Sony Patent | Hologram recording composition, hologram recording medium, hologram, and optical device and optical component using same

Patent: Hologram recording composition, hologram recording medium, hologram, and optical device and optical component using same

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Publication Number: 20220101878

Publication Date: 20220331

Applicant: Sony

Abstract

To provide a hologram recording composition capable of further improving diffraction characteristics. The present technology provides a hologram recording composition containing at least a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound. The present technology also provides a hologram recording medium including a photocurable resin layer containing at least a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound. Furthermore, the present technology also provides a hologram using the hologram recording medium. Moreover, the present technology also provides an optical device and an optical component using the hologram.

Claims

1. A hologram recording composition comprising at least a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound.

2. The hologram recording composition according to claim 1, comprising a monofunctional monomer and a polyfunctional monomer as the radically polymerizable monomer.

3. The hologram recording composition according to claim 1, wherein the radically polymerizable monomer has a refractive index of 1.6 or more.

4. The hologram recording composition according to claim 1, wherein the radically polymerizable monomer is at least one selected from the group consisting of a carbazole-based monomer, a fluorene-based monomer, and a dinaphthothiophene-based monomer.

5. The hologram recording composition according to claim 1, wherein the radically polymerizable monomer is a compound represented by the following general formula (1-10). ##STR00030## (In the general formula (1-10), X.sup.1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom. In a case where X.sup.1 is an oxygen atom, a is 0. In a case where X.sup.1 is a nitrogen atom or a phosphorus atom, a is 1. In a case where X.sup.1 is a carbon atom or a silicon atom, a is 2. Y.sup.1 and Y.sup.2 are each a benzene ring or a naphthalene ring, and Y.sup.1 and Y.sup.2 are not both benzene rings at the same time. In a case where Y.sup.1 or Y.sup.2 is a benzene ring, b or c corresponding to the benzene ring Y.sup.1 or Y.sup.2 is 4. In a case where Y.sup.1 and/or Y.sup.2 is a naphthalene ring, b and/or c corresponding to the naphthalene ring Y.sup.1 and/or Y.sup.2 is 6. R.sup.1 to R.sup.3 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). In a case where a plurality of R.sup.1s, a plurality of R.sup.2s, and a plurality of R.sup.3s are present, the plurality of R.sup.1s to R.sup.3s may be the same as or different from each other. However, R.sup.1s to R.sup.3s in the general formula (1-10) are not all hydrogen atoms at the same time. Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1. R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in the general formula (1-10) are not all hydrogen atoms at the same time.)

6. The hologram recording composition according to claim 1, further comprising inorganic fine particles.

7. The hologram recording composition according to claim 1, further comprising a cationically polymerizable compound.

8. The hologram recording composition according to claim 1, wherein the cationically polymerizable compound is at least one selected from the group consisting of an epoxy compound and an oxetane compound.

9. The hologram recording composition according to claim 1, further comprising a polymerization inhibitor.

10. A hologram recording medium comprising a photocurable resin layer containing at least a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound.

11. The hologram recording medium according to claim 10, comprising a monofunctional monomer and a polyfunctional monomer as the radically polymerizable monomer.

12. The hologram recording medium according to claim 10, wherein the radically polymerizable monomer has a refractive index of 1.6 or more.

13. The hologram recording medium according to claim 10, wherein the radically polymerizable monomer is at least one selected from the group consisting of a carbazole-based monomer, a fluorene-based monomer, and a dinaphthothiophene-based monomer.

14. The hologram recording medium according to claim 10, wherein the radically polymerizable monomer is a compound represented by the following general formula (1-10). ##STR00031## (In the general formula (1-10), X.sup.1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom. In a case where X.sup.1 is an oxygen atom, a is 0. In a case where X.sup.1 is a nitrogen atom or a phosphorus atom, a is 1. In a case where X.sup.1 is a carbon atom or a silicon atom, a is 2. Y.sup.1 and Y.sup.2 are each a benzene ring or a naphthalene ring, and Y.sup.1 and Y.sup.2 are not both benzene rings at the same time. In a case where Y.sup.1 or Y.sup.2 is a benzene ring, b or c corresponding to the benzene ring Y.sup.1 or Y.sup.2 is 4. In a case where Y.sup.1 and/or Y.sup.2 is a naphthalene ring, b and/or c corresponding to the naphthalene ring Y.sup.1 and/or Y.sup.2 is 6. R.sup.1 to R.sup.3 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). In a case where a plurality of R.sup.1s, a plurality of R.sup.2s, and a plurality of R.sup.3s are present, the plurality of R.sup.1s to R.sup.3s may be the same as or different from each other. However, R.sup.1s to R.sup.3s in the general formula (1-10) are not all hydrogen atoms at the same time. Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1. R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in the general formula (1-10) are not all hydrogen atoms at the same time.)

15. The hologram recording medium according to claim 10, further comprising inorganic fine particles.

16. The hologram recording medium according to claim 10, further comprising a cationically polymerizable compound.

17. The hologram recording medium according to claim 10, wherein the cationically polymerizable compound is at least one selected from the group consisting of an epoxy compound and an oxetane compound.

18. The hologram recording medium according to claim 10, further comprising a polymerization inhibitor.

19. A hologram using the hologram recording medium according to claim 10.

20. The hologram according to claim 19, having absorption derived from an anthracene skeleton.

21. An optical device using the hologram according to claim 19.

22. An optical component using the hologram according to claim 19.

Description

TECHNICAL FIELD

[0001] The present technology relates to a hologram recording composition, a hologram recording medium, a hologram, and an optical device and an optical component using the same.

BACKGROUND ART

[0002] A hologram is obtained by recording a light-dark (interference) pattern of light on a photosensitive material and the like as a pattern of a refractive index and the like, and is widely used in a field such as optical information processing, security, medicine, or a head-up display. The hologram is attracting attention as a next-generation recording medium because of being able to record three-dimensional information about an object as optical information in a large capacity.

[0003] So far, various proposals have been made for materials for the hologram. For example, Patent Document 1 proposes a photosensitive material containing a polymer matrix formed by radical polymerization of a radically polymerizable compound in the presence of a radical polymerization initiator, a photocationic polymerization initiator, and a cationically polymerizable compound, and characterized in that a reduction potential of the photocationic polymerization initiator is lower than an oxidation potential of radicals generated from the radical polymerization initiator.

CITATION LIST

Patent Document

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2010-210654

SUMMARY OF THE INVENTION

Problems to be Solved by the Invention

[0005] However, in hologram technology, it is required to further improve diffraction characteristics. Therefore, a main object of the present technology is to provide a hologram recording composition, a hologram recording medium, a hologram, and an optical device and an optical component using the same, which can further improve the diffraction characteristics.

Solutions to Problems

[0006] The present inventors made intensive studies in order to solve the above-described problem, and as a result, have succeeded in further improving diffraction characteristics, and have completed the present technology.

[0007] That is, the present technology provides a hologram recording composition containing at least a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound.

[0008] The hologram recording composition according to the present technology may contain a monofunctional monomer and a polyfunctional monomer as the radically polymerizable monomer.

[0009] In the hologram recording composition according to the present technology, the radically polymerizable monomer may have a refractive index of 1.6 or more.

[0010] In the hologram recording composition according to the present technology, the radically polymerizable monomer may be at least one selected from the group consisting of a carbazole-based monomer, a fluorene-based monomer, and a dinaphthothiophene-based monomer.

[0011] In the hologram recording composition according to the present technology, the radically polymerizable monomer may be a compound represented by the following general formula (1-10).

STR00001

[0012] (In the general formula (1-10), X.sup.1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom. In a case where X.sup.1 is an oxygen atom, a is 0. In a case where X.sup.1 is a nitrogen atom or a phosphorus atom, a is 1. In a case where X.sup.1 is a carbon atom or a silicon atom, a is 2.

[0013] Y.sup.1 and Y.sup.2 are each a benzene ring or a naphthalene ring, and Y.sup.1 and Y.sup.2 are not both benzene rings at the same time. In a case where Y.sup.1 or Y.sup.2 is a benzene ring, b or c corresponding to the benzene ring Y.sup.1 or Y.sup.2 is 4. In a case where Y.sup.1 and/or Y.sup.2 is a naphthalene ring, b and/or c corresponding to the naphthalene ring Y.sup.1 and/or Y.sup.2 is 6.

[0014] R.sup.1 to R.sup.3 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). In a case where a plurality of R.sup.1s, a plurality of Res, and a plurality of R.sup.3s are present, the plurality of R.sup.1s to R.sup.3s may be the same as or different from each other. However, R.sup.1s to R.sup.3s in the general formula (1-10) are not all hydrogen atoms at the same time.

[0015] Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1.

[0016] R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in the general formula (1-10) are not all hydrogen atoms at the same time.)

[0017] Furthermore, the hologram recording composition may further contain inorganic fine particles.

[0018] The hologram recording composition may further contain a cationically polymerizable compound.

[0019] In the hologram recording composition according to the present technology, the cationically polymerizable compound may be at least one selected from the group consisting of an epoxy compound and an oxetane compound.

[0020] The hologram recording composition may further contain a polymerization inhibitor.

[0021] Furthermore, the present technology also provides a hologram recording medium including a photocurable resin layer containing at least a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound.

[0022] The hologram recording medium according to the present technology may contain a monofunctional monomer and a polyfunctional monomer as the radically polymerizable monomer.

[0023] In the hologram recording medium according to the present technology, the radically polymerizable monomer may have a refractive index of 1.6 or more.

[0024] In the hologram recording medium according to the present technology, the radically polymerizable monomer may be at least one selected from the group consisting of a carbazole-based monomer, a fluorene-based monomer, and a dinaphthothiophene-based monomer.

[0025] In the hologram recording medium according to the present technology, the radically polymerizable monomer may be a compound represented by the following general formula (1-10).

STR00002

[0026] (In the general formula (1-10), X.sup.1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom. In a case where X.sup.1 is an oxygen atom, a is 0. In a case where X.sup.1 is a nitrogen atom or a phosphorus atom, a is 1. In a case where X.sup.1 is a carbon atom or a silicon atom, a is 2.

[0027] Y.sup.1 and Y.sup.2 are each a benzene ring or a naphthalene ring, and Y.sup.1 and Y.sup.2 are not both benzene rings at the same time. In a case where Y.sup.1 or Y.sup.2 is a benzene ring, b or c corresponding to the benzene ring Y.sup.1 or Y.sup.2 is 4. In a case where Y.sup.1 and/or Y.sup.2 is a naphthalene ring, b and/or c corresponding to the naphthalene ring Y.sup.1 and/or Y.sup.2 is 6.

[0028] R.sup.1 to R.sup.3 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). In a case where a plurality of R.sup.1s, a plurality of Res, and a plurality of R.sup.3s are present, the plurality of R.sup.1s to R.sup.3s may be the same as or different from each other. However, R.sup.1s to R.sup.3s in the general formula (1-10) are not all hydrogen atoms at the same time.

[0029] Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1.

[0030] R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in the general formula (1-10) are not all hydrogen atoms at the same time.)

[0031] Furthermore, the hologram recording medium according to the present technology may further contain inorganic fine particles.

[0032] The hologram recording medium according to the present technology may further contain a cationically polymerizable compound.

[0033] In the hologram recording medium according to the present technology, the cationically polymerizable compound may be at least one selected from the group consisting of an epoxy compound and an oxetane compound.

[0034] The hologram recording medium according to the present technology may further contain a polymerization inhibitor.

[0035] Moreover, the present technology also provides a hologram using the hologram recording medium according to the present technology.

[0036] The hologram according to the present technology may have absorption derived from an anthracene skeleton.

[0037] The present technology also provides an optical device using the hologram according to the present technology, and also provides an optical component using the hologram according to the present technology.

BRIEF DESCRIPTION OF DRAWINGS

[0038] FIG. 1 is a diagram schematically illustrating absorption derived from an anthracene skeleton.

[0039] FIG. 2 is a cross-sectional view schematically illustrating an example of a hologram recording medium according to an embodiment of the present technology.

MODE FOR CARRYING OUT THE INVENTION

[0040] Hereinafter, a preferable embodiment for carrying out the present technology will be described. Note that the embodiments described below exemplify typical embodiments of the present technology, and the scope of the present technology is not limited to the embodiments.

[0041] Note that the present technology will be described in the following order.

[0042] 1. Summary of the present technology

[0043] 2. First embodiment (hologram recording composition)

[0044] 2-1. Hologram recording composition

[0045] 2-2. Radically polymerizable monomer

[0046] 2-3. Matrix resin

[0047] 2-4. Photopolymerization initiator

[0048] 2-5. Anthracene-based compound

[0049] 2-6. Inorganic fine particles

[0050] 2-7. Plasticizer

[0051] 2-8. Polymerization inhibitor

[0052] 2-9. Other components

[0053] 2-10. Method for manufacturing hologram recording composition

[0054] 3. Second embodiment (hologram recording medium)

[0055] 3-1. Hologram recording medium

[0056] 3-2. Photocurable resin layer

[0057] 3-3. Transparent base material

[0058] 3-4. Method for manufacturing hologram recording medium

[0059] 4. Third embodiment (hologram)

[0060] 4-1. Hologram

[0061] 4-2. Method for manufacturing hologram

[0062] 5. Fourth embodiment (optical device and optical component)

1. Summary of the Present Technology

[0063] First, summary of the present technology will be described.

[0064] The present technology relates to a hologram recording composition, a hologram recording medium, a hologram, and an optical device and an optical component using the same.

[0065] So far, in order to obtain a hologram having a high refractive index modulation amount (.DELTA.n), it has been indispensable to go through a heating step after interference exposure, which has been a factor in complicating a process.

[0066] As a result of various studies, the present inventors have found that a reaction rate of a polymerization reaction occurring in a bright part during interference exposure can be controlled by using an anthracene-based compound as a material for a hologram, as a result, refractive index modulation is promoted, and the refractive index modulation amount (.DELTA.n) is increased. Furthermore, the present inventors have also found that the anthracene-based compound has a specific absorption region derived from an anthracene skeleton on a long wavelength side (around 350 nm to 400 nm) as illustrated in FIG. 1, therefore has high UV absorption efficiency, can improve UV energy utilization efficiency in a UV irradiation step, can suppress UV irradiation on a substance that is yellowed by UV, and therefore can suppress yellowing of a hologram.

[0067] That is, by combining a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound as materials for a hologram, the present technology can provide a hologram recording composition, a hologram recording medium, a hologram, and an optical device and an optical component using the same, having excellent diffraction characteristics without going through a heating step after exposure. Furthermore, the combination can also provide a hologram recording composition, a hologram recording medium, a hologram, and an optical device and an optical component using the same, having excellent transparency.

2. First Embodiment (Hologram Recording Composition)

[2-1. Hologram Recording Composition]

[0068] A hologram recording composition according to a first embodiment of the present technology is a hologram recording composition containing at least a radically polymerizable monomer, a matrix resin, a photopolymerization initiator, and an anthracene-based compound.

[0069] The hologram recording composition according to the first embodiment of the present technology can provide a hologram having a high refractive index modulation amount (.DELTA.n) without going through a heating step after exposure. Furthermore, the hologram recording composition can make the transparency of the hologram favorable. Hereinafter, each component will be described in detail.

[2-2. Radically Polymerizable Monomer]

[0070] The hologram recording composition according to the present embodiment contains a radically polymerizable monomer. The radically polymerizable monomer in the present embodiment preferably contains at least two radically polymerizable monomers, and more preferably further contains a monofunctional monomer and a polyfunctional monomer.

[0071] The radically polymerizable monomer in the present embodiment preferably has a refractive index of 1.6 or more from a viewpoint of making the diffraction characteristics of an obtained hologram favorable. Note that the refractive index can be measured by a critical angle method or a spectroscopic ellipsometry method. For example, in the critical angle method, the refractive index can be measured using an Abbe refractive index meter ER-1 manufactured by Erma Inc. (measurement is performed using a measurement wavelength such as 486 nm, 589 nm, or 656 nm in a visible light region).

[0072] The radically polymerizable monomer in the present embodiment is preferably at least one selected from the group consisting of a carbazole-based monomer, a fluorene-based monomer, and a dinaphthothiophene-based monomer.

[0073] In a preferable aspect, the hologram recording composition according to the present embodiment contains at least a monofunctional carbazole-based monomer and a polyfunctional fluorene-based monomer. In addition, the polyfunctional fluorene-based monomer is preferably a bifunctional fluorene-based monomer.

[0074] The monofunctional carbazole-based monomer is preferably a compound represented by the following general formula (1).

STR00003

[0075] In the above formula (1), only one of Y.sup.11 to Y.sup.15 is one of substituents represented by the following general formulas (2-1) to (2-7). Note that in a case where any two or more of Y.sup.11 to Y.sup.15 are two or more of the substituents represented by the following general formulas (2-1) to (2-7), the compound represented by general formula (1) is a polyfunctional (bifunctional or higher functional) carbazole-based monomer.

STR00004

[0076] Y.sup.11 to Y.sup.15 (excluding at least one of Y.sup.11 to Y.sup.15, which is at least one of the substituents represented by the above general formulas (2-1) to (2-7)) and R.sup.61 to R.sup.67 can be each independently, for example, an alkyl group (a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a trifluoromethyl group, and the like); a cycloalkyl group (a cyclopentyl group, a cyclohexyl group, and the like); an aryl group (a phenyl group, a naphthyl group, and the like); an acylamino group (an acetylamino group, a benzoylamino group, and the like); an alkylthio group (a methylthio group, an ethylthio group, and the like); an arylthio group (a phenylthio group, a naphthylthio group, and the like); an alkenyl group (a vinyl group, a 2-propenyl group, a 3-butenyl group, a 1-methyl-3-propenyl group, a 3-pentenyl group, a 1-methyl-3-butenyl group, a 4-hexenyl group, a cyclohexenyl group, and the like); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like); an alkynyl group (a propargyl group and the like); a heterocyclic group (a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, and the like); an alkylsulfonyl group (a methylsulfonyl group, an ethylsulfonyl group, and the like); an arylsulfonyl group (a phenylsulfonyl group, a naphthylsulfonyl group, and the like); an alkylsulfinyl group (a methylsulfinyl group and the like); an arylsulfinyl group (a phenylsulfinyl group and the like); a phosphono group; an acyl group (an acetyl group, a pivaloyl group, a benzoyl group, and the like); a carbamoyl group (an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a butylaminocarbonyl group, a cyclohexylaminocarbonyl group, a phenylaminocarbonyl group, a 2-pyridylaminocarbonyl group, and the like); a sulfamoyl group (an aminosulfonyl group, a methylaminosulfonyl group, a dimethylaminosulfonyl group, a butylaminosulfonyl group, a hexylaminosulfonyl group, a cyclohexylaminosulfonyl group, an octylaminosulfonyl group, a dodecylaminosulfonyl group, a phenylaminosulfonyl group, a naphthylaminosulfonyl group, a 2-pyridylaminosulfonyl group, and the like); a sulfonamide group (a methanesulfonamide group, a benzenesulfonamide group, and the like); a cyano group; an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, and the like); an aryloxy group (a phenoxy group, a naphthyloxy group, and the like); a heterocyclic oxy group; a siloxy group; an acyloxy group (an acetyloxy group, a benzoyloxy group, and the like); a sulfonic acid group; a sulfonate; an aminocarbonyloxy group; an amino group (an amino group, an ethylamino group, a dimethylamino group, a butylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, a dodecylamino group, and the like); an anilino group (a phenylamino group, a chlorophenylamino group, a toluidino group, an anisidino group, a naphthylamino group, a 2-pyridylamino group, and the like); an imide group; a ureido group (a methyl ureido group, an ethyl ureido group, a pentyl ureido group, a cyclohexyl ureido group, an octyl ureido group, a dodecyl ureido group, a phenyl ureido group, a naphthyl ureido group, a 2-pyridyl amino ureido group, and the like); an alkoxycarbonylamino group (a methoxycarbonylamino group, a phenoxycarbonylamino group, and the like); an alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, and the like); an aryloxycarbonyl group (a phenoxycarbonyl group and the like); a heterocyclic thio group; a thioureido group; a carboxyl group; a carboxylate; a hydroxyl group; a mercapto group; or a nitro group, but are not limited thereto. Furthermore, each of these groups may have a substituent, and examples of the substituent include similar groups to those described above.

[0077] The monofunctional carbazole-based monomer represented by the above general formula (1) can be synthesized by various known synthetic methods, but for example, can be synthesized on the basis of the synthetic method described in Japanese Patent Application Laid-Open No. 2015-105239.

[0078] In the present embodiment, among the carbazole-based monomers represented by general formula (1), a carbazole acrylate or an N-vinylcarbazole derivative is preferably used. For example, 2-(9H-carbazol-9-yl) ethyl acrylate (manufactured by SIGMA ALDRICH, refractive index: 1.65) and N-vinylcarbazole (manufactured by Tokyo Chemical Industry Co., Ltd., refractive index: 1.68) are preferably used.

[0079] The bifunctional fluorene-based monomer (polyfunctional fluorene-based monomer) is preferably a 9,9-bisarylfluorene, and examples thereof include a compound represented by the following general formula (3).

STR00005

[0080] In the above formula (3), a ring Z represents an aromatic hydrocarbon ring, R.sup.71 represents a substituent, R.sup.72 represents an alkylene group, R.sup.73 represents a hydrogen atom or a methyl group, R.sup.74 represents a substituent, k is an integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1. Note that in a case where p is 2 or more, the compound represented by general formula (3) is a polyfunctional fluorene-based monomer.

[0081] In the above formula (3), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring and a condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring. Among these rings, examples of the condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring include condensed bi- to tetra-cyclic arene rings such as a condensed bicyclic arene ring (a C.sub.8-20 condensed bicyclic arene ring such as an indene ring or a naphthalene ring, preferably a C.sub.10-16 condensed bicyclic arene ring); and a condensed tricyclic arene ring (an anthracene ring, a phenanthrene ring, and the like). Preferable examples of the condensed polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is more preferable of these rings. Note that the two rings Z in formula (3) may be the same ring or different rings, and usually may be the same ring.

[0082] The ring Z is typically a benzene ring or a naphthalene ring, and the ring Z may be a naphthalene ring from a viewpoint of high heat resistance, high refractive index, and the like of a hologram.

[0083] In the above formula (3), examples of the group R.sup.71 include a non-reactive substituent such as a cyano group; a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and the like); or a hydrocarbon group [an alkyl group, an aryl group (a C.sub.6-10 aryl group such as a phenyl group), and the like], but the group R.sup.71 is preferably a group which is not a halogen atom, such as an alkyl group. Examples of the alkyl group include a C.sub.1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a t-butyl group (for example, a C.sub.1-8 alkyl group, particularly a C.sub.1-4 alkyl group such as a methyl group). Note that in a case where k in formula (3) is plural (2 or more), the groups R.sup.71s may be different from or the same as each other. Furthermore, the groups R.sup.71s to be substituted for the two benzene rings constituting fluorene (or fluorene skeleton) may be the same as or different from each other. Furthermore, bond positions (substitution positions) of the groups R.sup.71s to the benzene rings constituting fluorene are not particularly limited. The substitution number k is preferably 0 or 1, and more preferably 0. Note that the two benzene rings constituting fluorene may have the same substitution number k as each other or different substitution numbers k from each other.

[0084] In the above formula (3), examples of the alkylene group represented by the group R.sup.72 include a C.sub.2-6 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, or a tetramethylene group. Preferable examples thereof include a C.sub.2-4 alkylene group. More preferable examples thereof include a C.sub.2-3 alkylene group. Note that in a case where m in formula (3) is 2 or more, the alkylene groups may be constituted by different alkylene groups, or may be usually constituted by the same alkylene group. Furthermore, in the two rings Z, the groups R.sup.72s may be the same as or different from each other, and may be usually the same.

[0085] The number (additional mol number) m of the oxyalkylene groups (OR.sup.72s) in the above formula (3) can be selected from a range of about 0 to 15 (for example, 0 to 12), and may be, for example, 0 to 8 (for example, 0 to 8), preferably 0 to 6 (for example, 1 to 6), and more preferably 0 to 4 (for example, 1 to 4). In particular, m may be 1 or more (for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, and particularly 1). Note that different rings Z may have the same substitution number m as each other or different substitution numbers m from each other. Furthermore, in the two rings Z, the total number of oxyalkylene groups (m.times.2) can be selected from a range of about 0 to 30 (for example, 2 to 24), and may be, for example, 0 to 16 (for example, 2 to 14), preferably 0 to 12 (for example, 2 to 10), more preferably 0 to 8 (for example, 0 to 6), and particularly 0 to 4 (for example, 2 to 4).

[0086] In the above formula (3), the substitution number p of the group containing the group R.sup.72 (also referred to as a (meth)acryloyl group-containing group and the like) is 1, but is 2 or more in a case of a polyfunctional fluorene-based monomer. Note that the different rings Z may have the same substitution number p as each other or different substitution numbers p from each other, and usually often have the same substitution number p. Note that a substitution position of the (meth)acryloyl group-containing group is not particularly limited, and the (meth)acryloyl group-containing group only needs to be substituted at an appropriate substitution position of the ring Z. For example, in a case where the ring Z is a benzene ring, the (meth)acryloyl group-containing group may be substituted at an appropriate position (particularly at least 4-position) among 2- to 6-positions of the benzene ring, and in a case where the ring Z is a condensed polycyclic hydrocarbon ring, the (meth)acryloyl group-containing group may be substituted at least for a hydrocarbon ring (for example, 5-position, 6-position, and the like of a naphthalene ring) different from the hydrocarbon ring bonded to 9-position of fluorene.

[0087] In the above formula (3), the substituent R.sup.74 substituted for the ring Z is usually a non-reactive substituent, and examples thereof include a hydrocarbon group such as an alkyl group (a C.sub.1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a C.sub.1-8 alkyl group, more preferably a C.sub.1-6 alkyl group, and the like), a cycloalkyl group (a C.sub.5-8 cycloalkyl group such as a cyclohexyl group, preferably a C.sub.5-6 cycloalkyl group, and the like), an aryl group (a C.sub.6-14 aryl group such as a phenyl group, a tolyl group, a xylyl group, or a naphthyl group, preferably a C.sub.6-10 aryl group, more preferably a C.sub.6-8 aryl group, and the like), or an aralkyl group (a C.sub.6-10 aryl-C.sub.1-4 alkyl group such as a benzyl group or a phenethyl group, and the like); a group-OR.sup.75 [in which R.sup.75 represents a hydrocarbon group (the above-exemplified hydrocarbon groups and the like)] such as an alkoxy group (a C.sub.1-8 alkoxy group such as a methoxy group or an ethoxy group, preferably a C.sub.1-6 alkoxy group, and the like), a cycloalkoxy group (a C.sub.5-10 cycloalkyloxy group such as a cyclohexyloxy group), an aryloxy group (a C.sub.6-10 aryloxy group such as a phenoxy group), or an aralkyloxy group (a C.sub.6-10 aryl-C.sub.1-4 alkyloxy group such as a benzyloxy group); a group-SR.sup.75 (in which R.sup.75 represents the same as above) such as an alkylthio group (a C.sub.1-8 alkylthio group such as a methylthio group or an ethylthio group, preferably a C.sub.1-6 alkylthio group, and the like), a cycloalkylthio group (a C.sub.5-10 cycloalkylthio group such as a cyclohexylthio group, and the like), an arylthio group (a C.sub.6-10 arylthio group such as a thiophenoxy group), or an aralkylthio group (a C.sub.6-10 aryl-C.sub.1-4 alkylthio group such as a benzylthio group); an acyl group (a C.sub.1-6 acyl group such as an acetyl group); an alkoxycarbonyl group (a C.sub.1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like); a nitro group; a cyano group; and a substituted amino group (a dialkylamino group such as a dimethylamino group, and the like).

[0088] Preferable examples of the group R.sup.74 include a hydrocarbon group [an alkyl group (for example, a C.sub.1-6 alkyl group), a cycloalkyl group (for example, a C.sub.5-8 cycloalkyl group), an aryl group (for example, a C.sub.6-10 aryl group), an aralkyl group (for example, a C.sub.6-8 aryl-C.sub.1-2 alkyl group), and the like], and an alkoxy group (for example, a C.sub.1-4 alkoxy group). Among these groups, an alkyl group [a C.sub.1-4 alkyl group (particularly a methyl group) and the like], an aryl group [a C.sub.6-10 aryl group (particularly a phenyl group) and the like], and the like are more preferable.

[0089] Note that in a case where n in the same ring Z is plural (2 or more), the groups R.sup.74s may be different from or the same as each other. Furthermore, in the two rings Z, the groups R.sup.74s may be the same as or different from each other. Furthermore, the preferable substitution number n can be selected according to the type of ring Z, and may be, for example, 0 to 8, preferably 0 to 4 (for example, 0 to 3), and more preferably 0 to 2. Note that different rings Z may have the same substitution number n as each other or different substitution numbers n from each other, and may usually have the same substitution number n.

[0090] The bifunctional fluorene-based monomer (polyfunctional fluorene-based monomer) represented by the above general formula (3) can be synthesized by various known synthetic methods, but for example, can be synthesized on the basis of the synthetic method described in Japanese Patent Application Laid-Open No. 2012-111942.

[0091] In the present embodiment, as the fluorene-based monomer represented by general formula (3), for example, bisphenoxyethanol fluorene diacrylate (“EA-0200” manufactured by Osaka Gas Chemicals Co., Ltd., refractive index: 1.62) is preferably used.

[0092] In a preferable aspect, the hologram recording composition according to the present embodiment contains at least a monofunctional dinaphthothiophene-based monomer and a polyfunctional fluorene-based monomer. In addition, the polyfunctional fluorene-based monomer is preferably a bifunctional fluorene-based monomer.

[0093] The monofunctional dinaphthothiophene-based monomer is preferably a compound represented by the following general formula (4).

STR00006

[0094] In the above formula (4), R.sup.4 is a substituent on a benzene ring not condensed with a thiophene ring, and is a hydroxy group, a 2-allyloxy group, a vinyloxy group, a 2,3-epoxypropoxy group, a 2-(meth)acryloyloxy group, a 2-(meth)acryloyloxyethoxy group, an R.sup.41O-group (in which R.sup.41 represents an alkyl group which may contain an oxygen atom or a sulfur atom as a heteroatom), or an HO–X–O– group (in which X represents an alkylene chain or an aralkylene chain which may contain an oxygen atom or a sulfur atom as a heteroatom).

[0095] In a case of a monofunctional dinaphthothiophene-based monomer, one of the two R.sup.4s in the above formula (4) is a group having a polymerizable unsaturated bond. In a case of a bifunctional dinaphthothiophene-based monomer, the two R.sup.4s in the above formula (4) are each a group having a polymerizable unsaturated bond.

[0096] In the above formula, R.sup.41 is an alkyl group which may contain an oxygen atom or a sulfur atom as a heteroatom. R.sup.41 may be, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a dodecyl group, a cetyl group, a methoxymethyl group, a 2-methoxyethyl group, an ethoxymethyl group, a 2-(ethoxy) ethyl group, and a 2-(methyl mercapto) ethyl group.

[0097] Furthermore, X is an alkylene chain or an aralkylene chain which may contain an oxygen atom or a sulfur atom as a heteroatom. The alkylene chain may be, for example, a linear or branched alkylene chain having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a decamethylene group, a propylene group, and a cyclohexylene group. Examples of the alkylene chain which may contain a heteroatom of oxygen or sulfur include a polyoxyalkylene chain having oxyethylene or oxypropylene as a repeating unit.

[0098] Examples of an alkylene portion of the aralkylene chain which may contain a heteroatom of oxygen or sulfur include the above-described alkylene chain.

[0099] The dinaphthothiophene-based monomer represented by the above general formula (4) can be synthesized by various known synthetic methods, but for example, can be synthesized on the basis of the synthetic method described in Japanese Patent Application Laid-Open No. 2014-196288.

[0100] In the present embodiment, as the dinaphthothiophene-based monomer represented by general formula (4), for example, dinaphthothiophene methacrylate (“DNTMA” manufactured by Sugai Chemical Industry Co., Ltd., refractive index: 1.89) is preferably used.

[0101] In another preferable aspect, the hologram recording composition according to the present embodiment contains at least monofunctional and polyfunctional acrylates or methacrylates and inorganic fine particles described later. In a case where the hologram recording composition contains inorganic fine particles, a radically polymerizable monomer having a low refractive index is preferably used.

[0102] Examples of the monofunctional acrylate include an alkyl acrylate (lauryl acrylate, tetradecyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate, and the like); isobornyl acrylate; methoxypolyethylene glycol acrylate; methoxypolypropylene glycol acrylate; and a benzene ring-containing acrylate (phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, and the like). Furthermore, examples of the monofunctional methacrylate include methacrylates of the above-described compounds.

[0103] On the other hand, examples of the polyfunctional acrylate include an alkyl diacrylate (1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, isononanediol diacrylate, 1,10-decanediol diacrylate, neopentyl glycol diacrylate, and the like); polyethylene glycol diacrylate; dipropylene glycol diacrylate; tripropylene glycol diacrylate; and polytetramethylene glycol diacrylate. Furthermore, examples of the polyfunctional methacrylate include methacrylates of the above-described compounds.

[0104] Note that among these compounds, a compound having a refractive index that is not high is preferably used from a viewpoint of combination with inorganic fine particles, and a monomer not having an aromatic structure such as a benzene ring is preferably used. More specifically, a monomer having a (saturated) alkyl or a (saturated) alicyclic hydrocarbon structure is preferably used.

[0105] Furthermore, the radically polymerizable monomer in the present embodiment may be a compound represented by the following general formula (1-10). The compound has a high refractive index, and has favorable transparency and solubility in an organic solvent.

STR00007

[0106] In general formula (1-10), X.sup.1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom. In a case where X.sup.1 is an oxygen atom, a is 0. In a case where X.sup.1 is a nitrogen atom or a phosphorus atom, a is 1. In a case where X.sup.1 is a carbon atom or a silicon atom, a is 2.

[0107] Y.sup.1 and Y.sup.2 are each a benzene ring or a naphthalene ring, and Y.sup.1 and Y.sup.2 are not both benzene rings at the same time. In a case where Y.sup.1 or Y.sup.2 is a benzene ring, b or c corresponding to the benzene ring Y.sup.1 or Y.sup.2 is 4. In a case where Y.sup.1 and/or Y.sup.2 is a naphthalene ring, b and/or c corresponding to the naphthalene ring Y.sup.1 and/or Y.sup.2 is 6.

[0108] R.sup.1 to R.sup.3 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). In a case where a plurality of R.sup.1s, a plurality of R.sup.2s, and a plurality of R.sup.3s are present, the plurality of R.sup.1s to R.sup.3s may be the same as or different from each other. However, R.sup.1s to R.sup.3s in general formula (1-10) are not all hydrogen atoms at the same time.

[0109] Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1.

[0110] R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in general formula (1-10) are not all hydrogen atoms at the same time.

[0111] That is, the compound represented by general formula (1-10) may have the following structure.

STR00008

[0112] In general formulas (2-11) to (2-15), Y.sup.1 and Y.sup.2 are each a benzene ring or a naphthalene ring, and Y.sup.1 and Y.sup.2 are not both benzene rings at the same time. In a case where Y.sup.1 or Y.sup.2 is a benzene ring, b or c corresponding to the benzene ring Y.sup.1 or Y.sup.2 is 4. In a case where Y.sup.1 and/or Y.sup.2 is a naphthalene ring, b and/or c corresponding to the naphthalene ring Y.sup.1 and/or Y.sup.2 is 6.

[0113] R.sup.1, R.sup.2, R.sup.3, R.sup.11, and R.sup.12 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). In a case where a plurality of R.sup.1s, a plurality of R.sup.2s, and a plurality of R.sup.3s are present, the plurality of R.sup.1s to R.sup.3s may be the same as or different from each other. However, R.sup.1s, R.sup.2s, R.sup.3s, R.sup.11, and R.sup.12 in general formulas (2-11) to (2-15) are not all hydrogen atoms at the same time.

[0114] Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1.

[0115] R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in general formulas (2-11) to (2-15) are not all hydrogen atoms at the same time.

[0116] Furthermore, in the above general formula (1-10), Y.sup.1 and Y.sup.2 are each a benzene ring or a naphthalene ring, and Y.sup.1 and Y.sup.2 are not both benzene rings at the same time.

[0117] Molecular refraction values of phenyl (C.sub.6H.sub.5) and naphthyl (C.sub.10H.sub.7) are phenyl (C.sub.6H.sub.5): 25.5 and naphthyl (C.sub.10H.sub.7): 43.3. (Optics, Vol. 44, No. 8, 2015, p 298-303). In the present embodiment, Y.sup.1 and Y.sup.2 are each preferably a naphthalene ring having a high molecular refraction value from a viewpoint of obtaining a compound having a high refractive index.

[0118] That is, the compound represented by general formula (1-10) may have the following structure.

STR00009## ##STR00010

[0119] In general formulas (3-1) to (3-3) and (4-1) to (4-6), X.sup.1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom. In a case where X.sup.1 is an oxygen atom, a is 0. In a case where X.sup.1 is a nitrogen atom or a phosphorus atom, a is 1. In a case where X.sup.1 is a carbon atom or a silicon atom, a is 2.

[0120] R.sup.1, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). R.sup.1, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 may be the same as or different from each other. Furthermore, in a case where a plurality of R.sup.1s is present, the plurality of R.sup.1s may be the same as or different from each other. However, R.sup.1, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 in general formulas (3-1) to (3-3) and (4-1) to (4-6) are not all hydrogen atoms at the same time.

[0121] Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1.

[0122] R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in general formulas (3-1) to (3-3) and (4-1) to (4-6) are not all hydrogen atoms at the same time.

[0123] In the above general formula (1), Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group. The saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond.

[0124] In a case where Z.sup.1 is a divalent or higher valent saturated hydrocarbon group, the saturated hydrocarbon group may be a linear, branched, or cyclic substituted or unsubstituted hydrocarbon group. In general, an organic compound tends to have higher solubility as the number of simple carbon chains is longer, while the organic compound tends to have a lower refractive index as the number of simple carbon chains is longer. Therefore, the simple carbon chain number of the saturated hydrocarbon group is preferably 1 to 15, and more preferably 1 to 10.

[0125] Furthermore, in a case where Z.sup.1 is a divalent or higher valent unsaturated hydrocarbon group, the unsaturated hydrocarbon group may be a linear, branched, or cyclic substituted or unsubstituted hydrocarbon group or aromatic group. The simple carbon chain number of the unsaturated hydrocarbon group is preferably 1 to 15, and more preferably 1 to 10. In a case where the unsaturated hydrocarbon group contains an aromatic group, the aromatic group is preferably a substituted or unsubstituted divalent or higher valent aromatic group represented by any one of the following chemical formulas (5-1) to (5-8). When four or more benzene rings are linearly connected to each other, the benzene rings have absorption in a visible light region and have a color, which is not preferable from a viewpoint of transparency in some cases. Therefore, the aromatic group preferably has a structure in which four or more benzene rings are not linearly arranged, and the linear shape is preferably up to a benzene ring, a naphthalene ring, or an anthracene ring.

STR00011## ##STR00012

[0126] In the above general formula (1-10), examples of the polymerizable substituent represented by R.sup.4 include a substituent having a polymerizable unsaturated group and a substituent having a reactive substituent. Examples of the substituent having a polymerizable unsaturated group include a vinyl group, an acrylic group, a methacrylic group, an acrylamide group, a methacrylamide group, a cyanoacrylate group, a cyanomethacrylate group, a vinyl ether group, a vinyl cyanide group, a vinyl nitrate group, a conjugate polyene group, a vinyl halide group, a vinyl ketone group, and a styryl group. Examples of the substituent having a reactive substituent include an epoxy group, an oxetane group, a hydroxy group, an amino group, a carboxyl group, an acid anhydride group, an acid halide group, and an isocyanate group.

[0127] In the above general formula (1-10), X.sup.1 is preferably a nitrogen atom, and Y.sup.1 and Y.sup.2 are each preferably a naphthalene ring. That is, the compound is preferably a compound represented by the following general formula (1-1).

STR00013

[0128] In general formula (1-1), R.sup.1, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). R.sup.1, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 may be the same as or different from each other. However, R.sup.1, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 are not all hydrogen atoms at the same time.

[0129] Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1.

[0130] R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in general formula (1-1) are not all hydrogen atoms at the same time.

[0131] In general formula (1-1), R.sup.1 is preferably a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position), and R.sup.21 to R.sup.26 and R.sup.31 to R.sup.36 are each preferably a hydrogen atom.

[0132] Furthermore, in the above general formula (1-10), X.sup.1 is preferably a carbon atom, and Y.sup.1 and Y.sup.2 are each preferably a naphthalene ring. That is, the compound is preferably a compound represented by the following general formula (1-2).

STR00014

[0133] In general formula (1-2), R.sup.11, R.sup.12, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 are each a hydrogen atom or a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position). R.sup.11, R.sup.12, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 may be the same as or different from each other. However, R.sup.11, R.sup.12, R.sup.21 to R.sup.26, and R.sup.31 to R.sup.36 in general formula (1-2) are not all hydrogen atoms at the same time.

[0134] Z.sup.1 represents a single bond, a divalent or higher valent saturated hydrocarbon group, or a divalent or higher valent unsaturated hydrocarbon group, and the saturated hydrocarbon group or the unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond. In a case where Z.sup.1 is a single bond, d is 1. In a case where Z.sup.1 is a saturated hydrocarbon group or an unsaturated hydrocarbon group, d is an integer equal to or larger than 1.

[0135] R.sup.4 represents a hydrogen atom or a polymerizable substituent. In a case where a plurality of R.sup.4s is present, the plurality of R.sup.4s may be the same as or different from each other. However, R.sup.4s in general formula (1-2) are not all hydrogen atoms at the same time.

[0136] In general formula (1-2), R.sup.11 and/or R.sup.12 is preferably a substituent represented by –Z.sup.1(R.sup.4).sub.d ( represents a bond position), and R.sup.21 to R.sup.26 and R.sup.31 to R.sup.36 are each preferably a hydrogen atom.

[0137] The chemical structural formulas of preferable monofunctional exemplified compounds of the compound represented by general formula (1-10) are as follows.

STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022

[0138] A lower limit of the refractive index of the compound represented by general formula (1-10) is preferably 1.60, more preferably 1.65, and still more preferably 1.70. On the other hand, an upper limit of the refractive index of the compound represented by general formula (1-10) is, for example, 1.80, but may be more than 1.80.

[0139] Note that the refractive index can be measured by a critical angle method or a spectroscopic ellipsometry method. For example, in the critical angle method, the refractive index can be measured using an Abbe refractive index meter ER-1 manufactured by Erma Inc. (measurement is performed using a measurement wavelength such as 486 nm, 589 nm, or 656 nm in a visible light region).

[2-3. Matrix Resin]

[0140] The matrix resin contained in the hologram recording composition according to the present embodiment is not particularly limited, and any matrix resin can be used.

[0141] Examples of the matrix resin include a vinyl acetate-based resin such as polyvinyl acetate or a hydrolyzate thereof; an acrylic resin such as poly (meth)acrylate or a partial hydrolyzate thereof; polyvinyl alcohol or a partial acetal product thereof; triacetylcellulose; polyisoprene; polybutadiene; polychloroprene; silicone rubber; polystyrene; polyvinyl butyral; polyvinyl chloride; polyarylate; chlorinated polyethylene; chlorinated polypropylene; poly-N-vinylcarbazole or a derivative thereof; poly-N-vinylpyrrolidone or a derivative thereof; polyarylate; a copolymer of styrene and maleic anhydride or a semiester thereof; and a copolymer containing, as a polymerization component, at least one of copolymerizable monomers such as acrylic acid, acrylate, methacrylic acid, methacrylate, acrylamide, acrylnitrile, ethylene, propylene, vinyl chloride, and vinyl acetate, and one or more of these can be used. Moreover, as the copolymerization component, a monomer containing a thermosetting or photocurable functional group can also be used.

[0142] Furthermore, as the matrix resin, an oligomer type curable resin can also be used. Examples thereof include epoxy compounds generated by a condensation reaction between various phenol compounds such as bisphenol A, bisphenol S, novolak, o-cresol novolak, and p-alkylphenol novolak, and epichlorohydrin, and one or more of these can be used.

[2-4. Photopolymerization Initiator]

[0143] The photopolymerization initiator contained in the hologram recording composition according to the present embodiment is not particularly limited, and any photopolymerization initiator can be used.

[0144] Examples of the photopolymerization initiator in the present embodiment include a radical polymerization initiator (radical generator), a cationic polymerization initiator (acid generator), and an agent having both of these functions. Note that as the photopolymerization initiator, an anionic polymerization initiator (base generator) may be used.

[0145] Examples of the radical polymerization initiator (radical generator) include an imidazole derivative, a bisimidazole derivative, an N-arylglycine derivative, an organic azide compound, a titanocene, an aluminate complex, an organic peroxide, an N-alkoxypyridinium salt, and a thioxanthone derivative.

[0146] Specific examples thereof include 1,3-di(t-butyldioxycarbonyl) benzophenone, 3,3’,4,4’-tetrakis(t-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Irgacure 651 manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), and bis(.eta.5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-p- henyl) titanium (trade name: Irgacure 784 manufactured by Ciba Specialty Chemicals Co., Ltd.), but are not limited thereto.

[0147] Examples of the cationic polymerization initiator (acid generator) include sulfonate, imide sulfonate, a dialkyl-4-hydroxysulfonium salt, an aryl sulfonic acid-p-nitrobenzyl ester, a silanol-aluminum complex, and (.eta.6-benzene) (.eta.5-cyclopentadienyl) iron (II).

[0148] Specific examples thereof include benzointosylate, 2,5-dinitrobenzyltosylate, and N-imide tosyphthalate, but are not limited thereto.

[0149] Examples of the agent used as both a radical polymerization initiator (radical generator) and a cationic polymerization initiator (acid generator) include a diaryliodonium salt, a diaryliodonium organic boron complex, an aromatic sulfonium salt, an aromatic diazonium salt, an aromatic phosphonium salt, a triazine compound, and an iron arene complex-based compound.

[0150] Specific examples thereof include: an iodonium salt such as a chloride, a bromide, a borofluoride salt, a hexafluorophosphate salt, or a hexafluoroantimonate salt of an iodonium such as 4-isopropyl-4’-methyldiphenyliodonium tetrakis(pentafluorophenyl) borate, diphenyliodonium, ditolyliodonium, bis(p-tert-butylphenyl) iodonium, or bis(p-chlorophenyl) iodonium; a sulfonium salt such as a chloride, a bromide, a borofluoride salt, a hexafluorophosphate salt, or a hexafluoroantimonate salt of a sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, or tris(4-methylphenyl) sulfonium; and a 2,4,6-substituted-1,3,5-triazine compound such as 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, or 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, but are not limited thereto.

[2-5. Anthracene-Based Compound]

[0151] The anthracene-based compound contained in the hologram recording composition according to the present embodiment has an effect of controlling a reaction rate of a polymerization reaction occurring in a bright part during interference exposure. Since the reaction rate control works advantageously for formation of a separated structure of a hologram, diffraction characteristics of an obtained hologram can be made favorable. Furthermore, the anthracene-based compound has a specific absorption region derived from an anthracene skeleton on a long wavelength side (around 350 nm to 400 nm) as illustrated in FIG. 1, therefore has high UV absorption efficiency, can improve UV energy utilization efficiency in a UV irradiation step, can suppress UV irradiation on a substance that is yellowed by UV, and therefore can suppress yellowing of a hologram to make transparency favorable.

[0152] The anthracene compound in the present embodiment is preferably a compound represented by the following general formula (5).

STR00023

[0153] In the above formula (5), examples of R.sup.51 and R.sup.52 include a hydrocarbon group such as an alkyl group (a C.sub.1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group), a cycloalkyl group (a cyclohexyl group and the like), an aryl group (a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like), or an aralkyl group (a benzyl group, a phenethyl group, and the like); a group-OR.sup.53 [in which R.sup.53 represents a hydrogen atom or a hydrocarbon group (the above-exemplified hydrocarbon groups and the like)] such as an alkoxy group (a C.sub.1-12 alkoxy group such as a methoxy group or an ethoxy group, and the like), a hydroxyalkyl group (a hydroxymethyl group, a hydroxyethyl group, and the like), a cycloalkoxy group (a cyclohexyloxy group and the like), an aryloxy group (a phenoxy group and the like), or an aralkyloxy group (a benzyloxy group and the like); a group-SR.sup.35 (in which R.sup.53 is the same as above) such as an alkylthio group (a methylthio group, an ethylthio group, and the like), a cycloalkylthio group (a cyclohexylthio group and the like), an arylthio group (a thiophenoxy group and the like), or an aralkylthio group (a benzylthio group and the like); an acyl group (an acetyl group and the like); an alkoxycarbonyl group (a methoxycarbonyl group and the like); a hydrogen atom; a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like); a nitro group; a cyano group; and a substituted amino group (a dialkylamino group such as a dimethylamino group, and the like). Note that R.sup.51 and R.sup.52 in formula (5) may be different from or the same as each other.

[0154] In the above formula (5), examples of Y.sup.51 and Y.sup.52 include a hydrocarbon group such as an alkyl group (a C.sub.1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a t-butyl group, and the like), or an aryl group (a C.sub.6-10 aryl group such as phenyl group); a hydrogen atom; and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and the like). Note that Y.sup.51 and Y.sup.52 in formula (5) may be different from or the same as each other.

[0155] The anthracene compound represented by the above general formula (5) can be synthesized by various known synthetic methods, but for example, can be synthesized on the basis of the synthetic method described in Japanese Patent Application Laid-Open No. 2018-018061.

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