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

Abstract

A compound represented by formula (1). [In formula (1), A1 and A2 are polymerizable groups. And n1 and n2 are integers from 1 to 3. And L1 represents a single bond or an optionally branched (n1 + 1)-valent linking group. L2 represents a single bond or an optionally branched (n2 + 1)-valent linking group; and X represents a single bond, a divalent organic group having 1-20 carbon atoms, a sulfonyl group, or a divalent oxygen atom or sulfur atom. R1 and R2 each represents a fused aromatic ring group which may have a substituent. And m1 and m2 are integers from 2 to 4. ]

Description

Technical Field

[0001] This invention relates to compounds with high refractive index, high transparency, easy polymerizability, excellent chemical stability, and excellent solubility in various solvents. Furthermore, this invention relates to polymerizable compositions comprising these compounds, holographic recording media using their polymers, optical materials, and optical components. Background Technology

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

[0003] In recent years, highly transparent plastics have attracted attention as an optical material to replace glass.

[0004] Compared to glass, plastic materials offer advantages such as ease of weight reduction, ease of improving mechanical strength, and ease of processing and molding. With the development of related technologies, the requirements for improving the performance of plastic optical materials are also increasing. For example, resin raw materials used in optical lenses require easy polymerization (polymerizability); good curability and solubility in various solvents; and a high refractive index.

[0005] Furthermore, in recent years, the use of multiple resin raw materials to manufacture resin materials has become increasingly common in order to meet various physical properties. For example, when combining polyurethane resin raw materials, epoxy resin raw materials, acrylic resin raw materials, methacrylic resin raw materials, and other resin raw materials with very different molecular structures and chemical properties into a composite material, excellent solubility and compatibility with other resin raw materials are important for the composite material to outperform the performance of individual resins.

[0006] To date, many resins have been developed to increase the refractive index.

[0007] Introducing an aromatic ring is effective in increasing the refractive index. For example, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene is frequently used as a polyfunctional high-refractive-index acrylate. However, the refractive index of this compound is around 1.62, which is not high enough (Patent Document 1).

[0008] Patent Documents 2 and 3 describe the use of high-refractive-index aromatic acrylate compounds with a large number of aromatic ring substitutions to obtain holographic recording media with high diffraction efficiency and light transmittance. However, it is known that there is usually a trade-off between the high molecular weight achieved by introducing aromatic substituents and solubility in various media and resin raw materials; if the number of aromatic substituents is increased, the solubility decreases significantly. Even the polymerizable compounds of the embodiments in Patent Documents 2 and 3, which exhibit practical holographic recording performance, do not have sufficient solubility in resin raw materials. Furthermore, there are concerns about the poor heat resistance of monofunctional compounds with a single polymerizable group compared to polyfunctional compounds that form cross-linked structures during polymerization.

[0009] Patent document 4 describes an increase in solubility by introducing alkylene linkers into phenols with a large number of aromatic ring substitutions. However, there is a concern about the trade-off between the increased molecular weight achieved by introducing aromatic rings and the decreased solubility, so this example is limited to disubstituted phenols.

[0010] Patent Document 5 describes fused aromatic substituted bisphenols with a fluorene skeleton as polyfunctional compounds as high-refractive-index resin raw materials. However, the aromatic ring substituents and the number of aromatic ring substituents in the embodiments are limited to monocyclic phenyl groups, and are monosubstituted relative to a single phenoxy skeleton.

[0011] Similarly, in Patent Document 6 concerning holographic acrylate monomers having polyaromatic substituted phenols and anilines, the total number of carbon atoms of the aromatic ring substituents exhibiting high refractive index is also limited to a total of 24 or less.

[0012] Besides introducing aromatic rings, introducing sulfur atoms into the molecule is also effective in increasing the refractive index of the compound. For example, Patent Document 7 describes an acrylate compound with a glycerol skeleton having two benzothiazole rings within one molecule, and its refractive index is 1.63.

[0013] Patent document 8 describes a diacrylate monomer with a pentaerythritol skeleton having 1 to 2 naphthalene thio groups in one molecule. However, the refractive index of this compound is also 1.62 to 1.65.

[0014] They cannot be said to be materials with a sufficient refractive index for applications requiring ultra-high refractive indices exceeding 1.65.

[0015] Patent documents 9 and 10 describe monomers with a refractive index exceeding 1.65 and containing a dibenzothiophene thio group. Patent documents 11 and 12 describe ultra-high refractive index acrylate compounds with a dibenzocarbazole group and a refractive index exceeding 1.7. However, these compounds contain alkylthio groups and alkylcarbazole groups that are easily oxidized by oxygen. Therefore, there are concerns about discoloration and hue changes due to heating in air, long-term storage, and light exposure, and they cannot be considered materials with high chemical stability.

[0016] Existing technical documents

[0017] Patent documents

[0018] Patent Document 1: Japanese Patent Application Publication No. 6-220131

[0019] Patent Document 2: International Publication No. 2009 / 151061

[0020] Patent Document 3: Japanese Patent No. 5664707

[0021] Patent Document 4: Japanese Patent No. 6089867

[0022] Patent Document 5: Japanese Patent Application Publication No. 2009-256342

[0023] Patent Document 6: European Patent Application Publication No. 2354845

[0024] Patent Document 7: Japanese Patent Application Publication No. 2005-133071

[0025] Patent Document 8: Japanese Patent Publication No. 2008-527413

[0026] Patent Document 9: Japanese Patent No. 6458645

[0027] Patent Document 10: International Publication No. 2021 / 100654

[0028] Patent Document 11: International Publication No. 2021 / 006011

[0029] Patent Document 12: International Publication No. 2021 / 006012 Summary of the Invention

[0030] The problem that the invention aims to solve

[0031] The technical problem of the present invention is to provide a multifunctional compound that combines the advantages of high refractive index, high transparency, easy polymerization, chemical stability, and high solubility or compatibility in various solvents and resin raw materials, which are useful as optical materials or optical components.

[0032] Solution for solving the problem

[0033] The inventors have discovered that by intentionally introducing a total of four or more fused aromatic ring substituents onto the two phenoxy rings of a multifunctional compound in a manner accompanying molecular weight increase, a high refractive index structure can be obtained. By bonding polymerizable groups to this high refractive index structure via linking groups, the trade-off between molecular weight increase achieved through the introduction of a large number of fused aromatic ring substituents and reduced solubility in various media and resin raw materials can be overcome. Thus, a compound that solves the technical problem of this invention is obtained. Furthermore, while maintaining the high refractive index, high transparency, easy polymerization, and chemical stability of the polymerizable composition and polymer, improved solubility in solvents and resin raw materials is achieved. Specifically, it has been found that by using the following compound (1), a high-performance holographic recording medium with high diffraction efficiency can be obtained.

[0034] That is, the main point of this invention is as follows.

[0035] [1] A compound represented by the following formula (1).

[0036] [Chemical Formula 1]

[0037]

[0038] In formula (1), A 1 and A 2 Each of them independently represents a polymeric group.

[0039] n1 and n2 each independently represent integers from 1 to 3. When n1 and n2 are 2 or 3, multiple A's... 1 A 2 They can be either the same or different.

[0040] L 1 L represents a (n1+1) valence linker group that is either single-bonded or optionally branched. 2 This indicates a (n²+1) valence linker group that is either single-bonded or optionally branched.

[0041] X represents a single bond, a divalent organic group with 1 to 20 carbon atoms, a sulfonyl group, or a divalent oxygen or sulfur atom. When n1 and n2 are 2 or 3, multiple A atoms... 1 A 2 They can be either the same or different.

[0042] R 1 and R 2 Each independently represents a fused aromatic ring group optionally having substituents.

[0043] m1 and m2 are each independent integers from 2 to 4, and multiple R 1 and R 2They can be optionally the same or different. It should be noted that R in the formula... 1 and R 2 The two benzene rings are each independent except for R. 1 and R 2 In addition, it may optionally have substituents.

[0044] [2] According to the compound described in [1], wherein m1 and m2 are 2.

[0045] [3] According to the compound described in [1] or [2], wherein X is a single bond or a divalent group selected from the group consisting of structures shown in the following formulas (1a) to (1h).

[0046] [Chemical Formula 2]

[0047]

[0048] In equation (1a), R 3 and R 4 Each can independently represent an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0049] [4] The compound according to any one of [1] to [3], wherein the R 1 and R 2 Each is independently a phenanthrene group optionally having a substituent, or a fused aromatic heterocyclic group optionally having a substituent.

[0050] [5] A polymerizable composition comprising a compound according to any one of [1] to [4] and a polymerization initiator.

[0051] [6] A holographic recording medium comprising the polymeric composition according to [5].

[0052] [7] A polymer formed by polymerizing the polymeric composition according to [5].

[0053] [8] An optical material comprising the polymer according to [7].

[0054] [9] An optical component comprising the polymer according to [7].

[0055]

[10] A mass storage device comprising a holographic recording medium according to [6].

[0056]

[11] An optical element obtained by holographic recording in a holographic recording medium according to [6].

[0057]

[12] An AR light guide plate (waveguide plate) comprising the optical elements according to

[11] .

[0058]

[13] An AR glasses comprising the optical element according to

[11] .

[0059] Invention Effects

[0060] According to the present invention, a multifunctional compound is provided, which combines the advantages of high refractive index, high transparency, easy polymerization, chemical stability, and high solubility or compatibility in various solvents and resin raw materials, which are useful as optical materials or optical components.

[0061] The compounds of this invention are particularly useful as reactive compounds for hard coatings of optical lenses or optical components, and for holographic recording media. By using the compounds of this invention, optical materials and optical components with high diffraction efficiency, high light transmittance, high chemical stability, and excellent processability can be achieved. Attached Figure Description

[0062] Figure 1 This is a schematic diagram showing the outline of the structure of a device for holographic recording. Detailed Implementation

[0063] The embodiments of the present invention will now be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within its scope.

[0064] In this invention, "(meth)acrylate" refers to the collective term for acrylates and methacrylates. "(meth)acryloyl" refers to the collective term for acryloyl and methacryloyl groups. The same applies to "(meth)acryloyloxy" and "(meth)acrylic(acrylo)".

[0065] In this invention, "aromatic ring" refers to the collective term for "aromatic hydrocarbon ring" and "aromatic heterocyclic ring". Similarly, "aromatic cyclic group" refers to the collective term for "aromatic hydrocarbon group" and "aromatic heterocyclic group".

[0066] In this invention, "optionally having substituents" means optionally having one or more substituents.

[0067] 1. Regarding the compounds of the present invention

[0068] The compounds of the present invention are represented by the following formula (1). Hereinafter, the compounds represented by the following formula (1) will sometimes be referred to as "compound (1)".

[0069] [Chemical Formula 3]

[0070]

[0071] In formula (1), A 1 and A 2 Each of them independently represents a polymeric group.

[0072] n1 and n2 each independently represent integers from 1 to 3. When n1 and n2 are 2 or 3, multiple A's... 1 A 2 They can be either the same or different.

[0073] L 1 L represents a (n1+1) valence linker group that is either single-bonded or optionally branched. 2 This indicates a (n²+1) valence linker group that is either single-bonded or optionally branched.

[0074] X represents a single bond, a divalent organic group with 1 to 20 carbon atoms, a sulfonyl group, or a divalent oxygen or sulfur atom. When n1 and n2 are 2 or 3, multiple A atoms... 1 A 2 They can be either the same or different.

[0075] R 1 and R 2 Each independently represents a fused aromatic ring group optionally having substituents.

[0076] m1 and m2 are each independent integers from 2 to 4, and multiple R 1 and R 2 They may be the same or different, optionally. The formula has R. 1 and R 2 The two benzene rings are each independent except for R. 1 and R 2 In addition, it may optionally have substituents.

[0077] 1-1. Regarding the structure of compound (1)

[0078] Compound (1) is characterized by having the following structure: in polymerizable group A 1 A 2 Via oxygen atom and linking group L 1 L 2 In a skeleton formed by the dimerization of a substituted benzene ring (hereinafter sometimes referred to as a "phenoxy ring" or "phenoxy skeleton"), one phenoxy skeleton directly substitutes for two or more fused aromatic ring groups (fused aromatic ring substituents), and a total of four or more fused aromatic ring groups (fused aromatic ring substituents) are directly substituted.

[0079] In optical materials, organic compounds with aromatic ring groups are sometimes used to increase the refractive index. However, organic compounds with highly planar aromatic ring groups generally have insufficient solubility in various solvents and resin raw materials, making it difficult to use them in the form of high-concentration solutions that achieve high refractive indices.

[0080] Furthermore, even if high-concentration solutions can be prepared, the high crystallinity of these organic compounds leads to their tendency to precipitate out of the storage solution over time. In particular, aromatic organic compounds used in optical materials with refractive indices exceeding 1.65, which have multiple aromatic rings as substituents, tend to exhibit decreasing solubility in various solvents as their molecular weight increases.

[0081] When high-refractive-index materials are mixed into polyurethane resin raw materials, epoxy resin raw materials, acrylic resin raw materials, methacrylic resin raw materials, etc., the refractive index and chemical properties of aromatic organic compounds and resin raw materials are very different. Therefore, their solubility and compatibility are low, which causes many problems in using them as composite materials that can be stored for a long time.

[0082] Compound (1) has multiple fused aromatic ring groups densely packed within two phenoxy skeletons, resulting in molecular torsion between the substituents and reducing the crystallinity of compound (1). In particular, the more fused aromatic ring substituents with high refractive indices are introduced, the higher the refractive index of compound (1) becomes, and the larger its molecular weight. This also tends to reduce the overall symmetry and planarity of the molecule, achieving high solubility in solvents and resin raw materials. Compound (1) with a large molecular weight, for example, in polymerizable groups A... 1 and A 2 In the case of (meth)acryloyl groups, the density of (meth)acryloyl groups in monomers and polymers is relatively reduced, making them very useful as optical materials with low shrinkage during curing.

[0083] Furthermore, by making the polymerizable group A 1 and A 2 via the linking group L 1 and L 2 By bonding to appropriate positions away from high-refractive-index sites with large steric hindrance, the flexibility of compound (1) can be significantly improved while achieving high reactivity as a polymerizable monomer. Therefore, it is possible to achieve high refractive index and improved chemical stability of the polymer.

[0084] 1-2. Regarding L in equation (1) 1 and L 2

[0085] L 1 This indicates a (n1+1) valence linker with a single bond or optional branching. L 2 This indicates a (n²+1) valence linker group that is either single-bonded or optionally branched. L1 and L 2 It may optionally have an oxygen atom, a sulfur atom, or a nitrogen atom with a substituent.

[0086] As a component of L 1 and L 2 From the viewpoint of ease of synthesis and ease of acquisition, the linking groups are preferably aliphatic hydrocarbon groups that optionally have substituents. The number of carbon atoms in the aliphatic hydrocarbon group (excluding the number of carbon atoms excluding substituents) is preferably 1 to 8. If the number of carbon atoms in the aliphatic hydrocarbon group is 8 or less, the refractive index of compound (1) is not easily reduced, the molecular weight is small, and therefore there is a tendency for the viscosity to decrease and the processability to improve. As a constituent L 1 and L 2 The aliphatic hydrocarbon group can be any type of cyclic aliphatic hydrocarbon group or chain aliphatic hydrocarbon group, or a combination of these structures. From the moderately polymerizable group A... 1 and A 2 Considering the steric hindrance of the surrounding environment, chain-like aliphatic hydrocarbon groups are preferred.

[0087] As a component of L 1 and L 2 Chain-like aliphatic hydrocarbon groups, when n1 and n2 are 1, can include alkyl groups with 1 to 8 carbon atoms. When n1 and n2 are 2 or 3, L 1 and L 2 Each can be a group composed of two or more alkyl groups having 1 to 8 carbon atoms.

[0088] Considering the high solubility of compound (1) in various media and resin raw materials, L 1 and L 2 Each linking group is preferably a nitrogen atom having an oxygen atom, a sulfur atom, or optionally a substituent. These linking groups optionally have substituents, and the number of carbon atoms (excluding substituents) is preferably 1 to 8. If the number of carbon atoms in the linking group is 8 or less, the refractive index of compound (1) is not easily reduced, the molecular weight is small, and therefore there is a tendency for reduced viscosity and improved processability. As a constituent of L... 1 and L 2 The linking groups can be any type of linking group, including cyclic and chain-like groups, or combinations of these structures. From the moderately polymerizable group A... 1 and A 2 Considering the steric hindrance of the surrounding area, chain-like connecting groups are preferred.

[0089] As a component of L 1 and L 2A chain linking group having an oxygen atom, a sulfur atom, or optionally a nitrogen atom with substituents, when n1 and n2 are 1, can be listed as: -CH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2(CO)-, -CH2CH2CH2(CO)-, -CH2CH2CH2CH2(CO)-, -CH2CH2CH2CH2CH2(C O)-, -CH2CH2OCH2CH2(CO)-, -CH2CH2NH(CO)-, -CH2CH2CH2NH(CO)-, -CH2CH2CH2CH2NH(CO)-, -CH2CH2 OCH2CH2NH(CO)-, -CH2CH2NH(CO)OCH2CH2-, -CH2CH2NH(CO)OCH2CH2CH2-, -CH2CH2OCH2CH2NH(CO)OCH2 CH2-, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2OCH2CH2-, -OCH2CH2OCH2CH2OCH2CH2-, -OCH2CH2SCH2CH2- , -OCH2CH2(CO)-, -OCH2CH2CH2(CO)-, -OCH2CH2CH2CH2(CO)-, -OCH2CH2CH2CH2CH2(CO)-, -OCH2CH2OC H2CH2(CO)-, -OCH2CH2NH(CO)-, -OCH2CH2CH2NH(CO)-, -OCH2CH2CH2CH2NH(CO)-, -OCH2CH2OCH2CH2NH (CO)-, -OCH2CH2NH(CO)OCH2CH2-, -OCH2CH2NH(CO)OCH2CH2CH2-, -OCH2CH2OCH2CH2NH(CO)OCH2CH2-, etc. L 1 and L 2 Two or more of these groups can also be combined.

[0090] L when n1 and n2 are 2 or 3 1 and L 2Examples include: -(CH2)2C(CH3)-, -(CH2)2C(CH3)(CO)-, -(CH2)2C(CH2CH3)(CO)-, -(CH2)3C(CO)-, -(CH2)2C(CH3)NH(CO)-, -(CH2)2C(CH3)NH(CO)OCH2CH2-, -(CH2)2C(CH3)NH(CO)OCH2CH2CH2-, -(OCH2)2C(CH3)-, -(OC Linking groups formed by replacing any hydrogen atom in the above chain-like linking groups with bonds bonded to polymerizable groups, such as H2)2C(CH3)(CO)-, -(OCH2)2C(CH2CH3)(CO)-, -(OCH2)3C(CO)-, -(OCH2)2C(CH3)NH(CO)-, -(OCH2)2C(CH3)NH(CO)OCH2CH2CH2-, and linking groups formed by replacing any hydrogen atom in the above chain-like linking groups with bonds bonded to polymerizable groups. In this case, it is also possible to bond to polymerizable groups through a branched structure.

[0091] From the perspective of high refractive index, L 1 and L 2 Preferably, it contains cyclic groups, constituting L 1 and L 2 The cyclic group contains either a monocyclic structure or a fused ring structure. 1 and L 2 The number of rings included is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. 1 and L 2 The rings included do not necessarily need to be aromatic, but aromatic hydrocarbon rings are preferred in order to keep their size in the overall molecule small and maintain a high refractive index. As constituent L 1 and L 2 Aromatic hydrocarbon rings can be categorized as follows: benzene ring, indene ring, naphthalene ring, azulene ring, fluorene ring, acenaphthene ring, anthracene ring, phenanthrene ring, pyrene ring, etc.

[0092] Linking group L 1 and L 2 Optionally has substituents. As L 1 and L 2Optional substituents include: halogen atoms (chlorine, bromine, iodine), hydroxyl, mercapto, alkyl with 1 to 8 carbon atoms, alkenyl with 2 to 8 carbon atoms, alkoxy with 1 to 8 carbon atoms, phenyl, mesitylene, tolyl, naphthyl, cyano, acetoxy, alkyl carbonyloxy with 2 to 9 carbon atoms, alkoxy carbonyl with 2 to 9 carbon atoms, aminosulfonyl, alkyl aminosulfonyl with 2 to 9 carbon atoms, alkyl carbonyl with 2 to 9 carbon atoms, phenethyl, hydroxyethyl, acetamyl, dialkylaminoethyl bonded with alkyl with 1 to 4 carbon atoms, trifluoromethyl, alkylthio with 1 to 8 carbon atoms, aromatic ring thio with 6 to 10 carbon atoms, nitro, etc.

[0093] 1-3. Regarding R in equation (1) 1 and R 2

[0094] R 1 and R 2 This indicates a fused aromatic ring group that optionally has substituents. The fused aromatic rings of fused aromatic ring groups are broadly classified into fused aromatic hydrocarbon rings and fused aromatic heterocycles.

[0095] Examples of fused aromatic hydrocarbon rings include: naphthalene ring, phenanthrene ring, perylene ring, tetraphenylene ring, pyrene ring, benzo[a]pyrene ring, etc. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, fluorene rings, anthracene rings, etc.

[0096] As a component of R 1 and R 2 From the viewpoint of ease of synthesis and availability, fused aromatic hydrocarbon rings are preferably naphthalene, phenanthrene, pyrene, or fluorene rings. From the viewpoint of fluorescence suppression of compound (1), R... 1 and R 2 The fused aromatic hydrocarbon ring is more preferably a naphthalene ring, a phenanthrene ring, or a fluorene ring, and even more preferably a phenanthrene ring.

[0097] As a component of R 1 and R 2 The fused aromatic heterocycle, from the viewpoint of having a tendency to increase the refractive index of compound (1), is preferably a fused sulfur-containing aromatic heterocycle. The fused sulfur-containing aromatic heterocycle has at least a sulfur atom as a heteroatom constituting the fused aromatic heterocycle. In addition to having a sulfur atom, it may also have an oxygen atom, or a nitrogen atom, or both oxygen and nitrogen atoms as heteroatoms. From the viewpoint of avoiding coloration and ensuring solubility, the number of heteroatoms constituting the fused sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.

[0098] Examples of fused sulfur-containing aromatic heterocycles include: benzothiophene rings, dibenzothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, naphthothiophene rings, dibenzothiam rings, etc., which contain one sulfur atom; thiathracene rings, etc., which contain two or more sulfur atoms; and fused aromatic heterocycles containing two or more heteroatoms, such as benzothiazole rings, naphthothiazole rings, phenothiazine rings, thiazolidinylazole rings, thiazolidinylazole rings, thiazolidinylazole rings, dioxazololidinylazole rings, thiazolidinylazole rings, thiazolidinylazole rings, dibenzothiophene rings, thiazolidinylazole rings, thiazolidinylazole rings, thiazolidinylazole rings, etc.

[0099] The number of rings constituting the fused sulfur-containing aromatic heterocycle is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5, considering the ease of obtaining raw materials and the ease of synthesis.

[0100] In particular, considering high refractive index and low colorability, the fused sulfur-containing aromatic heterocycles are preferably benzothiazole rings, dibenzothiophene rings, benzothiophene rings, benzonaphthothiophene rings, dinaphthothiophene rings, or thiathracene rings.

[0101] As a component of R 1 and R 2 From the viewpoint of ease of synthesis, the fused aromatic heterocycle can be a nitrogen-containing aromatic heterocycle. The fused nitrogen-containing aromatic heterocycle has at least a nitrogen atom as a heteroatom constituting the fused aromatic heterocycle. In addition to a nitrogen atom, it may also have an oxygen atom, or a sulfur atom, or both oxygen and sulfur atoms as heteroatoms. From the viewpoint of avoiding coloration, the number of heteroatoms constituting the fused nitrogen-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.

[0102] Examples of fused nitrogen-containing aromatic heterocycles include: indole rings, carbazole rings, benzo[a]carbazole rings, dibenzo[a]carbazole rings, quinoline rings, isoquinoline rings, benzo[a]oxazole rings, naphtho[a]oxazole rings, benzo[a]thiazole rings, naphtho[a]thiazole rings, phenoxazine rings, phenthiazine rings, thieno[a]oxazole rings, thiazole[a]oxazole rings, furano[a]thiazole rings, thieno[a]thiazole rings, and thiazole[a]thiazole rings, all containing one nitrogen atom. Fused aromatic heterocycles containing two or more nitrogen atoms, including benzimidazole ring, oxazobimidazole ring, oxazobpyridine ring, oxazobpyridazine ring, oxazobpyrazine ring, quinolineoxazole ring, dioxazobpyrazine ring, thiazomidazole ring, thienothiadiazole ring, thiazonothiadiazole ring, thiazonopyridine ring, thiazonopyridazine ring, thiazonopyridazine ring, thiazonopyrazine ring, and quinolinethiazazole ring.

[0103] The number of rings constituting the fused nitrogen-containing aromatic heterocycle 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 ease of synthesis.

[0104] In particular, considering high refractive index and low colorability, the fused nitrogen-containing aromatic heterocycles are preferably carbazole rings, benzo[a]carbazole rings, dibenzo[a]carbazole rings, quinoline rings, isoquinoline rings, benzo[a]oxazole rings, benzo[a]thiazole rings, benzimidazole rings, or thiadiazole rings, and more preferably carbazole rings, benzo[a]carbazole rings, dibenzo[a]carbazole rings, benzo[a]oxazole rings, benzo[a]thiazole rings, benzimidazole rings, or thiadiazole rings.

[0105] As a component of R 1 and R 2 The fused aromatic heterocycle can be a fused oxygen-containing aromatic heterocycle. By fused oxygen-containing aromatic heterocycles, there is a tendency for the heat resistance and weather resistance of polymers based on compound (1) to be improved. The fused oxygen-containing aromatic heterocycle has at least an oxygen atom as a heteroatom constituting the fused aromatic heterocycle. In addition to having an oxygen atom, it may also have a nitrogen atom, or a sulfur atom, or both nitrogen and sulfur atoms as heteroatoms. From the perspective of ensuring heat resistance, the number of oxygen atoms constituting the fused oxygen-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.

[0106] Examples of fused oxygen-containing aromatic heterocycles include: benzofuran ring, dibenzofuran ring, naphthofuran ring, benzonaphthofuran ring, dinaphthofuran ring, phenoxazine ring, oxazole ring, isoxazole ring, benzooxazole ring, benzoisooxazole ring, naphthooxazole ring, thienooxazole ring, thiazonooxazole ring, oxazoloimidazol ring, furanothiazolid ring, etc., which contain one oxygen atom; and dibenzodioxin ring, oxazolonooxazole ring, dioxazolopyrazine ring, etc., which contain two or more oxygen atoms.

[0107] The number of rings constituting the fused oxygen-containing aromatic heterocycle 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 ease of synthesis.

[0108] In particular, from the perspective of high refractive index and low colorability, the fused oxygen-containing aromatic heterocycle is preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a benzoxazole ring, a benzoisoxazole ring, or a naphthoxazole ring, and more preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, or a benzoxazole ring.

[0109] These constitute R 1 and R 2The fused aromatic ring optionally has substituents. Examples of optional substituents include: halogen atoms such as chlorine, bromine, and iodine; alkyl groups having 1 to 8 carbon atoms; alkenyl groups having 2 to 8 carbon atoms; alkynyl groups having 2 to 8 carbon atoms; alkoxy groups; cyanoyl groups; acetoxy groups; alkyl carbonyl groups having 2 to 9 carbon atoms; alkoxy carbonyl groups having 2 to 9 carbon atoms; aminosulfonyl groups; alkyl aminosulfonyl groups having 2 to 9 carbon atoms; alkyl carbonyl groups having 2 to 9 carbon atoms; phenethyl groups; hydroxyethyl groups; acetamyl groups; dialkylaminoethyl groups bonded with alkyl groups having 1 to 4 carbon atoms; trifluoromethyl groups; alkylthio groups having 1 to 8 carbon atoms; aromatic ring thio groups having 6 to 10 carbon atoms; and nitro groups. Preferred examples include: alkyl groups with 1 to 8 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkylthio groups with 1 to 8 carbon atoms, aromatic cyclothio groups with 6 to 10 carbon atoms, cyano groups, acetoxy groups, alkyl carboxyl groups with 2 to 8 carbon atoms, aminosulfonyl groups, alkyl aminosulfonyl groups with 2 to 9 carbon atoms, and nitro groups.

[0110] From the viewpoint of increasing the refractive index of compound (1), these components of R 1 and R 2 The fused aromatic ring preferably further has a group comprising the aromatic ring as a substituent. The aromatic ring contained in this substituent, in addition to constituting R... 1 and R 2 Besides the fused aromatic ring, benzene rings can also be listed. The aromatic rings contained in these substituents can be directly bonded at any position to the constituent R. 1 and R 2 The fused aromatic ring can also be bonded to the constituent R via an oxygen atom, a sulfur atom, or optionally a nitrogen atom with a substituent. 1 and R 2 The fused aromatic ring can also be bonded to the R-structure via any linking group. 1 and R 2 The fused aromatic ring. The substituent is more preferably directly bonded to the constituent R. 1 and R 2 fused aromatic rings.

[0111] By setting the aromatic ring contained in the substituent to a sulfur-containing aromatic heterocycle, there is a tendency for the refractive index of compound (1) to become higher. The definition of a sulfur-containing aromatic heterocycle is related to R. 1 The definition is the same as in the text. As a sulfur-containing aromatic heterocycle, a fused sulfur-containing aromatic heterocycle is more preferred, and particularly preferred are benzothiazole rings, dibenzothiphene rings, benzothiphene rings, benzonaphthothiphene rings, dinaphthothiphene rings, and thiathracene rings.

[0112] As R 1 and R 2The number of aromatic rings that serve as substituents is not particularly limited, but from the viewpoint of ease of synthesis and solubility, 1 to 4 is preferred, and 1 to 2 is even more preferred.

[0113] Considering both high refractive index and high solubility in various media and resin raw materials, R... 1 and R 2 The fused aromatic ring optionally having substituents is preferably a naphthalene ring, a fluorene ring, a thiathracene ring, a phenanthrene ring, a dibenzothiophene ring, and more preferably a phenanthrene ring.

[0114] Composition of R 1 and R 2 The fused aromatic ring may have two or more selected from the above-mentioned fused aromatic hydrocarbon rings, fused sulfur-containing aromatic heterocycles, fused nitrogen-containing aromatic heterocycles, and fused oxygen-containing aromatic heterocycles.

[0115] R 1 and R 2 As will be discussed later, there are multiple R's because m ranges from 2 to 4. 1 and R 2 They can be either the same or different.

[0116] 1-4. Regarding m1 and m2 in equation (1)

[0117] m1 and m2 each independently represent integers from 2 to 4. These m1 and m2 can be appropriately selected. For example, from the viewpoint of ease of synthesis of compound (1) and ease of obtaining raw materials, m1 and m2 are preferably 2 or 3, and more preferably 2.

[0118] On the other hand, considering the tendency to balance ultra-high refractive index and high solubility, m1 and m2 are preferably 3 or 4, and m1 and m2 are more preferably 4.

[0119] When m1 and m2 are both 2, for R in equation (1) 1 and R 2 There are no particular restrictions on the substitution position. From the viewpoint of ease of synthesis and ease of obtaining raw materials, it is preferable that X is meta-position relative to the phenoxy ring in formula (1), and preferably relative to (A). 1 ) n1 -L 1 -O-、(A 2 ) n2 -L 2 -O- replaces the adjacent position.

[0120] 1-5. Regarding X in equation (1)

[0121] X represents a single bond, a divalent organic group with 1 to 20 carbon atoms, a sulfonyl group, or a divalent oxygen or sulfur atom.

[0122] From the viewpoint of increasing the refractive index of compound (1), X is preferably a single bond, or a divalent oxygen atom or a sulfur atom. From the viewpoint of the chemical stability of the intermediate compound, it is more preferable that X is a single bond.

[0123] From the viewpoints of color suppression, ease of synthesis, and ease of obtaining raw materials of compound (1), X is more preferably a single bond or a divalent group selected from the group consisting of the structures shown in formulas (1a) to (1h) below, and particularly preferably R in formula (1a) below. 3 and R 4 It is a dimethylmethylene group of methyl, a phthalide group (formula (1e)), or a sulfonyl group (formula (1f)).

[0124] [Chemical Formula 4]

[0125]

[0126] In equation (1a), R 3 and R 4 Each can independently represent an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0127] 1-6. Regarding A in equation (1) 1 and A 2

[0128] A 1 and A 2 Each group is an independent polymerizable group. A polymerizable group is a group that possesses polymerizability through a polymerization initiator. Specifically, examples include: ethylene oxide, oxetane, glycidyl, oxetanemethyl, vinyl, allyl, and (meth)acryloyl. Among these, (meth)acryloyl is particularly preferred from the perspective of high reactivity.

[0129] 1-7. Regarding n1 and n2 in equation (1)

[0130] n1 and n2 each independently represent integers from 1 to 3. These n1 and n2 can be chosen appropriately. For example, from the viewpoint of the easy polymerization of compound (1), n1 and n2 can be set to 2 or 3.

[0131] From the perspective of achieving a high refractive index, compound (1) preferably has fewer polymerizable groups, and more preferably, the number of polymerizable groups is 1 relative to 1 phenoxy ring. From the viewpoint of achieving a high refractive index, n1 and n2 are preferably 1 or 2, and more preferably 1.

[0132] When n1 and n2 are 2 or 3, multiple polymerizable groups A 1 and A 2 They can be either the same or different.

[0133] 1-8. Regarding the phenoxy ring in formula (1), besides R 1 and R 2 Other substituents

[0134] The two phenoxy rings in formula (1) may optionally have, except for R 1 and R 2 Other substituents. Examples of substituents optionally present in the phenoxy ring 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 having 2 to 8 carbon atoms; cyanoyl groups; acetoxy groups having 2 to 9 carbon atoms; alkyl carbonyl groups having 2 to 9 carbon atoms; aminosulfonyl groups; alkyl aminosulfonyl groups having 2 to 9 carbon atoms; alkyl carbonyl groups having 2 to 9 carbon atoms; phenethyl groups; hydroxyethyl groups; acetamido groups; dialkylaminoethyl groups bonded with alkyl groups having 1 to 4 carbon atoms; trifluoromethyl groups; alkylthio groups having 1 to 8 carbon atoms; aromatic cyclic thio groups having 6 to 10 carbon atoms; and nitro groups.

[0135] From the viewpoint of ease of synthesis, the preferred phenoxy ring is one that excludes R. 1 and R 2 It does not have any substituents. On the other hand, from the viewpoint of improving refractive index and solubility, the phenoxy ring preferably has alkyl with 1 to 8 carbon atoms, alkoxy with 1 to 8 carbon atoms, alkylthio with 1 to 8 carbon atoms, aromatic ring thio with 6 to 10 carbon atoms, cyano, acetoxy, alkyl carboxyl with 2 to 8 carbon atoms, aminosulfonyl, alkyl aminosulfonyl with 2 to 9 carbon atoms, or nitro as substituents.

[0136] 1-9. Molecular weight

[0137] From the viewpoint of suppressing viscosity and maintaining good processability, the molecular weight of compound (1) is preferably 2500 or less, more preferably 2200 or less, and even more preferably 2000 or less. From the viewpoint of reducing shrinkage during polymerization, the molecular weight of compound (1) is preferably 600 or more, more preferably 700 or more, and even more preferably 800 or more.

[0138] 1-10. The Relationship Between Molecular Structure and Physical Properties

[0139] Compound (1) can appropriately introduce molecular torsion into monomers and polymers by bonding a total of four or more highly planar fused aromatic ring groups to two phenoxy rings, resulting in a dihedral angle of more than 1 degree at the connection sites between the phenoxy rings and the fused aromatic ring substituents. In particular, in R... 1 and R 2In the case of fused aromatic ring groups with substituents or ring structures at the ortho position of the phenoxy ring, such as 9-phenanthyl, 1-thiaanthrayl, 4-dibenzofuranyl, and 4-dibenzothiopheneyl, there is a tendency for the dihedral angle to become larger. Therefore, while suppressing the aggregation of high-refractive-index structures, high solubility in various media and resin raw materials can be achieved, enabling its use as a polymerizable monomer with ultra-high refractive index.

[0140] Moreover, the aforementioned molecular torsion has the effect of inhibiting the substituent R. 1 and R 2 The excessive conjugation elongation of the phenoxy ring suppresses the effect of increasing the absorption wavelength of compound (1). As a result, for example, it is possible to achieve colorless and transparent optical materials in the visible light region, and to improve the stability of the compound against heating, light irradiation, oxidation, etc.

[0141] Furthermore, in the development of high refractive index materials, increasing the electron density per unit volume in monomers and polymers, i.e., shortening the intermolecular distance, is crucial for improving the refractive index. In compound (1), it is believed that by introducing linkers of appropriate molecular length into the spatially large polyaromatic substitution high refractive index structure, the intermolecular distance is shortened compared to derivatives without linkers due to molecular interactions such as van der Waals forces and hydrogen bonds. Therefore, further high refractive index performance of the same high refractive index structure can be expected.

[0142] 1-11. Example Compounds

[0143] The following examples illustrate specific examples of compound (1). Compound (1) of the present invention is not limited thereto, provided that it does not depart from its spirit.

[0144] [Chemical Formula 5]

[0145]

[0146] [Chemical Formula 6]

[0147]

[0148] [Chemical Formula 7]

[0149]

[0150] [Chemical Formula 8]

[0151]

[0152] [Chemical Formula 9]

[0153]

[0154] [Chemical Formula 10]

[0155]

[0156] [Chemical Formula 11]

[0157]

[0158] [Chemical Formula 12]

[0159]

[0160] [Chemical Formula 13]

[0161]

[0162] [Chemical Formula 14]

[0163]

[0164] [Chemical Formula 15]

[0165]

[0166] [Chemical Formula 16]

[0167]

[0168] [Chemical Formula 17]

[0169]

[0170] [Chemical Formula 18]

[0171]

[0172] 1-12. Regarding the synthesis method

[0173] Compound (1) can be synthesized by combining various known methods. For example, it can be synthesized by reacting a compound represented by the following formula (2) (hereinafter, sometimes referred to as "compound (2)") with a compound having a group that can react with a hydroxyl group.

[0174] [Chemical Formula 19]

[0175]

[0176] [In the formula, X and R] 1 R 2 The meanings of m1 and m2 are the same as those in equation (1).

[0177] The following is an example of the synthesis of compound (1).

[0178] [Chemical Formula 20]

[0179]

[0180] [In the above reaction equation, X and R] 1 R 2 L 1 L 2 A 1 A 2 The meanings of m1, m2, n1, and n2 are the same as those in equation (1). 1 and Y 2 This indicates leaving groups such as halogen atoms, methanesulfonic acid groups, p-toluenesulfonic acid groups, trifluoromethanesulfonic acid groups, carboxyl groups, dimethylpyrazolyl groups, and 1-methylpropylene aminooxy groups. 1 L' 2 A' 1 A' 2 This indicates that each component becomes L through a chemical reaction. 1 L 2 A 1 A 2 The precursor structure. In the following reaction formulas, substances with the same symbol represent the same substance.

[0181] For example, compound (1) is a polymeric group A in formula (1). 1 and A 2 The compound (1A) is (meth)acryloyloxy. Compound (1A) can be prepared by reacting the hydroxyl group of compound (2) with a (meth)acrylic acid esterifying agent (hereinafter, sometimes referred to as (meth)acrylic acid esterifying agent (i) and (ii)) having polymerizable groups as shown in formulas (i) and (ii).

[0182] Examples of alkylating agents (i) and (ii) for (meth)acrylate esterification include, for example, 2-methanesulfonyl ethyl methacrylate, glycidyl methacrylate, 2,3-dibromopropyl acrylate, etc.

[0183] Examples of (meth)acrylate esterifying agents (i) and (ii) include isocyanates such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and carbonylating agents such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and 2-[O-(1'-methylpropyleneamino)carboxylamino]ethyl methacrylate.

[0184] Compound (1A) can also be produced by reacting a compound (hereinafter sometimes referred to as "compound (3)") as shown in formula (3) with the polymerizable groups of the (meth)acrylating reagents shown in formula (v) and (vi), wherein the compound shown in formula (3) is obtained by reacting compound (2) with compounds having linking groups shown in formula (iii) and (iv).

[0185] The reaction of the active hydrogen of the hydroxyl group in formula (2) with the reagents shown in (i) to (iv) above, and the reaction of compound (3) with the reagents shown in formulas (v) and (vi) can be carried out using known methods. For example, in the presence of a basic compound, compound (2) can be reacted with an isocyanate to give compound (1A).

[0186] The basic compound can be one or more of organic basic compounds (triethylamine, diisopropylethylamine, 1,1,3,3-tetramethylguanidine, diazabicycloundecene, diazabicyclononene, pyridine, imidazole, etc.), or one or more of inorganic basic compounds (sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, potassium tert-butoxide, etc.), or a combination of one or more organic basic compounds and one or more inorganic basic compounds.

[0187] In the reactions of compound (2) with the reagents shown in (i) to (iv) and in the reactions of compound (3) with the reagents shown in formulas (v) and (vi), organic solvents are preferably used. Examples of organic solvents include dichloromethane, tetrahydrofuran (THF), dimethoxyethane, toluene, and N,N-dimethylformamide (DMF). One organic solvent may be used, or two or more may be used in combination.

[0188] In the manufacture of compound (1A), it is preferable to purify the reactants (crude product) obtained in the synthesis reaction. Purification removes impurities and achieves low staining. Known methods can be used as purification methods. For example, purification can be performed by extraction, column chromatography, recrystallization, distillation, etc. These purification methods can be performed individually or in combination.

[0189] When compound (1A) is a solid at room temperature, recrystallization is preferred in order to facilitate the removal of coloring substances.

[0190] Examples of suitable recrystallization solvents include: aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and mesitylene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, tert-butyl methyl ether, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; nitrile solvents such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, 2-methoxyethanol, 2-butoxyethanol, and propylene glycol monomethyl ether; diols such as ethylene glycol and diethylene glycol; and water. These solvents can be used individually or in combination of two or more.

[0191] The compound (2) and intermediate compound (3), which are used as the raw material compound in the manufacture of the above compound (1A), can be manufactured by the following reaction.

[0192] [Chemical Formula 21]

[0193]

[0194] [In the above reaction equation, X and R] 1 R 2 m1 and m2 have the same meaning as defined in equation (1). 1 and L' 2 The meaning is the same as that in compounds (3) and formulas (iii) and (iv). 3 and Y 4 Represents a halogen atom or a leaving group such as a trifluoromethanesulfonic acid group. R 1 -M 1 and R 2 -M 2 This indicates that organolithium, organomagnesium, organozinc, organocerium, organosilicon, organoboron, and organotin reagents can react with Y. 3 Y 4 Organometallic reagents that form carbon-carbon bonds through reactions, or aromatic ring compounds that directly utilize carbon-hydrogen bonds to induce cross-coupling reactions.

[0195] For example, multiple aromatic cyclic R groups can be linked by the aromatic halide (hereinafter, sometimes referred to as "compound (4)") shown in formula (4) with the organic reagents shown in formula (vii) and (viii). 1 and R 2 Simultaneous or sequential connection allows for the synthesis of compound (2).

[0196] Compound (3) can be linked by a compound (hereinafter sometimes referred to as "compound (5)") as shown in formula (5) with an organic reagent as shown in formula (vii) and (viii) to form multiple aromatic cyclic R groups. 1 and R 2 Simultaneous or sequential linkage, thereby synthesizing the compound represented by formula (5) by reacting compound (4) with compounds having linking groups represented by formulas (iii) and (iv).

[0197] 2. Regarding the polymerizable composition of the present invention

[0198] The polymerizable composition of the present invention contains compound (1) and a polymerization initiator.

[0199] Through a polymerization initiator, the polymerizable group A of compound (1) 1 and A 2 A polymerization reaction occurs, yielding the polymer of the present invention.

[0200] 2-1. Polymerization initiator

[0201] There are no particular limitations on the type of polymerization initiator; it can be appropriately selected from known polymerization initiators based on the polymerization method. There are also no limitations on the polymerization method; polymerization can be carried out using known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and partial polymerization.

[0202] Examples of polymerization initiators included in the polymerizable compositions of the present invention include: free radical polymerization initiators, redox polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators. Furthermore, photocationic polymerization initiators that generate cations as active species through light irradiation may also be used.

[0203] The examples of polymerization initiators described later also include substances commonly referred to as polymerization catalysts.

[0204] 2-1-1. Free radical polymerization initiators

[0205] Photopolymerization initiators

[0206] The photopolymerization initiator that assists in the polymerization of the polymerizable composition of the present invention can be any known photoradical polymerization initiator. Examples include azo compounds, azido compounds, organic peroxides, organoborates, imidazolium derivatives, titanocene compounds, iodonium salts, organothiols, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanones, anthraquinones, ketals, phosphine oxides, sulfones, carbamic acid derivatives, sulfonamides, triarylethanols, and oxime esters. Among these, benzophenones, phosphine oxides, and oxime esters are preferred as photopolymerization initiators from the viewpoints of compatibility and ease of acquisition.

[0207] Specific examples of photopolymerization initiators include: benzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, tert-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligomer {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzoyladium dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholino)propanone, etc. Phosphoryl(2,4,6-trimethylbenzoyl)-butanone-1, diethylthioxanone, isopropylthioxanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one, methyl benzoylformate, 1-[4-(phenylthio)-2-(O-benzoyl oxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone, etc.

[0208] These photopolymerization initiators can be used alone, or in any combination and ratio of two or more.

[0209] The content of the photoinitiator in the polymerizable composition of the present invention is typically 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.05 parts by mass or more, when the total amount of all compounds capable of free radical polymerization in the polymerizable composition is set to 100 parts by mass. Its upper limit is typically 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 photoinitiator is too high, polymerization may proceed violently, resulting in increased birefringence of the cured product and deterioration of its color. If the content of the photoinitiator is too low, the polymerizable composition may not polymerize sufficiently.

[0210] <Thermal polymerization initiator>

[0211] As a thermal polymerization initiator to assist in the polymerization of the polymerizable composition of the present invention, any known thermal free radical polymerization initiator can be used. For example, organic peroxides and azo compounds can be listed. Among them, organic peroxides are preferred from the viewpoint that they are less likely to generate bubbles in the polymer obtained in the polymerization reaction.

[0212] Specific examples of organic peroxides include: ketone peroxides such as methyl ethyl ketone peroxide; ketal peroxides such as 1,1-di(tert-hexylperoxide)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxide)cyclohexane, and 1,1-di(tert-butylperoxide)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; and diisopropylphenyl peroxide. Dialkyl peroxides such as di-tert-butyl peroxide; dilauroyl peroxide, dibenzoyl peroxide, and other dialkyl peroxides; dicarbonates such as di(4-tert-butylcyclohexyl) peroxide and di(2-ethylhexyl) peroxide; and peroxide esters such as tert-butyl peroxide-2-ethylhexanoate, tert-hexyl peroxide isopropyl monocarbonate, tert-butyl peroxide, and 1,1,3,3-tetramethylbutyl 2-ethylhexanoate.

[0213] Specific examples of azo compounds include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 1,1'-azobis-1-cyclohexanecarboxylonitrile, dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanopentanoic acid, and 2,2'-azobis-(2-amidinylpropane)dihydrochloride.

[0214] These thermal polymerization initiators can be used alone, or in any combination and ratio of two or more.

[0215] The content of the thermal polymerization initiator in the polymerizable composition of the present invention is typically 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more, when the total amount of all compounds capable of free radical polymerization in the polymerizable composition is set to 100 parts by mass. Its upper limit is typically 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less. If there is too much thermal polymerization initiator, polymerization may proceed violently, which not only impairs the optical uniformity of the resulting polymer but also deteriorates its color. If there is too little thermal polymerization initiator, thermal polymerization may not proceed sufficiently.

[0216] When photopolymerization initiators and thermal polymerization initiators are used together, their mass ratio is typically "100:1" to "1:100" ("photopolymerization initiator: thermal polymerization initiator", the same applies hereinafter in this paragraph), preferably "10:1" to "1:10". If there is too little thermal polymerization initiator, polymerization may sometimes become incomplete; if there is too much thermal polymerization initiator, coloring may occur.

[0217] 2-1-2. Redox polymerization initiators

[0218] Redox polymerization initiators are free radical initiators that utilize redox reactions based on a combination of peroxides and reducing agents. They can generate free radicals even at low temperatures and are commonly used in emulsion polymerization and other processes.

[0219] Specific examples of redox polymerization initiators include: benzoyl peroxide as a peroxide and aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine as reducing agents; hydroperoxide as a peroxide and metal soaps as reducing agents; and hydroperoxide as a peroxide and thiourea as a reducing agent.

[0220] In water-soluble redox polymerization initiators, peroxides such as persulfate, hydrogen peroxide, and hydroperoxide are combined with water-soluble inorganic reducing agents (Fe... 2+ It can be used in combination with organic reducing agents (such as NaHSO3, etc.) or organic reducing agents (such as alcohols and polyamines).

[0221] The preferred range of the content of redox polymerization initiator in the polymerizable composition of the present invention is the same as that of thermal polymerization initiator.

[0222] 2-1-3. Anionic polymerization initiators

[0223] Examples of anionic polymerization initiators used in the polymerizable compositions of the present invention include: alkali metals, n-butyllithium, sodium amide, sodium naphthalene, Grignard reagents, lithium alkoxides, alkali metal benzophenone carbonyl radicals, etc. Any one of these can be used alone, or two or more can be used in any combination and ratio.

[0224] The amount of anionic polymerization initiator in the polymerizable composition of the present invention is typically 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more, relative to 100 parts by mass of all anionic polymerization-capable compounds in the polymerizable composition. Its upper limit is typically 5 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less. If the anionic polymerization initiator is less than 0.001 parts by mass, a sufficient reaction will not occur. If more than 5 parts by mass of anionic polymerization initiator is used, it is difficult to balance usable time and polymerization rate.

[0225] 2-1-4. Cationic polymerization initiators

[0226] Examples of cationic polymerization initiators used in the polymerizable compositions of the present invention include: Brønsted acids such as perchloric acid, sulfuric acid, and trichloroacetic acid; Lewis acids such as boron trifluoride, aluminum trichloride, aluminum tribromide, and tin tetrachloride; and iodine and trichlorotriphenylmethane. Any one of these can be used alone, or two or more can be used in any combination and ratio.

[0227] The amount of cationic polymerization initiator in the polymerizable composition of the present invention is typically 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more, relative to 100 parts by mass of all cationic polymerization-capable compounds in the polymerizable composition. Its upper limit is typically 5 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less. If the amount of cationic polymerization initiator is less than 0.001 parts by mass, a sufficient reaction will not occur. If more than 5 parts by mass of cationic polymerization initiator is used, it is difficult to balance usable time and polymerization rate.

[0228] 2-1-5. Photocationic polymerization initiators

[0229] The photocationic polymerization initiator in this invention refers to an initiator that generates cationic species through light. There are no particular limitations on the photocationic polymerization initiator; any compound that generates cationic species through light irradiation is acceptable. Onionium salts are commonly known. Examples of onionium salts include: diazonium salts of Lewis acids, iodonium salts of Lewis acids, and sulfonium salts of Lewis acids. Specifically, examples include: phenyldiazonium salt of boron tetrafluoride, diphenyliodonium salt of phosphorus hexafluoride, diphenyliodonium salt of antimony hexafluoride, tri-4-methylphenylsulfonium salt of arsenic hexafluoride, and tri-4-methylphenylsulfonium salt of antimony tetrafluoride. Aromatic sulfonium salts are preferred.

[0230] Specific examples of photocationic polymerization initiators include: S,S,S',S'-tetraphenyl-S,S'-(4,4'-thiodiphenyl)disulfonium bis(hexafluorophosphate), diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, and diphenyl-4-phenylthiophenylsulfonium hexafluoroantimonate. Commercially available photocationic polymerization initiators include: Dow Chemical's UVI-6992, SAN-APRO's CPI-100P, CPI-101A, and CPI-200K, and IGM Resins' Omnicat270.

[0231] These photocationic polymerization initiators can be used alone, or in any combination and ratio of two or more.

[0232] The amount of photocationic polymerization initiator in the polymerizable composition of the present invention is preferably 0.02 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of all compounds in the polymerizable composition capable of photocationic polymerization. If the amount of photocationic polymerization initiator is less than 0.02 parts by mass, a sufficient reaction will not occur. If more than 20 parts by mass of photocationic polymerization initiator are used, it is difficult to balance usable time and polymerization rate.

[0233] In the use of photocationic polymerization initiators, the aforementioned cationic polymerization initiators can be used concurrently. In this case, the cationic polymerization initiator is typically used in the range of 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, relative to 100 parts by mass of the cationic polymerizable compound in the polymerizable composition. If the amount of cationic polymerization initiator used is too small, the polymerization rate will slow down. If the amount of cationic polymerization initiator used is too large, the physical properties of the resulting polymer may decrease.

[0234] In the use of photocationic polymerization initiators, photocationic polymerization sensitizers can also be used concurrently. A photocationic polymerization sensitizer is a formulation used to efficiently transfer the energy of the irradiated light to the photocationic polymerization initiator when the irradiation wavelength of the light source used in photocationic polymerization does not well match the absorption wavelength of the photocationic polymerization initiator. Known photocationic polymerization sensitizers include phenolic compounds such as methoxyphenol (Japanese Patent Application Laid-Open No. 5-230189), thioxanthone compounds (Japanese Patent Application Laid-Open No. 2000-204284), and dialkoxyanthracene compounds (Japanese Patent Application Laid-Open No. 2000-119306).

[0235] The photocationic polymerization sensitizer, relative to 1 part by weight of the photocationic polymerization initiator, is typically used in the range of 0.2 to 5 parts by weight, preferably 0.5 to 1 part by weight. If the amount of photocationic polymerization sensitizer is too small, the sensitizing effect may be difficult to achieve. If the amount of photocationic polymerization sensitizer is too large, the physical properties of the polymer may decrease.

[0236] 2-2. On polymeric compounds

[0237] As a polymeric compound contained in the polymeric composition of the present invention, it may contain any one of the compounds (1) alone, or may contain two or more of the compounds (1) in any combination and ratio.

[0238] The polymeric compositions of the present invention may also contain other polymeric compounds besides compound (1).

[0239] The content of compound (1) in the polymeric composition of the present invention, in terms of the ratio of the total solid components of the polymeric composition of the present invention, is preferably 1% by mass or more and 99% by mass or less, and particularly preferably 5% by mass or more and 95% by mass or less. When the content of compound (1) is less than 1% by mass, the effect of using compound (1) cannot be fully realized. If the content of compound (1) exceeds 99% by mass, there is a tendency for reduced curability.

[0240] Examples of other polymerizable compounds besides compound (1) include cationic polymerizable monomers, anionic polymerizable monomers, and free radical polymerizable monomers. Any one of these polymerizable compounds can be used alone, or two or more can be used in any combination and ratio. Furthermore, polymerizable compounds having two or more polymerizable functional groups per molecule (sometimes called multifunctional monomers) can also be used. When using multifunctional monomers, a cross-linked structure is formed within the polymer, thus improving thermal stability, weather resistance, solvent resistance, etc.

[0241] When the polymeric composition of the present invention contains polymeric compounds other than compound (1), their content, as a ratio to the total solid components of the polymeric composition of the present invention, is preferably 0.1% by mass or more and 10% by mass or less, and particularly preferably 0.3% by mass or more and 5% by mass or less. When the content of other polymeric compounds is less than 0.1% by mass, the property-imparting effect brought about by their addition cannot be fully utilized. If the content of other polymeric compounds exceeds 5% by mass, there is a tendency to easily cause problems such as damage to optical properties and strength.

[0242] <Catonic polymerizable monomers>

[0243] Examples of cationic polymerizable monomers include: compounds with an ethylene oxide ring, styrene and its derivatives, vinyl naphthalene and its derivatives, vinyl ethers, N-vinyl compounds, and compounds with an oxobutane ring.

[0244] Preferably, a compound having at least an oxetane ring is used, and more preferably, a compound having both an oxetane ring and an ethylene oxide ring is used.

[0245] As compounds containing ethylene oxide rings, examples include prepolymers containing two or more ethylene oxide rings within one molecule.

[0246] Examples of such prepolymers include: alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyols, polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxides, and epoxidized polybutadienes.

[0247] Examples of styrene and its derivatives include: styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, divinylbenzene, etc.

[0248] Examples of vinylnaphthalene and its derivatives include: 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, etc.

[0249] Examples of vinyl ethers include: isobutyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether, etc.

[0250] Examples of N-vinyl compounds include: N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, N-vinylphenthiazide, etc.

[0251] Examples of compounds having an oxetane ring include various known oxetane compounds described in Japanese Patent Application Publication No. 2001-220526 and Japanese Patent Application Publication No. 2001-310937.

[0252] These cationic polymerizable monomers can be used alone or in any combination and ratio of two or more.

[0253] <Anionic polymerizable monomers>

[0254] Examples of anionic polymerizable monomers include hydrocarbon monomers and polar monomers.

[0255] Examples of hydrocarbon monomers include styrene, α-methylstyrene, butadiene, isoprene, vinylpyridine, vinylanthracene, and their derivatives.

[0256] Examples of polar monomers include: methacrylates (e.g., methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, etc.); acrylates (e.g., methyl acrylate, ethyl acrylate, etc.); vinyl ketones (e.g., methyl vinyl ketone, isopropyl vinyl ketone, cyclohexyl vinyl ketone, phenyl vinyl ketone, etc.); isopropenyl ketones (e.g., methyl isopropenyl ketone, phenyl isopropenyl ketone, etc.); and other polar monomers (e.g., acrylonitrile, acrylamide, nitrobenzene, methylene malonate, cyanoacrylate, dicyanoethylene, etc.).

[0257] These anionic polymerizable monomers can be used alone, or in any combination and ratio of two or more.

[0258] <Free radical polymerizable monomers>

[0259] Free radical polymerizable monomers are compounds that have one or more olefinic unsaturated double bonds in a single molecule. Examples include (meth)acrylates, (meth)acrylamides, vinyl esters, and styrene derivatives.

[0260] Examples of (meth)acrylates include: methyl methacrylate, ethyl methacrylate, (n- or iso)propyl methacrylate, (n-, iso, secondary, or tert-)butyl methacrylate, amyl methacrylate, adamantane methacrylate, ethyl chloromethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, benzyl methacrylate, methoxybenzyl methacrylate, benzyl chloromethacrylate, etc. hydroxybenzyl acrylate, hydroxyphenyl acrylate, dihydroxyphenyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, aminosulfonyl acrylate, 2-phenoxyethyl acrylate, 2-(hydroxyphenylcarbonyloxy)ethyl 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 diacrylates, bisphenol AEO-modified diacrylates, dibromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl acrylate, tricyclodecane dimethylolpropene di(meth)acrylate, bisphenoxyethanol fluorene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Here, "EO" refers to "ethylene oxide".

[0261] Examples of (meth)acrylamides include: (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-butyl (meth)acrylamide, N-benzyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-tolyl (meth)acrylamide, N-(hydroxyphenyl)(meth)acrylamide, N-(aminosulfonylphenyl)(meth)acrylamide, N-(phenylsulfonyl)(meth)acrylamide, N-(tolylsulfonyl)(meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc.

[0262] Examples of vinyl esters include: vinyl acetate, vinyl butyrate, vinyl benzoate, tert-butylvinyl benzoate, vinyl chlorobenzoate, 4-ethoxyvinyl benzoate, 4-ethylvinyl benzoate, 4-methylvinyl benzoate, 3-methylvinyl benzoate, 2-methylvinyl benzoate, 4-phenylvinyl benzoate, and vinyl tertvalerate.

[0263] Examples of styrene-based products include: styrene, p-acetylstyrene, p-benzoylstyrene, 2-butoxymethylstyrene, 4-butylstyrene, 4-sec-butylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, dichlorostyrene, 2,4-diisopropylstyrene, dimethylstyrene, p-ethoxystyrene, 2-ethylstyrene, 2-methoxystyrene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, p-methylstyrene, p-phenoxystyrene, p-phenylstyrene, divinylbenzene, etc.

[0264] These free radical polymerizable monomers can be used alone, or in any combination and ratio of two or more.

[0265] The anionic polymerizable monomers and free radical polymerizable monomers shown in the examples above can be of any kind, and more than two kinds can also be used together.

[0266] Considering the reason that it is not easy to hinder the reaction that forms the resin matrix, for example in high refractive index optical lenses and holographic recording media, free radical polymerizable monomers are preferred as other polymerizable compounds used in conjunction with compound (1).

[0267] 2-3 Other Added Ingredients

[0268] Other components may be incorporated into the polymeric composition of the present invention without impairing the effects of the present invention.

[0269] Other components include, for example, solvents, antioxidants, plasticizers, UV absorbers, sensitizers, chain transfer agents, defoamers, polymerization inhibitors, any fillers composed of organic or inorganic substances, dispersants, pigments, phosphors, and other wavelength conversion materials, as well as various additives.

[0270] The polymerizable compositions of the present invention may contain solvents to adjust viscosity.

[0271] Specific examples of solvents, based on the physical properties of the polymerizable composition, include: alcohols such as ethanol, propanol, isopropanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as hexane, pentane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; chain ethers such as dimethyl ether and diethyl ether; cyclic ethers such as dioxane and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and ethyl butyrate; and acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones such as cyclohexanone; methyl, ethyl, and butyl cellosolves; carbitols such as methyl carbitol, ethyl carbitol, and butyl carbitol; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; nitriles such as acetonitrile and benzonitrile; and organic solvents such as N-methylpyrrolidone.

[0272] These solvents can be used alone or in the form of mixed solvents. Additionally, water can also be used depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.).

[0273] When using a solvent (or dispersion medium), there is no particular limitation on its amount. It can be adjusted according to the polymerization method, processing method, and application to achieve a polymerizable composition of appropriate viscosity.

[0274] In this invention, in order to obtain a polymer with good heat resistance to yellowing and good weather resistance, it is preferable to add antioxidants and light stabilizers as additives to the polymeric composition.

[0275] Specific examples of antioxidants include: 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and other phenolic antioxidants; as well as triphenyl phosphite, triisodecyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, tetra(C12~C1) phenolic antioxidants; and tetra(C12~C1) phenolic antioxidants. Phosphorus-based antioxidants include (5-alkyl)-4,4'-isopropylidene diphenyl diphosphite, tri(nonylphenyl) phosphite, tri(tetrazyl) phosphite, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexane-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxophosphataoctacyclobenzene, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bisoctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and tri(2,4-di-tert-butylphenyl) phosphite. These can be used alone or in combination of two or more.

[0276] As antioxidants, it is preferable to use a combination of phenolic antioxidants and phosphorus antioxidants. A preferred combination of phenolic and phosphorus antioxidants includes: a combination of at least one selected from tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane and octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate as a phenolic antioxidant, and tris(2,4-di-tert-butylphenyl) phosphite as a phosphorus antioxidant.

[0277] From the viewpoint of ensuring good heat resistance and yellowing resistance of the obtained polymer, the content of antioxidant in the polymeric composition of the present invention is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the polymeric composition, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass.

[0278] Hindered amine light stabilizers (HALS) are preferred as light stabilizers. Specific examples of HALS include: 2,2,6,6-tetramethyl-4-piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, ADK STAB LA-68 (manufactured by ADEKA Co., Ltd.), and ADK STAB... LA-63P (manufactured by ADEKA Corporation), butane-1,2,3,4-tetracarboxylate tetra(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 1,2,3,4-butanetetracarboxylate tetra(2,2,6,6-tetramethyl-4-piperidinyl) ester, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 249, TINUVIN 292, TINUVIN 5100 (all manufactured by BASF), etc. These can be used alone or in combination of two or more.

[0279] From the viewpoint of ensuring that the obtained polymer has good heat resistance to yellowing and good weather resistance, the content of light stabilizer in the polymeric composition of the present invention is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the polymeric composition, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass.

[0280] Antioxidants and light stabilizers can be used alone or in combination of two or more.

[0281] 2-4 Method for manufacturing polymerizable compositions

[0282] The polymerizable composition of the present invention can be manufactured by mixing the components, or by premixing the components except for the polymerization initiator and adding the polymerization initiator just before the polymerization reaction begins.

[0283] 3. Polymerization method of the polymerizable composition of the present invention

[0284] The polymerization method of the polymerizable composition of the present invention is not particularly limited, and includes methods such as polymerization by irradiation with active energy rays and polymerization by heating.

[0285] 3-1. Polymerization Initiation Method (Active Energy Ray)

[0286] In the case of photoradical polymerization of the polymerizable composition of the present invention, the polymerization is carried out by irradiation with active energy rays.

[0287] The preferred active energy rays used are electron beams or light in the ultraviolet to infrared wavelength range. For example, if the active energy ray is ultraviolet, an ultra-high pressure mercury light source or a metal halide light source can be used. If it is visible light, a metal halide light source or a halogen light source can be used. If it is infrared, a halogen light source can be used. Additionally, lasers, LEDs, and other light sources can also be used.

[0288] The amount of irradiation by the active energy rays is appropriately set according to the type of light source, the film thickness, etc., preferably such that the total reaction rate of the polymerizable functional groups of compound (1) and other polymerizable compounds is 80% or more, more preferably 90% or more. The reaction rate is calculated by infrared absorption spectroscopy based on the change in the intensity of the absorption peaks of the polymerizable functional groups before and after the reaction.

[0289] After polymerization is induced by irradiation with active energy rays, further polymerization can be carried out by heat treatment or annealing as needed. The preferred heating temperature is in the range of 80–200°C, and the preferred heating time is in the range of 10–60 minutes.

[0290] 3-2. Polymerization Initiation Method (Heating)

[0291] When heat treatment is performed for the polymerization of the polymerizable composition of the present invention, 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 below 80°C, the heating time needs to be extended, which tends to be uneconomical. If the heating temperature is above 200°C, not only energy costs are incurred, but also heating and cooling times are consumed, which also tends to be uneconomical.

[0292] 4. Polymers

[0293] The polymers of the present invention, which are obtained by polymerizing the polymerizable compositions of the present invention, will be described below.

[0294] 4-1. Refractive Index

[0295] Typically, the overall density increases through polymerization, thus the refractive index of the polymer tends to be higher than that of the precursor compound (called the monomer). By using monomers with high refractive indices to ensure the polymerization reaction proceeds fully, the refractive index of the resulting polymer can be increased. Therefore, it is considered important to improve the refractive index of polymers through monomer molecular structure design.

[0296] Refractive index exhibits a large value when evaluated under short-wavelength illumination, but a sample showing a relatively large refractive index at short wavelengths also shows a relatively large refractive index at long wavelengths; the relationship is not reversed. Therefore, by evaluating and comparing the refractive index at a specific wavelength, the intrinsic refractive index of the material can be compared. In this invention, the value at an illumination wavelength of 587 nm is used as the benchmark.

[0297] The refractive index of compound (1) and the polymer of the present invention is preferably 1.60 or higher, more preferably 1.63 or higher, particularly preferably 1.65 or higher, and most preferably 1.67 or higher. The upper limit of the refractive index of compound (1) and the polymer of the present invention is not particularly limited, and is generally 2.0 or lower.

[0298] When compound (1) and the polymer of the present invention are used as recording layer materials in a holographic recording medium, the refractive index of compound (1) and the polymer of the present invention is typically 1.65 or higher and 1.78 or lower, preferably 1.77 or lower. If the refractive index is less than 1.65, the diffraction efficiency is low and the multiplicity is insufficient. If the refractive index is greater than 1.78, the difference between the refractive index and that of the matrix resin becomes too large, resulting in greater scattering and thus reduced transmittance, requiring more energy for recording and reproduction.

[0299] When compound (1) 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 becomes thicker, and sometimes the lightweight property, a characteristic of plastics, is compromised, which is undesirable. In the development of precision optical components such as lenses, it is also important to achieve optical properties suitable for the component by combining optical materials with multiple refractive indices. From this point of view, monomers and polymers with refractive indices greater than 1.65 can be considered particularly useful materials for optical components.

[0300] 4-2. Glass transition temperature

[0301] The glass transition temperature of the polymer of the present invention is preferably 90°C or higher, more preferably 100°C or higher, even more preferably 110°C or higher, particularly preferably 120°C or higher, and further preferably 250°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower. If the temperature is below this range, the optical properties may change from the design values ​​under the operating environment, potentially failing to meet the required heat resistance for practical use. If the temperature is above this range, the processability of the polymer decreases, potentially resulting in the inability to obtain molded articles with good appearance and high dimensional accuracy. Furthermore, there is a possibility that the polymer becomes brittle, its mechanical strength decreases, and the operability of the molded article deteriorates.

[0302] 5. Optical materials and optical components

[0303] The compounds, polymeric compositions, and polymers of the present invention possess properties such as high refractive index, easy processability, and high chemical stability, and therefore can be applied to various optical materials and optical components.

[0304] Examples of optical materials include: optical coatings, hard coatings, adhesives for optical components, resins for optical fibers, and acrylic resin modifiers.

[0305] Examples of optical components include: lenses, filters, diffraction gratings, prisms, light guides, glass covers for display devices, light sensors, optical switches, LEDs, light-emitting elements, optical waveguides, optical splitters, fiber optic adhesives, substrates for display elements, substrates for color filters, substrates for touch panels, polarizing plates, display backlights, light guide plates, anti-reflective films, viewing angle-enlarging films, optical recording, optical modeling, and photolithography.

[0306] In addition, it can also be used as a layer for them. For example, display protective films, etc.

[0307] Among these, especially considering the high refractive index characteristics of the compound (1) and polymer of the present invention, they are preferably used in plastic lenses. Examples of lenses include: imaging lenses for cameras (vehicle cameras, digital cameras, PC cameras, mobile phone cameras, surveillance cameras, etc.), eyeglass lenses, beam focusing lenses, and light diffusing lenses.

[0308] For lenses using the compound (1) and polymer of the present invention, physical or chemical treatments such as surface grinding, antistatic treatment, hard coating treatment, non-reflective coating treatment, and dyeing treatment may be performed as needed to improve anti-reflection, impart high hardness, improve wear resistance, improve chemical resistance, impart anti-fogging properties, or impart fashionability.

[0309] 6. Holographic recording medium

[0310] The polymerizable composition of the present invention is preferably used in the recording layer of a holographic recording medium. In this case, the polymerizable composition of the present invention is preferably a photoreactive composition that, in addition to containing the compound of the present invention, also contains a matrix resin, a photopolymerization initiator, a free radical scavenger, and other additives. Details regarding its use as a material for holographic recording media will be described below.

[0311] 6-1. About matrix resin

[0312] The polymeric composition of the present invention preferably comprises a matrix resin. In particular, the matrix resin constituting the recording layer of the holographic recording medium is an organic material that does not undergo significant chemical and physical changes due to light irradiation, and is mainly composed of polymers of organic compounds.

[0313] The matrix resin, together with the aforementioned polymerizable compound and the photopolymerization initiator described later, constitutes the polymerizable composition of the present invention. Therefore, excellent compatibility with the polymerizable compound, photopolymerization initiator, etc., is strongly required. If the matrix resin has low compatibility with the other components, an interface forms between the materials, causing light refraction or reflection at the interface, thus leading to light leakage to unwanted areas. Consequently, interference fringes are distorted or cut off and recorded in inappropriate locations, potentially causing information degradation. The compatibility of the matrix resin with the other components can be evaluated, for example, as described in Japanese Patent No. 3737306, based on the intensity of scattered light obtained by placing a detector in a direction different from the transmitted light for the sample.

[0314] As the matrix resin of the polymerizable composition of the present invention, a resin composed of a variety of materials soluble in a solvent in the polymerizable composition, which is formed by three-dimensional cross-linking of them after being formed into a usable state, can be used. Examples include thermoplastic resins, thermosetting resins, and photocurable resins described below.

[0315] The three-dimensionally cross-linked resin is solvent-insoluble and is a cured product resulting from the reaction of a polymeric compound, which is liquid at room temperature, with a compound reactive to the polymeric compound. The three-dimensionally cross-linked resin acts as a physical barrier, thus suppressing volume changes during recording. That is, in the recorded layer after recording, there is a tendency for bright areas to expand and dark areas to shrink, creating an uneven surface on the holographic recording medium. To suppress this volume change, it is more preferable to use a polymeric composition comprising a three-dimensionally cross-linked resin matrix in the recording layer.

[0316] From the viewpoint of good adhesion to the support, a thermosetting resin is preferred as the matrix resin. Hereinafter, resin materials that can be used as matrix resins will be described in detail.

[0317] 6-1-1. Thermoplastic resin

[0318] Examples of specific thermoplastic resins include: chlorinated polyethylene, polymethyl methacrylate (PMMA), copolymers of methyl methacrylate and other alkyl acrylates, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate resin (PVAC), polyvinyl alcohol, polyvinyl formal, polyvinylpyrrolidone, ethyl cellulose, nitrocellulose and other cellulose resins, polystyrene resin, and polycarbonate resin. They can be used individually or in combination with two or more.

[0319] There are no particular restrictions on the solvents used to dissolve these thermoplastic resins, as long as they are dissolved. Examples of solvents include: ketones such as acetone and methyl ethyl ketone; esters such as butyl acetate and propylene glycol methyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ethers such as tetrahydrofuran and 1,2-dimethoxyethane; and amides such as N,N-dimethylacetamide and N-methylpyrrolidone. Only one solvent may be used, or two or more may be used in combination.

[0320] 6-1-2. Thermosetting resins

[0321] When using thermosetting resins as the base resin, the curing temperature varies depending on the type of crosslinking agent and catalyst.

[0322] Examples of combinations of functional groups that cure at room temperature include epoxy and amine, epoxy and thiol, and isocyanate and amine. Furthermore, examples of combinations using catalysts include epoxy and phenol, epoxy and acid anhydride, and isocyanate and polyol.

[0323] The former reacts immediately after mixing, making it simple, but in cases involving molding such as holographic recording media, there is no time buffer, making adjustment difficult. On the other hand, the latter allows for free selection of curing temperature and time by appropriately choosing the type and amount of catalyst, making it suitable for curing in cases involving molding such as holographic recording media. These resin raw materials, ranging from low to high molecular weight, are commercially available. Therefore, it is possible to maintain and select compatibility with polymerizable reactive compounds and photoinitiators, as well as adhesion to the substrate.

[0324] The following describes each raw material, but any one raw material can be used alone or in combination with two or more.

[0325] <Epoxy>

[0326] Examples of epoxy compounds include: polyglycidyl ether compounds of polyols such as polyethylene glycol, polypropylene glycol, tetramethylene glycol, trimethylolpropane, and glycerol; alicyclic epoxy compounds with cyclic aliphatic groups such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexylcarboxylate; bisphenol A type epoxy compounds; hydrogenated bisphenol A type epoxy compounds; bisphenol F type epoxy compounds; and phenol or cresol phenolic varnish type epoxy compounds.

[0327] The epoxy resin preferably has two or more epoxy groups per molecule, and there is no particular limitation on the type of epoxy groups. If the number of epoxy groups is small, the hardness required as a matrix may not be achieved. There is no particular upper limit to the number of epoxy groups per molecule, but it is usually 8 or less, and particularly preferably 4 or less. If the number of epoxy groups is too large, the consumption of epoxy groups may take a long time, and the formation of the matrix resin may be too time-consuming.

[0328] <amine>

[0329] As amines, amines containing primary or secondary amino groups can be used. Examples of such amines include: aliphatic polyamines such as ethylenediamine and diethylenetriamine or their derivatives; alicyclic polyamines such as isophorone diamine, menthane diamine, and N-aminoethylpiperazine or their derivatives; aromatic polyamines such as m-phenylenediamine and diaminodiphenylmethane or their derivatives; polyamides such as dicarboxylic acids and condensates of the above polyamines such as dimer acids; imidazole compounds such as 2-methylimidazole or their derivatives; and dicyandiamide, adipate dihydrazide, etc.

[0330] <Thiols>

[0331] Examples of thiols include: 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, 1,9-nonanedithiol, and other dithiols; polythiols such as THIOKOL (manufactured by TORAY FINE CHEMICALS) and jERCURE QX40 (manufactured by Mitsubishi Chemical Co., Ltd.). Among these, commercially available, fast-curing polythiols such as jERCURE QX40 are preferred.

[0332] Phenol

[0333] Examples of phenols include bisphenol A, phenolic resins in the form of phenolic varnishes, and methyl phenolic resins.

[0334] <acid anhydride>

[0335] Examples of acid anhydrides include: phthalic anhydride, tetrahydrophthalic anhydride or its derivatives, which are monofunctional acid anhydrides; and pyromellitic dianhydride, benzophenone tetracarboxylic anhydride or its derivatives, which are difunctional acid anhydrides.

[0336] <Dosage of amines, thiols, phenols, and acid anhydrides>

[0337] The amount of amines, thiols, phenols, and acid anhydrides used, in proportion to the molar number of epoxy groups, is preferably 0.1 equivalents or more, especially 0.7 equivalents or more, usually 2.0 equivalents or less, especially 1.5 equivalents or less. Using too little or too much of amines, thiols, phenols, or acid anhydrides can sometimes result in a large number of unreacted functional groups, impairing storage stability.

[0338] Polymerization initiators for thermosetting resins

[0339] As catalysts for curing thermosetting resins, anionic polymerization initiators and cationic polymerization initiators can be used depending on the curing temperature and curing time.

[0340] Anionic polymerization initiators are substances that generate anions through irradiation with heat or active energy rays. Examples include amines. Examples of amines include: dimethylbenzylamine, dimethylaminomethylphenol, 1,8-diazabicyclo[5.4.0]undecene-7, and other amino-containing compounds, as well as their derivatives; imidazole compounds such as imidazole, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, and their derivatives. One or more of these can be used depending on the curing temperature and curing time.

[0341] Cationic polymerization initiators are substances that generate cations through irradiation with heat or active energy rays. Examples include aromatic onium salts. Specific examples include compounds formed from anionic components such as SbF6-, BF4-, AsF6-, PF6-, CF3SO3-, and B(C6F5)4-, and aromatic cationic components containing atoms such as iodine, sulfur, nitrogen, and phosphorus. Diaryliodoium salts and triarylsulfonium salts are preferred. One or more of these can be used depending on the curing temperature and time.

[0342] The amount of polymerization initiator used in these thermosetting resins relative to the matrix resin is preferably typically 0.001% by mass or more, particularly 0.01% by mass or more, typically 50% by mass or less, particularly 10% by mass or less. If the amount of polymerization initiator used in these thermosetting resins is too small, the concentration of the polymerization initiator is too low, and therefore the polymerization reaction sometimes takes too long. If the amount of polymerization initiator used in these thermosetting resins is too large, sometimes the continuous ring-opening reaction that is the polymerization reaction cannot be generated.

[0343] Isocyanates

[0344] As isocyanates, isocyanates having two or more isocyanate groups per molecule are preferred, and there is no particular limitation on the type. If the number of isocyanate groups per molecule is small, the hardness required as a matrix resin may sometimes not be obtained. There is no particular upper limit to the number of isocyanate groups per molecule, but it is preferably usually 8 or less, especially 4 or less. If the number of isocyanate groups per molecule is too large, the consumption of isocyanate groups may sometimes take a long time, and the formation of the matrix resin may be too time-consuming. There is no particular upper limit to the number of isocyanate groups per molecule, but it is usually around 20 or less.

[0345] Examples of isocyanates include: aliphatic isocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and 4,4'-methylene bis(cyclohexyl isocyanate); aromatic isocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenyl dimethyl diisocyanate, and naphthalene-1,5'-diisocyanate; and their polymers. Among these, 3- to 7-polymers are preferred.

[0346] In addition to the above, other isocyanates include: reactants of water, trimethylolethane, trimethylolpropane and other polyols with the above isocyanates; polymers of hexamethylene diisocyanate or its derivatives.

[0347] The molecular weight of the isocyanate, in terms of number average molecular weight, is preferably 100 or more and 50,000 or less, more preferably 150 or more and 10,000 or less, and even more preferably 150 or more and 5,000 or less. If the number average molecular weight is too low, the crosslinking density increases, which may result in excessively high hardness of the matrix resin and a decrease in recording speed. If the number average molecular weight is too high, the compatibility with other components decreases or the crosslinking density decreases, which may result in excessively low hardness of the matrix resin and loss of recorded content.

[0348] <Polyols>

[0349] Examples of polyols include: polypropylene polyol, polycaprolactone polyol, polyester polyol, and polycarbonate polyol.

[0350] (Polypropylene polyol)

[0351] Polypropylene polyols are obtained by reacting propylene oxide with diols or polyols. Examples of diols or polyols include: ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decanediol, polyethylene glycol, and polytetramethylene glycol. Commercially available polypropylene polyols include SANNIX GP-400 and GP-1000 (both manufactured by Sanyo Chemical Co., Ltd., trade names), and ADEKA POLYETHER G400, G700, and G1500 (all manufactured by ADEKA Corporation, trade names), etc.

[0352] (Polycaprolactone polyol)

[0353] Polycaprolactone polyols are obtained by reacting a lactone with a diol or polyol. Examples of lactones include α-caprolactone, β-caprolactone, γ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, and β-methyl-ε-caprolactone.

[0354] Examples of diols or polyols include: ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decanediol, polyethylene glycol, polytetramethylenediol, etc.

[0355] Commercially available products of polycaprolactone polyols obtained from the reaction of ε-caprolactone include PLACCEL 205, PLACCEL 205H, PLACCEL 205U, PLACCEL 205UT, PLACCEL 210, PLACCEL 210N, PLACCEL210CP, PLACCEL 220, PLACCEL 230, PLACCEL 230N, PLACCEL 240, PLACCEL 220EB, PLACCEL220EC, PLACCEL 303, PLACCEL 305, PLACCEL 308, PLACCEL 309, PLACCEL 312, PLACCEL320, PLACCEL 401, PLACCEL L205AL, PLACCEL L212AL, PLACCEL L220AL, PLACCEL L320AL, PLACCEL T2103, PLACCEL T2205, and PLACCEL... P3403, PLACEL 410 (both manufactured by Daicel Co., Ltd., trade names), etc.

[0356] (Polyester polyols)

[0357] Polyester polyols include those obtained by polycondensation of dicarboxylic acids or their anhydrides with polyols.

[0358] Examples of dicarboxylic acids include: succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, maleic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, etc.

[0359] Examples of polyols include: ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decanediol, polyethylene glycol, and polytetramethylenediol.

[0360] Examples of polyester polyols include polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate. Commercially available polyester polyols include the ADEKA NEWACE F series, ADEKA NEWACE Y series, ADEKA NEWACE NS series (manufactured by ADEKA Corporation, trade name), and KURARAY POLYOL N-2010, P-4011, and P-1020 (all manufactured by KURARAY Corporation, trade name).

[0361] (Polycarbonate polyols)

[0362] Examples of polycarbonate polyols include: polycarbonate polyols obtained by the de-alcoholization condensation reaction of diols with dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate, etc.); polycarbonate polyols obtained by the dephenolization condensation reaction of diols with diphenyl carbonates; and polycarbonate polyols obtained by the de-diolization condensation reaction of diols with carbonates (e.g., ethylene carbonate, diethyl carbonate, etc.).

[0363] Examples of diols include: 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, neopentanediol, and other aliphatic diols, or 1,4-cyclohexanediol, 1,4-cyclohexanediol, and other alicyclic diols.

[0364] Examples of polycarbonate polyols include poly(hexamethylene carbonate) polyol obtained by the condensation reaction of 1,6-hexanediol and diethyl carbonate, poly(pentylene carbonate) obtained by the condensation reaction of pentanediol and diethyl carbonate, and poly(butylene carbonate) obtained by the condensation reaction of 1,4-butanediol and diethyl carbonate.

[0365] Commercially available polycarbonate polyols include PLACEL CD CD205, PLACEL CD CD210, PLACEL CD CD220 (all manufactured by Daicel Co., Ltd., trade names), DURANOL T5651, DURANOL T5652, and DURANOL T5650J (all manufactured by Asahi Kasei Corporation, trade names), etc.

[0366] (Molecular weight of polyols)

[0367] The molecular weight of the polyols described above, in terms of number average molecular weight, is preferably 100 or more and 50,000 or less, more preferably 150 or more and 10,000 or less, and even more preferably 150 or more and 5,000 or less. If the number average molecular weight is too small, the crosslinking density increases, which may result in excessively high hardness of the matrix resin and a decrease in recording speed. If the number average molecular weight is too large, the compatibility with other components decreases or the crosslinking density decreases, which may result in excessively low hardness of the matrix resin and loss of recorded content.

[0368] <Other Ingredients>

[0369] In this embodiment, the matrix resin may contain other components in addition to the above-mentioned components, as long as it does not violate the spirit of the present invention.

[0370] Other such components include, for example, compounds containing hydroxyl groups such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, decanediol, trimethylolpropane, polyethylene glycol, and polytetramethylene glycol, used for the purpose of altering the physical properties of the matrix resin.

[0371] <Carbamate Polymerization Catalyst>

[0372] To facilitate the reaction between isocyanates and polyols, a suitable urethane polymerization catalyst may be included.

[0373] Examples of carbamate polymerization catalysts include: bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonic acid, bis(4-tert-butylphenyl)iodonium p-toluenesulfonic acid, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonic acid, (4-bromophenyl)diphenylsulfonium trifluoromethanesulfonate, (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyliodonium perfluoro-1-butanesulfonic acid, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium trifluoromethanesulfonic acid, bis(alkylphenyl)iodonium hexafluorophosphonic acid, and other ononium salts, as well as Lewisite such as zinc chloride, tin chloride, ferric chloride, aluminum chloride, and BF3. Catalysts with succinic acid as the main component, protic acids such as hydrochloric acid and phosphoric acid, amines such as trimethylamine, triethylamine, triethylenediamine, dimethylbenzylamine, and diazabicycloundecene, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-undecylimidazoleonium trimellitic acid, alkalis such as sodium hydroxide, potassium hydroxide, and potassium carbonate, tin catalysts such as dibutyltin laurate, dioctyltin laurate, and dibutyltin octanoate, bismuth catalysts such as tris(2-ethylhexanoate)bismuth and tribenzoyloxybismuth, zirconium catalysts such as tetra(ethyl acetoacetate), 1,1'-isopropylidene dichloride, and tetra(2,4-pentanedione)zirconium catalysts, etc.

[0374] In order to improve storage stability, bismuth catalysts and zirconium catalysts are preferred.

[0375] As a bismuth-based catalyst, there are no particular restrictions as long as it contains bismuth and is a compound that promotes the reaction of isocyanates and polyols.

[0376] Examples of bismuth-based catalysts include: bismuth tris(2-ethylhexanoate), bismuth tribenzoyloxybismuth, bismuth triacetate, bismuth tris(dimethyldithiocarbamate), bismuth hydroxide, triphenylbismuth(V)bis(trichloroacetate), tris(4-methylphenyl)oxobismuth(V), and triphenylbis(3-chlorobenzoyloxy)bismuth(V).

[0377] From the perspective of catalytic activity, trivalent bismuth compounds are preferred, and bismuth carboxylate and compounds of the general formula Bi(OCOR)3 (where R is a straight-chain or branched alkyl, cycloalkyl, or substituted or unsubstituted aromatic group) are more preferred. Any of the above bismuth-based catalysts can be used alone, or two or more can be used in any combination and ratio.

[0378] As a zirconium-based catalyst, there are no particular restrictions as long as it contains zirconium and is a compound that promotes the reaction of isocyanates and polyols.

[0379] Examples of such products include: cyclopentadienyl zirconium trichloride, decamethylzirconia dichloride, 1,1'-dibutylzirconia dichloride, 1,1'-isopropylidenezirconia dichloride, tetra(2,4-pentanedione)zirconia, tetra(trifluoro-2,4-pentanedione)zirconia, tetra(hexafluoro-2,4-pentanedione)zirconia, zirconium butoxide, zirconium tert-butoxide, zirconium propoxide, zirconium isopropoxide, zirconium ethoxide, bis(ethyl acetoacetate)dibutoxyzirconia, tetra(ethyl acetoacetate)zirconia, zirconium oxide, barium zirconium oxide, calcium zirconium oxide, zirconium bromide, zirconium chloride, zirconium fluoride, zirconium dichloride (indenyl)zirconia, zirconium carbonate, etc.

[0380] From the perspective of compatibility with other components, compounds having organic ligands are preferred, and alkoxides or compounds having an acetylacetonate (2,4-pentanedione) structure are more preferred.

[0381] The zirconium compounds mentioned above can be used alone, or in any combination and ratio of two or more.

[0382] Bismuth-based catalysts and zirconium-based catalysts can be used separately or in combination.

[0383] The amount of urethane polymerization catalyst used, in terms of the ratio to the matrix resin, is preferably 0.0001% by mass or more, particularly 0.001% by mass or more, and typically 10% by mass or less, particularly 5% by mass or less. If the amount of urethane polymerization catalyst used is too small, curing may sometimes take too long. On the other hand, if the amount used is too large, it may sometimes be difficult to control the curing reaction.

[0384] By using a urethane polymerization catalyst, it can be cured at room temperature or by increasing the temperature. The preferred temperature for this is between 40°C and 90°C.

[0385] 6-1-3. Light-curable resins

[0386] When using a photocurable resin as the base resin, a photoinitiator for the base resin corresponding to the wavelength used is required for curing. Since curing during light irradiation can create obstacles in molding and bonding, ideally, a stable curing reaction should occur near the primary operating temperature, i.e., room temperature. Considering this, catalytic curing using a photoinitiator for the base resin is an ideal choice.

[0387] Typically, light irradiation allows a photoinitiator to generate any type of active matrix, either cationic or anionic, from a matrix resin. Therefore, it is preferable to select and cure substances that are induced to cure by these active matrices to produce a matrix resin.

[0388] Examples of functional groups that react with cations such as protons include: epoxy groups and oxocyclic butyl groups. Specifically, examples of compounds containing epoxy groups include: polyglycidyl ether compounds of polyols such as polyethylene glycol, polypropylene glycol, tetramethylene glycol, trimethylolpropane, and glycerol; alicyclic epoxy compounds with cyclic aliphatic groups having 4 to 7 membered rings, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexylcarboxylate; bisphenol A type epoxy compounds; hydrogenated bisphenol A type epoxy compounds; bisphenol F type epoxy compounds; and phenol or cresol phenolic varnish type epoxy compounds. Examples of compounds containing oxetane groups include 2-ethyl-2-oxetane butyl ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetanebutyloxy)hexane. (It should be noted that the reference to "(poly)ethylene glycol" here refers to both "ethylene glycol" and its polymer "polyethylene glycol".)

[0389] Functional groups that react with anions include epoxy groups and cyclic sulfide groups. Specifically, compounds containing cyclic sulfide groups include phenyl cyclic sulfides and methyl ethers of bisphenol A dicyclic sulfide.

[0390] When photoinitiator for the matrix resin is used to light-cur the aforementioned matrix resin, the amount used, in terms of the ratio to the polymerizable compound, is preferably typically 0.01% by mass or more, particularly 0.1% by mass or more, typically 1% by mass or less, particularly 0.5% by mass or less. If the amount of photoinitiator for the matrix resin used is too small, curing may sometimes take too long. If the amount of photoinitiator for the matrix resin used is too large, the curing reaction may sometimes be difficult to control.

[0391] Especially when used as a holographic recording material, light is also irradiated during recording, so it is important that the wavelength during curing differs from the wavelength during recording. This wavelength difference is at least 10 nm, and preferably 30 nm. The selection of the photoinitiator for the matrix resin can be roughly predicted based on the absorption wavelength of the initiator.

[0392] 6-2. Photopolymerization initiator

[0393] The photopolymerization initiator that assists in the polymerization of the compounds of the present invention can be any known photoradical polymerization initiator. Examples include azo compounds, azido compounds, organic peroxides, organoborates, ononium salts, diimidazole derivatives, titanocene compounds, iodonium salts, organothiols, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanones, anthraquinones, ketals, phosphine oxides, sulfones, carbamic acid derivatives, sulfonamides, triarylethanols, and oxime esters. Among these, titanocene compounds, phosphine oxides, and oxime esters are preferred as photopolymerization initiators, considering that polymerization occurs under visible light.

[0394] 6-2-1. Titanium eccentricity compounds

[0395] When using titanium eccentricate compounds as photopolymerization initiators, there are no particular limitations on the types of compounds that can be used. For example, appropriate selections can be made from various titanium eccentricate compounds described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197.

[0396] Specific examples of titanium diacene compounds include: bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)bisphenyltitanium, bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(2,3,5,6-tetrafluorophenyl-1-yl)titanium, bis(2,4,6-trifluorophenyl-1-yl)titanium, and bis(2,6-difluorophenyl-1-yl)titanium. Titanium, bis(2,4-difluorophenyl-1-yl)titanium, bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(2,3,5,6-tetrafluorophenyl-1-yl)titanium, bis(2,6-difluorophenyl-1-yl)titanium, bis(2,6-difluorophenyl-1-yl)titanium, bis(2,6-difluoro-3-(pyridin-1-yl)-phenyl-1-yl)titanium, etc.

[0397] 6-2-2. Acylphosphine oxide compounds

[0398] Specific examples of acylphosphine oxide compounds include monofunctional initiators with only one photo-based cleavage site per molecule and difunctional initiators with two photo-based cleavage sites per molecule.

[0399] Examples of monofunctional initiators include triphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide.

[0400] Examples of difunctional initiators include: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, and bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide.

[0401] 6-2-3. Oxime ester compounds

[0402] Specific examples of oxime ester compounds include: 1-[4-(phenylthio)-2-(O-benzoyl oxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone, 4-(acetoxyimino)-5-[9-ethyl-6-(2-methylbenzoyl)-9H- Methyl carbazol-3-yl]-5-oxovalerate, methyl 1-(9-ethyl-6-cyclohexanoyl-9H-carbazol-3-yl)-1-(O-acetyl oxime) glutarate, methyl 1-(9-ethyl-9H-carbazol-3-yl)-1-(O-acetyl oxime) glutarate, methyl 1-(9-ethyl-9H-carbazol-3-yl)-1-(O-acetyl oxime)-3-methyl-butyrate, etc.

[0403] 6-2-4. Dosage of photopolymerization initiator

[0404] The above-mentioned photopolymerization initiators can be used alone, or in any combination and ratio of two or more.

[0405] The content of the photopolymerization initiator in the polymerizable composition of the present invention, based on the molar amount per unit weight of the polymerizable composition, is preferably 0.5 μmol / g or more, more preferably 1 μmol / g or more, more preferably 100 μmol / g or less, and more preferably 50 μmol / g or less.

[0406] If the amount of photopolymerization initiator is too small, the amount of free radicals generated will be less, which may slow down the photopolymerization process and reduce the recording sensitivity in the holographic recording medium. If the amount of photopolymerization initiator is too large, the free radicals generated by light irradiation may recombine or disproportionate. Therefore, their contribution to photopolymerization will be reduced, and the recording sensitivity in the holographic recording medium may still decrease. When using two or more photopolymerization initiators, it is preferable to ensure that their combined amount meets the above-mentioned range.

[0407] 6-3. Free radical scavengers

[0408] In holographic recording, radical scavengers can be added to precisely fix the intensity pattern of the interference light as a polymer distribution in the holographic recording medium. The radical scavenger preferably has both functional groups that scavenge radicals and reactive groups that are covalently fixed to the matrix resin. Examples of functional groups that scavenge radicals include stable nitrocellulose radicals.

[0409] 6-3-1. Types of Free Radical Scavengers

[0410] Examples of reactive groups that are covalently fixed to the matrix resin include: hydroxyl, amino, isocyanate, and thiol groups. Examples of free radical scavengers include: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen radical (TEMPOL), 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxygen radical, 3-hydroxy-8-azabicyclo[3.2.1]octane N-oxygen radical, and 5-HO-AZADO:5-hydroxy-2-azatricyclo[3.3.1.1] 3,7 ] Decane N-oxygen free radical.

[0411] 6-3-2. Content of free radical scavengers

[0412] The aforementioned free radical scavengers can be used individually or in any combination and ratio of two or more.

[0413] The content of the free radical scavenger in the polymerizable composition of the present invention, based on the molar amount per unit weight of the polymerizable composition, is preferably 0.5 μmol / g or more, more preferably 1 μmol / g or more, more preferably 100 μmol / g or less, and more preferably 50 μmol / g or less.

[0414] If the content of the free radical scavenger is too low, the efficiency of free radical scavenging will be low, resulting in the diffusion of low-polymerization-degree polymers and a tendency for more components that do not contribute to the signal. If the content of the free radical scavenger is too high, the polymerization efficiency of the polymer will decrease, and there is a tendency for signal recording to fail. When using two or more free radical scavengers, it is preferable that their combined dosage meets the above-mentioned range.

[0415] 6-4. Other ingredients

[0416] The polymeric composition of the present invention may contain other components in addition to the above-mentioned components, provided that it does not violate the spirit of the present invention.

[0417] Other components include: solvents, plasticizers, dispersants, leveling agents, defoamers, and adhesion promoters used in the preparation of polymerizable compositions; and, particularly in the case of holographic recording media, chain transfer agents, polymerization terminators, compatibilizers, reaction aids, and sensitizers used for reaction control during recording. Examples of additives that may be needed for other property improvements include: preservatives, stabilizers, antioxidants, UV absorbers, and light stabilizers. These components can be used individually or in any combination and ratio of two or more.

[0418] <Sensers>

[0419] In the polymerizable composition of the present invention, a compound that controls the excitation of the photopolymerization initiator may be added. Examples of such compounds include sensitizers and sensitizing aids.

[0420] As a sensitizer, any sensitizer can be selected from a variety of known sensitizers. Generally, colored compounds such as pigments are mostly used as sensitizers to absorb visible and ultraviolet lasers. In the case of holographic recording media, although it also depends on the wavelength of the laser used in recording and the type of initiator used, specific examples of preferred sensitizers in systems using green lasers include compounds described in Japanese Patent Application Publication Nos. 5-241338, 2-69, and 2-55446. In systems using blue lasers, compounds described in Japanese Patent Application Publication Nos. 2000-10277 and 2004-198446 are examples. These sensitizers can be used alone or in any combination and ratio of two or more.

[0421] When the obtained holographic recording medium requires colorless transparency, anthocyanin pigments are preferably used as sensitizers. Anthocyanin pigments are generally easily decomposed by light, therefore post-exposure is performed. That is, by placing the medium under indoor light or sunlight for several hours to several days, the anthocyanin pigments in the holographic recording medium are decomposed and no longer absorb in the visible light region, resulting in a colorless and transparent holographic recording medium.

[0422] The amount of sensitizer needs to be adjusted according to the thickness of the recording layer formed. Preferred to be 0.01% by mass or more, particularly 0.1% by mass or more, and typically 10% by mass or less, particularly 5% by mass or less, relative to the ratio of the photopolymerization initiator described in 6-2 above. If too little sensitizer is used, the initiation efficiency decreases, and recording may sometimes require a long time. If too much sensitizer is used, the absorption of light used in recording and reproduction increases, and sometimes light may have difficulty reaching the depth direction. When using two or more sensitizers, their combined dosage should meet the above-mentioned range.

[0423] <Plasticizer>

[0424] In order to improve reaction efficiency and adjust the physical properties of the recording layer of the holographic recording medium, the polymeric composition of the present invention may contain a plasticizer.

[0425] Examples of plasticizers include: dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, di(undecyl) phthalate and other phthalate esters; bis(2-ethylhexyl) adipate, diisononyl adipate, di-n-butyl adipate and other adipate esters; dioctyl sebacate, dibutyl sebacate and other sebacate esters; tricresyl phosphate and other phosphate esters; acetyl tributyl citrate and other citrate esters; trioctyl trimellitate and other trimellitate esters; epoxidized soybean oil; chlorinated paraffin; acetoxymethoxypropane and other alkoxylated (poly)alkylene glycol esters; dimethoxy polyethylene glycol and other terminally alkoxylated polyalkylene glycols, etc.

[0426] Plasticizers containing fluorine elements, as exemplified in Japanese Patent No. 6069294, can also be used. Examples of plasticizers containing fluorine elements include: 2,2,2-trifluoroethyl butyl carbamate, bis(2,2,2-trifluoroethyl)-(2,2,4-trimethylhexane-1,6-diyl)dicarbamate, bis(2,2,2-trifluoroethyl)-[4-({[(2,2,2-trifluoroethoxy)carbonyl]amino}-methyl)octane-1,8-diyl]dicarbamate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl butyl carbamate, and 2,2,2-trifluoroethyl phenyl carbamate, etc.

[0427] These plasticizers are typically used in a ratio of 0.01% by mass to 50% by mass, preferably 0.05% by mass to 20% by mass, relative to the total solids content of the polymerizable composition. If the plasticizer content is less than the above range, it will not be able to achieve the effects of improving reaction efficiency and adjusting physical properties. If the plasticizer content is greater than this range, the transparency of the recording layer will decrease, or the plasticizer exudation will become significant.

[0428] Leveling agent

[0429] In the polymerizable compositions of the present invention, leveling agents can be used. Examples of leveling agents include: sodium polycarboxylate salts, ammonium polycarboxylate salts, amine polycarboxylate salts, silicone-based leveling agents, acrylic-based leveling agents, ester compounds, ketone compounds, fluorinated compounds, etc. Any one of these can be used alone, or two or more can be used in any combination and ratio.

[0430] <Chain transfer agent>

[0431] In the polymerizable composition of the present invention, a chain transfer agent may be used. Examples of chain transfer agents include: sodium phosphite, sodium hypophosphite, and other phosphonates; mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, and other thiols; acetaldehyde, propionaldehyde, and other aldehydes; acetone, methyl ethyl ketone, and other ketones; trichloroethylene, perchloroethylene, and other halogenated hydrocarbons; terpenes such as terpinene, α-terpinene, β-terpinene, and γ-terpinene; 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,4-cyclooctadiene, 1,4-heptadiene, 1,4-hexadiene, 2... Non-conjugated dienes such as methyl-1,4-pentadiene, 3,6-nonadien-1-ol, and 9,12-octadecadienol; linolenic acids such as alpha-linolenic acid, gamma-linolenic acid, methyl linoleate, ethyl linoleate, isopropyl linoleate, and linolenic anhydride; linoleic acids such as linoleic acid, methyl linoleate, ethyl linoleate, isopropyl linoleate, and linolenic anhydride; eicosapentaenoic acid and ethyl eicosapentaenoic acid; and docosahexaenoic acid and ethyl docosahexaenoic acid.

[0432] The amount of these additives used, in terms of the ratio of the total solids content of the polymeric composition of this embodiment, is preferably set to a range of 0.001% by mass or more, particularly 0.01% by mass or more, typically 30% by mass or less, particularly 10% by mass or less. When two or more additives are used together, their total amount should satisfy the above range.

[0433] 6-5. Composition ratio of each component in a polymeric composition

[0434] The content of each component in the polymeric composition of the present invention is arbitrary, provided it does not violate the spirit of the invention. The proportions of each component shown below are preferably within the following ranges based on the molar amount per unit mass of the polymeric composition.

[0435] Sufficient diffraction efficiency can be obtained in holographic recording media when the content of the polymerizable compound is above or above the aforementioned lower limit. When the content of the polymerizable compound is below the aforementioned upper limit, there is a tendency to maintain compatibility of the recording layer with the resin matrix and keep the shrinkage of the recording layer caused by recording low.

[0436] When isocyanate and polyol are used as the matrix resin in the polymerizable composition of the present invention, their combined content is generally 0.1% by mass or more, preferably 10% by mass or more, more preferably 35% by mass or more, generally 99.9% by mass or less, preferably 99% by mass or less. By setting this content to the lower limit value mentioned above or above, it is easy to form a recording layer.

[0437] In this case, the ratio of the number of isocyanate reactive functional groups in the polyol to the number of isocyanate groups in the isocyanate is preferably 0.1 or more, more preferably 0.5 or more, typically 10.0 or less, and preferably 2.0 or less. When this ratio falls within the above range, there are fewer unreacted functional groups, resulting in improved storage stability.

[0438] In this polymerizable composition, the content of the urethane polymerization catalyst is preferably determined by considering the reaction rate of the isocyanate and the polyol. The content of the urethane polymerization catalyst is preferably 5% by mass or less, more preferably 4% by mass or less, more preferably 1% by mass or less, and preferably 0.003% by mass or more.

[0439] The total amount of other components besides those mentioned above should be 30% by mass or less, preferably 15% by mass or less, and more preferably 5% by mass.

[0440] 6-6. Methods for manufacturing polymeric compositions

[0441] In this invention, the method for manufacturing the polymeric composition comprising a polymeric compound, a matrix resin, and a photopolymerization initiator is not particularly limited, and the mixing order can be appropriately adjusted. Furthermore, when the polymeric composition contains components other than those described above, the components can be mixed in any combination and order.

[0442] Polymerizable compositions using isocyanates and polyols as matrix resins can be obtained, for example, by the following methods, but the present invention is not limited thereto.

[0443] In addition to the polymerizable compound and the photopolymerization initiator, all components except the isocyanate and urethane polymerization catalysts are mixed to form a photoreactive composition (liquid A). The substance formed by mixing the isocyanate and urethane polymerization catalysts is called liquid B.

[0444] Alternatively, all components except isocyanate can be mixed into the polymerizable compound and the photopolymerization initiator to prepare a photoreactive composition (liquid A).

[0445] Each liquid is preferably dehydrated and degassed. If dehydration and degassed inadequately, bubbles may be generated during the fabrication of the holographic recording medium, resulting in an uneven recording layer. During dehydration and degassed processes, heating and depressurization can be performed as long as the components are not damaged.

[0446] The manufacture of the polymeric composition formed by mixing liquid A and liquid B is preferably carried out just before the holographic recording medium is formed. At this time, mixing techniques based on existing methods can also be used. During the mixing of liquid A and liquid B, degassing can be performed as needed to remove residual gases. Furthermore, liquid A and liquid B are preferably filtered separately or after mixing to remove foreign matter and impurities. In this case, filtering each liquid separately is more preferable.

[0447] Alternatively, an isocyanate-functionalized prepolymer can be obtained by reacting an isocyanate having an excess of isocyanate groups with a polyol, and this isocyanate-functionalized prepolymer can be used as a matrix resin. Furthermore, an isocyanate-reactive prepolymer can be obtained by reacting a polyol having an excess of isocyanate-reactive functional groups with an isocyanate, and this isocyanate-reactive prepolymer can be used as a matrix resin.

[0448] 6-7. Regarding the holographic recording medium of the present invention

[0449] The holographic recording medium of the present invention, which uses the polymeric composition of the present invention, comprises a recording layer, and further comprises a support and other layers as needed. Typically, the holographic recording medium has a support, on which the recording layer and other layers are stacked to form the holographic recording medium. The holographic recording medium may not have a support if the recording layer or other layers have the strength and durability required by the medium. Examples of other layers include: protective layers, reflective layers, anti-reflective layers (anti-reflective films), etc.

[0450] 6-7-1. Recording Layer

[0451] The recording layer of the holographic recording medium of the present invention is a layer formed from the polymeric composition of the present invention, and is a layer for recording information. The information is typically recorded in the form of a hologram. As described later in the recording method, the polymeric compound (hereinafter referred to as the polymeric monomer) contained in this recording layer is a compound in which a portion undergoes a chemical change such as polymerization due to holographic recording. Therefore, in the holographic recording medium after recording, a portion of the polymeric monomer is consumed, existing as a compound resulting from the reaction of a polymer or the like.

[0452] The thickness of the recording layer is not particularly limited and can be appropriately determined considering the recording method, etc. The thickness of the recording layer is preferably 1 μm or more, more preferably 10 μm or more, more preferably 1 cm or less, and more preferably 3 mm or less. By setting the thickness of the recording layer to the lower limit or above, the selectivity of each hologram tends to increase during multiple recording in the holographic recording medium, thus improving the degree of multiple recording. By setting the thickness of the recording layer to the upper limit or below, there is a tendency to achieve uniform overall forming of the recording layer, resulting in multiple recording with uniform diffraction efficiency and a high S / N ratio for each hologram.

[0453] From the perspective of record reproducibility, the shrinkage rate of the recording layer caused by exposure during information recording and reproduction is preferably less than 0.25%.

[0454] 6-7-2. Support body

[0455] There are no particular restrictions on the details of the support, as long as it has the strength and durability required for the holographic recording medium; any support can be used.

[0456] There are no restrictions on the shape of the support, which is usually formed into a flat plate or a membrane.

[0457] There are no restrictions on the materials used to form the support; they can be transparent or opaque.

[0458] Materials used as supports, if transparent materials are listed, include: organic materials such as acrylic acid, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, amorphous polyolefins, polystyrene, polycyclic olefins, and cellulose acetate; and inorganic materials such as glass, silicon, and quartz. Among these, polycarbonate, acrylic acid, polyester, amorphous polyolefins, and glass are preferred, and more particularly, polycarbonate, acrylic acid, amorphous polyolefins, polycyclic olefins, and glass are even more preferred.

[0459] If we list opaque materials as the support body, we can include: metals such as aluminum, materials made by coating the transparent support body with metals such as gold, silver, or aluminum, or dielectrics such as magnesium fluoride or zirconium oxide, etc.

[0460] There are no particular restrictions on the thickness of the support, but it is preferably set to a range of 0.05 mm or more and 1 mm or less. If the thickness of the support is above the lower limit, 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 can be increased, and the weight and cost of the holographic recording medium can be reduced.

[0461] Surface treatment can be applied to the surface of the support. This surface treatment is usually performed to improve the adhesion between the support and the recording layer. Examples of surface treatments include corona discharge treatment of the support or pre-forming a primer coating on the support. Examples of primer coating compositions include halogenated phenols, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, etc.

[0462] The surface treatment of the support can be performed for purposes other than improving adhesion. Examples include: reflective coating treatment to form a reflective coating made of metals such as gold, silver, or aluminum; and dielectric coating treatment to form a dielectric layer such as magnesium fluoride or zirconium oxide. These layers can be formed as a single layer or as two or more layers.

[0463] These surface treatments can be applied to control the permeability of gas and moisture to the substrate. For example, by making the support sandwiching the recording layer also suppress the permeability of gas and moisture, the reliability of the holographic recording medium can be improved.

[0464] The support can be provided on either the upper or lower side of the recording layer of the holographic recording medium of the present invention, or it can be provided on both sides. When the support is provided on the upper and lower sides of the recording layer, at least one of the supports is configured to be transparent so that active energy lines (excitation light, reference light, reproduction light, etc.) can be transmitted.

[0465] In the case of a holographic recording medium with supports on one or both sides of the recording layer, transmissive or reflective holograms can be recorded. Furthermore, when a support with reflective properties is used on one side of the recording layer, reflective holograms can be recorded.

[0466] The support body can be patterned for data addressing. There are no restrictions on the patterning method in this case. For example, the pattern can be formed on the support body itself, on the reflective layer described later, or by combining these methods.

[0467] 6-7-3. Protective Layer

[0468] A protective layer is a layer used to prevent degradation of the recording and reproduction characteristics of the recording layer. There are no restrictions on the specific composition of the protective layer; any known composition can be used. For example, a layer formed from water-soluble polymers, organic / inorganic materials, etc., can be used as a protective layer.

[0469] There are no particular restrictions on the location where the protective layer is formed. For example, the protective layer can be formed on the surface of the recording layer, between the recording layer and the support, or on the outer surface of the support. The protective layer can also be formed between the support and other layers.

[0470] 6-7-4. Reflective layer

[0471] The reflective layer is formed when the holographic recording medium is configured as a reflective type. In the case of a reflective holographic recording medium, the reflective layer can be formed between the support and the recording layer, or it can be formed on the outer surface of the support. Generally, the reflective layer is preferably located between the support and the recording layer.

[0472] As a reflective layer, any known reflective layer can be used, such as a thin film of metal.

[0473] 6-7-5. Anti-reflective film

[0474] For any type of holographic recording medium, whether transmissive or reflective, an anti-reflective film can be placed on the incident and exit sides of the information light, reference light, and reproduction light, or between the recording layer and the support. The anti-reflective film improves light utilization efficiency and suppresses noise generation.

[0475] As an anti-reflective film, any known anti-reflective film can be used.

[0476] 6-7-6. Methods for manufacturing holographic recording media

[0477] There are no limitations on the method for manufacturing the holographic recording medium of the present invention. For example, it can be manufactured by coating the polymeric composition of the present invention onto a support in a solvent-free manner to form a recording layer. In this case, any coating method can be used. Specific examples include: spray coating, spin coating, wire rod coating, dip coating, air knife coating, roller coating, and doctor blade coating, doctor blade roller coating, etc.

[0478] When forming the recording layer, especially in the case of forming a thicker recording layer, methods such as molding in a mold or coating on a release film and punching out the mold can be used. Alternatively, the polymeric composition of the present invention can be mixed with a solvent or additive to prepare a coating liquid, which is then coated onto a support and dried to form the recording layer. In this case, any coating method can be used. For example, the same method as described above can be employed.

[0479] There are no restrictions on the solvents used in the coating solution, but solvents that have sufficient solubility for the components used, impart good film properties, and do not corrode the support such as the resin substrate are generally preferred. A single solvent can be used, or two or more solvents can be used in any combination and ratio.

[0480] There is no limit to the amount of solvent used. However, considering coating efficiency and operability, it is preferable to prepare a coating solution with a solid content of approximately 1–100% by mass.

[0481] Examples of solvents include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl pentyl ketone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, propanol, n-butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; ketol-alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; ether solvents such as tetrahydrofuran and dioxane; halogen solvents such as dichloromethane, dichloroethane, and chloroform; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; and propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether. Propylene glycol solvents such as dimethyl ether acetate and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, and methyl 3-methoxypropionate; perfluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, and hexafluorobutanol; highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; chain hydrocarbon solvents such as n-hexane and n-octane; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, tert-butylcyclohexane, and cyclooctane; or mixtures thereof.

[0482] Methods for manufacturing holographic recording media include, for example, coating a support with a polymeric composition that is melted by heat, cooling it to solidify it, and forming a recording layer; coating a support with a liquid polymeric composition, thermally polymerizing it to solidify it, and forming a recording layer; and coating a support with a liquid polymeric composition, photopolymerizing it to solidify it, and forming a recording layer.

[0483] Holographic recording media manufactured in this way can take the form of self-supporting plates or disks and can be used in three-dimensional image display devices, diffractive optical elements, high-capacity memory, and others.

[0484] In particular, the holographic recording medium of the present invention, which uses the polymeric composition of the present invention, exhibits high refractive index modulation and is also useful as a light guide plate (waveguide plate) for AR glasses. Here, AR is an abbreviation for augmented reality.

[0485] 6-7-7. Applications of Holographic Recording Media

[0486] Applications of high-capacity storage devices

[0487] The writing (recording) and reading (reproducing) of information on the holographic recording medium of the present invention are both performed by irradiation with light.

[0488] When recording information, light that can cause chemical changes in polymerizable monomers, that is, light that causes their polymerization and concentration changes, is used as object light (also known as recording light).

[0489] For example, when information is recorded in the form of a volumetric hologram, object light and reference light are irradiated together onto the recording layer, causing interference between the object light and the reference light within the recording layer. This interference light induces polymerization and concentration changes of polymerizable monomers within the recording layer, resulting in a refractive index difference in the interference fringes. These interference fringes are then recorded in the recording layer as a hologram.

[0490] In reproducing a volumetric hologram recorded in a recording layer, a predetermined reproduction light (typically a reference light) is irradiated onto the recording layer. The irradiated reproduction light diffracts in accordance with the interference fringes. This diffracted light contains the same information as the recording layer, and therefore, by reading the diffracted light using an appropriate detection unit, the information recorded in the recording layer can be reproduced.

[0491] The wavelength regions of object light, reconstructed light, and reference light are arbitrary depending on their respective applications; they can be in the visible light region or the ultraviolet region. Preferred light sources among these include, for example: solid-state lasers such as ruby, glass, Nd-YAG, and Nd-YVO4; diode lasers such as GaAs, InGaAs, and GaN; gas lasers such as helium-neon, argon, krypton, excimer, and CO2; and dye lasers with excellent monochromaticity and directionality.

[0492] There are no restrictions on the irradiation amounts of the object light, reproduction light, and reference light; the irradiation amounts are arbitrary as long as recording and reproduction are possible. With extremely low irradiation amounts, the chemical changes of the polymerizable monomers may be incomplete, potentially failing to adequately express the heat resistance and mechanical properties of the recording layer. Conversely, with extremely high irradiation amounts, there is a possibility of degradation of the components of the recording layer (the components of the polymeric composition of this invention). Therefore, the object light, reproduction light, and reference light are typically around 0.1 J / cm², depending on the composition of the polymeric composition of this invention used to form the recording layer, the type of photopolymerization initiator, and its dosage. 2 Above and 20J / cm 2 Irradiate the following area.

[0493] As holographic recording methods, there are polarization collinear holographic recording methods, reference light incident angle multiplexed holographic recording methods, etc. When the holographic recording medium of the present invention is used as a recording medium, good recording quality can be provided by any recording method.

[0494] <Usage of AR glasses light guide plate (Usage of AR glass light guide plate)>

[0495] For the holographic recording medium of the present invention, volume holograms are recorded in the same manner as in the above-mentioned large-capacity memory applications.

[0496] For the volume hologram recorded in the recording layer, a prescribed reproduction light is irradiated onto the recording layer. The irradiated reproduction light diffracts corresponding to the interference fringes. At this time, even if the wavelength of the reproduction light does not match the wavelength of the recording light, diffraction occurs if the Bragg condition is satisfied with respect to the interference fringes. Therefore, if the corresponding interference fringes are pre-recorded according to the wavelength and incident angle of the reproduction light to be diffracted, diffraction can be generated for reproduction light in a wide wavelength region. Thereby, the display color gamut of the AR glasses can be expanded.

[0497] If the corresponding interference fringes are pre-recorded according to the wavelength and diffraction angle of the reproduction light, the reproduction light incident from the outside of the holographic recording medium can be guided into the holographic recording medium, or the reproduction light that can be wave-guided inside the holographic recording medium can be reflected, split, magnified, reduced, or made to exit from the inside of the holographic recording medium to the outside. Thereby, the viewing angle of the AR glasses can be expanded.

[0498] The wavelength regions of the object light and the reproduction light are arbitrary according to their respective uses, and can be the visible light region or the ultraviolet region. As the preferred light among these lights, the above-mentioned lasers, etc. can be cited. As the reproduction light, it is not limited to lasers, etc., and display devices such as liquid crystal displays (LCDs) and organic electroluminescent displays (OLEDs) are also cited as preferred lights.

[0499] There is no limitation on the irradiation amounts of the object light, the reproduction light, and the reference light, and as long as it is within the range where recording and reproduction can be performed, the irradiation amounts are arbitrary. In the case where the irradiation amount is extremely small, the chemical change of the polymerizable monomer is too incomplete, and there is a possibility that the heat resistance and mechanical properties of the recording layer cannot be fully exhibited. On the contrary, in the case where the irradiation amount is extremely large, there is a possibility that the components of the recording layer (the components of the polymerizable composition of the present invention) deteriorate. Therefore, the object light, the reproduction light, and the reference light are usually irradiated in the range of 0.1 J / cm 2 or more and 20 J / cm 2 or less according to the composition of the polymerizable composition of the present invention used to form the recording layer, the type and blending amount of the photoinitiator, etc.

[0500] 6-8. Performance Indicators of Holographic Recording Media

[0501] The performance of a holographic recording medium is indicated by a total Δn, calculated using the sum of diffraction efficiencies across the entire multi-recording system. 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. Based on 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), with the sum across the entire multi-recording system defined as the total Δn.

[0502] [Formula 1]

[0503]

[0504] Total Δn = ∑Δn

[0505] 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.

[0506] In the case of large-capacity storage, a high total Δn means that a large amount of information can be recorded per unit volume, which is preferred. In the case of AR glasses, a high total Δn enables the projected image of the projector to be clearly transmitted to the pupil, or can suppress power consumption, or can expand the viewing angle, which is preferred.

[0507] Example

[0508] The present invention will be further described in detail below through embodiments. The present invention is not limited to the following embodiments without departing from its spirit.

[0509] [Ingredients Used]

[0510] The raw materials used in the compositions in the examples and comparative examples are described below.

[0511] Isocyanates

[0512] ·DURANATE (registered trademark) TSS-100: Hexamethylene diisocyanate polyisocyanate (NCO 17.6%) (manufactured by Asahi Kasei Corporation).

[0513] <Polyols>

[0514] PLACEL PCL-205U: Polycaprolactone diol (molecular weight 530) (manufactured by Daicel).

[0515] PLACEL PCL-305: Polycaprolactone Triol (molecular weight 550) (manufactured by Daicel).

[0516] Photopolymerization initiators

[0517] HLI02: Methyl 1-(9-ethyl-6-cyclohexanoyl-9H-carbazole-3-yl)-1-(O-acetyloxime)glutarate.

[0518] Free radical scavengers

[0519] ·TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo radical (manufactured by Tokyo Chemical Co., Ltd.)

[0520] <Carbamate Polymerization Catalyst>

[0521] • Octanoic acid solution of bismuth tri(2-ethylhexanoate) (active ingredient amount 56% by mass).

[0522] [Example 1]

[0523] <Preparation of Compound M-1>

[0524] Compound M-1 was synthesized using the following synthetic method.

[0525] [Chemical Formula 22]

[0526]

[0527] Tetrabromobisphenol A (10.0 g), phenanthrene-9-boronic acid (18.1 g), and sodium carbonate (9.9 g) were suspended in 250 mL of toluene, 250 mL of ethanol, and 125 mL of water, and degassed by passing nitrogen gas through the liquid. 1.4 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the liquid for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 4 hours. After cooling to room temperature, 100 mL of water was added, and the mixture was extracted with toluene. The organic layer was dried over sodium sulfate and then concentrated. 19.9 g of crude compound S-1 obtained through the concentration was given.

[0528] The NMR data for compound S-1 are as follows.

[0529] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.81-8.67 (Ar, 8H), 7.94-7.31 (Ar, 32H), 4.92-4.87 (OH, 2H), 1.91-1.76 (CH3, 6H).

[0530] Under a nitrogen atmosphere, 15.7 g of the crude product of compound S-1, 5.3 g of ethyl 2-isocyanate methacrylate, and 100 mL of dichloromethane were mixed. 2.0 mg of diazabicycloundecene was added, and the mixture was stirred at room temperature. After the reaction was complete, 8 g of neutral silica gel was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The silica gel and solid components were filtered off, and the solid was washed with dichloromethane / ethyl acetate (10:1). The resulting organic layer was concentrated and dissolved in 30 mL of dichloromethane, then added dropwise to 300 mL of methanol cooled to 0 °C. The resulting solid was filtered, washed with a small amount of cold methanol, and dried using a vacuum dryer to obtain 14.5 g of compound M-1.

[0531] The NMR data for compound M-1 are as follows.

[0532] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.82-8.61 (Ar, 8H), 8.01-7.51 (Ar, 28H), 7.44-7.18 (Ar, 4H), 5.62-5.48 (C=CH2, 2H), 5.32-5 .19(C=CH2,2H), 4.20-3.78(NH,2H), 3.33-2.73(CH2,4H), 2.73-2.05(CH2,4H), 1.98-1.79(CH3,6H), 1.65-1.52(CH3,6H).

[0533] <The Production of Holographic Recording Media>

[0534] Solution A is prepared by dissolving 0.3821g of compound M-1 (as a polymerizable monomer), 0.0096g of photopolymerization initiator HLI02, and 3.29mg of free radical scavenger TEMPOL in 2.51g of DURANATE (registered trademark) TSS-100.

[0535] In addition, 1.74g of PLACEL PCL-205U and 0.75g of PLACEL PCL-305 were mixed (PLACCELPCL-205U:PLACCEL PCL-305 = 70:30 (mass ratio)) and 0.2mg of tris(2-ethylhexanoic acid)bismuth in octanoic acid solution was dissolved to prepare solution B.

[0536] After degassing solutions A and B separately under reduced pressure and at room temperature or 45°C for 2 hours, 3.23g of solution A and 2.77g of solution B are stirred and mixed, and then further degassed under vacuum for a few minutes.

[0537] Next, the vacuum-degassed mixture is allowed to flow onto a glass slide with 0.5 mm thick spacers placed at opposite ends. Another glass slide is placed on top, and the perimeter is secured with clamps. The mixture is then heated at 80°C for 24 hours to create a holographic recording medium for evaluation. This evaluation sample has a 0.5 mm thick recording layer formed between the cover glass slides.

[0538] The holographic recording medium is formulated with a ratio of 1.0 between the number of isocyanate groups in solution A and the number of isocyanate reactive groups in solution B, and contains 56.9 μmol / g of polymerizable monomer, 3.54 μmol / g of photopolymerization initiator, and 3.54 μmol / g of free radical scavenger.

[0539] <Holographic Recording and Evaluation>

[0540] Using a holographic recording medium prepared as an evaluation sample, the holographic recording and the evaluation of the holographic recording performance of the holographic recording medium were carried out according to the steps described below.

[0541] Holographic recording uses a semiconductor laser with a wavelength of 405nm. Figure 1 The exposure apparatus shown has an exposure power density of 10.2 mW / cm² per beam. 2 Holographic recording of a plane wave using a two-beam array was performed. The medium was rotated from -22.5° to 22.5°, and multiple angular recordings were performed at the same location. The diffraction efficiency in each multiple recording was measured. Δn was calculated based on the obtained diffraction efficiency, and the sum of the total diffraction efficiencies in the entire set of multiple recordings was taken as the total Δn.

[0542] The following is a detailed explanation.

[0543] (Holographic Recording)

[0544] Figure 1 This is a structural diagram showing an outline of a device used for holographic recording.

[0545] exist Figure 1 In this diagram, S represents the holographic recording medium sample, and M1 through M3 all represent mirrors. PBS represents a polarizing beam splitter. L1 represents a laser source emitting light at a wavelength of 405 nm for recording (TOPTICA Photonics single-mode laser capable of producing light near 405 nm). Figure 1 In the diagram, "L1" indicates L2, which represents a laser source for reproducing light emitting a wavelength of 633nm. PD1, PD2, and PD3 represent photodetectors. 1 represents an LED unit.

[0546] like Figure 1As shown, a polarizing beam splitter (PBS) is used to split light with a wavelength of 405 nm, so that the two beams intersect on the recording plane at an angle of 59.3°. At this time, the bisector of the angle between the two beams is perpendicular to the recording plane, and the plane containing the intersecting two beams is perpendicular to the plane of the beams.

[0547] After holographic recording, a laser source (Melles Griot V05-LHP151: "L2" in the figure) using a He-Ne laser to obtain light with a wavelength of 633nm is used. The holographic recording medium is illuminated with this light at an angle of 50.7°, and the diffracted light is detected using a photodiode and a photodetector amplifier (Hamamatsu Photonics S2281, C9329: "PD1" in the figure) to determine whether the holographic recording was performed correctly.

[0548] (Determination of diffraction efficiency)

[0549] The angle by which the sample is moved relative to the optical axis (dual beam, i.e. from...) Figure 1 The angle between the bisecting line of the interior angle at the point where the incident light from mirrors M1 and M2 intersects and the normal from the sample is recorded 151 times at 0.3° increments from -22.5° to 22.5°.

[0550] After multiple recordings, the remaining initiator and monomers are consumed by illuminating the LED unit (Figure 1, center wavelength 405nm) for a certain period of time. This process is called post-exposure. The LED power is set to 30mW / cm². 2 With a cumulative energy of 3.6 J / cm 2 Irradiation is performed in this manner.

[0551] 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. Illumination from... Figure 1 The diffraction efficiency of the light (wavelength 405 nm) from the reflector M1 was measured 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 sum of the multiple records was taken as the total Δn.

[0552] [Formula 2]

[0553]

[0554] Total Δn = ∑Δn

[0555] 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°).

[0556] Using multiple prepared samples, the irradiation energy conditions were repeatedly evaluated by varying the initial irradiation energy and the total irradiation energy. The goal was to find the condition that almost completely depletes the polymerizable monomers (resulting in a near-equilibrium total Δn in multiple recordings), maximizing the total Δn. This maximum value was then used as the total Δn for the medium.

[0557] The evaluation results are shown in Table 2 below.

[0558] [Example 2]

[0559] <Preparation of Compound M-2>

[0560] Compound M-2 was synthesized using the following synthetic method.

[0561] [Chemical Formula 23]

[0562]

[0563] Under a nitrogen atmosphere, 8.0 g of crude compound S-1 prepared in the same manner as in Example 1, 2.5 g of ethyl 2-isocyanate acrylate, and 60 mL of dichloromethane were mixed. 11.4 mg of diazabicycloundecene was added, and the mixture was stirred for 30 minutes.

[0564] After the reaction was complete, the reaction solution was injected into 50 mL of ammonium chloride aqueous solution, extracted with 50 mL of dichloromethane, washed with 50 mL of saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give 7.2 g of compound M-2.

[0565] The NMR data for compound M-2 are as follows.

[0566] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.76-8.66 (Ar, 8H), 7.90-7.51 (Ar, 28H), 7.41-7.21 (Ar, 4H), 6.05-5.91 (CH=CH2,2 H), 5.64-5.48(CH=CH2,4H), 4.24-3.72(NH,2H), 3.28-2.74(CH2,4H), 2.74-2.04(CH2,4H), 1.94-1.79(CH3,6H).

[0567] [Example 3]

[0568] <Manufacturing of Compound M-3>

[0569] Compound M-3 was synthesized using the following synthetic method.

[0570] [Chemical Formula 24]

[0571]

[0572] Tetrabromobisphenol A bis(2-hydroxyethyl) ether (5.0 g), phenanthrene-9-boronic acid (7.4 g), and sodium carbonate (3.8 g) were suspended in 125 mL of toluene, 125 mL of ethanol, and 63 mL of water. The solution was degassed by purging nitrogen gas. 0.6 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further purged for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, 50 mL of water was added, and the mixture was extracted with 50 mL of toluene. The organic layer was dried over sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give 7.1 g of compound S-2.

[0573] The NMR data for compound S-2 are as follows.

[0574] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.81-8.71 (Ar, 8H), 7.94-7.31 (Ar, 32H), 3.21-3.11 (CH2,4H), 2.79-2.62 (CH2,4H) 1.90-1.80 (CH3,6H), 0.54-0.38 (OH, 2H).

[0575] Under a nitrogen atmosphere, compound S-2 (5.0 g) and triethylamine (1.5 g) were added to 30 mL of dichloromethane, and acryloyl chloride (1.2 g) was slowly added dropwise in an ice bath. After the reaction was complete, 20 mL of 5% sodium bicarbonate aqueous solution was added to the reaction solution, and the mixture was extracted with 50 mL of dichloromethane. The organic layer was dried over sodium sulfate and then concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give 3.5 g of compound M-3.

[0576] The NMR data for compound M-3 are as follows.

[0577] 1H-NMR (400MHz, CDCl3, δ, ppm) 8.78-8.69 (Ar, 8H), 7.92-7.28 (Ar, 32H), 5.51-5.43 (CH=CH2,2H ), 5.13-5.07(CH=CH2,2H), 4.95-4.83(CH=CH2,2H), 3.42-3.24(CH2,8H), 1.87-1.76(CH3,6H).

[0578] [Example 4]

[0579] <The manufacture of compound M-4>

[0580] Compound M-4 was synthesized using the following synthetic method.

[0581] [Chemical Formula 25]

[0582]

[0583] Under a nitrogen atmosphere, compound S-2 (8.1 g), prepared in the same manner as in Example 3, and triethylamine (2.4 g) were added to 80 mL of dichloromethane. Acryloyl chloride (2.1 g) was then slowly added dropwise under an ice bath. After the reaction was complete, 20 mL of a 5% sodium bicarbonate aqueous solution was added to the reaction mixture. The mixture was extracted with 50 mL of dichloromethane, and the organic layer was dried over sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give 4.8 g of compound M-4.

[0584] The NMR data for compound M-4 are as follows.

[0585] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.84-8.62 (Ar, 8H), 7.92-7.74 (Ar, 12H), 7.71-7.56 (Ar, 12H), 7.55-7.31 (Ar, 8H) , 5.01-4.91(C=CH2,2H), 4.82-4.76(C=CH2,2H), 3.45-3.15(CH2,8H), 1.91-1.73(CH3,6H), 1.21-1.14(CH3,6H).

[0586] [Example 5]

[0587] <Manufacturing of Compound M-5>

[0588] Compound M-5 was synthesized using the following synthetic method.

[0589] [Chemical Formula 26]

[0590]

[0591] Tetrabromobisphenol A bis(2-hydroxyethyl) ether (5.0 g), dibenzothiophene-4-boronic acid (7.6 g), and sodium carbonate (3.8 g) were suspended in 125 mL of toluene, 125 mL of ethanol, and 63 mL of water. The solution was degassed by passing nitrogen gas through it. 0.6 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the solution for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, 50 mL of water was added, and the mixture was extracted with 100 mL of toluene. The organic layer was dried over sodium sulfate and concentrated to give 9.9 g of crude compound S-3.

[0592] The NMR data for compound S-3 are as follows.

[0593] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.20-8.14 (Ar, 8H), 7.73 (s, Ar, 4H), 7.72-7.31 (Ar, 20H), 3.22-3.17 (CH2, 4H), 3.01-2.92 (CH2, 4H), 0.84 (t, OH, 2H).

[0594] Under a nitrogen atmosphere, compound S-3 (8.0 g) and triethylamine (2.1 g) were added to 80 mL of dichloromethane, and acryloyl chloride (1.6 g) was slowly added dropwise under an ice bath.

[0595] After the reaction was complete, 30 mL of 5% sodium bicarbonate aqueous solution was added to the reaction solution. After extraction with 80 mL of dichloromethane, the organic layer was dried with sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 4.1 g of compound M-5.

[0596] The NMR data for compound M-5 are as follows.

[0597] 1 H NMR (400MHz, CDCl3, δ, ppm) 8.15 (td, Ar, 8H), 7.72 (s, Ar, 4H), 7.67 (dd, Ar, 4H), 7.60 (d, Ar, 4H), 7.53 (t, Ar, 4H), 7.49-7.33 (Ar, 8H ), 5.82 (dd, CH=CH2,2H), 5.41 (dd, CH=CH2,2H), 5.32 (dd, CH=CH2,2H), 3.63-3.51 (CH2,4H), 3.38-3.22 (CH2,4H), 1.89 (s, CH3,6H).

[0598] [Example 6]

[0599] <Manufacturing of Compound M-6>

[0600] Compound M-6 was synthesized using the following synthetic method.

[0601] [Chemical Formula 27]

[0602]

[0603] 10.0 g of 3',3”,5',5”-tetrabromophenolphthalein, 15.8 g of diphenoxy-9-boronic acid, and 3.7 g of sodium carbonate were suspended in 100 mL of toluene, 100 mL of ethanol, and 50 mL of water. The solution was degassed by passing nitrogen gas through it. 0.6 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the solution for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, 100 mL of water was added, and the mixture was filtered. The resulting solid was washed with a small amount of toluene and ethanol, dried, and 12.6 g of crude compound S-4 was obtained.

[0604] The NMR data for compound S-4 are as follows.

[0605] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.85-8.68 (Ar, 8H), 7.99-7.12 (Ar, 36H), 5.07-5.01 (OH, 2H).

[0606] Under a nitrogen atmosphere, 12.6 g of the crude product of compound S-4, 3.8 g of ethyl 2-isocyanate methacrylate, and 100 mL of dichloromethane were mixed. 1.9 mg of diazabicycloundecene was added, and the mixture was stirred at room temperature. After the reaction was complete, 7 g of neutral silica gel was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The silica gel and solid components were filtered off, and the solid was washed with dichloromethane / ethyl acetate (10:1). The resulting organic layer was concentrated and dissolved in 100 mL of dichloromethane, then added dropwise to 300 mL of methanol cooled to 0 °C. The resulting solid was filtered, washed with a small amount of cold methanol, and dried using a vacuum dryer to obtain 13.9 g of compound M-6.

[0607] The NMR data for compound M-6 are as follows.

[0608] 1H NMR (400MHz, CDCl3, δ, ppm) 8.83-8.61 (Ar, 8H), 8.02-7.18 (Ar, 36H), 5.62-5.48 (C=CH2,2 H), 5.32-5.21(C=CH2,2H), 4.21-3.73(NH,2H), 3.31-1.90(CH2,8H), 1.64-1.53(CH3,6H).

[0609] [Example 7]

[0610] <Manufacturing of Compound M-7>

[0611] Compound M-7 was synthesized using the following synthetic method.

[0612] [Chemical Formula 28]

[0613]

[0614] Tetrabromobisphenol A bis(2-hydroxyethyl) ether (5.0 g), 2-naphthylboronic acid (5.7 g), and sodium carbonate (3.8 g) were suspended in 40 mL of toluene, 40 mL of ethanol, and 20 mL of water. The solution was degassed by passing nitrogen gas through it. 0.6 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the solution for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, 50 mL of water was added, and the mixture was extracted with 50 mL of toluene. The organic layer was dried over sodium sulfate and concentrated. The crude product was diluted in 25 mL of toluene and added dropwise to 100 mL of hexane. The resulting solid was dried to give 6.3 g of compound S-5.

[0615] The NMR data for compound S-5 are as follows.

[0616] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.03 (s, Ar, 4H), 7.97-7.78 (Ar, 16H), 7.56-7.42 (Ar , 12H), 3.40-3.28(CH2,4H)3.22-3.11(CH2,4H), 1.90(s, CH3,6H), 1.06(t, OH, 2H).

[0617] Under a nitrogen atmosphere, compound S-5 (6.1 g) and triethylamine (2.3 g) were added to 40 mL of dichloromethane, and acryloyl chloride (1.6 g) was slowly added dropwise in an ice bath. After the reaction was complete, 40 mL of 5% sodium bicarbonate aqueous solution was added to the reaction solution, and after stirring for 1 hour, the mixture was extracted with 50 mL of dichloromethane. The organic layer was then dried over sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give 3.0 g of compound M-7.

[0618] The NMR data for compound M-7 are as follows.

[0619] 1 H-NMR (400MHz, CD3OD, δ, ppm) 8.04 (s, Ar, 4H), 7.92-7.77 (Ar, 16H), 7.56-7.39 (Ar, 12H), 5.90-5.79 (CH=CH2,2H), 5.44-5.32(CH=CH2,4H), 3.79-3.70(CH2,4H), 3.49-3.38(CH2,4H), 1.89(s, CH3,6H).

[0620] [Example 8]

[0621] <Manufacturing of Compound M-8>

[0622] Compound M-8 was synthesized using the following synthetic method.

[0623] [Chemical Formula 29]

[0624]

[0625] Under a nitrogen atmosphere, compound S-2 (8.0 g), 2-(2-isocyanate ethoxy)ethyl methacrylate (3.75 g), and 50 mL of dichloromethane were mixed. Dibutyltin diacetate (82.5 mg) was added, and the mixture was stirred for 6 days. After the reaction was complete, 11 g of diamine silica (manufactured by FUJI SILYSIACHEMICAL Co., Ltd.) was added, and the mixture was stirred for 30 minutes. Then, 4 g of neutral silica gel was added, and the mixture was stirred for another 30 minutes. The silica gel and solid components were then filtered off. The resulting organic layer was concentrated, and 40 mL of dichloromethane was added dropwise to 240 mL of methanol cooled to -10°C. The resulting solid was filtered, washed with a small amount of cold methanol, and dried using a vacuum dryer to obtain 7.84 g of compound M-8.

[0626] The NMR data for compound M-8 are as follows.

[0627] 1H-NMR (400MHz, CD3OD, δ, ppm) 8.84-8.68 (Ar, 8H), 8.02-7.30 (Ar, 32H), 6.09 (C=CH2,2H), 5.53 (C=CH 2,2H), 4.36-3.94(CH2,4H), 3.65-3.02(NH, CH2,18H), 2.83-2.61(CH2,4H), 2.10-1.72(s, CH3,12H).

[0628] [Example 9]

[0629] <Manufacturing of Compound M-9>

[0630] Compound M-9 was synthesized using the following synthetic method.

[0631] [Chemical Formula 30]

[0632]

[0633] Tetrabromobisphenol A (5.1 g), 4-phenylnaphthyl-1-boronic acid (9.7 g), and sodium carbonate (2.1 g) were suspended in 25 mL of toluene, 25 mL of ethanol, and 12 mL of water, and degassed by passing nitrogen gas through the liquid. 0.7 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the liquid for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 3 hours. After cooling to room temperature, 50 mL of water was added, and the mixture was extracted with toluene. The organic layer was dried over sodium sulfate and then concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give 8.7 g of compound S-6.

[0634] The NMR data for compound S-6 are as follows.

[0635] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.07-7.77 (Ar, 8H), 7.73-7.29 (Ar, 40H), 4.97-4.86 (OH, 2H), 1.95-1.73 (CH3, 6H).

[0636] Under a nitrogen atmosphere, compound S-6 (3.6 g), ethyl 2-isocyanate acrylate (1.1 g), and 45 mL of dichloromethane were mixed. Diazabicycloundecene (3.0 mg) was added, and the mixture was stirred at room temperature. After the reaction was complete, 8 g of neutral silica gel was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The silica gel and solid components were filtered off, and the solid was washed with dichloromethane / ethyl acetate (10:1). The resulting organic layer was concentrated and dissolved in 20 mL of dichloromethane, then added dropwise to 100 mL of methanol cooled to 0 °C. The resulting solid was filtered, washed with a small amount of cold methanol, and dried using a vacuum dryer to obtain 4.2 g of compound M-9.

[0637] The NMR data for compound M-9 are as follows.

[0638] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.01-7.69 (Ar, 8H), 7.68-7.32 (Ar, 40H), 6.22-6.09 (CH=CH2,2H), 5.88-5.74 (CH=CH2 ,2H), 5.71-5.60(CH=CH2,2H), 4.40-4.02(NH,2H), 3.68-3.34(CH2,4H), 3.08-2.14(CH2,4H), 1.98-1.71(CH3,6H).

[0639] Using compound M-9 (0.4054 g) as the polymerizable monomer, the holographic recording medium was prepared in the same manner as in Example 1, and its evaluation was carried out. The results are shown in Table 2 below.

[0640] [Example 10]

[0641] <Manufacturing of Compound M-10>

[0642] Compound M-10 was prepared using the following synthetic method.

[0643] [Chemical Formula 31]

[0644]

[0645] 14 g of 4,4'-dihydroxybiphenyl was dissolved in 400 mL of methanol and cooled to 0 °C. 50 g of bromine was slowly added dropwise, and the mixture was stirred at 0 °C for 1 hour after the addition. The resulting pale yellow solid was filtered off and washed with cold methanol to obtain 34.6 g of tetrabromosine S-7.

[0646] The NMR data for compound S-7 are as follows.

[0647] 1H-NMR (400MHz, CDCl3, δ, ppm) 7.56 (s, Ar, 4H), 5.90 (s, OH, 2H).

[0648] Tetrabromosyl S-7 (12.6 g), phenanthrene-9-boronic acid (22.3 g), and sodium carbonate (10.6 g) were suspended in 100 mL of toluene, 100 mL of ethanol, and 50 mL of water. The solution was degassed by passing nitrogen gas through it. 2.3 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the solution for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 3 hours. After cooling to room temperature, 150 mL of water was added, and the resulting solid was filtered off. The solid was washed with ethanol and dried using a vacuum dryer to obtain 16.0 g of compound S-8.

[0649] The NMR data for compound S-8 are as follows.

[0650] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.78-8.67 (Ar, 8H), 8.01-7.80 (Ar, 16H), 7.71-7.53 (Ar, 16H), 4.99-4.95 (OH, 2H).

[0651] Under a nitrogen atmosphere, compound S-8 (7.0 g), ethyl 2-isocyanate acrylate (52.4 g), and 70 mL of dichloromethane were mixed. Diazabicycloundecene (1.3 mg) was added, and the mixture was stirred at room temperature. After the reaction was complete, 4 g of neutral silica gel was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The silica gel and solid components were filtered off, and the solid was washed with dichloromethane. The resulting organic layer was concentrated and purified by silica gel column chromatography using dichloromethane / ethyl acetate. The target compound was dissolved in 35 mL of dichloromethane and added dropwise to 300 mL of ice-cold methanol. The precipitated solid was filtered off, washed with a small amount of cold methanol, and dried under reduced pressure to obtain 7.4 g of compound M-10.

[0652] The NMR data for compound M-10 are as follows.

[0653] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.78-8.59 (Ar, 8H), 8.10-7.81 (Ar, 16H), 7.70-7.49 (Ar, 16H), 6.04-5.9 1(CH=CH2,2H), 5.65-5.43(CH=CH2,4H), 4.23-3.85(NH,2H), 3.23-2.75(CH2,4H), 2.74-2.01(CH2,4H).

[0654] Using compound M-10 (0.3625 g) as the polymerizable monomer, the holographic recording medium was prepared in the same manner as in Example 1, and its evaluation was carried out. The results are shown in Table 2 below.

[0655] [Example 11]

[0656] <Manufacturing of Compound M-11>

[0657] Compound M-11 was synthesized using the following synthetic method.

[0658] [Chemical Formula 32]

[0659]

[0660] Tetrabromobisphenol A (2.5 g), dibenzothiophene-2-boronic acid (4.4 g), and sodium carbonate (1.07 g) were suspended in 13 mL of toluene, 13 mL of ethanol, and 7 mL of water. The solution was degassed by passing nitrogen gas through it. 1.0 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the solution for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, 30 mL of water was added and the mixture was filtered. The resulting solid was washed with small amounts of toluene and ethanol and dried to give 1.8 g of compound R-1.

[0661] The NMR data for compound R-1 are as follows.

[0662] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.35 (d, Ar, 4H), 8.15 (d, Ar, 4H), 7.96 (d, Ar, 4H), 7.87 (d , Ar, 4H), 7.68 (dd, Ar, 4H), 7.53-7.37 (dd, Ar, 12H), 5.43 (s, OH, 2H), 1.88 (s, CH3, 6H).

[0663] Under a nitrogen atmosphere, compound R-1 (1.7 g), ethyl 2-isocyanate acrylate (0.55 g), and 30 mL of dichloromethane were mixed. Diazabicycloundecene (3.0 mg) was added, and the mixture was stirred at room temperature. After the reaction was complete, 2 g of neutral silica gel was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The silica gel and solid components were filtered off, and the solid was washed with dichloromethane. The resulting organic layer was concentrated and dissolved in 10 mL of dichloromethane, then added dropwise to 50 mL of methanol cooled to 0 °C. The resulting solid was filtered, washed with a small amount of cold methanol, and dried using a vacuum dryer to obtain 1.7 g of compound M-11.

[0664] The NMR data for compound M-11 are as follows.

[0665] 1 H-NMR (400MHz, CDCl3, δ, ppm) 8.32-8.19 (Ar, 4H), 8.17-8.03 (Ar, 4H), 7.94-7.81 (Ar, 8H), 7.63-7.36 (Ar, 16H), 6.15-6.05 (CH=CH2,2H), 5.72-5.51(CH=CH2,4H), 4.98-4.36(NH,2H), 3.82-3.61(CH2,4H), 3.27-2.99(CH2,4H), 2.12-1.74(CH3,6H).

[0666] Using compound M-11 (0.3804 g) as the polymerizable monomer, the holographic recording medium was prepared in the same manner as in Example 1, and its evaluation was carried out. The results are shown in Table 2 below.

[0667] [Comparative Example 1]

[0668] Compound R-1 was used as the compound in Comparative Example 1.

[0669] [Comparative Example 2]

[0670] <Preparation of Compound R-2>

[0671] Compound R-2 was synthesized using the following synthetic method.

[0672] [Chemical Formula 33]

[0673]

[0674] Tetrabromobisphenol A bis(2-hydroxyethyl) ether (5.0 g), phenylboronic acid (4.1 g), and sodium carbonate (3.8 g) were suspended in 40 mL of toluene, 40 mL of ethanol, and 20 mL of water. The solution was degassed by passing nitrogen gas through it. 0.6 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the solution for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, 50 mL of water was added, and the mixture was extracted with 50 mL of toluene. The organic layer was dried over sodium sulfate and concentrated. The crude product was diluted in 20 mL of toluene and added dropwise to 80 mL of hexane. The resulting solid was dried to give 3.6 g of compound L-1.

[0675] The NMR data for compound L-1 are as follows.

[0676] 1 H-NMR (400MHz, DMSO-d6, δ, ppm) 7.58-7.52 (Ar, 8H), 7.46-7.39 (Ar, 8H), 7.38-7.31 (Ar, 4 H), 7.26 (s, Ar, 4H), 4.25 (t, OH, 2H), 3.15 (t, CH2, 4H), 3.03 (q, CH2, 4H), 1.79 (s, CH3, 6H).

[0677] Under a nitrogen atmosphere, compound L-1 (3.5 g) and triethylamine (1.8 g) were added to 25 mL of dichloromethane, and acryloyl chloride (1.2 g) was slowly added dropwise in an ice bath. After the reaction was complete, 40 mL of 5% sodium bicarbonate aqueous solution was added to the reaction solution, and after stirring for 1 hour, the mixture was extracted with 50 mL of dichloromethane. The organic layer was then dried over sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give 1.8 g of compound R-2.

[0678] The NMR data for compound R-2 are as follows.

[0679] 1 H-NMR (400MHz, CD3OD, δ, ppm) 7.57-7.52 (Ar, 8H), 7.43-7.36 (Ar, 8H), 7.35-7.28 (Ar, 4H), 7.26 (s, Ar, 4H), 6.15 (dd, C H=CH2,2H), 5.88(dd, CH=CH2,2H), 5.76(dd, CH=CH2,2H), 3.81-3.76(CH2,4H), 3.44-3.40(CH2,4H), 1.80(s, CH3,6H).

[0680] Using compound R-2 (0.2252 g) as the polymerizable monomer, the holographic recording medium was prepared in the same manner as in Example 1, and its evaluation was carried out. The results are shown in Table 2.

[0681] [Comparative Example 3]

[0682] <Preparation of Compound R-3>

[0683] Compound R-3 was synthesized using the following synthetic method.

[0684] [Chemical Formula 34]

[0685]

[0686] Tetrabromobisphenol A (15.1 g), phenylboronic acid (14.2 g), and sodium carbonate (14.6 g) were suspended in 120 mL of toluene, 120 mL of ethanol, and 60 mL of water. The solution was degassed by passing nitrogen gas through it. 2.0 mg of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II) was added to the reaction solution, and nitrogen gas was further passed through the solution for 10 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 2 hours. After cooling to room temperature, 100 mL of water was added, and the mixture was extracted with 100 mL of toluene. The organic layer was dried over sodium sulfate and concentrated. The crude product was washed with hexane and then with a small amount of toluene. The resulting solid was dried to give 9.69 g of compound L-2.

[0687] The NMR data for compound L-2 are as follows.

[0688] 1 H-NMR (400MHz, CDCl3, δ, ppm) 7.60-7.31 (Ar, 20H), 7.20 (Ar, 4H), 5.28 (s, OH, 2H), 1.74 (s, CH3, 6H).

[0689] Under a nitrogen atmosphere, compound L-2 (5.0 g), ethyl 2-isocyanate methacrylate (3.5 g), and 30 mL of dichloromethane were mixed. Diazabicycloundecene (14.3 mg) was added, and the mixture was stirred for 1 hour. After the starting material disappeared, 4 g of neutral silica gel was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The silica gel and solid components were filtered off, and the solid was washed with dichloromethane. The resulting organic layer was concentrated and dissolved in 20 mL of dichloromethane, then added dropwise to 125 mL of methanol cooled to 0 °C. The resulting solid was filtered, washed with a small amount of cold methanol, and dried using a vacuum dryer to obtain 4.0 g of compound R-3.

[0690] The NMR data for compound R-3 are as follows.

[0691] 1 H-NMR (400MHz, CD3OD, δ, ppm) 7.51-7.26 (Ar, 24H), 6.06 (brs, C=CH2,2H), 5.58 (brs, C=CH2,2H), 4 .99-4.43(NH,2H), 3.94-3.72(CH2,4H), 3.32-3.12(CH2,4H), 1.92(s, CH3,6H), 1.78(s, CH3,6H).

[0692] The polymerizable monomer compound R-3 has low solubility in solution A, making it unsuitable for fabricating holographic recording media and thus unevaluable.

[0693] [Comparative Example 4]

[0694] As a comparative example 4, NK ESTER A-BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene manufactured by Shin-Nakamura Chemical Industry Co., Ltd. was used as compound R-4 for evaluation.

[0695] [Comparative Example 5]

[0696] As a comparative example 5, DNFE-A: 2,12-bis(hydroxyethoxyacryloyl)dinaphthofuran, as described in Japanese Patent Application Publication No. 2023-26379, was synthesized according to the method of Example 2 of Japanese Patent Application Publication No. 2023-26379 and used as compound R-5 for evaluation.

[0697] [Determination of Refractive Index]

[0698] The refractive index of the polymeric monomers manufactured in the Examples and Comparative Examples was determined using the following methods. The results are shown in Table 1.

[0699] The test solution is prepared by dissolving the sample in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate in a mass ratio of 4:1 to achieve a specified concentration.

[0700] The sample concentration of the test solution was set to either 10% by mass or 20% by mass.

[0701] The refractive index of each test solution was determined using a Kalnew precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-2000). The temperature of the test solution was set to 23°C, and the measurement wavelength was set to helium lamp d-rays (587.6 nm). Based on the measurement results, a calibration curve showing the correlation between sample concentration and refractive index was constructed. The refractive index at a sample concentration of 100% by mass was determined from the obtained calibration curve and used as the refractive index of the sample.

[0702] Of these, compound R-1 of Comparative Example 1, compound R-3 of Comparative Example 3, and compound R-5 of Comparative Example 5 were not dissolved in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate in a mass ratio of 4:1. The refractive index of compound R-5 is shown in Japanese Patent Application Publication No. 2023-26379 (sample concentration 100% by mass).

[0703] [Solubility test in resin raw materials]

[0704] The condition of the solutions containing 100 mg of polymerizable monomers M-1 to M-11 and R-1 to R-5 dissolved in 400 mg of DURANATE (registered trademark) TSS-100 was visually observed, and evaluated as 0 (completely dissolved) or × (dissolved solid residue). The results are shown in Table 1.

[0705] [Table 1]

[0706] Polymerizable monomers Refractive index Solubility test Example 1 M-1 1.7048 〇 Example 2 M-2 1.6802 〇 Example 3 M-3 1.7058 〇 Example 4 M-4 1.6876 〇 Example 5 M-5 1.6923 〇 Example 6 M-6 1.7048 〇 Example 7 M-7 1.6788 〇 Example 8 M-8 1.6673 〇 Example 9 M-9 1.6804 〇 Example 10 M-10 1.7184 〇 Example 11 M-11 1.7016 〇 Comparative Example 1 R-1 - × Comparative Example 2 R-2 1.6211 〇 Comparative Example 3 R-3 - × Comparative Example 4 R-4(A-BPEF) 1.6198 × Comparative Example 5 R-5(DNFE-A) <![CDATA[1.673 * ]]> ×

[0707] ※Value recorded in Japanese Patent Application Publication No. 2023-26379

[0708] As clearly shown in Table 1, the refractive indices of the compounds in the examples are all 1.65 or higher, which is the same as or higher than that of the compounds in the comparative examples. Furthermore, the solubility test results show good solubility in resin raw materials compared to the compounds in the comparative examples. Therefore, the compounds of the present invention are excellent high-refractive-index materials.

[0709] [Table 2]

[0710]

[0711]

[0712] As shown in Table 2, the total Δn of the holographic recording medium of Compound R-2 of Comparative Example 2, which has a monocyclic aromatic ring substituted with a phenyl group on the phenoxy ring, is 0.0086. Compound R-3 of Comparative Example 3 is insoluble and cannot be evaluated. Furthermore, Compound R-1 of Comparative Example 1 and Compound R-5 of Comparative Example 5, which have hydroxyl groups, react with isocyanates under appropriate reaction conditions, and therefore cannot be used to prepare holographic recording media and are unsuitable.

[0713] In contrast, the total Δn of the compounds of the present invention in Examples 1, 9 to 11 is all above 0.0150, which is significantly higher.

[0714] In the optical element application of AR glasses light guide plates, a high total Δn of the holographic recording medium results in a clearer projected image and a wider viewing angle. Furthermore, in memory applications, increasing the total Δn increases the recording capacity. On the other hand, holographic recording media require high transparency; turbidity caused by the incorporation and formation of insoluble substances leads to absorption and scattering of recorded light, thus degrading the performance of the holographic recording medium. Particularly in the application of AR glasses waveguide plates, light scattering caused by insoluble substances reduces light utilization efficiency and aesthetics. Furthermore, as insoluble substances precipitate from the waveguide plate over time, the absorption intensity of the waveguide light also changes over time, leading to a decrease in the performance stability of the waveguide plate. Therefore, by using the compounds of the present invention, which combine high total Δn and compositional stability, particularly high solubility in resin raw materials, it is possible to produce AR glasses light guide plates with excellent light utilization efficiency, aesthetics, and long-term performance stability.

[0715] Based on the above, it can be said that the compounds of the present invention used in the embodiments are superior to the compounds of the comparative examples.

[0716] The present invention has been described in detail using specific methods, but it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.

[0717] This application is based on Japanese Patent Application 2023-053749, filed on March 29, 2023, the entire contents of which are incorporated herein by reference.

[0718] Explanation of reference numerals in the attached figures

[0719] S: Holographic recording medium;

[0720] M1, M2, M3: Reflectors;

[0721] L1: A semiconductor laser light source for recording light;

[0722] L2: Laser light source for reproducing light;

[0723] PD1, PD2, PD3: photodetectors;

[0724] PBS: Polarizing beam splitter;

[0725] 1: LED unit.

Claims

1. A compound, said compound being represented by the following formula (1), [Chemical Formula 1] In equation (1), A 1 and A 2 Each independently represents a polymeric group. n1 and n2 each independently represent integers from 1 to 3. When n1 and n2 are 2 or 3, multiple A's 1 A 2 The same or different, can be chosen. L 1 L represents a (n1+1) valence linker group that is either single-bonded or optionally branched. 2 This indicates a (n²+1) valence linker group that is either a single bond or optionally branched. X represents a single bond, a divalent organic group with 1 to 20 carbon atoms, a sulfonyl group, or a divalent oxygen or sulfur atom. R 1 and R 2 Each independently represents a fused aromatic ring group optionally having substituents. m1 and m2 are each independent integers from 2 to 4, and multiple R 1 and R 2 Whether they are arbitrarily the same or different, it should be noted that R in the formula 1 and R 2 The two benzene rings are each independent except for R. 1 and R 2 In addition, it may optionally have substituents.

2. The compound according to claim 1, wherein, The values ​​of m1 and m2 are 2.

3. The compound according to claim 1, wherein, X is a single bond, or a divalent group selected from the group consisting of structures shown in formulas (1a) to (1h) below. [Chemical Formula 2] In equation (1a), R 3 and R 4 Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

4. The compound according to claim 1, wherein, The R 1 and R 2 Each is independently a phenanthrene group optionally having a substituent, or a fused aromatic heterocyclic group optionally having a substituent.

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

6. A holographic recording medium comprising the polymeric composition according to claim 5.

7. A polymer, said polymer being formed by polymerizing the polymeric composition according to claim 5.

8. An optical material comprising the polymer according to claim 7.

9. An optical component comprising the polymer according to claim 7.

10. A high-capacity memory comprising the holographic recording medium according to claim 6.

11. An optical element obtained by holographic recording in a holographic recording medium according to claim 6.

12. An AR light guide plate, the AR light guide plate comprising the optical element according to claim 11.

13. An AR glasses, the AR glasses comprising the optical element according to claim 11.

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