples of the substituent include halogen atoms such as chlorine, bromine, and iodine, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an alkoxy 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, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, a dialkylaminoethyl group bonded to an alkyl group having 1 to 4 carbon atoms, 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. Among them, preferred are 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, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a nitro group.

[0165] From the viewpoint of increasing the refractive index of compound (1), these R 1-1 The aromatic ring of the present invention preferably further has a group containing an aromatic ring as a substituent. The aromatic ring contained in the substituent and the aromatic ring constituting R 1-1 The aromatic rings contained in these substituents may be directly bonded to the aromatic rings constituting R at any position. 1-1 The aromatic ring may be bonded via an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent, or may be bonded via an arbitrary connecting group. The substituent is more preferably directly bonded to the aromatic ring constituting R 1-1 Aromatic ring.

[0166] 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. Definition of sulfur-containing aromatic heterocyclic ring and R 1-1 The sulfur-containing aromatic heterocyclic ring in has the same meaning as that in . 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 thianthrene ring is particularly preferred.

[0167] As R 1-1 The number of aromatic rings present 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.

[0168] From the viewpoint of achieving both high refractive index and high solubility in various media, the composition R 1-1 The aromatic ring is preferably a condensed aromatic ring which may have a substituent, or a monocyclic aromatic ring substituted with an aromatic ring group, and more preferably a condensed aromatic heterocyclic ring which may have a substituent, or an aromatic hydrocarbon ring having an aromatic heterocyclic ring as a substituent.

[0169] Composition R 1-1 The aromatic ring may have two or more selected from the group consisting of the above-mentioned aromatic hydrocarbon rings, sulfur-containing aromatic heterocycles, nitrogen-containing aromatic heterocycles and oxygen-containing aromatic heterocycles.

[0170] In addition, R 1-1 As described below, by setting m to 3 to 5, a plurality of R 1-1 It can be the same or different.

[0171] The 3 to 5 R in formula (1) 1-1 The total number of carbon atoms is 25-70.

[0172] When the total number of carbon atoms is 25 or more, the refractive index of the compound (1) can be expected to be high. On the other hand, when the total number of carbon atoms is 70 or less, the compound (1) can be easily synthesized.

[0173] From the above point of view, the m R in formula (1) 1-1 The total number of carbon atoms is preferably 25-64, more preferably 30-56.

[0174] 1-4. About m in formula (1)

[0175] m represents an integer of 3 to 5. This m can be appropriately selected. For example, from the viewpoint of the ease of synthesis of compound (1) and the ease of obtaining raw materials, m is preferably 3 or 5, and more preferably m=3.

[0176] On the other hand, m is preferably 4 or 5, and more preferably m=5, since there is a tendency to achieve both an ultrahigh refractive index and high solubility.

[0177] When m=3, R 1-1 It is preferably bonded to the ortho position or the para position relative to the bonding position to X on the benzene ring.

[0178] 1-5. About X in formula (1)

[0179] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0180] From the viewpoint of suppressing the coloration of compound (1), easiness of synthesis and availability of raw materials, X is preferably an oxygen atom. When X is an oxygen atom, the chemical stability of the intermediate compound during the synthesis of compound (1) tends to be excellent, and it is not easily oxidized, and coloration is easily avoided, so it is preferred.

[0181] On the other hand, from the viewpoint of improving compatibility with various solvents or holographic recording media, X is preferably a nitrogen atom which may have a substituent. In particular, when X is a nitrogen atom which does not have a substituent, multi-point hydrogen bonding with various solvents or holographic recording media can be achieved, and it can be expected that a low haze material with less turbidity can be provided, which is more preferred.

[0182] 1-6. About R in Formula (1) 2

[0183] R 2 represents a hydrogen atom or a methyl group. 2 For example, from the viewpoint of improving the stability of the polymer of compound (1), R 2 On the other hand, from the viewpoint of the polymerizability of the compound (1), R 2 Preferred is methyl.

[0184] 1-7. About n in formula (1)

[0185] n represents an integer of 1 to 3. This n can be appropriately selected. For example, n=2 or 3 may be used from the viewpoint of the easy polymerizability of the compound (1).

[0186] 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, and is more preferably a monofunctional compound having 1 polymerizable group. That is, from the viewpoint of a higher refractive index, n=1 or 2 is preferred, and n=1 is more preferred.

[0187] It should be noted that when n is 2 or 3, multiple R 2 -C(=CH2)-C(=O)-O-, that is, the (meth)acrylate polymerizable groups may be the same or different.

[0188] 1-8. Regarding the benzene ring in formula (1) except R 1-1 Substituents other than

[0189] The benzene ring in formula (1) may also have 1-1 Substituents other than . Examples of the substituents that the benzene ring may have include halogen atoms such as fluorine, 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, sulfamoyl groups, alkylsulfamoyl groups having 2 to 9 carbon atoms, alkylcarbonyl groups having 2 to 9 carbon atoms, phenethyl groups, hydroxyethyl groups, acetylamide groups, dialkylaminoethyl groups to which alkyl groups having 1 to 4 carbon atoms are bonded, trifluoromethyl groups, alkylthio groups having 1 to 8 carbon atoms, aromatic ring thio groups having 6 to 10 carbon atoms, and nitro groups.

[0190] From the viewpoint of ease of synthesis, the benzene ring is preferably 1-1 It has no substituent other than this.

[0191] On the other hand, from the viewpoint of improving the refractive index and improving the solubility, the benzene ring preferably has 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, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, or a nitro group as a substituent.

[0192] 1-9. Molecular weight of compound (1)

[0193] 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 even more preferably 1200 or less. From the viewpoint of reducing the shrinkage during polymerization, the molecular weight of the compound (1) is preferably 500 or more, more preferably 600 or more, and even more preferably 650 or more.

[0194] 1-10. Relationship between molecular structure and physical properties of compound (1)

[0195] Compound (1) has three or more highly planar aromatic ring groups bonded to one benzene ring of a phenol compound or an aniline compound, thereby being able to appropriately introduce molecular distortion into a monomer or polymer such that the dihedral angle of the connection site with the benzene ring as the central skeleton becomes 1 degree or more. 1-1 In the case of an aromatic ring group having a substituent or a ring structure at the ortho position of the connection site to the central benzene skeleton, such as 1-naphthyl, 9-phenanthrenyl, 1-thianthrenyl, 4-dibenzofuranyl, and 4-dibenzothiophenyl, the dihedral angle tends to become larger. As a result, the aggregation of high refractive index structures can be suppressed, and high solubility in various media can be achieved, and it can be used in the form of a polymerizable monomer with an ultra-high refractive index. In particular, in R 1-1 In the case of 1-naphthyl, 9-phenanthrenyl, and 9-anthryl, since they have hydrogen atoms near the connection site with the benzene ring as the central skeleton, they are mixtures of a plurality of atropisomers and have high solubility as a monomer or a polymer, and are therefore more preferred.

[0196] Furthermore, the above molecular distortion has the effect of inhibiting the substituent R 1-1 Excessive conjugation extension with the central benzene skeleton suppresses the effect of increasing the absorption wavelength of the compound (1). This can, for example, realize a colorless and transparent optical material in the visible light region and improve the stability of the compound to heating, light irradiation, oxidation, etc.

[0197] In addition, in the development of high refractive index materials, it is very important to increase the electron density per unit volume in monomers and polymers, that is, to shorten the intermolecular distance to increase the refractive index. In compound (1), the following situation is considered: by introducing a linker with a suitable molecular length in a stereoscopically large polyaromatic substituted high refractive index structure, thereby, by molecular interactions such as van der Waals forces and hydrogen bonds, the intermolecular distance is shortened compared to derivatives without linkers. Thus, it is also possible to expect that the same high refractive index structure will show a further high refractive index.

[0198] 1-11. Exemplary compounds of compound (1)

[0199] Specific examples of the compound (1) are shown below. The compound (1) of the present invention is not limited to these unless the gist thereof is exceeded. Hereinafter, Et represents an ethyl group.

[0200]

[0201]

[0202]

[0203] 1-12. About L in formula (2)

[0204] L represents a (n+1)-valent chain saturated aliphatic hydrocarbon group which may have a substituent. That is, L is a linking group consisting of carbon atoms and hydrogen atoms which do not have a double bond or a cyclic structure. When n=1, L is an alkylene group. When n=2, L is a group formed by further directly bonding to an alkylene group or another alkylene group branching. When n=3, L is an alkylene group having two such branches.

[0205] If L is a chain saturated aliphatic hydrocarbon group which may have a substituent, it is preferred from the viewpoint of ease of synthesis and availability. The number of carbon atoms of the chain saturated aliphatic hydrocarbon group (excluding the number of carbon atoms of the substituent) is preferably 1 to 8. If the number of carbon atoms of the chain saturated aliphatic hydrocarbon group is 8 or less, the refractive index of the compound (2) is not easily reduced, the viscosity is reduced due to the small molecular weight, and the processability tends to be improved.

[0206] If L is a chain saturated aliphatic hydrocarbon group, then the polymerizable group R 2 -C(=CH2)-C(=O)-O- is preferred from the viewpoint of steric hindrance around the periphery.

[0207] Examples of the chain saturated aliphatic hydrocarbon group constituting L include an alkylene group having 1 to 8 carbon atoms when n=1. When n=2 or 3, L may be a group composed of two or more alkylene groups having 1 to 8 carbon atoms.

[0208] 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 mesityl 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, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide 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.

[0209] 1-13. About R in Formula (2) 1-2

[0210] R 1-2 It represents an aromatic ring group represented by the following formula (2-1).

[0211]

[0212] [In formula (2-1), R 3 represents a substituent,

[0213] In formula (2-1), there are multiple R 3 In the case of, they may be bonded to each other to form a ring condensed with the naphthalene ring in formula (2-1), and the condensed ring may further have a substituent,

[0214] p represents 0 or an integer whose upper limit is the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1),

[0215] * represents the bonding site to the benzene ring in formula (2).]

[0216] As R 1-2 , preferably, 1-naphthyl which may have a substituent. 1-2 The group may be a group represented by the following formula (2-1-1).

[0217]

[0218] The structure shown in the above formula (2-1-1) is that the adjacent R in formula (2-1) 3 A structure in which the naphthalene rings are bonded to each other and condensed with the naphthalene ring in formula (2-1) to form a ring.

[0219] As such R 1-2 , for example, 9-phenanthryl can be mentioned.

[0220] From the viewpoint of easy availability and good solubility, R 1-2 Preferred is 1-naphthyl or 9-phenanthrenyl.

[0221] These may further have a substituent, and examples of the substituent in this case include the benzene ring in formula (2) except R 1-2 The substituents that may be present in addition to the above are described below.

[0222] As R in formula (2-1) 3 , R in formula (1) can be 1-1 or R 1-1 The groups are exemplified by the substituents that may be possessed.

[0223] Among these, R 3 , preferably naphthyl or phenyl, more preferably phenyl.

[0224] In addition, there is no R 3 , that is, the group represented by formula (2-1) is also preferably 1-naphthyl.

[0225] When the compound (2) has such a group represented by the formula (2-1), a colorless and transparent material can be provided.

[0226] It should be noted that R 1-2 As described below, when m is 3 to 5, there are multiple R 1-2 It can be the same or different.

[0227] The 3 to 5 R in formula (2) 1-2 The total number of carbon atoms is 25-70.

[0228] When the total number of carbon atoms is 25 or more, the refractive index of the compound (2) can be expected to be high. On the other hand, when the total number of carbon atoms is 70 or less, the compound (2) can be easily synthesized.

[0229] From the above point of view, the m R in formula (2) 1-2 The total number of carbon atoms is preferably 25-64, more preferably 30-56.

[0230] 1-14. About m in formula (2)

[0231] m represents an integer of 3 to 5. This m can be appropriately selected. For example, from the viewpoint of the ease of synthesis of compound (2) and the ease of obtaining raw materials, m is preferably 3 or 5, and more preferably m=3.

[0232] On the other hand, m is preferably 4 or 5, and more preferably m=5, since there is a tendency to achieve both an ultrahigh refractive index and high solubility.

[0233] When m=3, R 1-2 It is preferably bonded to the ortho position and the para position relative to the bonding position to X on the benzene ring.

[0234] 1-15. About X in formula (2)

[0235] X represents an oxygen atom or a nitrogen atom which may have a substituent.

[0236] X in the formula (2) has the same meaning as X in the formula (1), and the preferred groups are also the same.

[0237] From the viewpoint of suppressing the coloration of compound (2), the ease of synthesis and the ease of obtaining raw materials, X is preferably an oxygen atom. When X is an oxygen atom, the chemical stability of the intermediate compound in the synthesis of compound (2) tends to be excellent, and it is not easily oxidized, and coloration is easily avoided, so it is preferred.

[0238] On the other hand, from the viewpoint of improving compatibility with various solvents or holographic recording media, X is preferably a nitrogen atom which may have a substituent. In particular, when X is a nitrogen atom which does not have a substituent, multi-point hydrogen bonding with various solvents or holographic recording media can be performed, and it can be expected that a low haze material with less turbidity can be provided, which is more preferred.

[0239] 1-16. About R in formula (2) 2

[0240] R 2 represents a hydrogen atom or a methyl group. 2 For example, from the viewpoint of improving the stability of the polymer of compound (2), R 2 On the other hand, from the viewpoint of the polymerizability of compound (2), R 2 Preferred is methyl.

[0241] 1-17. About n in formula (2)

[0242] n represents an integer of 1 to 3. This n can be appropriately selected. For example, n=2 or 3 may be used from the viewpoint of the easy polymerizability of the compound (2).

[0243] On the other hand, from the viewpoint of the tendency to achieve a higher refractive index, the compound (2) preferably has a smaller number of polymerizable groups, and is more preferably a monofunctional compound having 1 polymerizable group. That is, from the viewpoint of a higher refractive index, n=1 or 2 is preferred, and n=1 is more preferred.

[0244] It should be noted that when n is 2 or 3, multiple R 2-C(=CH2)-C(=O)-O-, that is, the (meth)acrylate polymerizable groups may be the same or different.

[0245] 1-18. Regarding the benzene ring in formula (2) except R 1-2 Substituents other than

[0246] The benzene ring in formula (2) may also have 1-2 Examples of the substituent that the benzene ring may have include the groups described above as the substituent that the benzene ring in the formula (1) may have.

[0247] From the viewpoint of ease of synthesis, the benzene ring is preferably 1-2 It has no substituent other than this.

[0248] On the other hand, from the viewpoint of improving the refractive index and improving the solubility, the benzene ring preferably has 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, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, or a nitro group as a substituent.

[0249] 1-19. Molecular weight of compound (2)

[0250] From the viewpoint of suppressing the viscosity to be low and maintaining good processability, the molecular weight of the compound (2) is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1200 or less. From the viewpoint of reducing the shrinkage during polymerization, the molecular weight of the compound (2) is preferably 500 or more, more preferably 600 or more, and even more preferably 650 or more.

[0251] 1-20. Relationship between the molecular structure and physical properties of compound (2)

[0252] Compound (2) has three or more highly planar aromatic ring groups bonded to one benzene ring of a phenol compound or an aniline compound, thereby being able to appropriately introduce molecular distortion into a monomer or polymer such that the dihedral angle of the connection site with the benzene ring as the central skeleton becomes 1 degree or more. 1-2 In the case of an aromatic ring group having a substituent or a ring structure at the ortho position of the connection site to the central benzene skeleton, such as 1-naphthyl and 9-phenanthryl, the dihedral angle tends to become larger. As a result, the aggregation of high refractive index structures can be suppressed, and high solubility in various media can be achieved, and it can be used in the form of a polymerizable monomer with an ultra-high refractive index. In particular, in R 1-2In the case of 1-naphthyl, 9-phenanthrenyl, and 9-anthryl, since they have hydrogen atoms near the connection site with the benzene ring as the central skeleton, they are mixtures of a plurality of atropisomers and have high solubility as a monomer or a polymer, and are therefore more preferred.

[0253] Furthermore, the above molecular distortion has the effect of inhibiting the substituent R 1-2 Excessive conjugation extension with the central benzene skeleton suppresses the effect of increasing the absorption wavelength of the compound (2). This can, for example, realize a colorless and transparent optical material in the visible light region and improve the stability of the compound to heating, light irradiation, oxidation, etc.

[0254] In addition, in the development of high refractive index materials, it is very important to increase the electron density per unit volume in monomers and polymers, that is, to shorten the intermolecular distance to increase the refractive index. In compound (2), the following situation is considered: a linker with a suitable molecular length is introduced into a stereoscopically large polyaromatic substituted high refractive index structure, thereby, by molecular interactions such as van der Waals forces and hydrogen bonds, the intermolecular distance is shortened compared to derivatives without linkers. Thus, it is also possible to expect that the same high refractive index structure will show further high refractive index.

[0255] 1-21. Exemplary compounds of compound (2)

[0256] Specific examples of the compound (2) are shown below. The compound (2) of the present invention is not limited to these unless the gist of the invention is exceeded.

[0257]

[0258] 1-22. Synthesis method

[0259] Compound (1) can be synthesized by combining various known methods.

[0260] For example, it can be synthesized 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.

[0261]

[0262] [Where X, R 1-1 , m and X, R in the above formula (1) 1-1 , m have the same meaning.]

[0263] Hereinafter, one example of the synthesis of compound (1) will be described.

[0264]

[0265] [In the above reaction formula, X, R1 , R 2 , L 1 , m, n and X, R in the above formula (1) 1 , R 2 , L 1 , m, and n have the same meaning. 1 , Y 2 , Y 3 represents a halogen atom or a sulfonic acid group such as methanesulfonic acid group, p-toluenesulfonic acid group, trifluoromethanesulfonic acid group, a carboxyl group, a dimethylpyrazolyl group, a 1-methylpropyleneaminooxy group, or a leaving group. In the following reaction formula, the same symbol also represents the same meaning.]

[0266] For example, compound (1) can be produced by reacting the hydroxyl group or amino group of -XH of compound (3) with an alkylating agent compound having a polymerizable group represented by formula (i) (hereinafter, sometimes referred to as alkylating agent (i)). Alternatively, compound (1) can be produced by using a carbonylating agent represented by an isocyanate represented by formula (ii) (hereinafter, sometimes referred to as carbonylating agent (ii)).

[0267] Examples of the alkylating agent (i) include 2-methylsulfonylethyl (meth)acrylate, glycidyl (meth)acrylate, and 2,3-dibromopropyl acrylate.

[0268] In addition, examples of the carbonylating agent (ii) include isocyanates such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and 2-[0-(1'-methylpropyleneamino)carboxyamino]ethyl methacrylate.

[0269] Furthermore, compound (1) can also be produced by subjecting a (meth)acrylating agent represented by formula (v) to a polymerizable group-forming reaction with a compound represented by formula (4) (hereinafter sometimes referred to as "compound (4)") obtained by reacting compound (3) with a compound having a linking group represented by formula (iii) or formula (iv).

[0270] The reaction of the active hydrogen of the hydroxyl or amino group in formula (3) with the reagents represented by (i) to (iv) above and the reaction of compound (4) with the reagent represented by formula (v) can be carried out by known methods. For example, compound (3) can be reacted with isocyanates in the presence of a basic compound to obtain compound (1).

[0271] The basic compound can be one or more of the organic basic compounds (triethylamine, diisopropylethylamine, 1,1,3,3-tetramethylguanidine, diazabicycloundecene, diazabicyclononene, pyridine, imidazole, etc.), or one or more of the inorganic basic compounds (sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, potassium tert-butoxide, etc.), or one or more of the organic basic compounds can be combined with one or more of the inorganic basic compounds.

[0272] In the reaction of compound (3) with the reagents represented by formula (i) to (iv) and the reaction of compound (4) with the reagent represented by formula (v), 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.

[0273] In the manufacture of compound (1), the reactant (bold) obtained in the synthesis reaction is preferably purified. Impurities can be removed by purification to achieve low coloring. As a purification method, a known method can be applied. For example, purification can be performed by extraction, column chromatography, recrystallization, distillation, etc. These purification methods can be implemented alone or in combination.

[0274] When the compound (1) is solid at room temperature, it is preferred to use a recrystallization method from the viewpoint of facilitating the removal of coloring matter to a high degree.

[0275] 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, diethyl ether, diisopropyl ether, tetrahydrofuran, tert-butyl methyl ether, 1,4-dichloroethane, and the like. Ethers such as alkane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, nitrile such as acetonitrile, propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, 2-methoxyethanol, 2-butoxyethanol, propylene glycol monomethyl ether, glycols such as ethylene glycol, diethylene glycol, water, etc. These solvents may be used alone or in combination of two or more.

[0276] Compound (3) which is a raw material compound for producing the above-mentioned compound (1) can be produced by the following reaction.

[0277]

[0278] [In the above reaction formula, X, R 1-1 , m and X, R in the above formula (1) 1-1, m have the same meaning. 4 represents a leaving group such as a halogen atom or a trifluoromethanesulfonic acid group. 1-1 -M 1 It indicates that an organolithium reagent, an organomagnesium reagent, an organozinc reagent, an organocerium reagent, an organosilicon reagent, an organoboron reagent, an organotin reagent, etc. can react with Y 4 Organometallic reagents that react to form carbon-carbon bonds.]

[0279] For example, multiple aromatic ring groups R 1 Compound (3) can be synthesized by connecting them simultaneously or sequentially.

[0280] Alternatively, the compound (3) can be synthesized by directly utilizing the carbon-hydrogen bond of the aromatic hydrocarbon ring represented by the formula (vii) to carry out a cross-coupling reaction.

[0281] Compound (2) is obtained by removing the aromatic ring group R 1-1 Changed to aromatic ring group R 1-2 , the linking group L 1 The compound (1) can be produced in the same manner as in the compound (1) except that the group L is changed to a chain-like saturated aliphatic hydrocarbon group.

[0282] 2. Regarding the polymerizable composition of the present invention

[0283] The polymerizable composition of the present invention contains the compound of the present invention, that is, compound (1) or compound (2), and a polymerization initiator.

[0284] The polymer of the present invention having a structure represented by Formula (P1-1) or the following Formula (P1-2) can be obtained by polymerizing the (meth)acrylic acid group of the compound of the present invention with a polymerization initiator.

[0285]

[0286] [In formula (P1-1), n, L 1 ,X,R 1-1 ,m,R 2 With n, L in formula (1) 1 ,X,R 1-1 ,m,R 2 Same meaning.

[0287] In formula (P1-2), n, L, X, R 1-2 ,m,R 2 and n, L, X, R in formula (2) 1-2 ,m,R 2 Same meaning.

[0288] q represents the number of repetitions of the structure represented by formula (P1-1) or formula (P1-2).]

[0289] 2-1. Polymerization initiator

[0290] The type of the polymerization initiator is not particularly limited, and may be appropriately selected from known polymerization initiators according to the polymerization method.

[0291] 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.

[0292] Examples of the polymerization initiator contained in the polymerizable composition of the present invention include radical polymerization initiators, redox polymerization initiators, and anionic polymerization initiators.

[0293] The polymerization initiators exemplified below also include those generally called polymerization catalysts.

[0294] 2-1-1. Radical polymerization initiator

[0295] <Photopolymerization initiator>

[0296] The photopolymerization initiator that assists the polymerization of the polymerizable composition of the present invention may be any known photoradical polymerization initiator. For example, azo compounds, azide compounds, organic peroxides, organic borates, Salts, biimidazole derivatives, titanocene compounds, iodine Salts, organic thiol compounds, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, acylphosphine oxides, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylcarbinols, oxime esters, etc. Among them, as the photopolymerization initiator, benzophenones, acylphosphine oxide compounds, oxime ester compounds, etc. are preferred from the viewpoints of compatibility and availability.

[0297] Specific examples of the photopolymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, tert-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 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-morpholinylphenyl)propanone, 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.

[0298] These photopolymerization initiators may be used alone or in combination of two or more in any combination and ratio.

[0299] When the total amount of all compounds capable of free radical polymerization in the polymerizable composition is set to 100 parts by mass, the content of the photopolymerization initiator in the polymerizable composition of the present invention is usually 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.05 parts by mass or more. 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 rapidly, not only increasing the birefringence of the cured body, but also deteriorating the hue. On the other hand, if it is too little, there is a concern that the polymerizable composition will not be fully polymerized.

[0300] <Thermal polymerization initiator>

[0301] As the thermal polymerization initiator for assisting the polymerization of the polymerizable composition of the present invention, any thermal polymerization initiator can be used as long as it is a known thermal free radical polymerization initiator. For example, organic peroxides and azo compounds can be mentioned. Among them, organic peroxides are preferred from the viewpoint that bubbles are not easily generated in the polymer obtained in the polymerization reaction.

[0302] Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; peroxy ketals such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, and 1,1-di(tert-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; dicumyl 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-ethyl hexanoate.

[0303] 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, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane) dihydrochloride.

[0304] These thermal polymerization initiators may be used alone or in combination of two or more in any combination and ratio.

[0305] When the total amount of all compounds capable of free radical polymerization in the polymerizable composition is set to 100 parts by mass, the content of the thermal polymerization initiator in the polymerizable composition of the present invention is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more. 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 the hue deteriorates. On the other hand, if it is too little, there is a concern that the thermal polymerization will not be fully carried out.

[0306] When a photopolymerization initiator and a thermal polymerization initiator are used together, the mass ratio thereof is usually "100:1" to "1:100" ("photopolymerization initiator: thermal polymerization initiator", hereinafter the same in this paragraph), preferably "10:1" to "1:10". If the thermal polymerization initiator is too little, the polymerization may become insufficient, and if it is too much, there is a concern of coloration.

[0307] 2-1-2. Redox polymerization initiator

[0308] The redox polymerization initiator is a radical initiator that utilizes a redox reaction that proceeds through a combination of a peroxide and a reducing agent, and can generate radicals even at low temperatures, and is generally used in emulsion polymerization and the like.

[0309] Specific examples of redox polymerization initiators include a combination system of benzoyl peroxide as a peroxide and aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine as a reducing agent; a combination system of hydrogen peroxide as a peroxide and metal soaps as a reducing agent; a combination system of hydrogen peroxide as a peroxide and thioureas as a reducing agent, etc.

[0310] A water-soluble redox polymerization initiator is a peroxide such as persulfate, hydrogen peroxide, or hydroperoxide, and a water-soluble inorganic reducing agent (Fe 2+ Or NaHSO3, etc.) or organic reducing agents (alcohols, polyamines, etc.) are used in combination.

[0311] 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.

[0312] 2-1-3. Anionic polymerization initiator

[0313] Examples of the anionic polymerization initiator used in the polymerizable composition of the present invention include alkali metals, n-butyl lithium, sodium amide, sodium naphthalene, Grignard reagents, lithium alkoxides, alkali metal benzophenone ketyls, etc. These may be used alone or in combination of two or more in any combination and ratio.

[0314] 2-2. About polymerizable compounds

[0315] The polymerizable compound contained in the polymerizable composition of the present invention may include any one of the compounds of the present invention alone, or may include two or more of them in any combination and ratio. That is, one of the compounds (1) may be included alone, or may include two or more of them in any combination and ratio. In addition, one of the compounds (2) may be included alone, or may include two or more of them in any combination and ratio. Furthermore, one or more of the compounds (1) and one or more of the compounds (2) may be included.

[0316] The polymerizable composition of the present invention may contain other polymerizable compounds in addition to the compound of the present invention.

[0317] The content of the compound of the present invention in the polymerizable composition of the present invention is preferably 1% by mass or more and 99% by mass or less, and more preferably 5% by mass or more and 95% by mass or less, based on 100% by mass of the total solid content of the polymerizable composition of the present invention. If the content of the compound of the present invention is less than 1% by mass, the effect of using the compound of the present invention cannot be fully exerted, while if it exceeds 99% by mass, there is a tendency for curability to decrease.

[0318] As examples of other polymerizable compounds except the compound of the present invention, anionic polymerizable monomers, free radical polymerizable monomers, etc. can be enumerated. These polymerizable compounds can be used alone, or two or more can be used in any combination and ratio. In addition, polymerizable compounds (sometimes referred to as multifunctional monomers) having more than two polymerizable functional groups in one molecule can also be used. When using multifunctional monomers, a cross-linked structure is formed inside the polymer, so thermal stability, weather resistance, solvent resistance, etc. can be improved.

[0319] When the polymerizable composition of the present invention contains other polymerizable compounds other than the compound of the present invention, the content thereof is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 5% by mass or less, based on 100% by mass of the total solid content of the polymerizable composition of the present invention. If the content of other polymerizable compounds is less than 0.1% by mass, the property-imparting effect by adding other polymerizable compounds cannot be fully exerted, while if it exceeds 5% by mass, there is a tendency to easily cause problems such as impairment of optical properties and strength.

[0320] <Anionic polymerizable monomer>

[0321] Examples of the anionic polymerizable monomer include hydrocarbon monomers and polar monomers.

[0322] Examples of the hydrocarbon monomer include styrene, α-methylstyrene, butadiene, isoprene, vinylpyridine, vinylanthracene, and derivatives thereof.

[0323] 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, vinylidene cyanide, etc.), etc.

[0324] These anionic polymerizable monomers may be used alone or in combination of two or more in any combination and ratio.

[0325] <Free radical polymerizable monomer>

[0326] The radical polymerizable monomer is a compound having one or more ethylenically unsaturated double bonds in one molecule, and examples thereof include (meth)acrylates, (meth)acrylamides, vinyl esters, and styrenes.

[0327] Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (n- or iso-)propyl (meth)acrylate, (n-, iso-, sec- 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, Hydroxybenzyl (meth)acrylate, hydroxyphenylethyl (meth)acrylate, dihydroxyphenylethyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenyl (meth)acrylate, hydroxyphenyl (meth)acrylate, chlorophenyl (meth)acrylate, sulfamoylphenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-(hydroxyphenylcarbonyloxy)ethyl (meth)acrylate, phenol EO-modified (meth)acrylate, phenylphenol EO-modified (meth)acrylate, p-isopropylphenylphenol EO-modified (meth)acrylate, nonylphenol EO-modified (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, bisphenol F EO modified diacrylate, bisphenol AEO 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".

[0328] Examples of the (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.

[0329] Examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoate, vinyl tert-butylbenzoate, vinyl chlorobenzoate, vinyl 4-ethoxybenzoate, vinyl 4-ethylbenzoate, vinyl 4-methylbenzoate, vinyl 3-methylbenzoate, vinyl 2-methylbenzoate, vinyl 4-phenylbenzoate, and vinyl tert-valerate.

[0330] 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.

[0331] These radical polymerizable monomers may be used alone or in combination of two or more in any combination and ratio.

[0332] Any of the anionic polymerizable monomers and radical polymerizable monomers exemplified above may be used, or two or more of them may be used in combination.

[0333] For example, in the case of a high refractive index optical lens or a holographic recording medium, it is preferable to use a radical polymerizable monomer as the other polymerizable compound used together with the compound (1) because the reaction of forming the resin matrix is ​​less likely to be inhibited.

[0334] 2-3. Other added ingredients

[0335] The polymerizable composition of the present invention may contain other components within a range not impairing the effects of the present invention.

[0336] Examples of other components include various additives such as solvents, antioxidants, plasticizers, ultraviolet absorbers, sensitizers, chain transfer agents, defoamers, polymerization inhibitors, any fillers made of organic or inorganic substances, diffusing agents, pigments, and wavelength conversion materials such as phosphors.

[0337] The polymerizable composition of the present invention may contain a solvent in order to adjust the viscosity.

[0338] 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 alkanes and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; carbitols such as methyl carbitol, ethyl carbitol, butyl carbitol; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, etc.), sulfoxides (amides such as dimethyl sulfoxide; nitriles such as acetonitrile and benzonitrile; organic solvents such as N-methylpyrrolidone.

[0339] These solvents may be used alone or in the form of a mixed solvent. In addition, water may be used depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.).

[0340] 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 a preferred viscosity according to the polymerization method, processing method, and application.

[0341] 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.

[0342] Specific examples of the antioxidant 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, tetrakis(C 2-hydroxyphenyl) diphosphite, and the like. Phosphorus-based antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, tridecyl triphosphite, 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 can be used alone or in combination of two or more.

[0343] 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.

[0344] From the viewpoint of improving the heat yellowing resistance of the obtained polymer, 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, relative to 100 parts by mass of the total amount of the polymerizable composition.

[0345] As the light stabilizer, a hindered amine light stabilizer (HALS) can be preferably used. Specific examples of HALS include 2,2,6,6-tetramethyl-4-piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, Adekastab LA-68 (manufactured by ADEKA Corporation), and Adekastab LA-63P (manufactured by ADEKA Corporation), 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.

[0346] 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.

[0347] The antioxidant or the light stabilizer may be used alone or in combination of two or more.

[0348] 2-4. Method for producing polymerizable composition

[0349] 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.

[0350] 3. Polymerization method of the polymerizable composition of the present invention

[0351] The polymerization method of the polymerizable composition of the present invention is not particularly limited, and there are a method of polymerizing by irradiating an active energy ray and a method of polymerizing by heating.

[0352] 3-1. Polymerization initiation method (active energy rays)

[0353] When the polymerizable composition of the present invention is subjected to photoradical polymerization, the polymerization is carried out by irradiation with active energy rays.

[0354] As the active energy ray used, an electron beam or light in the wavelength range from ultraviolet to infrared is preferred. As the light source, for example, if the active energy ray 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 (Light Emitting Diodes) can also be used.

[0355] 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 reaction rate of the total amount of the polymerizable functional groups of the compound (1) and other polymerizable compounds is 80% or more, more preferably 90% or more. The reaction rate is calculated based on the change in the absorption peak intensity of the polymerizable functional group before and after the reaction by infrared absorption spectroscopy.

[0356] After polymerization by irradiation with active energy rays, further polymerization may be performed by heating treatment or annealing treatment as needed. 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.

[0357] 3-2. Polymerization initiation method (heating)

[0358] When the polymerizable composition of the present invention is subjected to heat treatment in order to polymerize it, 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 uneconomical, and if the heating temperature is higher than 200° C., energy costs are incurred, and heating temperature rise time and temperature fall time are consumed, which tends to be uneconomical.

[0359] 4. Polymer

[0360] Hereinafter, the polymer of the present invention obtained by polymerizing the polymerizable composition of the present invention will be described.

[0361] 4-1. Refractive index

[0362] Generally speaking, overall density is improved by polymerization reaction, therefore, there is a tendency that the refractive index of polymer is higher than the compound (referred to as monomer) before the polymerization as its precursor. By fully carrying out polymerization reaction using monomers with high refractive index, the refractive index of the resulting polymer can be improved, therefore, it is considered that it is more important to improve the refractive index of polymer by designing the molecular structure of monomer.

[0363] If the refractive index is evaluated using short-wavelength irradiation light, a larger value is shown. 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 the relationship is not reversed. Therefore, by evaluating and comparing the refractive index at a constant wavelength, the essential size of the refractive index of the material can be compared. In the present invention, the value at the irradiation light wavelength of 587nm is used as a reference.

[0364] The refractive index of the compound of the present invention and the polymer of the present invention is preferably 1.60 or more, more preferably 1.63 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the compound of the present invention and the polymer of the present invention is not particularly limited, but is usually 2.0 or less.

[0365] When the compound of the present invention and the polymer of the present invention are used as recording layer materials of holographic 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 insufficient. In addition, if the refractive index is greater than 1.78, the difference with the refractive index of the matrix resin becomes too large and the scattering becomes larger, so the transmittance is reduced, and more energy is required during recording or regeneration.

[0366] When the compound of the present invention and the polymer of the present invention are used as optical materials such as lenses, if the refractive index is less than 1.60, the central portion of the optical lens etc. is thickened, and the lightness as a feature of plastics is sometimes damaged, so it is not preferred. In addition, in the development of precision optical components such as lenses, it is also important to realize the optical properties suitable for components by combining optical materials with multiple refractive indices. From this viewpoint, the monomer and polymer having a refractive index exceeding 1.65 can be said to be particularly useful materials facing optical components.

[0367] 4-2. Glass transition temperature

[0368] 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 may change from the designed values ​​under the use environment, and the heat resistance required for actual use may not be satisfied. In addition, if it is higher than this range, the processability of the polymer is reduced, and a molded product with good appearance or high dimensional accuracy may not be obtained. In addition, the polymer becomes brittle and the mechanical strength is reduced, and the handleability of the molded product may be deteriorated.

[0369] 5. Optical materials and optical components

[0370] The compound, polymerizable composition and polymer of the present invention have properties such as high refractive index, easy processability and high chemical stability, and therefore can be applied to various optical materials and optical parts.

[0371] Examples of the optical material include optical overcoats, hard coating agents, adhesives for optical members, resins for optical fibers, and acrylic resin modifiers.

[0372] As optical components, for example, lenses, filters, diffraction gratings, prisms, light guide components (light cabinets), cover glass for display devices, optical sensors, optical switches, LEDs, light emitting elements, optical waveguides, light splitters, optical fiber adhesives, substrates for display elements, substrates for color filters, substrates for touch panels, polarizing plates, display backlights, light guide plates, anti-reflection films, viewing angle expansion films, optical recording, optical shaping, optical relief printing, etc. can be cited.

[0373] In addition, it can also be used as these layers. For example, a display protective film etc. are mentioned.

[0374] Among these, the compounds and polymers of the present invention can be preferably applied to plastic lenses due to their high refractive index characteristics. Examples of the lenses include imaging lenses for cameras (vehicle cameras, digital cameras, PC cameras, mobile phone cameras, surveillance cameras, etc.), eyeglass lenses, beam focusing lenses, light diffusion lenses, and the like.

[0375] In the lenses using the compounds and polymers of the present invention, in order to achieve improvements such as anti-reflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting anti-fogging properties or imparting fashion, physical or chemical treatments such as surface grinding, antistatic treatment, hard coating treatment, non-reflective coating treatment, dyeing treatment, etc. can be implemented as needed.

[0376] 6. Holographic recording media

[0377] The polymerizable composition of the present invention can be preferably used for the recording layer of a holographic 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 as a material for a holographic recording medium are described below.

[0378] 6-1. About Matrix Resin

[0379] The polymerizable composition of the present invention preferably contains a matrix resin. In particular, the matrix resin constituting the recording layer of the holographic recording medium is an organic substance that does not undergo significant chemical and physical changes due to light irradiation and is mainly composed of a polymer of an organic compound.

[0380] The matrix resin, together with the above-mentioned polymerizable compound and the photopolymerization initiator described later, constitutes the polymerizable composition of the present invention, and therefore, it is strongly required to have excellent compatibility with the polymerizable compound and the photopolymerization initiator. If the compatibility of the matrix resin with the above-mentioned other components is low, an interface is formed between the materials, and light is refracted or reflected at the interface, thereby causing light leakage to unnecessary parts, so that the interference fringes are deformed or cut and recorded in inappropriate parts, and therefore, information degradation may occur. The compatibility of the matrix resin with the above-mentioned other components can be evaluated based on the scattered light intensity obtained by setting a detector in a direction different from the transmitted light, etc., as described in Japanese Patent Gazette No. 3737306, etc.

[0381] As the matrix resin of the polymerizable composition of the present invention, a resin composed of a plurality of materials soluble in a solvent in the polymerizable composition and three-dimensionally crosslinked after being formed into a use state can also be used, for example, the thermoplastic resin, thermosetting resin, and photocurable resin described below.

[0382] 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 becomes a physical barrier, thereby suppressing the volume change during recording. That is, in the recording layer after recording, there is a tendency that the bright part expands and the dark part shrinks, resulting in unevenness on the surface of the holographic recording medium. In order to suppress this volume change, it is more preferable to use a polymerizable composition containing a three-dimensionally cross-linked resin matrix in the recording layer.

[0383] Among them, from the viewpoint of adhesion with the support, the matrix resin is preferably a thermosetting resin. Hereinafter, resin materials that can be used as the matrix resin will be described in detail.

[0384] 6-1-1. Thermoplastic resin

[0385] 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.

[0386] The solvent for these thermoplastic resins is not particularly limited as long as it is a solvent that dissolves 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.

[0387] 6-1-2. Thermosetting resin

[0388] When a thermosetting resin is used as the matrix resin, the curing temperature varies depending on the type of the crosslinking agent or catalyst.

[0389] Examples of combinations of functional groups that cure at room temperature include epoxides and amines, epoxides and thiols, and isocyanates and amines. Examples of combinations using catalysts include epoxides and phenols, epoxides and acid anhydrides, and isocyanates and polyols.

[0390] The former is simple because it reacts immediately after mixing, but in the case of molding such as holographic recording media, there is no time margin and it is difficult to adjust. On the other hand, the latter can freely select the curing temperature and curing time by appropriately selecting the type and amount of the catalyst, so it is suitable for curing accompanied by molding such as holographic recording media. Various types of resin raw materials from low molecular weight to high molecular weight are commercially available, so it is possible to maintain and select compatibility with polymerizable reactive compounds and photoinitiators or adhesion with substrates.

[0391] Hereinafter, each raw material will be described, and any raw material may be used alone or in combination of two or more.

[0392] <Epoxide>

[0393] Examples of the epoxide include polyglycidyl ether compounds of polyhydric alcohols 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-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and phenol or cresol novolac type epoxy compounds.

[0394] Epoxide preferably has 2 or more epoxy groups in 1 molecule, and its type is not particularly limited. If the number of epoxy groups is small, the hardness required as a matrix cannot be obtained sometimes. The upper limit of the number of epoxy groups in 1 molecule is not particularly limited, and is usually 8 or less, wherein preferably 4 or less. If the number of epoxy groups is too much, sometimes it takes a lot of time to consume epoxy groups and form a matrix resin excessively consuming time.

[0395] <Amine>

[0396] As the amine, an amine containing a primary amino group or a secondary amino group can be used. Examples of such amines include aliphatic polyamines such as ethylenediamine, diethylenetriamine or derivatives thereof, alicyclic polyamines such as isophoronediamine, menthanediamine, N-aminoethylpiperazine 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 dicyandiamide and adipic acid dihydrazide other than these.

[0397] <Mercaptan>

[0398] Examples of the thiol include thiol compounds such as 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 polythiols such as Thiokol (manufactured by Toray Fine Chemical Co., Ltd.) and jERCURE QX40 (manufactured by Mitsubishi Chemical Corporation). Among them, commercially available fast-curing polythiols such as jERCURE QX40 are preferably used.

[0399] <Phenol>

[0400] Examples of the phenol include bisphenol A, novolac-type phenolic resins, and resol-type phenolic resins.

[0401] <Acid anhydride>

[0402] Examples of the acid anhydride include monofunctional acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, or derivatives thereof, and difunctional acid anhydrides such as pyromellitic dianhydride, benzophenonetetracarboxylic anhydride, or derivatives thereof.

[0403] <Amount of amine, thiol, phenol, and acid anhydride used>

[0404] The amount of amine, thiol, phenol, or acid anhydride used is preferably usually 0.1 equivalent or more, particularly 0.7 equivalent or more, and usually 2.0 equivalent or less, particularly 1.5 equivalent or less, based on the molar ratio of the epoxy group. If the amount of amine, thiol, phenol, or acid anhydride used is too small or too large, the number of unreacted functional groups is large, thereby impairing storage stability.

[0405] <Polymerization initiator for thermosetting resin>

[0406] 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.

[0407] Anionic polymerization initiators generate anions by heat or active energy ray irradiation, 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 and curing time.

[0408] Cationic polymerization initiators generate cations by heat or active energy ray irradiation, and examples thereof include aromatic As specific examples, compounds composed of 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, diaryliodonium is preferred. Onium salts, triarylsulfonium salts, etc. These can be used alone or in combination depending on the curing temperature and curing time.

[0409] The usage amount of these thermosetting resin polymerization initiators is relative to the matrix resin, usually more than 0.001 mass %, wherein, preferably more than 0.01 mass %, in addition, usually below 50 mass %, wherein, preferably the scope below 10 mass %. If the usage amount of these thermosetting resin polymerization initiators is too little, the concentration of the thermosetting resin polymerization initiator is too low, therefore, sometimes the polymerization reaction is excessively time-consuming. On the other hand, if the usage amount of the thermosetting resin polymerization initiator is too much, then sometimes the continuous ring-opening reaction as the polymerization reaction will not be produced.

[0410] <Isocyanate>

[0411] As isocyanate, it is preferred to have more than 2 isocyanate groups in 1 molecule, and its type is not particularly limited. If the number of isocyanate groups in 1 molecule is small, the hardness required as the matrix resin cannot be obtained sometimes. The upper limit of the number of isocyanate groups in 1 molecule is not particularly limited, and is usually 8 or less, wherein, preferably 4 or less. If the number of isocyanate groups in 1 molecule is too much, it sometimes takes a lot of time to consume the isocyanate groups and form a matrix resin that consumes too much time. The upper limit of the number of isocyanate groups in 1 molecule is not particularly limited, and is usually about 20 or less.

[0412] 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 trimers to heptamers are preferred.

[0413] In addition, there can be mentioned reaction products of water, polyols such as trimethylolethane and trimethylolpropane and the above-mentioned isocyanates, polymers of hexamethylene diisocyanate, or derivatives thereof.

[0414] The molecular weight of isocyanate is preferably more than 100 and less than 50000 in number average molecular weight, more preferably more than 150 and less than 10000, further preferably more than 150 and less than 5000.If the number average molecular weight is too small, then the cross-linking density rises, and therefore, the hardness of the matrix resin becomes too high, and the recording speed may be reduced.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 disappears.

[0415] <Polyol>

[0416] Examples of the polyol include polypropylene polyol, polycaprolactone polyol, polyester polyol, and polycarbonate polyol.

[0417] (Polypropylene polyol)

[0418] Polypropylene polyol is obtained by the reaction of propylene oxide with a diol or a polyol. As diols or polyols, for example, 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 as polypropylene polyols include Sannix GP-400, GP-1000 (both manufactured by Sanyo Chemical Co., Ltd., trade names), Adeka Polyether G400, G700, G1500 (all manufactured by ADEKA Co., Ltd., trade names), etc.

[0419] (Polycaprolactone polyol)

[0420] Polycaprolactone polyol is obtained by the reaction of a lactone with a diol or a polyol. Examples of the lactone include α-caprolactone, β-caprolactone, γ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, and β-methyl-ε-caprolactone.

[0421] 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.

[0422] 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 305, Placcel 308, Placcel 309, Placcel 312, Placcel 320, Placcel 401, Placcel L205AL, Placcel L212AL, Placcel L220AL, Placcel L320AL, Placcel T2103, Placcel L210 T2205, Placel P3403, Placel 410 (all manufactured by Daicel Co., Ltd., trade names), etc.

[0423] (Polyester polyol)

[0424] Examples of the polyester polyol include polyester polyols obtained by polycondensing dicarboxylic acids or anhydrides thereof with polyols.

[0425] Examples of the dicarboxylic acid include succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, maleic anhydride, isophthalic acid, terephthalic acid, and trimellitic acid.

[0426] 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.

[0427] Examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyhexylene adipate, etc. Examples of the polyester polyol commercially available include ADEKANEWACE F series, ADEKANEWACE Y series, ADEKANEWACE NS series (manufactured by ADEKA Corporation, trade names), Kuraray polyol N-2010, P-4011, and P-1020 (all manufactured by Kuraray Corporation, trade names), etc.

[0428] (Polycarbonate polyol)

[0429] Examples of the polycarbonate polyol include polycarbonate polyols obtained by a dealcoholization condensation reaction of a glycol and a dialkyl carbonate (e.g., dimethyl carbonate, diethyl carbonate, etc.), polycarbonate polyols obtained by a dephenolization condensation reaction of a glycol and a diphenyl carbonate, and polycarbonate polyols obtained by a dealcoholization condensation reaction of a glycol and a carbonate (e.g., ethylene carbonate, diethyl carbonate, etc.).

[0430] 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.

[0431] 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.

[0432] Commercially available polycarbonate polyols include Placcel CD CD205, Placcel CDCD210, 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.

[0433] (Molecular weight of polyol)

[0434] The molecular weight of the polyol described above is preferably more than 100 and less than 50000 in terms of number average molecular weight, more preferably more than 150 and less than 10000, further preferably more than 150 and less than 5000. If the number average molecular weight is too small, the cross-linking density rises, and therefore, the hardness of the matrix resin becomes too high, and the recording speed may be reduced. 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, and therefore, the hardness of the matrix resin becomes too low, and sometimes the recorded content disappears.

[0435] <Other ingredients>

[0436] The matrix resin in the present embodiment may contain other components in addition to the above-mentioned components unless it violates the gist of the present invention.

[0437] 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 to change the physical properties of the matrix resin.

[0438] <Urethane polymerization catalyst>

[0439] In order to promote the reaction of isocyanate and polyol, a suitable urethane polymerization catalyst may also be included.

[0440] Examples of urethane polymerization catalysts include bis(4-tert-butylphenyl)iodide. Perfluoro-1-butanesulfonic acid, bis(4-tert-butylphenyl)iodide p-Toluenesulfonic acid, bis(4-tert-butylphenyl)iodide Trifluoromethanesulfonic acid, (4-bromophenyl)diphenylsulfonium trifluoromethanesulfonate, (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyl iodide Perfluoro-1-butanesulfonic acid, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium trifluoromethanesulfonic acid, bis(alkylphenyl)iodide Hexafluorophosphonic acid, etc. Salts; catalysts based on Lewis acids such as zinc chloride, tin chloride, ferric chloride, aluminum chloride, and BF3; protonic acids such as hydrochloric acid and phosphoric acid; amines such as trimethylamine, triethylamine, triethylenediamine, dimethylbenzylamine, and diazabicycloundecene; 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-undecylimidazole of trimellitic acid Imidazoles; bases such as sodium hydroxide, potassium hydroxide, potassium carbonate; tin catalysts such as dibutyltin laurate, dioctyltin laurate, and dibutyltin octoate; bismuth catalysts such as tri(2-ethylacetate)bismuth and tribenzoyloxybismuth; zirconium catalysts such as tetrakis(ethylacetoacetate), 1,1'-isopropylidene dichlorozirconium, and tetrakis(2,4-pentanedionate).

[0441] Among them, bismuth catalysts and zirconium catalysts are preferred in order to improve storage stability.

[0442] The bismuth-based catalyst is not particularly limited as long as it is a catalyst containing a bismuth element and is a compound that promotes the reaction between isocyanate and polyol.

[0443] 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).

[0444] Among them, from the aspect of catalyst activity, a trivalent bismuth compound is preferred, and a bismuth carboxylate, a bismuth compound 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-mentioned bismuth-based catalysts can be used alone or in combination of two or more in any combination and ratio.

[0445] The zirconium-based catalyst is not particularly limited as long as it is a catalyst containing a zirconium element and is a compound that promotes the reaction between isocyanate and polyol.

[0446] Examples thereof include cyclopentadienyl zirconium trichloride, decamethyl zirconium cyclopentadienyl chloride, 1,1'-dibutyl zirconium cyclopentadienyl chloride, 1,1'-isopropylidene zirconium cyclopentadienyl chloride, 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.

[0447] Among them, from the aspect of compatibility with other components, compounds having an organic ligand are preferred, and compounds having an alkoxide or acetylacetonate (2,4-pentanedionate) structure are more preferred. The above zirconium compounds may be used alone or in combination of two or more in any combination and ratio.

[0448] The bismuth-based catalyst and the zirconium-based catalyst may be used alone or as a mixture.

[0449] The amount of the carbamate polymerization catalyst used is preferably usually 0.0001% by mass or more, particularly 0.001% by mass or more, and usually 10% by mass or less, particularly 5% by mass or less, based on the ratio to the matrix resin. If the amount of the carbamate polymerization catalyst used is too small, curing may take too long. On the other hand, if the amount used is too large, it may be difficult to control the curing reaction.

[0450] By using a urethane polymerization catalyst, curing can be performed at room temperature, but curing can also be performed at a higher temperature. The temperature at this time is preferably between 40°C and 90°C.

[0451] 6-1-3. Photocurable resin

[0452] When a photocurable resin is used as the matrix resin, it is necessary to use a matrix resin photoinitiator corresponding to the wavelength used for curing. Since curing during light irradiation causes obstacles to molding or bonding, it is preferred to have a stable curing reaction at a temperature near room temperature, which is the main operating temperature. Considering this, it can be said that catalytic curing using a matrix resin photoinitiator is a preferred choice.

[0453] It is common that active substrates such as cations and anions are generated from a photoinitiator for a matrix resin by light irradiation. Therefore, it is considered that a resin that is cured by these active substrates can be selected and cured to form a matrix resin.

[0454] Examples of functional groups that react with cations such as protons include epoxy groups and oxetane groups. Examples of compounds having these groups include polyglycidyl ether compounds of polyhydric alcohols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerol; alicyclic epoxy compounds having cyclic aliphatic groups with 4 to 7-membered rings such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol or cresol novolac type epoxy compounds, and the like. Examples of compounds having an oxetane group include 2-ethyl-2-oxetane ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetaneoxy)hexane. (It should be noted that the description of "(poly)ethylene glycol" and the like herein refers to both "ethylene glycol" and "polyethylene glycol" of its polymer.)

[0455] 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.

[0456] The amount of the matrix resin photoinitiator used when the matrix resin is subjected to photocuring is preferably generally 0.01% by mass or more, particularly 0.1% by mass or more, and generally 1% by mass or less, particularly 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 used is too large, it may be difficult to control the curing reaction.

[0457] In addition, especially when used as a holographic 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 difference in wavelength is at least 10 nm, preferably 30 nm. The selection of the photoinitiator for the matrix resin can be roughly predicted based on the absorption wavelength of the initiator.

[0458] 6-2. Photopolymerization initiator

[0459] The photopolymerization initiator that assists the polymerization of the compound of the present invention may be any known photo-radical polymerization initiator. For example, azo compounds, azide compounds, organic peroxides, organic borates, Salts, biimidazole derivatives, titanocene compounds, iodine Salts, organic thiol compounds, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, acylphosphine oxides, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylcarbinols, oxime esters, etc. Among them, as the photopolymerization initiator, titanocene compounds, acylphosphine oxide compounds, oxime ester compounds, etc. are preferred because they utilize light in the visible region to cause a polymerization reaction.

[0460] 6-2-1. Titanocene compounds

[0461] When a titanocene compound is used as the photopolymerization initiator, the type thereof is not particularly limited, and for example, the initiator may be appropriately selected from various titanocene compounds described in JP-A Nos. 59-152396 and 61-151197.

[0462] 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-tetrafluorophenyl-1-yl)titanium, bis(cyclopentadienyl)titanium bis(2,4,6-trifluorophenyl-1-yl)titanium, bis(cyclopentadienyl)titanium bis(2,6-difluorophenyl-1-yl)titanium , bis(cyclopentadienyl)bis(2,4-difluorobenzene-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,5,6-tetrafluorobenzene-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorobenzene-1-yl)titanium, bis(cyclopentadienyl)bis(2,6-difluoro-3-(pyrrol-1-yl)-benzene-1-yl)titanium, etc.

[0463] 6-2-2. Acylphosphine oxide compounds

[0464] Specific examples of the acylphosphine oxide compound include a monofunctional initiator having only one photoinduced cleavage point in one molecule and a bifunctional initiator having two photoinduced cleavage points in one molecule.

[0465] Examples of the monofunctional initiator include triphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide.

[0466] 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.

[0467] 6-2-3. Oxime ester compounds

[0468] 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, -3-yl]-5-oxopentanoic acid methyl ester, 1-(9-ethyl-6-cyclohexanoyl-9H-carbazole-3-yl)-1-(O-acetyloxime)glutaric acid methyl ester, 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetyloxime)glutaric acid methyl ester, 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetyloxime)glutaric acid methyl ester, 1-(9-ethyl-9H-carbazole-3-yl)-1-(O-acetyloxime)-3-methyl-butyric acid, etc.

[0469] 6-2-4. Amount of photopolymerization initiator used

[0470] The above-mentioned various photopolymerization initiators may be used alone or in combination of two or more in any combination and ratio.

[0471] 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.

[0472] 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, and the recording sensitivity in the holographic recording medium decreases. On the other hand, if the content of the photopolymerization initiator is too high, the free radicals generated by light irradiation re-bond or disproportionate with each other, so the contribution to photopolymerization sometimes decreases, and the recording sensitivity in the holographic recording medium still decreases. When two or more photopolymerization initiators are used in combination, it is preferred that their total amount meets the above range.

[0473] 6-3. Free radical scavengers

[0474] In holographic recording, in order to fix the interference light intensity pattern as the polymer distribution in the holographic recording medium with high precision, a free radical scavenger may also be added. The free radical scavenger preferably has both a functional group for catching free radicals and a reactive group fixed to the matrix resin by covalent bonds. As the functional group for catching free radicals, a stable nitroxide free radical may be cited.

[0475] 6-3-1. Types of free radical scavengers

[0476] Examples of reactive groups that can be fixed to the matrix resin by covalent bonds include hydroxyl groups, amino 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, 5-HO-AZADO: 5-hydroxy-2-azatricyclo[3.3.1.1 3,7 ]Decane N-oxyl.

[0477] 6-3-2. Content of free radical scavenger

[0478] The above-mentioned various radical scavengers may be used alone or in combination of two or more in any combination and ratio.

[0479] 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, based on the 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.

[0480] If the content of the radical scavenger is too little, the efficiency of catching free radicals is reduced, and the polymer with low polymerization degree diffuses and does not contribute to the trend of the component of the signal becoming more. On the other hand, if the content of the radical scavenger is too much, the polymerization efficiency of the polymer is reduced and the signal cannot be recorded. When using more than two radical scavengers, it is preferred that their total amount meets the above range.

[0481] 6-4. Other ingredients

[0482] The polymerizable composition of the present invention may contain other components in addition to the above components unless it violates the gist of the present invention.

[0483] As other components, solvents, plasticizers, dispersants, leveling agents, defoamers, adhesion promoters, etc. used to prepare polymerizable compositions can be cited. In particular, when used for holographic recording media, chain transfer agents, polymerization terminators, compatibilizers, reaction aids, sensitizers, etc. used to control recording reactions can be cited. In addition, examples of additives that may be required to improve other properties include preservatives, stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, etc. These components can be used alone, or two or more can be used in any combination and ratio.

[0484] <Sensitizer>

[0485] A compound for controlling 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 sensitization auxiliary.

[0486] As a sensitizer, any sensitizer can be selected from various known sensitizers and used. Generally speaking, in order to absorb visible and ultraviolet lasers, there are many cases where colored compounds such as pigments are used as sensitizers. In the case of a holographic recording medium, it also depends on the wavelength of the laser used in the recording and the type of the initiator used. In the case of a system using a green laser, as a specific example of a preferred sensitizer, 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. can be cited. 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. These sensitizers can be used alone, or two or more can be used in any combination and ratio.

[0487] When the obtained holographic recording medium is required 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, leaving the holographic recording medium under room light or sunlight for several hours to several days, the cyanine pigment in the holographic recording medium is decomposed and has no absorption in the visible light region, thereby obtaining a colorless and transparent holographic recording medium.

[0488] 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 generally 0.01% by mass or more, particularly 0.1% by mass or more, and generally 10% by mass or less, particularly 5% by mass or less, in terms of the ratio relative to 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 large amount 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 in recording or regeneration sometimes becomes large, and the light is not easy to reach the depth direction. When two or more sensitizers are used in combination, their total amount is made to meet the above range.

[0489] <Plasticizer>

[0490] The polymerizable composition of the present invention may contain a plasticizer in order to improve the reaction efficiency or adjust the physical properties of the recording layer of the holographic recording medium.

[0491] Examples of plasticizers include phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and diundecyl phthalate, adipates such as bis(2-ethylhexyl) adipate, diisononyl adipate, and di-n-butyl adipate, sebacic acid esters such as dioctyl sebacate and dibutyl sebacate, phosphates such as tricresyl phosphate, citrates such as acetyl tributyl citrate, trimellitic acid esters such as trioctyl trimellitic acid, epoxidized soybean oil, chlorinated paraffin, alkoxylated (poly) alkylene glycol esters such as acetoxymethoxypropane, and terminal alkoxylated polyalkylene glycols such as dimethoxypolyethylene glycol.

[0492] A plasticizer containing fluorine as exemplified in Japanese Patent No. 6069294 may also be used. Examples of plasticizers containing fluorine include 2,2,2-trifluoroethyl butyl carbamate, bis(2,2,2-trifluoroethyl)-(2,2,4-trimethylhexane-1,6-diyl) biscarbamate, bis(2,2,2-trifluoroethyl)-[4-({[(2,2,2-trifluoroethoxy)carbonyl]amino}-methyl)octane-1,8-diyl] biscarbamate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecanoylbutyl carbamate, and 2,2,2-trifluoroethylphenyl carbamate.

[0493] 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, based on 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 cannot be achieved, while if it is more than the above range, the transparency of the recording layer decreases or the plasticizer bleeds out significantly.

[0494] <Leveling agent>

[0495] 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, silicone leveling agents, acrylic leveling agents, ester compounds, ketone compounds, fluorine compounds, and the like. Any one of these may be used alone, or two or more of them may be used in any combination and ratio.

[0496] <Chain transfer agent>

[0497] A chain transfer agent may be used in the polymerizable composition of the present invention. Examples of the chain transfer agent include phosphinates such as sodium phosphite and sodium hypophosphite, thiols such as mercaptoacetic 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, 2- Non-conjugated dienes such as methyl-1,4-pentadiene, 3,6-nonadien-1-ol, and 9,12-octadecadienol, linolenic acid, γ-linolenic acid, linolenic acid methyl ester, linolenic acid ethyl ester, linolenic acid isopropyl ester, and linolenic anhydride, linoleic acid, linoleic acid methyl ester, linoleic acid ethyl ester, linoleic acid isopropyl ester, and linoleic anhydride, eicosapentaenoic acid, eicosapentaenoic acid ethyl ester, and other eicosapentaenoic acid, docosahexaenoic acid, docosahexaenoic acid ethyl ester, and the like.

[0498] The amount of these additives used is preferably usually 0.001% by mass or more, particularly 0.01% by mass or more, and usually 30% by mass or less, particularly 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, their total amount is adjusted to meet the above range.

[0499] 6-5. Composition ratio of each component in the polymerizable composition

[0500] The content of each component in the polymerizable composition of the present invention is arbitrary unless it violates the gist of the present invention. The ratio of each component shown below is based on the molar amount per unit mass of the polymerizable composition, and is preferably in the following range.

[0501] 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.

[0502] When the content of the polymerizable compound is greater than the above lower limit, there is a tendency to obtain sufficient diffraction efficiency in the holographic recording medium, and when the content of the polymerizable compound is less than the above upper limit, there is a tendency to ensure compatibility with the resin matrix in the recording layer and keep the shrinkage of the recording layer due to recording at a low level.

[0503] When isocyanate and polyol are used as the matrix resin in the polymerizable composition of the present invention, their total content is usually 0.1% by mass or more, preferably 10% by mass or more, more preferably 35% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less. When the content is not less than the above lower limit, it is easy to form a recording layer.

[0504] 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. When the ratio is within the above range, the number of unreacted functional groups is small and the storage stability is improved.

[0505] 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, more 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.

[0506] 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.

[0507] 6-6. Method for producing polymerizable composition

[0508] 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 contains components other than those described above, the components can be mixed in any combination and order.

[0509] The polymerizable composition in the case of using isocyanate and polyol as the matrix resin can be obtained, for example, by the following method, but the present invention is not limited thereto.

[0510] 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 composition prepared by mixing the isocyanate and the urethane polymerization catalyst is prepared as liquid B.

[0511] Alternatively, all components except isocyanate may be mixed with the polymerizable compound and the photopolymerization initiator to prepare a photoreactive composition (liquid A).

[0512] Each liquid is preferably dehydrated and degassed. If the dehydration and degassing are insufficient, bubbles are sometimes generated when making the holographic recording medium, and a uniform recording layer cannot be obtained. As long as each component is not damaged, heating and decompression can also be performed during the dehydration and degassing.

[0513] The preparation of the polymerizable composition obtained by mixing liquid A and liquid B is preferably carried out immediately before the holographic recording medium is formed. In this case, a mixing technique based on an existing method can also be used. In addition, when 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.

[0514] 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 may be used as the matrix resin.

[0515] 6-7. Holographic Recording Medium of the Present Invention

[0516] The holographic recording medium of the present invention using the polymerizable composition of the present invention has a recording layer, and further has a support and other layers as needed. Generally, the holographic recording medium has a support, and the recording layer and other layers are stacked on the support to constitute the holographic recording medium. However, in the case where the recording layer or other layers have the strength and durability required for the medium, the holographic 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.

[0517] 6-7-1. Recording layer

[0518] The recording layer of the holographic 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. Information is usually recorded in the form of a hologram. As described in the following recording method, the polymerizable compound (hereinafter referred to as a polymerizable monomer) contained in the recording layer undergoes a chemical change such as polymerization due to holographic recording or the like. Therefore, in the holographic 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.

[0519] 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, more preferably 3 mm or less. By making the thickness of the recording layer greater than the above lower limit, there is a tendency that the selectivity of each hologram becomes higher during multiple recording in the holographic recording medium, and the degree of multiple recording can be improved. By making the thickness of the recording layer less than the above upper limit, there is a tendency that the entire recording layer can be uniformly formed, and multiple recording can be performed with uniform diffraction efficiency of each hologram and high S / N.

[0520] From the viewpoint of recording and reproducibility, the shrinkage rate of the recording layer due to exposure during recording and reproduction of information is preferably 0.25% or less.

[0521] 6-7-2. Support body

[0522] The details of the support are not particularly limited as long as they have the strength and durability required for the holographic recording medium, and any support may be used.

[0523] The shape of the support is not limited, but is usually formed in a flat plate shape or a film shape.

[0524] The material constituting the support is not limited either, and may be transparent or opaque.

[0525] When transparent materials are cited as materials for the support, organic materials such as acrylic acid, 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 acid, polyester, amorphous polyolefin, and glass are preferred, and polycarbonate, acrylic acid, amorphous polyolefin, polycycloolefin, and glass are more preferred.

[0526] Examples of the material of the support include opaque materials such as metals such as aluminum, and materials obtained by coating the above-mentioned transparent support with metals such as gold, silver, and aluminum, or dielectrics such as magnesium fluoride and zirconium oxide.

[0527] The thickness of the support is not particularly limited, and is preferably in the 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 recording medium can be obtained, and the warping of the substrate can be prevented. If the thickness of the support is below the upper limit, the light transmittance is increased, and the weight and cost of the holographic recording medium are reduced.

[0528] The surface of the support may also be subjected to a surface treatment. This surface treatment is usually performed to improve the adhesion between the support and the recording layer. Examples of surface treatments include subjecting the support to a corona discharge treatment or pre-forming a primer layer on the support. Compositions of the primer layer include halogenated phenols or partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, and the like.

[0529] 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 using metals such as gold, silver, and aluminum as raw materials; and 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.

[0530] These surface treatments may be provided for the purpose of controlling the gas or water permeability of the substrate. For example, by providing the support body sandwiching the recording layer with a function of suppressing the gas or water permeability, the reliability of the holographic recording medium can be improved.

[0531] The support may be disposed only on one of the upper side and the lower side of the recording layer of the holographic recording medium of the present invention, or may be disposed on both sides. However, when the support is disposed on both the upper and lower sides of the recording layer, at least one of the supports is transparently configured to allow active energy rays (excitation light, reference light, regeneration light, etc.) to pass therethrough.

[0532] In the case of a holographic recording medium having a support on one or both sides of the recording layer, a reflective or reflective holographic recording can be performed. In addition, in the case of using a support having a reflective property on one side of the recording layer, a reflective holographic recording can be performed.

[0533] 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 a reflective layer described later, or a combination of these methods may be used.

[0534] 6-7-3. Protective layer

[0535] The protective layer is a layer for preventing the degradation of the recording and reproducing characteristics of the recording layer. The specific composition of the protective layer is not limited, and any known composition can be applied. For example, a layer composed of a water-soluble polymer, an organic / inorganic material, etc. can be formed as the protective layer.

[0536] 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 or 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.

[0537] 6-7-4. Reflection layer

[0538] The reflective layer is formed when the holographic recording medium is configured as a reflective type. In the case of a reflective type holographic recording medium, the reflective layer may be formed between the support and the recording layer or on the outer side of the support, and is usually preferably located between the support and the recording layer.

[0539] As the reflective layer, any known reflective layer can be applied, and for example, a metal thin film or the like can be used.

[0540] 6-7-5. Anti-reflection film

[0541] For any of the transmissive and reflective holographic recording media, an antireflection 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 antireflection film improves the efficiency of light utilization and suppresses noise generation.

[0542] As the antireflection film, any known antireflection film can be used.

[0543] 6-7-6. Method for manufacturing holographic recording medium

[0544] The method for producing the holographic recording medium of the present invention is not limited. For example, the polymerizable composition of the present invention can be coated on a support in the absence of a solvent to form a recording layer. In this case, any method can be used as a coating method. If specific examples are given, spraying, spin coating, wire bar coating, dipping, air knife coating, roll coating, blade coating, and blade roll coating can be given.

[0545] When forming a recording layer, especially when forming a thick recording layer, a method of molding in a mold or a method of applying to 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, which can be applied to 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 the above method can be used.

[0546] The solvent used in the coating liquid is not limited. It is usually preferred to use a solvent that has sufficient solubility for the used components, imparts good film coating properties, and does not penetrate into the support body such as the resin substrate. The solvent can be used alone or in any combination and ratio. In addition, the amount of the solvent used is not limited. However, from the aspect of coating efficiency and operability, it is preferred to prepare a coating liquid with a solid component concentration of about 1 to 100 mass%.

[0547] Examples of solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, propanol, n-butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; ketoalcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; tetrahydrofuran, dimethicone, and dimethicone. ether solvents such as alkane; 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 solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, diethyl oxalate, ethyl pyruvate, 2-hydroxy Ester solvents such as ethyl butyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, and methyl 3-methoxypropionate; perfluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, and hexafluorobutanol; highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; chain hydrocarbon solvents such as n-hexane and n-octane; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, tert-butylcyclohexane, and cyclooctane; or mixed solvents thereof.

[0548] As a method for manufacturing a holographic 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; a method in which a liquid polymerizable composition is applied to a support, solidified by thermal polymerization to form a recording layer; a method in which a liquid polymerizable composition is applied to a support, solidified by photopolymerization to form a recording layer.

[0549] The holographic recording medium manufactured in this manner can be in the form of a self-supporting flat plate or disk, and can be used in three-dimensional image display devices, diffractive optical elements, large-capacity storage devices, and other applications.

[0550] In particular, the holographic recording medium of the present invention using the polymerizable composition of the present invention has a high refractive index modulation and is also useful as an AR glasses light guide plate or an AR glasses wave guide plate. Here, AR is an abbreviation obtained by omitting augmented reality.

[0551] 6-7-7. Application of holographic recording media

[0552] <Application of large-capacity storage>

[0553] Both writing (recording) and reading (reproducing) information on the holographic recording medium of the present invention can be performed by irradiating light.

[0554] When recording information, light that can cause a chemical change in a polymerizable monomer, that is, polymerization and concentration change thereof, is used as object light (also referred to as recording light).

[0555] For example, when information is recorded in the form of a volume hologram, the object light and the reference light are simultaneously irradiated on the recording layer, and the object light and the reference light are caused to interfere with each other in the recording layer. Thus, the interference light causes the polymerization and concentration change of the polymerizable monomer in the recording layer, and as a result, the interference fringes cause a refractive index difference in the recording layer, and the information is recorded in the recording layer in the form of a hologram through the interference fringes recorded in the recording layer.

[0556] When reproducing the volume hologram recorded in the recording layer, the recording layer is irradiated with a predetermined reproducing light (usually a reference light). The irradiated reproducing light is diffracted according to the interference fringes. Since the diffracted light contains the same information as the recording layer, the diffracted light can be read by an appropriate detection mechanism, thereby reproducing the information recorded in the recording layer.

[0557] The wavelength region of the object light, the regeneration light, and the reference light is arbitrary according to each application, and may be in the visible light region or in the ultraviolet region. Preferred light among these lights includes, for example, solid 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 having pigments, and the like.

[0558] There is no limitation on the irradiation amount of the object light, regeneration light and reference light, and the irradiation amount is arbitrary as long as it is within the range that can record and reproduce. When the irradiation amount is too small, the chemical change of the polymerizable monomer is too incomplete, and the heat resistance and mechanical properties of the recording layer may not be fully manifested. On the contrary, 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, regeneration light and reference light are usually 0.1 J / cm2 depending on the composition of the polymerizable composition of the present invention used to form the recording layer, the type and amount of the photopolymerization initiator, etc. 2 Above and 20J / cm 2 The following ranges are irradiated.

[0559] As holographic recording methods, there are polarization collinear holographic recording methods, reference light incident angle multiplexing type holographic recording methods, etc. When the holographic recording medium of the present invention is used as a recording medium, any recording method can provide good recording quality.

[0560] <Application of light guide plates for AR glasses (Application of light guide plates for AR glasses)>

[0561] The volume hologram is recorded on the holographic recording medium of the present invention in the same manner as in the above-mentioned large-capacity storage application.

[0562] For the volume hologram recorded on the recording layer, the recording layer is irradiated with a predetermined 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 satisfied 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, which can expand the display color gamut of the AR glasses.

[0563] If the corresponding interference fringes are pre-recorded according to the wavelength and diffraction angle of the regenerated light, the regenerated light incident from the outside of the holographic recording medium can be guided into the inside of the holographic recording medium, or the regenerated light guided inside the holographic recording medium can be reflected, split, enlarged, or reduced, or the regenerated light guided inside the holographic recording medium can be emitted to the outside of the holographic recording medium, thereby expanding the viewing angle of the AR glasses.

[0564] The wavelength region of the object light and the regeneration light is arbitrary according to each application, and can be a visible light region or an ultraviolet region. As preferred light among these lights, the above-mentioned laser etc. can be cited. As the regeneration light, it is not limited to laser etc., and display devices such as liquid crystal display (LCD) or organic electroluminescent display (OLED) can also be cited as preferred regeneration light.

[0565] There is no limitation on the irradiation amount of the object light, regeneration light and reference light, and the irradiation amount is arbitrary as long as it is within the range that can record and reproduce. When the irradiation amount is too small, the chemical change of the polymerizable monomer is too incomplete, and the heat resistance and mechanical properties of the recording layer may not be fully manifested. On the contrary, 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, regeneration light and reference light are usually 0.1 J / cm2 depending on the composition of the polymerizable composition of the present invention used to form the recording layer, the type and amount of the photopolymerization initiator, etc. 2 Above and 20J / cm 2 The following ranges are irradiated.

[0566] 6-8. Performance indicators of holographic recording media

[0567] The performance of the holographic recording medium is measured by the total Δn calculated using the sum of the diffraction efficiencies over the entire multiple recording. In the case of a transmission hologram, the diffraction efficiency of the hologram is given by the ratio of the intensity of the diffracted light to the sum of the intensity of the transmitted light and the intensity of the diffracted light. From the obtained diffraction efficiency, Δn is calculated using the following formula based on Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the sum of the entire multiple recording is taken as the total Δn.

[0568]

[0569] Total Δn = ∑Δn

[0570] 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.

[0571] In the case of a large-capacity memory, a high total Δn means that a large amount of information can be recorded per unit volume, which can be said to be preferred. In addition, in the case of AR glasses, a high total Δn means that the projected image of the projector can be clearly transmitted to the pupil, or that power consumption can be suppressed, or that the viewing angle can be expanded, which can be said to be preferred.

[0572] Example

[0573] The present invention will be described in further detail below by way of examples, but the present invention is not limited to the following examples unless it departs from the gist of the present invention.

[0574] [Raw materials used]

[0575] The composition raw materials used in Examples and Comparative Examples are as follows.

[0576] <Isocyanate>

[0577] · Duranate (registered trademark) TSS-100: Hexamethylene diisocyanate-based polyisocyanate (NCO 17.6%) (manufactured by Asahi Kasei Corporation)

[0578] <Polyol>

[0579] Placel PCL-205U: polycaprolactone diol (molecular weight 530) (manufactured by Daicel)

[0580] Placel PCL-305: polycaprolactone triol (molecular weight 550) (manufactured by Daicel)

[0581] <Photopolymerization initiator>

[0582] HLI02: 1-(9-ethyl-6-cyclohexanoyl-9H-carbazole-3-yl)-1-(O-acetyloxime)glutaric acid methyl ester

[0583] <Free Radical Scavenger>

[0584] TEMPOL: 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0585] <Light stabilizer>

[0586] ·Adekastab LA-63P (manufactured by ADEKA Co., Ltd.)

[0587] <Urethane polymerization catalyst>

[0588] Bismuth tris(2-ethylhexanoate)octanoate solution (active ingredient content 56% by mass)

[0589] [Example 1]

[0590] <Production of Compound M-1>

[0591] Compound M-1 was produced by the following synthesis method.

[0592]

[0593] 2,4,6-Tribromophenol (1.3 g), dibenzothiophene-4-boric acid (3.0 g) and potassium carbonate (1.5 g) were suspended in distilled water. 50mL of alkane and 10mL of water were added, and degassed by passing nitrogen through the liquid. 2mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was further passed through the liquid for 5 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred for 5 hours under reflux. After cooling to room temperature, 50mL of water was added, and 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 2.4g of compound S-1.

[0594] The NMR measurement data of compound S-1 are as follows.

[0595] 1H-NMR(400MHz, CDCl3, δ, ppm)8.26-8.16(Ar,5H),8.15(dd,Ar,1H),7.99(brs,Ar,2H),7.90-7.83( Ar,3H),7.70(dd,Ar,2H),7.66-7.61(Ar,3H),7.56(dd,Ar,1H),7.50-7.43(Ar,6H),5.39(s,HO,1H)

[0596] Compound S-1 (1.5 g), 2-isocyanatoethyl methacrylate (0.5 g) and THF (10 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 3 hours.

[0597] After the reaction, the reaction solution was poured into 50 mL of aqueous ammonium chloride solution, extracted with 50 mL of ethyl acetate, washed with 50 mL of saturated brine, dried with anhydrous magnesium sulfate, filtered, and concentrated. The obtained crude product was purified by column chromatography to obtain 1.2 g of compound M-1.

[0598] The NMR measurement data of compound M-1 are as follows.

[0599] 1 H-NMR (400MHz, CDCl3, δ, ppm)8.21-8.14(Ar,6H),8.08(brs,Ar,2H),7.90-7.81(Ar,3H),7.69-7.50(Ar,6H),7.50-7.42(Ar, 6H),5.77(brs,C=CH2,1H),5.35(brs,C=CH2,1H),4.63(brt,NH,1H),3.57(brt,CH2,2H),3.01(brq,CH2,2H),1.70(s,Me,3H)

[0600] <Production of holographic recording media>

[0601] Liquid A was prepared by dissolving 0.261 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 Duranate (registered trademark) TSS-100.

[0602] 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.

[0603] 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.

[0604] Next, the vacuum degassed mixed solution was poured onto slide glasses with spacers of 0.5 mm thickness placed on two opposing end portions, and the slide glasses were covered thereon, and the periphery was fixed with a clamp and heated at 80° C. for 24 hours to prepare a holographic recording medium as an evaluation sample. The evaluation sample had a recording layer of 0.5 mm thickness formed between the slide glasses as a cover.

[0605] The holographic recording medium was formulated so that the ratio of the number of isocyanate groups in liquid A to the number of isocyanate reactive groups in liquid B was 1.0, and the polymerizable monomer was 58.3 μmol / g, the photopolymerization initiator was 3.05 μmol / g, and the radical scavenger was 3.05 μmol / g.

[0606] <Holographic Recording and Evaluation>

[0607] Using the hologram recording medium produced as an evaluation sample, hologram recording and evaluation of the hologram recording performance of the hologram recording medium were performed in accordance with the procedure described below.

[0608] Holographic recording uses a semiconductor laser with a wavelength of 405nm and an exposure power density of 10.2mW / cm 2 ,use Figure 1 The exposure device shown performs holographic recording of a two-beam plane wave. The medium is rotated from -22.5° to 22.5°, and angle multiple recording is performed at the same location. The diffraction efficiency in each multiple recording is measured. Δn is calculated from the obtained diffraction efficiency, and the sum of the multiple recording as a whole is set as the total Δn.

[0609] The following is a detailed description.

[0610] (Holographic Recording)

[0611] Figure 1 This is a diagram showing the outline of the structure of a device for holographic recording.

[0612] Figure 1In the figure, S is a sample of the holographic recording medium, M1 to M3 are mirrors, PBS is a polarization beam splitter, and L1 is a laser light source for recording light emitting light of wavelength 405 nm (a single-mode laser manufactured by TOPTICA Photonics that obtains light of wavelength near 405 nm). Figure 1 1 is a LED unit.

[0613] like Figure 1 As shown, light of a wavelength of 405 nm is split by a polarization beam splitter ("PBS" in the figure) and the two beams intersect on the recording surface in such a manner that the angle formed by the two beams becomes 59.3°.

[0614] At this time, the bisector of the angle formed by the two light beams is made perpendicular to the recording surface, and further, the vibration planes of the electric field vectors of the two light beams obtained by spectral separation are made perpendicular to the plane including the two intersecting light beams.

[0615] After holographic recording, a light source that utilizes He-Ne laser to produce light with a wavelength of 633nm (V05-LHP151 manufactured by Melles Griot: "L2" in the figure) is used to irradiate the holographic recording medium with this light at an angle of 50.7°, and a photodiode and a photoelectric sensor amplifier (S2281, C9329 manufactured by Hamamatsu Photonics: "PD1" in the figure) are used to detect the diffracted light to determine whether the holographic recording has been accurately performed.

[0616] (Determination of diffraction efficiency)

[0617] The angle of the sample relative to the optical axis (double beam, i.e. from Figure 1 The angle (the angle formed by the bisector of the inner angle at the point where the incident light from the mirrors M1 and M2 intersects with the normal line from the sample) was recorded 151 times in increments of 0.3° from -22.5° to 22.5°.

[0618] After multiple recording, the LED unit (1 in the figure, central wavelength 405nm) is illuminated for a certain period of time to consume the remaining initiator and monomer. This process is called post-exposure. The power of the LED is 100mW / cm 2 , with a cumulative energy of 12 J / cm 2 way of irradiation.

[0619] The diffraction efficiency of a hologram is given by the ratio of the intensity of the diffracted light to the sum of the intensity of the transmitted light and the intensity of the diffracted light. Figure 1The light from mirror M1 (wavelength 405 nm) was measured to measure the diffraction efficiency at angles from -23° to 23°. Based on the obtained diffraction efficiency, Δn was calculated using the following formula based on Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the total of the multiple recording was set as the total Δn.

[0620]

[0621] Total Δn = ∑Δn

[0622] 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 (29.65°).

[0623] Using the prepared multiple samples, multiple evaluations were performed by changing the irradiation energy conditions, such as increasing or decreasing the irradiation energy at the beginning of recording and increasing or decreasing the total irradiation energy, to find the conditions under which the polymerizable monomer is almost exhausted (the total Δn is roughly balanced in multiple recording) and the total Δn becomes the maximum value. The obtained maximum value is then set as the total Δn of the medium.

[0624] (Preparation of refractive index measurement data)

[0625] The refractive index of compound M-1 was measured by the following method. In addition, the refractive index of the polymerizable monomers produced in Examples and Comparative Examples was measured by the same method.

[0626] A test solution was prepared by dissolving a sample in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate at a mass ratio of 4:1 so as to have a predetermined concentration.

[0627] The test solutions were prepared in two types: sample concentrations of 10% by mass and 20% by mass.

[0628] (Determination of refractive index)

[0629] The refractive index of each test solution was measured using a Kalnew precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-2000). The temperature of the test solution was 23°C, and the measurement wavelength was a helium lamp d-ray (587.6 nm). Based on the measurement results, a calibration curve showing the correlation between the sample concentration and the 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.

[0630] The total Δn of compound M-1 is 0.0222, and the refractive index is 1.6818.

[0631] [Example 2]

[0632] Compound M-2 was prepared by the following synthesis method.

[0633]

[0634] 2,4,6-tribromophenol (2.3 g), phenanthrene-9-boric acid (5.8 g) and sodium carbonate (3.5 g) were dissolved in distilled water. 100mL of alkane and 25mL of water were added, and nitrogen was passed through the liquid for degassing. 10mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was further passed through the liquid for 5 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred for 5 hours under reflux. After cooling to room temperature, 100mL of ethyl acetate and 50mL of water were added to perform a liquid separation operation. The obtained organic layer was washed with an aqueous sodium bicarbonate solution. After the organic layer was dried, the obtained solid was washed with hexane. The solid was dried using a vacuum dryer to obtain 4.4g of a crude compound S-2.

[0635] The NMR measurement data of compound S-2 are as follows.

[0636] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.84-8.66 (Ar, 6H), 8.32 (dd, Ar, 1H), 8.11 (dd, Ar, 1 H),8.07(dd,Ar,1H),8.04-7.86(Ar,8H),7.75-7.57(Ar,12H),5.18-5.13(OH,1H)

[0637] Compound S-2 (4.4 g), 2-isocyanatoethyl acrylate (0.4 g), and THF (10 mL) were mixed. Diazabicycloundecene (0.01 g) was added thereto and stirred for 3 hours. After the reaction was completed, 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 with anhydrous magnesium sulfate, filtered, and concentrated. The obtained crude body was purified by column chromatography to obtain 3.4 g of compound M-2.

[0638] The NMR measurement data of compound M-2 are as follows.

[0639] 1H NMR (400MHz, CDCl3, δ, ppm)8.81-8.66(Ar,6H),8.33-8.26(Ar,1H),8.13-8.01(Ar,2H),7.99-7.85(Ar,6H),7.84-7.78(Ar,2H),7.73-7.57 (Ar,12H),5.67-5.54(C=CH2,1H),5.34-5.26(C=CH2,1H),4.28-3.83(NH,1H),3.29-2.82(CH2,2H),2.78-2.13(CH2,2H),1.67-1.58(Me,3H)

[0640] 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 total Δn of the compound M-2 was 0.0250, and the refractive index was 1.6898.

[0641] [Example 3]

[0642] Compound M-3 was prepared by the following synthesis method.

[0643]

[0644] Compound S-1 (9.0 g), 2-isocyanatoethyl acrylate (2.0 g) and THF (50 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 3 hours.

[0645] 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 50 mL of saturated brine, dried with anhydrous magnesium sulfate, filtered, and concentrated. The obtained crude product was purified by column chromatography to obtain 6.8 g of compound M-3.

[0646] The NMR measurement data of compound M-3 are as follows.

[0647] 1 H-NMR (400MHz, CDCl3, δ, ppm)8.22-8.11(Ar,6H),8.08(brs,Ar,2H),7.91-7.81(Ar,3H),7.69-7.51(Ar,6H),7.51-7. 41(Ar,6H),6.16(brd,CH=CH2,1H),5.79-5.60(CH=CH2,2H),4.65(brt,NH,1H),3.58(brt,CH2,2H),2.99(brq,CH2,2H)

[0648] 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 total Δn of the compound M-3 was 0.0195, and the refractive index was 1.6891.

[0649] [Example 4]

[0650] Compound M-4 was prepared by the following synthesis method.

[0651]

[0652] Compound S-2 (3.1 g), 2-isocyanatoethyl acrylate (1.1 g) and THF (20 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 2 hours.

[0653] 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 50 mL of saturated brine, dried with anhydrous magnesium sulfate, filtered, and concentrated. The obtained crude product was purified by column chromatography to obtain 2.2 g of compound M-4.

[0654] The NMR measurement data of compound M-4 are as follows.

[0655] 1 H NMR (400MHz, CDCl3, δ, ppm) 8.82-8.66 (Ar, 6H), 8.33-8.25 (Ar, 1H), 8.15-8.01 (Ar, 2H), 7.99-7.85 (Ar, 6H), 7.84-7.77 (Ar, 2H), 7. 74-7.55(Ar,12H),6.09-5.95(CH=CH2,1H),5.69-5.53(CH=CH2,2H),4.42-3.89(NH,1H),3.29-2.80(CH2,2H),2.79-2.13(CH2,2H)

[0656] A hologram recording medium was prepared and evaluated in the same manner as in Example 1 except that the compound M-4 was used as the polymerizable monomer. The total Δn of the compound M-4 was 0.0194, and the refractive index was 1.6894.

[0657] [Example 5]

[0658] Compound M-5 was prepared by the following synthesis method.

[0659]

[0660] 2,4,6-tribromophenol (2.3g), naphthalene-2-boric acid (3.7g), sodium carbonate (2.3g) were suspended in 50mL toluene, 50mL ethanol, and 25mL water, and degassed by passing nitrogen through the liquid. 2mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen was further passed through the liquid for 5 minutes. Under a nitrogen atmosphere, the reaction solution was heated and stirred at reflux for 5 hours. After cooling to room temperature, 100mL of ethyl acetate and 50mL of water were added to perform a liquid separation operation. The obtained organic layer was washed with an aqueous sodium bicarbonate solution. After drying the organic layer, the obtained solid was washed with hexane to obtain 3.0g of the crude form of compound S-3.

[0661] The crude body (3.0 g) of the above-mentioned compound S-3, 2-isocyanatoethyl methacrylate (0.9 g) and THF (10 mL) were mixed. Diazabicycloundecene (0.01 g) was added thereto and stirred for 3 hours. After the reaction was completed, 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 with anhydrous magnesium sulfate, filtered and concentrated. The obtained crude body was purified by column chromatography to obtain 1.9 g of compound M-5.

[0662] The NMR measurement data of compound M-5 are as follows.

[0663] 1 H NMR(400MHz, CDCl3, δ, ppm)8.14(brs,Ar,1H),8.05(brs,Ar,2H),7.97-7.82(Ar,12H),7.72(dd,Ar,2H),7.54-7.48(Ar, 6H),5.90(brs,C=CH2,1H),5.46(dd,C=CH2,1H),4.95(brt,NH,1H),3.67(t,CH2,2H),3.11(dt,CH2,2H),1.81(s,Me,3H)

[0664] [Example 6]

[0665] Compound M-6 was prepared by the following synthesis method.

[0666]

[0667] Compound S-2 (18.0 g), 2-(2-methacryloyloxyethoxy)ethyl isocyanate (5.8 g) and dichloromethane (50 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.02 g) was added thereto, followed by stirring for 1 hour.

[0668] After the reaction was completed, 9 g of silica gel was added to the reaction solution and stirred at room temperature for 1 hour. The solid was separated by filtration and then washed with dichloromethane. The obtained solution was concentrated and then slowly added dropwise to methanol cooled to 0°C. The generated solid was separated by filtration and dried to obtain 9.2 g of compound M-6.

[0669] The NMR measurement data of compound M-6 are as follows.

[0670] 1 H NMR (400MHz, CDCl3, δ, ppm)8.80-8.66(Ar,6H),8.32-8.27(Ar,1H),8.13-8.01(Ar,2H),7.99-7.75(Ar,8H),7.73-7.57(Ar, 12H),5.97-5.88(CH=CH2,1H),5.47-5.42(CH=CH2,1H),4.44-4.08(NH,1H),3.75-3.68(CH2,2H),2.75-2.35(CH2,6H),1.84

[0671] -1.77(Me,3H)

[0672] [Example 7]

[0673] Compound M-7 was prepared by the following synthesis method.

[0674]

[0675] The crude compound S-2 (4.0 g) and potassium carbonate (2.0 g) were added to DMF (40 mL) and heated to 60°C, followed by dropwise addition of 2-bromoethanol (1.8 g). The reaction mixture was stirred for 8 hours and then returned to room temperature, ice water was added and the solid was filtered out. The obtained solid was purified by column chromatography to obtain 1.95 g of compound S-4.

[0676] The NMR measurement data of compound S-4 are as follows.

[0677] 1 H NMR (400MHz, CDCl3, δ, ppm)8.83-8.69(Ar,6H),8.33-8.26(Ar,1H),8.18-8.08(Ar,2H),8.03-7.86(Ar,6H) ,7.82-7.76(Ar,2H),7.76-7.56(Ar,12H),3.38-3.27(CH2,2H),2.89-2.70(CH2,2H),0.60,0.51(t,OH,total 1H)

[0678] Compound S-4 (6.03 g), 2-isocyanatoethyl acrylate (1.53 g) and dichloromethane (36 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (1.38 g) was added thereto, followed by stirring for 1 hour.

[0679] After the reaction, 6 g of neutral silica gel was added to the reaction solution, and the mixture was stirred for 1 hour, filtered, and concentrated. Dichloromethane (30 mL) was added to the concentrate, and the mixture was added dropwise to ice-cold methanol (150 mL) and stirred for 1 hour. The precipitated solid was filtered and dried to obtain 5.76 g of compound M-7.

[0680] The NMR measurement data of compound M-7 are as follows.

[0681] 1 H NMR (400MHz, CDCl3, δ, ppm)8.83-8.68(Ar,6H),8.34-8.25(Ar,1H),8.20-8.08(Ar,2H),8.05-7.95(Ar,4H),7.94-7.85(Ar,2H),7.79-7.58( Ar,14H),6.40(d,CH=CH2,1H),6.11(dd,CH=CH2,1H),5.87(d,CH=CH2,1H),3.89-3.80(CH2,2H),3.60-3.12(CH2,NH,5H),2.92-2.78(CH2,2H)

[0682] [Example 8]

[0683] Compound M-8 was prepared by the following synthesis method.

[0684]

[0685] Compound S-4 (6.00 g), 2-isocyanatoethyl methacrylate (1.68 g) and dichloromethane (36 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (1.37 g) was added thereto, followed by stirring for 1 hour.

[0686] After the reaction, 6 g of neutral silica gel was added to the reaction solution, and the mixture was stirred for 1 hour, filtered, and concentrated. Dichloromethane (30 mL) was added to the concentrate, and the mixture was added dropwise to ice-cold methanol (150 mL) and stirred for 1 hour. The precipitated solid was filtered and dried to obtain 5.98 g of compound M-8.

[0687] The NMR measurement data of compound M-8 are as follows.

[0688] 1H NMR (400MHz, CDCl3, δ, ppm)8.83-8.68(Ar,6H),8.34-8.25(Ar,1H),8.18-8.07(Ar,2H),8.05-7.95(Ar,4H),7.94-7.85(Ar,2H),7.79-7.56(Ar,14 H),6.05(s,CH=CH2,1H),5.58(s,CH=CH2,1H),3.87-3.77(CH2,2H),3.55-3.28(CH2,4H),3.26-3.13(NH,1H),2.92-2.75(CH2,2H),1.92(s,CH3,3H)

[0689] [Example 9]

[0690] Compound M-9 was prepared by the following synthesis method.

[0691] [Chemistry 28]

[0692]

[0693] Compound S-4 (4.00 g), 2-(2-methacryloyloxyethoxy)ethyl isocyanate (2.15 g) and dichloromethane (24 mL) were mixed under a nitrogen atmosphere, and diazabicycloundecene (0.91 g) was added thereto, followed by stirring for 2 hours.

[0694] After the reaction was completed, 4 g of neutral silica gel was added to the reaction solution, and the mixture was stirred for 30 minutes, filtered, and concentrated. The obtained crude product was purified by column chromatography to obtain 3.77 g of compound M-9.

[0695] The NMR measurement data of compound M-9 are as follows.

[0696] 1 H NMR (400MHz, CDCl3, δ, ppm)8.83-8.68(Ar,6H),8.34-8.25(Ar,1H),8.18-8.06(Ar,2H),8.05-7.85(Ar,6H),7.79-7.56(Ar,14H ),6.11(s,CH=CH2,1H),5.55(s,CH=CH2,1H),4.33-4.08(CH2,2H),3.65-3.12(CH2,NH,9H),2.87-2.65(CH2,2H),1.93(CH3,3H)

[0697] [Example 10]

[0698] Compound M-10 was prepared by the following synthesis method.

[0699]

[0700] Compound S-4 (1.92 g) and triethylamine (0.95 g) were added to THF (20 mL) under a nitrogen atmosphere, and acryloyl chloride (0.78 g) was slowly added dropwise under an ice bath. After the reaction was completed, the reaction solution was injected into 20 mL of 1N sodium hydroxide aqueous solution, extracted with 50 mL of ethyl acetate, washed with 50 mL of saturated brine, dried with sodium sulfate, filtered, and concentrated. The obtained crude product was purified by column chromatography to obtain 580 mg of compound M-10.

[0701] The NMR measurement data of compound M-10 are as follows.

[0702] 1 H NMR (400MHz, CDCl3, δ, ppm)8.81-8.68(Ar,6H),8.32-8.26(Ar,1H),8.17-8.07(Ar,2H),8.03-7.85(Ar,6H),7.79-7.57 (Ar,14H),5.58,5.54(dd,CH=CH2,total 1H),5.21,5.19(dd,CH=CH2,total 1H),5.06-4.94(CH=CH2,1H),3.56-3.37(CH2-CH2,4H)

[0703] A hologram recording medium was prepared and evaluated in the same manner as in Example 1 except that the compound M-10 was used as the polymerizable monomer. The total Δn of the compound M-10 was 0.0160, and the refractive index was 1.7323.

[0704] [Example 11]

[0705] Compound M-11 was prepared by the following synthesis method.

[0706]

[0707] The crude form of compound S-2 (10 g), potassium carbonate (2.55 g), and trimethylene carbonate (1.58 g) were added to DMF (100 mL) and heated to 130 ° C for reaction. After stirring the reaction solution for 9 hours, it was returned to room temperature, ice water was added and the solid was filtered out. The obtained solid was dissolved in 50 mL of dichloromethane and repeatedly washed with 100 mL of water. After washing the organic layer with 100 mL of saturated brine, it was concentrated and dried to obtain 8.40 g of the crude form of compound S-5.

[0708] The NMR measurement data of compound S-5 are as follows.

[0709] 1 H NMR (400MHz, CDCl3, δ, ppm)8.85-8.66(Ar,6H),8.34-8.25(Ar,1H),8.18-8.07(Ar,2H),8.04-7.85(Ar,6H), 7.82-7.56(Ar,14H),3.43-3.29(CH2,2H),2.61,2.42(CH2,2H),0.97-0.75(CH2,2H),0.45,0.29(t,OH,total 1H)

[0710] Compound S-5 (8.09 g) and triethylamine (1.75 g) were added to dichloromethane (80 mL) under a nitrogen atmosphere, and acryloyl chloride (1.36 g) was slowly added dropwise under an ice bath. After the reaction was completed, 70 mL of a 5 wt% sodium bicarbonate aqueous solution was added to the reaction solution and stirred for 2 hours, extracted with 100 mL of dichloromethane, then washed with 100 mL of saturated brine, dried with sodium sulfate, filtered, and concentrated. The obtained crude product was purified by column chromatography to obtain 6.39 g of compound M-11.

[0711] The NMR measurement data of compound M-11 are as follows.

[0712] 1 H NMR (400MHz, CDCl3, δ, ppm)8.81-8.68(Ar,6H),8.34-8.28(Ar,1H),8.20-8.07(Ar,2H),8.03-7.84(Ar,6H),7 .81-7.57(Ar,14H),5.77(dd,CH=CH2,1H),5.43-5.24(CH=CH2,2H),3.40-2.98(CH2,4H),1.06-0.86(CH2,2H)

[0713] A hologram recording medium was prepared and evaluated in the same manner as in Example 1 except that the compound M-11 was used as the polymerizable monomer. The total Δn of the compound M-11 was 0.0181, and the refractive index was 1.7316.

[0714] [Comparative Example 1]

[0715] Compound R-1 was produced by the following synthesis method.

[0716]

[0717] 2,4-dibromophenol (5g), dibenzothiophene-4-boric acid (11g), potassium phosphate (5.5g) were suspended in 70mL of toluene, 70mL of ethanol, and 35mL of water, and degassed by passing nitrogen through the liquid. 1.2mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution. The reaction solution was heated under a nitrogen atmosphere and stirred at reflux for 1.5 hours. After cooling to room temperature, 500mL of water was added and extracted with toluene. After drying the organic layer with sodium sulfate, the obtained organic layer was concentrated. The resulting solid was dried using a vacuum dryer to obtain 8.8g of compound L-1.

[0718] The NMR measurement data of compound L-1 are as follows.

[0719] 1 H NMR (400MHz, CDCl3, δ, ppm)8.30-8.10(Ar,4H),7.88-7.82(Ar,3H),7.82-7.75(dd,Ar,1H),7.68-7.41(Ar,8H),7.25(d,Ar,1H),5.18(s,OH,1H)

[0720] Compound L-1 (8.8 g) was dissolved in 60 mL of THF, and 2-isocyanatoethyl acrylate (3.1 g) was added. Triethylamine (2.2 g) was added to the solution, and the reaction was carried out at room temperature. After 4 hours, an aqueous solution of ammonium chloride was added to the reaction solution, and 50 mL of ethyl acetate was used for extraction. The obtained organic layer was dried with sodium sulfate and concentrated below 30°C. The crude product obtained by the above concentration was purified using a silica gel column (hexane-ethyl acetate) to obtain 9.7 g of compound R-1.

[0721] The NMR measurement data of compound R-1 are as follows.

[0722] 1 H NMR (400MHz, CDCl3, δ, ppm)8.22-8.11(Ar,4H),7.95(d,Ar,1H),7.90-7.80(Ar,3H),7.60-7.40(Ar,9H),6.33(d d,CH=CH2,1H),5.96(dd,CH=CH2,1H),5.78(dd,CH=CH2,1H),5.01(t,NH,1H),4.03(t,CH2,2H),3.37(dt,CH2,2H)

[0723] 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 total Δn of the compound R-1 was 0.0115, and the refractive index was 1.6762.

[0724] [Comparative Example 2]

[0725] Compound R-2 was prepared by the following synthesis method.

[0726]

[0727] Compound S-1 (2.0 g) was dissolved in 10 mL of dichloromethane, and triethylamine (0.48 g) was added. Acryloyl chloride (0.37 g) and dimethylaminopyridine (DMAP, 10 mg) were added to the solution at 0°C and stirred. After 1 hour, a saturated aqueous sodium bicarbonate solution was added to the reaction solution, and 50 mL of dichloromethane was used for extraction. The obtained organic layer was dried with magnesium sulfate and concentrated. The obtained crude product was purified by a silica gel column (hexane-ethyl acetate) to obtain 1.2 g of compound R-2.

[0728] The NMR measurement data of compound R-2 are as follows.

[0729] 1 H NMR (400MHz, CDCl3, δ, ppm)8.21-8.11(Ar,8H),7.90-7.82(Ar,3H),7.68(dd,Ar,1H),7.62-7.43(Ar, 1 H),5.97(dd,CH=CH2,1H),5.62(dd,CH=CH2,1H),5.44(dd,CH=CH2,1H)

[0730] 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 total Δn of the compound R-2 was 0.0070, and the refractive index was 1.7056.

[0731] [Comparative Example 3]

[0732] Compound R-3 was prepared by the following synthesis method.

[0733]

[0734] Compound S-1 (12.2 g), potassium carbonate (0.5 g), and ethylene carbonate (2.01 g) were added to DMF (12 mL) and heated to 130° C. The reaction solution was stirred for 3 hours and then returned to room temperature. Ice water was added and the solid was filtered out. The obtained solid was washed with ethyl acetate and dried to obtain 11.9 g of compound L-2.

[0735] The NMR measurement data of compound L-2 are as follows.

[0736] 1 H NMR (400MHz, CDCl3, δ, ppm)8.28-8.14(Ar,6H),8.07(s,Ar,2H),7.93-7.81(Ar,3H),7.77-7.71(Ar, 2H),7.68-7.54(Ar,4H),7.53-7.42(Ar,6H),3.35(t,CH2,2H),3.09-3.01(CH2,2H),0.91(t,OH,1H)

[0737] Compound L-2 (4.99 g) and triethylamine (0.73 g) were added to THF (50 mL) under a nitrogen atmosphere, and acryloyl chloride (1.32 g) was slowly added dropwise under an ice bath. After the reaction was completed, the reaction solution was injected into 50 mL of a 5 wt% sodium bicarbonate aqueous solution, stirred for 30 minutes, and extracted with 500 mL of dichloromethane. The mixture was washed with 200 mL of water, dried with sodium sulfate, filtered, and concentrated to obtain 3.60 g of compound R-3.

[0738] The NMR measurement data of compound R-3 are as follows.

[0739] 1 H NMR (400MHz, CDCl3, δ, ppm)8.26-8.12(Ar,6H),8.06(s,Ar,2H),7.92-7.81(Ar,3H),7.76-7.70(Ar,2H),7.67-7.54(Ar,4H),7. 53-7.40(Ar,6H),5.84(dd,CH=CH2,1H),5.44(dd,CH=CH2,1H),5.36(dd,CH=CH2,1H),3.68-3.61(CH2,2H),3.51-3.44(CH2,2H)

[0740] [Comparative Example 4]

[0741] Compound R-4 was prepared by the following synthesis method.

[0742]

[0743] Compound S-1 (7.0 g) and potassium carbonate (11.1 g) were added to DMF (40 mL), and 4-bromo-1-butanol (12.5 g) was added dropwise. The reaction solution was stirred for 30 hours, and then water was added and the solid was filtered out. The obtained solid was purified by column chromatography to obtain 3.79 g of compound L-3.

[0744] The NMR measurement data of compound L-3 are as follows.

[0745] 1 H NMR (400MHz, CDCl3, δ, ppm)8.26-8.13(Ar,6H),8.04(s,Ar,2H),7.93-7.81(Ar,3H),7.75-7.69(Ar,2H),7.67-7.53(Ar,4 H),7.53-7.43(Ar,6H),3.27(t,CH2,2H),2.97-2.90(CH2,2H),1.02-0.92(CH2,2H),0.86-0.75(CH2,2H),0.71(t,OH,1H)

[0746] Compound L-3 (1.77 g) and triethylamine (1.26 g) were added to THF (180 mL) under a nitrogen atmosphere, and acryloyl chloride (0.90 g) was slowly added dropwise under an ice bath. After the reaction was completed, the reaction solution was injected into 100 mL of a 5 wt% sodium bicarbonate aqueous solution, extracted with 1000 mL of dichloromethane, and concentrated. The obtained crude product was purified by column chromatography to obtain 1.06 g of compound R-4.

[0747] The NMR measurement data of compound R-4 are as follows.

[0748] 1 H NMR (400MHz, CDCl3, δ, ppm)8.26-8.13(Ar,6H),8.04(s,Ar,2H),7.93-7.81(Ar,3H),7.75-7.69(Ar,2H),7.67-7.53(Ar,4H),7.5 3-7.40(Ar,6H),6.15(dd,CH2,1H),5.83(dd,CH2,1H),5.65(dd,CH2,1H),3.50(t,CH2,2H),3.27(t,CH2,2H),1.02-0.81(CH2,4H)

[0749] [Evaluation of total Δn]

[0750] The total Δn value obtained in the multiple recording of the holographic recording medium using the polymerizable monomers of the examples and comparative examples was evaluated as ◎ (0.019 or more), ○ (0.015 or more and less than 0.019), △ (0.010 or more and less than 0.015), and × (less than 0.010). In addition, samples not suitable for multiple recording were set to - (unable to measure).

[0751] [Evaluation of refractive index]

[0752] The values ​​obtained in the refractive index measurement of each polymerizable monomer were evaluated as ◎ (1.73 or more), ○ (1.68 or more and less than 1.73), △ (1.65 or more and less than 1.68), and × (less than 1.65). Samples not suitable for refractive index measurement were marked as - (unable to measure).

[0753] [Evaluation of solubility and storage stability]

[0754] The state of the solution when 0.63 g of each of M-1 to M-11 and R-1 to R-4 as polymerizable monomers was dissolved in 2.53 g of Duranate (registered trademark) TSS-100 was visually observed, and the solubility was evaluated as ○ (completely dissolved), △ (turbid), and × (solids remaining after dissolution). In addition, the state of each solution when stored at room temperature for 10 days was visually observed, and the storage stability was evaluated as ○ (completely dissolved), △ (turbid), and × (solids remaining after dissolution).

[0755] Table 1 shows the evaluation results of the refractive index, solubility, and storage stability of Examples 1 to 9 and Comparative Examples 1 to 4.

[0756] [Table 1]

[0757] monomer Refractive Index Solubility Storage stability Example 1 M-1 1.6818 ○ ○ Example 2 M-2 1.6898 ○ ○ Example 3 M-3 1.6891 ○ ○ Example 4 M-4 1.6894 ○ ○ Example 5 M-5 1.6798 ○ ○ Example 6 M-6 1.7013 ○ ○ Example 7 M-7 1.7104 ○ ○ Example 8 M-8 1.7042 ○ ○ Example 9 M-9 1.6975 ○ ○ Comparative Example 1 R-1 1.6762 ○ Δ Comparative Example 2 R-2 1.7056 Δ Δ Comparative Example 3 R-3 × × Comparative Example 4 R-4 × ×

[0758] Table 2 shows the evaluation results of the refractive index, solubility, and storage stability of Examples 10 and 11 and Comparative Examples 1 to 4.

[0759] [Table 2]

[0760] monomer Refractive Index Solubility Storage stability Example 10 M-10 1.7323 ○ ○ Embodiment 11 M-11 1.7316 ○ ○ Comparative Example 1 R-1 1.6762 ○ Δ Comparative Example 2 R-2 1.7056 Δ Δ Comparative Example 3 R-3 × × Comparative Example 4 R-4 × ×

[0761] Table 3 shows the evaluation results of the total Δn of Examples 1 to 4 and Comparative Examples 1 to 4.

[0762] [Table 3]

[0763] monomer Total Δn Example 1 M-1 0.0222 Example 2 M-2 0.0250 <![CDATA[Example 3]]> M-3 0.0195 <![CDATA[Example 4]]> M-4 0.0194 Comparative Example 1 R-1 0.0115 Comparative Example 2 R-2 0.0070 Comparative Example 3 R-3 Comparative Example 4 R-4

[0764] Table 4 shows the evaluation results of the total Δn of Examples 10 and 11 and Comparative Examples 1 to 4.

[0765] [Table 4]

[0766] monomer Total Δn Example 10 M-10 0.0160 Embodiment 11 M-11 0.0181 Comparative Example 1 R-1 0.0115 Comparative Example 2 R-2 0.0070 Comparative Example 3 R-3 Comparative Example 4 R-4

[0767] As shown in Tables 3 and 4, the total Δn of the hologram recording media of Comparative Examples 1 and 2 is less than 0.015, whereas the total Δn of the examples of the present invention is 0.015 or more. In particular, the total Δn of the hologram recording media produced using the polymerizable monomers of Examples 1 to 4 is 0.019 or more, which is very excellent as a hologram recording material.

[0768] According to Table 1 and Table 2, the refractive index of the compounds of the examples is 1.68 or more, which is equal to or higher than that of the compounds of the comparative examples, and thus is an excellent high refractive index material. In particular, the refractive index of the polymerizable monomers of Examples 10 and 11 exceeds 1.73, which is very useful as an ultra-high refractive index material.

[0769] As shown in Tables 1 and 2, the polymerizable monomers of Comparative Examples 1 to 4 have insufficient storage stability and low solubility in Duranate TSS-100. On the other hand, the polymerizable monomers of the compounds of the present invention all have high solubility in TSS-100 and excellent storage stability.

[0770] In the use of optical elements of AR glasses light guide plates, the one with a high total Δn of the holographic recording medium can make the projected image clear and can expand the viewing angle. In addition, in the use of memory, increasing the total Δn can increase the recording capacity. On the other hand, the holographic recording medium requires high transparency, and the turbidity caused by the mixing and generation of insolubles can cause the absorption or scattering of the recording light, thereby reducing the performance of the holographic recording medium. In particular, in the use of AR glasses waveguide plates, light scattering caused by insolubles can reduce light utilization efficiency and aesthetics. In addition, when insolubles are precipitated into the waveguide plate over time, the absorption intensity of the waveguide light also changes over time, resulting in reduced performance stability of the waveguide plate. Therefore, by using the compound of the present invention having both high total Δn and stability of the composition, especially high solubility in the medium, it is possible to produce an AR glasses light guide plate with excellent light utilization efficiency, aesthetics, and long-term performance stability.

[0771] From the above, it can be said that the compounds of the present invention used in Examples are superior to the compounds of Comparative Examples.

[0772] Although the present invention has been described in detail using specific embodiments, it is apparent to one skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention.

[0773] This application is based on Japanese patent application No. 2022-167398 filed on October 19, 2022, and the entire contents thereof are incorporated herein by reference.

[0774] Explanation of symbols

[0775] S holographic recording medium

[0776] M1, M2, M3 mirror

[0777] L1 semiconductor laser light source for recording light

[0778] L2 laser source for regeneration light

[0779] PD1, PD2, PD3 Photodetectors

[0780] PBS Polarization Beamsplitter

[0781] 1LED unit

Claims

1. A compound represented by the following formula (1): In the formula, n represents an integer of 1 to 3, L 1 represents a branchable (n+1)-valent linking group, wherein The linking group does not include a chain saturated aliphatic hydrocarbon group, X represents an oxygen atom or a nitrogen atom which may have a substituent, R 1-1 represents an aromatic ring group which may have a substituent, m is an integer from 3 to 5, and multiple R 1-1 Can be the same or different. Among them, in the formula, the composition-(R 1-1 )m shown in multiple R 1-1 The total number of carbon atoms is 25 to 70. In addition, the formula with R 1-1 The benzene ring is R 1-1 In addition, it may further have a substituent, R 2 represents a hydrogen atom or a methyl group.

2. A compound represented by the following formula (2): In the formula, n represents an integer of 1 to 3, L represents a (n+1)-valent chain saturated aliphatic hydrocarbon group which may have a substituent, X represents an oxygen atom or a nitrogen atom which may have a substituent, R 1-2 represents an aromatic ring group represented by the following formula (2-1), m is an integer from 3 to 5, and multiple R 1-2 Can be the same or different. in, In the formula, the composition -(R 1-2 )m shown in multiple R 1-2 The total number of carbon atoms is 25 to 70. In addition, the formula with R 1-2 The benzene ring is R 1-2 In addition, it may further have a substituent, R 2 represents a hydrogen atom or a methyl group, In formula (2-1), R 3 represents a substituent, In formula (2-1), there are multiple R 3 In the case of, they may be bonded to each other to form a ring condensed with the naphthalene ring in formula (2-1), and the condensed ring may further have a substituent, p represents 0 or an integer whose upper limit is the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1), * represents a bonding site to the benzene ring in formula (2).

3. The compound according to claim 1 or 2, wherein The above m is 3 or 5.

4. The compound according to claim 1, wherein The above R 1-1 It is a condensed aromatic ring group which may have a substituent or a monocyclic aromatic ring group substituted with an aromatic ring group.

5. The compound according to claim 2, wherein The above R 1-2 It is a condensed aromatic ring group which may have a substituent or a monocyclic aromatic ring group substituted with an aromatic ring group.

6. The compound according to claim 1 or 2, wherein The above-mentioned X is an oxygen atom.

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

8. The compound according to claim 1 or 2, wherein The above m is 3.

9. A polymerizable composition comprising the compound according to claim 1 or 2 and a polymerization initiator.

10. A holographic recording medium comprising the polymerizable composition according to claim 9.

11. An optical material comprising the polymerizable composition according to claim 9.

12. An optical component comprising the polymerizable composition according to claim 9.

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

14. An optical element obtained by performing holographic recording on the holographic recording medium according to claim 10.

15. An AR light guide plate comprising the optical element according to claim 14.

16. AR glasses, comprising the optical element according to claim 14.

17. A polymer comprising a structure represented by the following formula (P1-1) or the following formula (P1-2), In formula (P1-1), n ​​represents an integer of 1 to 3, L 1 represents a branchable (n+1)-valent linking group, wherein The linking group does not include a chain saturated aliphatic hydrocarbon group, X represents an oxygen atom or a nitrogen atom which may have a substituent, R 1-1 represents an aromatic ring group which may have a substituent, m is an integer from 3 to 5, and multiple R 1-1 Can be the same or different. Among them, in the formula, the composition-(R 1-1 )m shown in multiple R 1-1 The total number of carbon atoms is 25 to 70. In addition, the formula with R 1-1 The benzene ring is R 1-1 In addition, it may further have a substituent, R 2 represents a hydrogen atom or a methyl group, In formula (P1-2), n represents an integer of 1 to 3, L represents a (n+1)-valent chain saturated aliphatic hydrocarbon group which may have a substituent, X represents an oxygen atom or a nitrogen atom which may have a substituent, R 1-2 represents an aromatic ring group represented by the following formula (2-1), m is an integer from 3 to 5, and multiple R 1-2 Can be the same or different. Among them, in the formula, the composition-(R 1-2 )m shown in multiple R 1-2 The total number of carbon atoms is 25 to 70. In addition, the formula with R 1-2 The benzene ring is R 1-2 In addition, it may further have a substituent, R 2 represents a hydrogen atom or a methyl group, q represents the number of repetitions of the structure represented by formula (P1-1) or formula (P1-2), In formula (2-1), R 3 represents a substituent, In formula (2-1), there are multiple R 3 In the case of, they may be bonded to each other to form a ring condensed with the naphthalene ring in formula (2-1), and the condensed ring may further have a substituent, p represents 0 or an integer whose upper limit is the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1), * represents a bonding site to the benzene ring in formula (2).

18. A holographic recording medium comprising the polymer according to claim 17.

19. An optical material comprising the polymer according to claim 17.

20. An optical component comprising the polymer according to claim 17.

21. A large-capacity storage device comprising the holographic recording medium according to claim 18.

22. An optical element obtained by performing holographic recording on the holographic recording medium according to claim 18.

23. An AR light guide plate comprising the optical element according to claim 22.

24. AR glasses, comprising the optical element according to claim 22.

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