Compound, polymerizable composition, hologram recording medium, polymer, optical material, and optical component

Abstract

Provided is a compound which is useful as an optical material or an optical component, exhibits a high refractive index and high transparency, is easily polymerizable, exhibits chemical stability and high solubility in a variety of solvents, and exhibits storage stability as a solution. The compound is represented by formula (1). In the formula, n denotes an integer between 1 and 3. L denotes an optionally branched linking group having a valency of (n+1). Y1 and Y2 each independently denote an aromatic group having a total of 7-20 carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms. Ar1 and Ar2 each independently denote an optionally substituted aromatic hydrocarbon group. A ring structure may not be formed by Ar1 and T1 nor by Ar2 and Y2. p and q each independently denote an integer between 0 and 5. However, p and q may not both be 0. R1 denotes a hydrogen atom or a methyl group.

Description

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

[0001] The present invention relates to a compound useful as an optical material or optical component, which has a high refractive index, high transparency, easy polymerization, chemical stability, high solubility in various solvents, and storage stability of the solution. The present invention also relates to a polymerizable composition containing the compound, and a holographic recording medium, an optical material, and an optical component using a polymer of the compound.

[0002] Glass has traditionally been widely used as an optical material. For example, when manufacturing optical lenses using a material with a high refractive index, even lenses with the same focal length can be made thinner, offering the advantages of reduced weight and increased freedom in designing the optical path. High refractive index optical lenses are also effective in reducing the size, increasing the resolution, and widening the angle of view of optical imaging devices.

[0003] In recent years, highly transparent plastics have been attracting attention as optical materials to replace glass. Compared to glass, plastic materials have advantages such as being easier to reduce in weight, improving mechanical strength, and being easier to process and mold. With the development of peripheral technologies, there is also an increasing demand for improved performance in plastic optical materials. For example, materials for optical lenses are required to be easily polymerizable (easily polymerizable), have good curability and solubility in various solvents, and have a high refractive index after polymerization.

[0004] Many resins have been developed to increase the refractive index. Incorporating sulfur atoms or aromatic rings into the molecule is effective for increasing the refractive index. For example, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene is frequently used as a high refractive index acrylate. However, the refractive index of this compound is only about 1.62, which is not sufficiently high (Patent Document 1).

[0005] Patent Documents 2 and 3 describe acrylate compounds having a dibenzocarbazole group and a refractive index exceeding 1.7. However, these compounds have electron-rich alkylcarbazole groups that are easily oxidized by oxygen, and therefore there is concern that discoloration or changes in color tone may occur when heated in air, stored for a long period of time, or exposed to light, and therefore the compounds cannot be said to be materials with high chemical stability.

[0006] Patent Documents 4 and 5 describe acrylate compounds having a glycerin skeleton and two sulfur-containing heteroaromatic ring groups per molecule. While these compounds are excellent acrylate monomers with refractive indices exceeding 1.65, they have multiple alkyl sulfide bonds, making them susceptible to air oxidation and presenting problems with chemical stability. Furthermore, because (meth)acrylate is directly bonded to the glycerin skeleton, the periphery of the polymerizable group is sterically shielded by the high-refractive-index aromatic ring group, resulting in poor solubility in various solvents and low polymerization.

[0007] Patent Documents 6 to 8 describe high refractive index (meth)acrylate monomers with a pentaerythritol structure as the main skeleton. These documents provide ultra-high refractive index compounds with two or three high refractive index structures and a refractive index exceeding 1.70. However, the introduction of a high refractive index unit into the pentaerythritol skeleton is a nucleophilic substitution reaction at the neopentyl position, which requires the use of a sulfur atom with high nucleophilicity. As a result, a single molecule contains multiple alkyl sulfide structures, raising concerns about chemical stability, such as decomposition of the high refractive index structure due to air oxidation and yellowing.

[0008] Patent Documents 9 and 10 describe that linear molecular monomers in which a phenol substituted with multiple aromatic rings is linked to a polymerizable group via a linker exhibit high solubility. These compounds, in which a polymerizable (meth)acrylate group and a high-refractive-index aromatic structure are localized at both ends via a linking group, exhibit high polymerizability because the polymerizable group is isolated from the aromatic ring group, which has high steric hindrance. However, because the periphery of the linking group constituting the (meth)acrylate main chain or side chain of the resulting polymer is far from the aromatic ring group, which has high chemical stability, the polymer is susceptible to decomposition by external factors such as acids and bases, which can cause problems with the heat resistance of the polymer. Furthermore, due to their high polymerizability, when used as raw materials for precision optical materials, there is a concern that excessive reaction may result in a deterioration in some optical performance.

[0009] Japanese Patent Publication No. 6-220131 International Publication No. 2021 / 006011 International Publication No. 2021 / 006012 Japanese Patent Publication No. 2005-133071 Japanese Patent No. 6458645 Japanese Patent No. 7371699 International Publication No. 2022 / 202538 International Publication No. 2024 / 063135 Japanese Patent No. 6089867 International Publication No. 2024 / 085208

[0010] An object of the present invention is to provide a compound that, when used as a recording medium such as a hologram, has a high refractive index yet is less likely to cause unintended recording. Another object of the present invention is to provide a compound that is useful as an optical material or optical component and has a high refractive index, high transparency, easy polymerization, chemical stability, high solubility in various solvents, and storage stability of the solution. Another object of the present invention is to provide a polymerizable composition containing the compound, and a hologram recording medium, optical material, and optical component using a polymer thereof.

[0011] As a result of extensive research, the present inventors have found that a compound having two high-refractive index molecular structures consisting of aromatic groups at the ends of a glycerin-like skeleton and a polymerizable group linked to a secondary alcohol-derived moiety located in the center of the skeleton via a linker of appropriate chain length can solve the problems of the present invention. This has led to the discovery that polymerizable compositions and polymers containing the compound of the present invention are materials with excellent optical performance, combining a high refractive index, high heat resistance, high transparency, easy polymerization, and chemical stability. Specifically, the present inventors have found that the use of a compound represented by the following formula (1) can produce high-performance holographic recording media with high diffraction efficiency and high heat resistance, leading to the completion of the present invention.

[0012] That is, the gist of the present invention lies in the following.

[0013] [1] A compound represented by the following formula (1):

[0014]

[0015] [In the formula, n represents an integer of 1 to 3. L represents an optionally branched (n+1)-valent linking group. Y 1 , Y 2 each independently represents an aromatic ring group having a total of 7 to 20 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. １ , Ar 2 each independently represents an aromatic hydrocarbon group. １ , Ar 2 are Y 1 , Y 2 Ar may have a substituent other than １ and Y 1 , Ar 2 and Y 2 p and q each independently represent an integer of 0 to 5, provided that p and q are not both 0. Y １ , Y ２ When there are multiple Y １ and Y ２ may be the same or different. １ represents a hydrogen atom or a methyl group. １ If there are multiple R１ may be the same or different.]

[0016] [2] The Ar １ , Ar 2 are each independently an aromatic hydrocarbon group having 6 to 16 carbon atoms.

[0017] [3] The Y １ , Y ２ each independently represent an aromatic hydrocarbon group having a total of 10 to 14 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms.

[0018] [4] The Y １ , Y ２ are each independently a naphthyl group or a phenanthryl group which may have a substituent.

[0019] [5] The Y １ and Y ２ is a naphthyl group which may have a substituent, and Y １ is a naphthyl group, Ar is at the 1st or 2nd position of the naphthyl group １ and Y ２ is a naphthyl group, Ar is at the 1st or 2nd position of the naphthyl group ２ The compound according to [4], wherein

[0020] [6] The Y １ and Y ２ is a phenanthryl group which may have a substituent, and Y １ is a phenanthryl group, Ar is at the 9-position of the phenanthryl group １ and Y ２ is a phenanthryl group, Ar is at the 9-position of the phenanthryl group ２ The compound according to [4], wherein

[0021] [7] The compound according to any one of [1] to [6], wherein L is a group containing a urethane bond.

[0022] [8] The Y １ and Y ２The compound according to any one of [1] to [7], wherein

[0023] [9] The Ar １ and Ar 2 The compound according to any one of [1] to [8], wherein the aromatic hydrocarbon groups of Ar １ and Ar 2 are both benzene rings.

[0024]

[11] A polymerizable composition containing the compound according to any one of [1] to

[10] and a polymerization initiator.

[0025]

[12] A polymerizable composition containing a compound represented by the following formula (1) and a polymerization initiator:

[0026]

[0027] [In the formula, n represents an integer of 1 to 3. L represents an optionally branched (n+1)-valent linking group. Y 1 , Y 2 each independently represents an aromatic ring group having a total of 7 to 20 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. １ , Ar 2 each independently represents an aromatic hydrocarbon group. １ , Ar 2 are Y 1 , Y 2 Ar may have a substituent other than １ and Y 1 , Ar 2 and Y 2 p and q each independently represent an integer of 0 to 5, provided that p and q are not both 0. Y １ , Y ２ When there are multiple Y １ and Y ２ may be the same or different. １ represents a hydrogen atom or a methyl group. １ If there are multiple R １ may be the same or different.]

[0028]

[13] A holographic recording medium comprising the polymerizable composition according to

[11] or

[12] .

[14] A polymer obtained by polymerizing the polymerizable composition according to

[11] or

[12] .

[0029]

[15] An optical material comprising the polymer according to

[14] .

[16] An optical component comprising the polymer according to

[14] .

[0030]

[17] A large-capacity memory including the holographic recording medium according to

[13] .

[18] An optical element obtained by holographically recording the holographic recording medium according to

[13] .

[0031]

[19] An AR (Augmented Reality) light guide plate including the optical element according to

[18] .

[20] AR glasses including the optical element according to

[18] .

[0032] The present invention provides a high refractive index compound useful as an optical material, which has a high refractive index, high transparency, easy polymerization, chemical stability, high solubility in various solvents, and storage stability of the solution. The compound of the present invention is particularly useful as a reactive compound used in hard coat layers of optical lenses and optical members, and holographic recording media. By using the compound of the present invention, it is possible to realize optical materials and optical components that have high diffraction efficiency, high light transmittance, high chemical stability, and excellent processability.

[0033] Fig. 1 is a schematic diagram showing the outline of the configuration of the device used for holographic recording, and Fig. 2 is a schematic diagram of the device for measuring the holographic scatter intensity ratio.

[0034] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof. In the present invention, "(meth)acrylate" is a general term for acrylate and methacrylate. "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. The same applies to "(meth)acrylic". In the present invention, "aromatic ring" is a general term for "aromatic hydrocarbon ring" and "aromatic heterocyclic ring". Similarly, "aromatic ring group" is a general term for "aromatic hydrocarbon group" and "aromatic heterocyclic group". Furthermore, in the present invention, "optionally having a substituent" means that the group may have one or more substituents.

[0035] 1. Compound of the Present Invention The compound of the present invention is represented by the following formula (1): Hereinafter, the compound represented by the following formula (1) may be referred to as "compound (1)."

[0036]

[0037] [In the formula, n represents an integer of 1 to 3. L represents an optionally branched (n+1)-valent linking group. Y 1 , Y 2 each independently represents an aromatic ring group having a total of 7 to 20 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. １ , Ar 2 each independently represents an aromatic hydrocarbon group. １ , Ar 2 are Y 1 , Y 2 Ar may have a substituent other than １ and Y 1 , Ar 2 and Y 2 p and q each independently represent an integer of 0 to 5, provided that p and q are not both 0. Y １ , Y ２ When there are multiple Y １ and Y ２ may be the same or different. １ represents a hydrogen atom or a methyl group.１ If there are multiple R １ may be the same or different.]

[0038] 1-1. Compound (1) Compound (1) is characterized by having two high refractive index molecular structures consisting of aromatic ring groups at the ends of a glycerin-like skeleton, and a polymerizable group linked to a secondary alcohol located in the center of the skeleton via a linker of an appropriate chain length.

[0039] In optical materials, organic compounds having aromatic ring groups are sometimes used to improve the refractive index. However, organic compounds having highly planar aromatic ring groups generally have poor solubility in various solvents, making them difficult to use as high-concentration solutions that achieve high refractive indexes. Even if a high-concentration solution can be prepared, the organic compounds have a high degree of crystallinity, which can lead to the problem of precipitation from the storage solution over time. In particular, aromatic organic compounds used in optical materials with a refractive index exceeding 1.65 have multiple aromatic rings as substituents, and their solubility in various solvents tends to decrease as their molecular weight increases.

[0040] Compound (1) has a high refractive index structure consisting of a large number of aromatic ring groups that are rigid and easily crystallizable due to aromatic ring-aromatic ring interactions, separated by a glycerin-like skeleton having moderate flexibility, and therefore has low crystallinity as a whole molecule and high solubility in various solvents. Furthermore, when linking the aromatic ring groups, which are a high refractive index structure, to the glycerin-like skeleton, a highly reactive glycerin precursor can be used, and therefore it is possible to link the aromatic ring groups not only via sulfur atoms, which are susceptible to air oxidation, but also via oxygen atoms, which are highly chemically stable. Furthermore, a polymerizable (meth)acrylate group ("R" in formula (1)) can be linked to an appropriate position via a linking group L from the secondary alcohol moiety of the glycerin-like skeleton, which is located at the center of the high refractive index structure, which has a large steric hindrance. １ -C(=CH ２)-C(═O)-O-", hereinafter sometimes referred to as a "polymerizable (meth)acrylate group" or simply a "polymerizable group." By bonding the (meth)acrylate group (1), the flexibility of compound (1) can be significantly improved while exhibiting high polymerizability as a (meth)acrylate monomer, thereby achieving a high refractive index and improved chemical stability of the polymer. In addition, since the polymerizable (meth)acrylate group of compound (1) has two aromatic high refractive index structures approximately equidistant via a branched glycerin-like skeleton, it is believed that the (meth)acrylate main chain and linking group L of the oligomer or polymer after polymerization are likely to be three-dimensionally shielded by the high refractive index structure composed of aromatic groups that have high heat resistance and excellent chemical stability. Therefore, higher heat resistance can be expected compared to polymers composed of conventional high refractive index (meth)acrylate monomers that are linear molecules.

[0041] 1-2. L in formula (1) represents an optionally branched (n+1)-valent linking group. L may have an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.

[0042] The linking group constituting L may be an aliphatic hydrocarbon group which may have a substituent, from the viewpoint of ease of synthesis and availability. The number of carbon atoms in the aliphatic hydrocarbon group (not including the number of carbon atoms in the substituent) is preferably 1 to 8. When the number of carbon atoms in the aliphatic hydrocarbon group is 8 or less, the refractive index of compound (1) is less likely to decrease, and the viscosity is reduced due to the small molecular weight, which tends to improve processability. The aliphatic hydrocarbon group constituting L may be either a cyclic aliphatic hydrocarbon group or a chain aliphatic hydrocarbon group, or a combination of these structures. A chain aliphatic hydrocarbon group is preferred from the viewpoint of reducing steric hindrance around the polymerizable (meth)acrylate group.

[0043] When n=1, the chain aliphatic hydrocarbon group constituting L may be an alkyl group having 1 to 8 carbon atoms. When n=2 or 3, L may be a combination of two or more alkyl groups having 1 to 8 carbon atoms.

[0044] From the viewpoint of imparting high solubility to various media to compound (1), L is preferably an (n+1)-valent linking group having an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent, more preferably an (n+1)-valent linking group having an oxygen atom or a nitrogen atom which may have a substituent, and even more preferably an (n+1)-valent linking group having an oxygen atom and a nitrogen atom which may have a substituent. These linking groups may have a substituent, and preferably have a carbon number (not including the carbon number of the substituent) of 1 to 8. When the (n+1)-valent linking group has 8 or less carbon atoms, the refractive index of compound (1) is less likely to decrease, and the viscosity is reduced due to the small molecular weight, which tends to improve processability. The (n+1)-valent linking group constituting L may be either a cyclic linking group or a chain linking group, or a combination of these structures may be used. From the viewpoint of reducing steric hindrance around the polymerizable (meth)acrylate group, a chain linking group is preferred.

[0045] The (n+1)-valent chain linking group having an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent, which constitutes L, is, when n=1, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ OCH ２ CH ２ -, -CH ２ CH ２ OCH ２ CH ２ OCH ２ CH ２ -, -CH ２ CH ２ SCH ２ CH ２ -, -CH ２ CH ２ (CO)-, -CH ２ CH ２ CH ２ (CO)-, -CH ２ CH ２ CH ２ CH ２ (CO)-, -CH ２ CH ２ CH ２ CH ２CH ２ (CO)-, -CH ２ CH ２ OCH ２ CH ２ (CO)-, -CH ２ CH ２ NH(CO)-, -CH ２ CH ２ CH ２ NH(CO)-, -CH ２ CH ２ CH ２ CH ２ NH(CO)-, -CH ２ CH ２ OCH ２ CH ２ L may be a combination of two or more of these groups. Among these, from the viewpoint of solubility, -CH ２ CH ２ NH(CO)-, -CH ２ CH ２ CH ２ NH(CO)-, -CH ２ CH ２ CH ２ CH ２ NH(CO)-, -CH ２ CH ２ OCH ２ CH ２ NH(CO)- is preferred, and -CH ２ CH ２ NH(CO)-, -CH ２ CH ２ OCH ２ CH ２ NH(CO)- is more preferred. When n=2 or 3, L is -(CH ２ ) ２ C(CH ３ ) -, -(CH ２ ) ２ C(CH ３ )(CO)-,-(CH ２ ) ２ C(CH ２ CH ３ )(CO)-,-(CH ２ ) ３ C(CO)-,-(CH ２ ) ２ C(CH３ )NH(CO)-, or a linking group in which any hydrogen atom in the chain linking group is substituted with a bond to the polymerizable (meth)acrylate group. In this case, the linking group may be formed via a branched structure.

[0046] From the viewpoint of a high refractive index, L preferably contains a cyclic group, and the ring contained in the cyclic group constituting L may have a monocyclic structure or a fused ring structure. The number of rings contained in L is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. The ring contained in L does not necessarily need to be aromatic, but is preferably an aromatic hydrocarbon ring in order to maintain a high refractive index while keeping its size in the entire molecule small. Examples of the aromatic hydrocarbon ring constituting L include a benzene ring, an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.

[0047] In particular, L is preferably a group containing a urethane bond (—NH—C(═O)—) from the viewpoint of imparting high solubility to various media to the compound (1), more specifically, from the viewpoint of solubility with the isocyanate compound and polyol compound constituting the composition and compatibility with polyurethanes formed therefrom. When n=1, such L is preferably a group containing a urethane bond (—NH—C(═O)—). ２ CH ２ NH(CO)-, -CH ２ CH ２ CH ２ NH(CO)-, -CH ２ CH ２ CH ２ CH ２ NH(CO)-, -CH ２ CH ２ OCH ２ CH ２ NH(CO)-, and the like, and may be a combination of two or more of these groups. Furthermore, when n=2 or 3, L containing a urethane bond is -(CH ２ ) ２ C(CH ３ )NH(CO)-, and linking groups in which any hydrogen atom in the chain linking group is substituted with a bond to a polymerizable (meth)acrylate group.

[0048] The linking group L may have a substituent. Examples of the substituent that L may have include a halogen atom (a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamido group, a dialkylaminoethyl group having an alkyl group having 1 to 4 carbon atoms bonded thereto, a trifluoromethyl group, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, and a nitro group.

[0049] 1-3. Y in formula (1) １ , Y ２ Y １ , Y ２ each independently represents an aromatic ring group having a total of 7 to 20 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. Aromatic ring groups are broadly classified into aromatic hydrocarbon groups and aromatic heterocyclic groups, and aromatic hydrocarbon groups are preferred from the viewpoint of low coloration. The aromatic ring of these aromatic ring groups may have a monocyclic structure or a condensed ring structure. Alternatively, it may have a structure in which two or more aromatic rings are linked via a direct bond. Y １ , Y ２ From the viewpoint of achieving both a high refractive index and high solubility in various media, the aromatic ring constituting the compound (I) is preferably a fused aromatic ring which may have a substituent or a monocyclic aromatic ring substituted with an aromatic ring group, and more preferably a fused aromatic ring which may have a substituent.

[0050] Examples of the aromatic hydrocarbon ring of the aromatic hydrocarbon group include a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a biphenylene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0051] Y １ , Y ２From the viewpoint of ease of synthesis and availability, the aromatic hydrocarbon ring constituting Y is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a biphenylene ring, or a fluorene ring. １ , Y ２ The aromatic hydrocarbon ring constituting the formula (I) is more preferably a naphthalene ring, a phenanthrene ring, a biphenylene ring, or a fluorene ring, and even more preferably a naphthalene ring or a phenanthrene ring.

[0052] Examples of the aromatic heterocyclic group include aromatic heterocyclic rings containing one heteroatom such as a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a benzothiophene ring, a dibenzothiophene ring, a naphthothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a quinoline ring, and an isoquinoline ring; aromatic heterocyclic rings containing two or more heteroatoms such as a purine ring and a pyrrolopyrrole ring; a benzoxazole ring, a thienoxazole ring, a thiazolooxazole ring, an oxazolooxazole ring, an oxazoloimidazole ring, and an oxazo and a ring in which two or three rings are condensed, including an aromatic heterocycle containing two or more heteroatoms, such as an oxazolopyridine ring, an oxazolopyridazine ring, an oxazolopyrimidine ring, an oxazolopyrazine ring, a naphthoxazole ring, a quinolinoxazole ring, a dioxazolopyrazine ring, a phenoxazine ring, a benzothiazole ring, a furothiazole ring, a thienothiazole ring, a thiazolothiazole ring, a thiazoloimidazole ring, a thienothiadiazole ring, a thiazolothiadiazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a thiazolopyrazine ring, a naphthothiazole ring, a quinolinothiazole ring, a thianthrene ring, and a phenothiazine ring.

[0053] Y １ , Y ２As the aromatic heterocycle constituting the compound (1), a sulfur-containing aromatic heterocycle is preferred because it tends to increase the refractive index of the compound (1). The sulfur-containing aromatic heterocycle has at least a sulfur atom as a heteroatom constituting the aromatic heterocycle. In addition to the sulfur atom, the heteroatom may have an oxygen atom, a nitrogen atom, or both an oxygen atom and a nitrogen atom. From the viewpoints of avoiding coloration and ensuring solubility, the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2. Examples of sulfur-containing aromatic heterocycles include aromatic heterocycles containing one sulfur atom, such as a benzothiophene ring, a dibenzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, a naphthothiophene ring, a dinaphthothiophene ring, and a dibenzothiopyran ring; aromatic heterocycles containing two or more sulfur atoms, such as a thianthrene ring; and aromatic heterocycles containing two or more types of heteroatoms, such as a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazoloimidazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a dioxazolopyrazine ring, a thiazolopyrazine ring, a thiazolooxazole ring, a dibenzobenzothiophene ring, a thienoxazole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring.

[0054] The sulfur-containing aromatic heterocycle may be a single ring or a fused ring. From the viewpoint of increasing the refractive index, a fused ring is preferred. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5, from the viewpoint of facilitating raw material availability and synthesis. In particular, from the viewpoints of increasing the refractive index and reducing coloration, the sulfur-containing aromatic heterocycle is preferably a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, or a thianthrene ring.

[0055] Y １ , Y ２From the viewpoint of ease of synthesis, the aromatic heterocycle constituting the above may be a nitrogen-containing aromatic heterocycle. The nitrogen-containing aromatic heterocycle has at least a nitrogen atom as a heteroatom constituting the aromatic heterocycle. In addition to the nitrogen atom, the heteroatom may have an oxygen atom, a sulfur atom, or both an oxygen atom and a sulfur atom. From the viewpoint of avoiding coloration, the number of heteroatoms constituting the nitrogen-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2. Examples of the nitrogen-containing aromatic heterocycle include rings containing one nitrogen atom such as an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a quinoline ring, an isoquinoline ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a naphthoxazole ring, a benzothiazole ring, a naphthothiazole ring, a phenoxazine ring, a phenothiazine ring, a thienoxazole ring, a thiazolooxazole ring, an oxazolooxazole ring, a furothiazole ring, a thienothiazole ring, and a thiazolothiazole ring. aromatic heterocycles containing two or more nitrogen atoms, such as a benzimidazole ring, an oxazoloimidazole ring, an oxazolopyridine ring, an oxazolopyridazine ring, an oxazolopyrimidine ring, an oxazolopyrazine ring, a quinolinoxazole ring, a dioxazolopyrazine ring, a thiazoloimidazole ring, a thienothiadiazole ring, a thiazolothiadiazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a thiazolopyrazine ring, and a quinolinothiazole ring.

[0056] The nitrogen-containing aromatic heterocycle may be a single ring or a fused ring. From the viewpoint of increasing the refractive index, a fused ring is preferred. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5, from the viewpoint of facilitating raw material availability and synthesis. In particular, from the viewpoint of increasing the refractive index and reducing coloration, the nitrogen-containing aromatic heterocycle is preferably a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a quinoline ring, an isoquinoline ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, or a thiadiazole ring, and more preferably a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, or a thiadiazole ring.

[0057] Y １ , Y ２ The aromatic heterocycle constituting the compound (1) may be an oxygen-containing aromatic heterocycle. The oxygen-containing aromatic heterocycle tends to improve the heat resistance and weather resistance of a polymer made from compound (1). The oxygen-containing aromatic heterocycle has at least an oxygen atom as a heteroatom constituting the aromatic heterocycle. In addition to the oxygen atom, the heteroatom may have a nitrogen atom, a sulfur atom, or both a nitrogen atom and a sulfur atom. From the viewpoint of ensuring heat resistance, the number of oxygen atoms constituting the oxygen-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2. Examples of the oxygen-containing aromatic heterocycle include aromatic heterocycles containing one oxygen atom such as a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a phenoxazine ring, an oxazole ring, an isoxazole ring, a benzoxazole ring, a benzisoxazole ring, a naphthoxazole ring, a thienoxazole ring, a thiazolooxazole ring, an oxazoloimidazole ring, and a furothiazole ring; and aromatic heterocycles containing two or more oxygen atoms such as a dibenzodioxin ring, an oxazolooxazole ring, and a dioxazolopyrazine ring.

[0058] The oxygen-containing aromatic heterocycle may be a single ring or a fused ring. From the viewpoint of increasing the refractive index, a fused ring is preferred. The number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5, from the viewpoint of facilitating raw material availability and synthesis. In particular, from the viewpoint of increasing the refractive index and reducing coloration, the oxygen-containing aromatic heterocycle is preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, an oxazole ring, an isoxazole ring, a benzoxazole ring, a benzisoxazole ring, or a naphthoxazole ring, and more preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, or a benzoxazole ring.

[0059] These Y １ , Y ２The aromatic ring constituting the formula (I) may have a substituent. Examples of the substituent include a halogen atom such as chlorine, bromine, or iodine, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamido group, a dialkylaminoethyl group formed by bonding alkyl groups having 1 to 4 carbon atoms, a trifluoromethyl group, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, and a nitro group. Among these, preferred are alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkylthio groups having 1 to 8 carbon atoms, aromatic ring thio groups having 6 to 10 carbon atoms, cyano groups, acetyloxy groups, alkylcarbonyloxy groups having 2 to 9 carbon atoms, sulfamoyl groups, alkylsulfamoyl groups having 2 to 9 carbon atoms, and nitro groups.

[0060] These Y １ , Y ２ The aromatic ring constituting the compound (1) may further have a group containing an aromatic ring as a substituent, from the viewpoint of increasing the refractive index of the compound (1). １ , Y ２ The aromatic rings contained in these substituents are the same as those constituting Y. １ , Y ２ The substituent may be directly bonded to the aromatic ring constituting Y at any position, or may be bonded via an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent, or may be bonded via an arbitrary linking group. １ , Y ２ It is more preferable that the aromatic ring contained in the substituent is directly bonded to the aromatic ring constituting Y. In addition, by making the aromatic ring contained in this substituent a sulfur-containing aromatic heterocycle, the refractive index of the compound (1) tends to be higher. The definition of a sulfur-containing aromatic heterocycle is １ , Y ２The sulfur-containing aromatic heterocycle is more preferably a fused ring, and particularly preferably a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, or a thianthrene ring.

[0061] Y １ , Y ２ The number of aromatic rings which the aryl group has as a substituent is not particularly limited, but from the viewpoints of ease of synthesis and solubility, 1 to 4 is preferred, and 1 or 2 is more preferred.

[0062] Y １ , Y ２ The aromatic rings constituting the formula (I) may have two or more selected from the aromatic hydrocarbon ring, sulfur-containing aromatic heterocycle, nitrogen-containing aromatic heterocycle, and oxygen-containing aromatic heterocycle described above.

[0063] Y １ and Y 2 The aromatic rings constituting Y may be the same or different. １ and Y 2 In the case where Y are the same aromatic ring, it is more preferable from the viewpoint of easy availability of raw materials. １ and Y 2 In the case where Y is a different aromatic ring, it is more preferable from the viewpoint of solubility. １ and Y ２ It is particularly preferred that Y １ , Y ２ As described later, there may be multiple Y １ , Y ２ may be the same or different.

[0064] Y present in formula (1) is 0 to 5 １ , Y ２ The total number of carbon, nitrogen, oxygen, and sulfur atoms constituting the compound (1) is 7 to 20. If the total number of carbon, nitrogen, oxygen, and sulfur atoms is 7 or more, a high refractive index of the compound (1) can be expected. On the other hand, if the total number of carbon, nitrogen, oxygen, and sulfur atoms is 20 or less, the compound (1) can be easily synthesized. From the above viewpoints, the compound (1) is １ , Y ２The total number of carbon, nitrogen, oxygen and sulfur atoms constituting the group is preferably 9 to 18, and more preferably 10 to 14.

[0065] In particular, Y １ , Y ２ are preferably each independently a naphthyl group or a phenanthryl group which may have a substituent, from the viewpoint of imparting a high refractive index to the compound (1). １ is a naphthyl group, Y １ is at the 1st or 2nd position of the naphthyl group, and Ar １ From the viewpoint of synthetic chemistry or stereochemistry, it is preferable to bond with Y. ２ is a naphthyl group, Y ２ is at the 1st or 2nd position of the naphthyl group, and Ar ２ From the viewpoints of synthetic chemistry and stereochemistry, it is preferable to bond with Y. １ is a phenanthryl group, Y １ is Ar at the 9th position of the phenanthryl group １ From the viewpoints of synthetic chemistry and stereochemistry, it is preferable to bond with Y. ２ is a phenanthryl group, Y ２ is Ar at the 9th position of the phenanthryl group ２ is preferable from the viewpoints of synthetic chemistry and stereochemistry.

[0066] 1-4. p and q in Formula (1) p and q each independently represent an integer of 0 to 5. However, p = q = 0 is not satisfied. These p and q can be selected appropriately. For example, from the viewpoint of ease of obtaining the raw materials for compound (1), p and q each independently are preferably 0 to 3, and since a high refractive index material can be provided, p and q each independently are more preferably 1 to 3. When p and q each independently are 1 or 2, high solubility in various solvents can be expected, and this is particularly preferred.

[0067] 1-5. Ar in formula (1) 1 , Ar 2 Ar １ , Ar 2each independently represents an aromatic hydrocarbon group which may have a substituent. The aromatic ring of the aromatic hydrocarbon group may have a monocyclic structure or a condensed ring structure. It may also have a structure in which two or more aromatic rings are connected via a direct bond. When p is 1 or more and Y in formula (1) １ If Ar is present, １ Is Y １ Similarly, when q is 1 or more and Y ２ If Ar is present, １ Is Y １ It does not form a ring structure with

[0068] Examples of the aromatic hydrocarbon ring of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a biphenylene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0069] Ar １ , Ar 2 From the viewpoints of ease of synthesis and availability, the aromatic hydrocarbon ring constituting the formula (I) is preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a biphenylene ring, or a fluorene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0070] Ar １ and Ar 2 The aromatic hydrocarbon rings constituting Ar may be the same or different. １ and Ar 2 In the case where Ar is the same aromatic hydrocarbon ring, it is more preferable from the viewpoint of easy availability of raw materials. １ and Ar 2 In the case where the aromatic hydrocarbon rings are different from each other, this is more preferable from the viewpoint of solubility.

[0071] Ar １ , Ar 2 From the viewpoints of ease of synthesis and low coloration, each of the groups is preferably an aromatic hydrocarbon group having a total of 6 to 16 carbon atoms, more preferably an aromatic hydrocarbon group having a total of 6 to 10 carbon atoms.

[0072] Ar １ , Ar 2 From the viewpoint of ease of synthesis and heat resistance, it is preferable that the groups be the same aromatic hydrocarbon group, and it is particularly preferable that both be benzene rings.

[0073] 1-6. Ar in formula (1) 1 , Ar 2 Y has １ , Y ２ Substituents other than Ar in formula (1) 1 , Ar 2 The aromatic ring group is Y １ , Y ２ In addition, each of Ar may independently have a substituent. 1 , Ar 2 Examples of the substituent that Ar may have include a halogen atom such as fluorine, chlorine, bromine, or iodine, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, a dialkylaminoethyl group formed by bonding alkyl groups having 1 to 4 carbon atoms, a trifluoromethyl group, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, and a nitro group. 1 , Ar 2 Is Y １ , Y ２ On the other hand, from the viewpoint of improving the refractive index and solubility, it is preferable that the compound has no substituent other than Ar. 1 , Ar 2 It is preferable that the alkyl group having 1 to 8 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, the alkylthio group having 1 to 8 carbon atoms, the aromatic ring thio group having 6 to 10 carbon atoms, the cyano group, the acetyloxy group, the alkylcarbonyloxy group having 2 to 8 carbon atoms, the sulfamoyl group, the alkylsulfamoyl group having 2 to 9 carbon atoms, or the nitro group be contained as a substituent.

[0074] 1-7. R in formula (1) １R １ represents a hydrogen atom or a methyl group. １ can be appropriately selected. For example, from the viewpoint of improving the stability of the polymer of compound (1), R １ On the other hand, from the viewpoint of the polymerizability of compound (1), R １ is preferably a methyl group.

[0075] 1-8. n in formula (1) represents an integer of 1 to 3. This n can be selected appropriately. For example, from the viewpoint of making compound (1) easily polymerizable, n can be set to 2 or 3. On the other hand, since there is a tendency to be able to achieve a high refractive index, compound (1) preferably has a smaller number of polymerizable groups, and is more preferably a monofunctional compound having 1 polymerizable group. That is, from the viewpoint of achieving a high refractive index, n is preferably 1 or 2, and n is more preferably 1. When n is 2 or 3, it is possible to achieve a high refractive index by using a plurality of R １ -C(=CH ２ )-C(=O)-O-, ie, polymerizable (meth)acrylate groups, may be the same or different.

[0076] 1-9. Molecular Weight From the viewpoint of keeping the viscosity low and maintaining good processability, the compound (1) preferably has a molecular weight of 2,000 or less, more preferably 1,500 or less, and even more preferably 1,200 or less. From the viewpoint of reducing the shrinkage rate during polymerization, the compound (1) preferably has a molecular weight of 500 or more, more preferably 600 or more, and even more preferably 650 or more.

[0077] 1-10. Exemplary Compounds Specific examples of compound (1) are shown below. Compound (1) of the present invention is not limited to these examples as long as it does not depart from the gist of the invention. In the following, Et represents an ethyl group.

[0078]

[0079]

[0080]

[0081]

[0082] 1-11. Synthesis Method 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 carbonylation reagent such as an isocyanate having a polymerizable group.

[0083]

[0084] [In the formula, Ar １ , Ar ２ , Y １ , Y ２ , p, and q have the same meanings as in formula (1).

[0085] An example of the synthesis of compound (1) will be described below.

[0086]

[0087] [In the above reaction formula, Ar １ , Ar ２ , Y １ , Y ２ , p, q, n, R １ has the same meaning as in the formula (1). １ , Z ２ , Z ３ represents a leaving group such as a halogen atom, a sulfonic acid group such as a methanesulfonic acid group, a tosylic acid group, or a trifluoromethanesulfonic acid group, a carboxyl group, a dimethylpyrazolyl group, or a 1-methylpropylideneaminooxy group. L' represents a precursor structure that becomes L through a chemical reaction. In the following reaction formulas, the same symbols represent the same things.]

[0088] For example, compound (1) can be produced by reacting the hydroxyl group of compound (2) with an alkylating reagent compound having a polymerizable group represented by formula (i) (hereinafter, sometimes referred to as alkylating reagent (i)). Alternatively, compound (1) can be produced using a carbonylating reagent represented by formula (ii), such as an isocyanate (hereinafter, sometimes referred to as carbonylating reagent (ii)).

[0089] Examples of the alkylating reagent (i) include 2-methanesulfonylethyl (meth)acrylate, glycidyl (meth)acrylate, and 2,3-dibromopropyl acrylate.

[0090] Examples of the carbonylation reagent (ii) include isocyanates such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate; 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate; and 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate.

[0091] Furthermore, compound (1) can also be produced by subjecting a compound represented by formula (3) (hereinafter, sometimes referred to as “compound (3)”), which is obtained by reacting compound (2) with a compound having a linking group represented by formula (iii) or formula (iv), to a polymerizable group-forming reaction with a (meth)acryloylating reagent represented by formula (v).

[0092] The reaction of the active hydrogen of the hydroxyl group in formula (2) with the reagents represented by (i) to (iv) above, and the reaction of compound (3) with the reagent represented by formula (v) can be carried out by known methods. For example, compound (1) can be obtained by reacting compound (2) with an isocyanate in the presence of a basic compound or a Lewis acid catalyst.

[0093] The basic compound may be one or more organic basic compounds (triethylamine, diisopropylethylamine, 1,1,3,3-tetramethylguanidine, diazabicycloundecene, diazabicyclononene, pyridine, imidazole, etc.), or one or more inorganic basic compounds (sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, potassium tert-butoxide, etc.), or a combination of one or more organic basic compounds and one or more inorganic basic compounds.

[0094] Examples of Lewis acid catalysts include tin catalysts such as dibutyltin diacetate, dibutyltin dilaureate, dioctyltin laurate, and dibutyltin octoate, bismuth catalysts such as tris(2-ethylhexanoate)bismuth and tribenzoyloxybismuth, and zirconium catalysts such as tetrakis(ethylacetoacetate)zirconium, 1,1'-isopropylidene zirconocene dichloride, and tetrakis(2,4-pentanedionato)zirconium. These may be used alone or in combination.

[0095] In the reaction of compound (2) with the reagents represented by (i) to (iv) and the reaction of compound (3) with the reagent represented by formula (v), it is preferable to use an organic solvent. Examples of organic solvents include dichloromethane, tetrahydrofuran (THF), dimethoxyethane, toluene, and N,N-dimethylformamide (DMF). One type of organic solvent may be used, or two or more types may be used in combination.

[0096] In the production of compound (1), it is preferable to purify the reaction product (crude product) obtained in the synthesis reaction. By purifying and removing impurities, low coloration can be achieved. Known methods can be applied as the purification method. For example, purification can be performed by extraction, column chromatography, recrystallization, distillation, etc. These purification methods may be performed alone or in combination.

[0097] When compound (1) is a solid at room temperature, it is preferable to use a recrystallization method, since colored substances can be easily removed to a high degree.

[0098] Examples of recrystallization solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and mesitylene, halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, t-butyl methyl ether, and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, 2-methoxyethanol, 2-butoxyethanol, and propylene glycol monomethyl ether, glycols such as ethylene glycol and diethylene glycol, and water. These solvents may be used alone or in combination of two or more.

[0099] Compound (2), which is a starting compound used in the production of compound (1), can be produced, for example, by the following reaction.

[0100]

[0101] [In the above reaction formula, Ar １ , Ar ２ , Y １ , Y ２ , p, and q have the same meanings as in the formula (1). ４ , Z ５ , Z ６ represents a leaving group such as a halogen atom, a sulfonic acid group such as a methanesulfonic acid group, a tosylic acid group, or a trifluoromethanesulfonic acid group, a carboxyl group, a dimethylpyrazolyl group, or a 1-methylpropylideneaminooxy group. １ or Y ２ Y-M represents an organolithium reagent, an organomagnesium reagent, an organozinc reagent, an organocerium reagent, an organosilicon reagent, an organoboron reagent, an organotin reagent, etc., and Z ５ , Z ６represents an organometallic reagent that can react with to form a carbon-carbon bond.

[0102] Compound (2) can be produced by reacting the hydroxyl groups in formula (4) and formula (4') with the reagent represented by (vi) above or the compound represented by formula (5) (hereinafter, sometimes referred to as "compound (5)"). This production method can be performed using known techniques. For example, compound (5) is obtained by reacting reagent (vi) with the compound represented by formula (4) (hereinafter, sometimes referred to as "compound (4)") in the presence of a basic compound, and then compound (5) is reacted with a compound represented by formula (4') (hereinafter, sometimes referred to as "compound (4')") in the presence of a basic compound to obtain compound (2).

[0103] Furthermore, compound (2) can be produced by reacting the hydroxyl groups in reagent (vii) and reagent (viii) with a reagent represented by reagent (vi) or a compound represented by formula (6), respectively, to obtain an organic halide of formula (7), and then linking multiple aromatic ring groups Y simultaneously or sequentially through a linking reaction between organic halide (7) and an organometallic reagent represented by formula (xi). Compound (2) can also be synthesized by directly utilizing the carbon-hydrogen bonds of the aromatic hydrocarbon ring represented by formula (x) and performing a cross-coupling reaction.

[0104] Compound (4) and compound (4'), which are raw material compounds used in the production of compound (2), can be produced, for example, by the following reaction.

[0105]

[0106] [In the above reaction formula, Ar is Ar １ or Ar ２ , Y is Y １ or Y ２ , r represents p or q, Ar １ , Ar ２ , Y １ , Y ２ , p, and q have the same meanings as in the formula (1). ７represents a leaving group such as a halogen atom or a trifluoromethanesulfonic acid group. Y-M represents an organolithium reagent, an organomagnesium reagent, an organozinc reagent, an organocerium reagent, an organosilicon reagent, an organoboron reagent, an organotin reagent, etc., and Z ７ represents an organometallic reagent that can react with to form a carbon-carbon bond.

[0107] For example, compound (4) or (4') can be synthesized by simultaneously or sequentially linking multiple aromatic ring groups Y through a linking reaction between an aromatic halide or the like represented by formula (8) and an organometallic reagent represented by formula (xi). Compound (4) or (4') can also be synthesized by directly utilizing the carbon-hydrogen bond of the aromatic hydrocarbon ring represented by formula (xii) and performing a cross-coupling reaction.

[0108] 2. Polymerizable Composition of the Present Invention The polymerizable composition of the present invention contains compound (1) and a polymerization initiator. The polymerization initiator causes a polymerization reaction of the polymerizable (meth)acrylate group of compound (1), thereby producing the polymer of the present invention.

[0109] 2-1. Polymerization initiator The type of polymerization initiator is not particularly limited, and may be appropriately selected from known polymerization initiators depending on the polymerization method. The polymerization method is also not limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and partial polymerization can be used.

[0110] Examples of the polymerization initiator contained in the polymerizable composition of the present invention include a radical polymerization initiator, a redox polymerization initiator, an anionic polymerization initiator, etc. The examples of polymerization initiators described below also include those generally called polymerization catalysts.

[0111] 2-1-1. Radical Polymerization Initiator <Photopolymerization Initiator> Any known photoradical polymerization initiator can be used as the photopolymerization initiator that assists in the polymerization of the polymerizable composition of the present invention. Examples include azo compounds, azide compounds, organic peroxides, organic borates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, acylphosphine oxides, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, and oxime esters. Among these, benzophenones, acylphosphine oxide compounds, and oxime ester compounds are preferred as photopolymerization initiators from the viewpoints of compatibility, availability, and the like.

[0112] Specific examples of the photopolymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-mol), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, methyl benzoyl formate, 1-[4-(phenylthio)-2-(O-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, and the like.

[0113] These photopolymerization initiators may be used either alone or as a mixture of two or more kinds in any combination and ratio.

[0114] The content of the photopolymerization initiator in the polymerizable composition of the present invention is usually 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.05 parts by mass or more, when the total amount of all radically polymerizable compounds in the polymerizable composition is 100 parts by mass. The upper limit is usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If the content of the photopolymerization initiator is too high, polymerization may proceed too rapidly, which may not only increase the birefringence of the cured product but also worsen the hue. On the other hand, if the content is too low, the polymerizable composition may not polymerize sufficiently.

[0115] <Thermal Polymerization Initiator> Any known thermal radical polymerization initiator can be used as the thermal polymerization initiator that assists the polymerization of the polymerizable composition of the present invention. Examples include organic peroxides and azo compounds. Among them, organic peroxides are preferred from the viewpoint of preventing bubbles from forming in the polymer obtained by the polymerization reaction.

[0116] Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; dicumyl peroxide, di-t-butyl peroxide, and the like. diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; and peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutyl-2-ethylhexanoate.

[0117] Specific examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane) dihydrochloride.

[0118] These thermal polymerization initiators may be used either alone or as a mixture of two or more kinds in any combination and ratio.

[0119] The content of the thermal polymerization initiator in the polymerizable composition of the present invention is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more, when the total amount of all radically polymerizable compounds in the polymerizable composition is 100 parts by mass. The upper limit is usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less. If the amount of thermal polymerization initiator is too much, the polymerization may proceed too rapidly, which may impair the optical uniformity of the obtained polymer and may also deteriorate the hue. On the other hand, if the amount is too little, the thermal polymerization may not proceed sufficiently.

[0120] When a photopolymerization initiator and a thermal polymerization initiator are used in combination, the mass ratio thereof is usually 100:1 to 1:100 (photopolymerization initiator:thermal polymerization initiator, hereinafter the same in this paragraph), preferably 10:1 to 1:10. If the amount of thermal polymerization initiator is too small, polymerization may be insufficient, and if the amount is too large, coloration may occur.

[0121] 2-1-2. Redox Polymerization Initiators Redox polymerization initiators are radical initiators that utilize a redox reaction involving a combination of a peroxide and a reducing agent. They are capable of generating radicals even at low temperatures and are typically used in emulsion polymerization.

[0122] Specific examples of redox polymerization initiators include a combination of dibenzoyl peroxide as a peroxide and aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine as a reducing agent; a combination of hydroperoxide as a peroxide and metal soaps as a reducing agent; and a combination of hydroperoxide as a peroxide and thioureas as a reducing agent. Water-soluble redox polymerization initiators include a combination of a peroxide such as persulfate, hydrogen peroxide, or hydroperoxide with a water-soluble inorganic reducing agent (Fe ２＋ or NaHSO ３ etc.) or in combination with an organic reducing agent (alcohol, polyamine, etc.).

[0123] The preferred range of the content of the redox polymerization initiator in the polymerizable composition of the present invention is the same as that of the thermal polymerization initiator.

[0124] 2-1-3. Anionic Polymerization Initiator Examples of the anionic polymerization initiator used in the polymerizable composition of the present invention include alkali metals, n-butyllithium, sodium amide, sodium naphthalenide, Grignard reagents, lithium alkoxides, alkali metal benzophenone ketyl, etc. Any one of these may be used alone, or two or more may be used in any combination and in any ratio.

[0125] 2-2. Polymerizable Compounds Other than Compound (1) The polymerizable compound contained in the polymerizable composition of the present invention may contain any one kind of compound (1) alone, or may contain two or more kinds in any combination and ratio.

[0126] The polymerizable composition of the present invention may contain a polymerizable compound other than the compound (1).

[0127] The content of compound (1) in the polymerizable composition of the present invention is, relative to the total solid content of the polymerizable composition of the present invention, preferably 1% by mass or more and 99% by mass or less, and more preferably 5% by mass or more and 95% by mass or less. If the content of compound (1) is less than 1% by mass, the effect of using compound (1) is not fully exhibited, while if it exceeds 99% by mass, curability tends to decrease.

[0128] Examples of polymerizable compounds other than compound (1) include anionic polymerizable monomers, radical polymerizable monomers, etc. These polymerizable compounds may be used alone or in any combination and ratio of two or more. Polymerizable compounds having two or more polymerizable functional groups in one molecule (sometimes referred to as polyfunctional monomers) can also be used. When a polyfunctional monomer is used, a crosslinked structure is formed within the polymer, which can improve thermal stability, weather resistance, solvent resistance, etc.

[0129] When the polymerizable composition of the present invention contains a polymerizable compound other than compound (1), the content thereof is preferably 0.1 mass % or more and 10 mass % or less, and more preferably 0.3 mass % or more and 5 mass % or less, relative to the total solid content of the polymerizable composition of the present invention. If the content ratio of the other polymerizable compound is less than 0.1 mass %, the effect of imparting properties by its addition is not fully exhibited, while if it exceeds 5 mass %, problems such as impairment of optical properties and strength tend to occur.

[0130] <Anionically Polymerizable Monomer> Examples of the anionically polymerizable monomer include hydrocarbon monomers and polar monomers.

[0131] Examples of hydrocarbon monomers include styrene, α-methylstyrene, butadiene, isoprene, vinylpyridine, vinylanthracene, and derivatives thereof.

[0132] Examples of polar monomers include methacrylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, etc.); acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, etc.); vinyl ketones (e.g., methyl vinyl ketone, isopropyl vinyl ketone, cyclohexyl vinyl ketone, phenyl vinyl ketone, etc.); isopropenyl ketones (e.g., methyl isopropenyl ketone, phenyl isopropenyl ketone, etc.); and other polar monomers (e.g., acrylonitrile, acrylamide, nitroethylene, methylene malonic acid esters, cyanoacrylic acid esters, vinylidene cyanide, etc.).

[0133] These anionically polymerizable monomers may be used either alone or as a mixture of two or more kinds in any combination and ratio.

[0134] <Radical Polymerizable Monomer> The radical polymerizable monomer is a compound having one or more ethylenically unsaturated double bonds in one molecule, and examples thereof include (meth)acrylic acid esters, (meth)acrylamides, vinyl esters, and styrenes.

[0135] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, (n- or i-)propyl (meth)acrylate, (n-, i-, sec- or t-)butyl (meth)acrylate, amyl (meth)acrylate, adamantyl (meth)acrylate, chloroethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, benzyl (meth)acrylate, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, hydroxybenzyl (meth)acrylate, Dimethyl (meth)acrylate, hydroxyphenethyl (meth)acrylate, dihydroxyphenethyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenyl (meth)acrylate, hydroxyphenyl (meth)acrylate, chlorophenyl (meth)acrylate, sulfamoylphenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-(hydroxyphenylcarbonyloxy)ethyl (meth)acrylate, phenol EO-modified (meth)acrylate, phenylphenol EO-modified (meth)acrylate, paracumylphenol EO-modified (meth)acrylate, nonylphenol EO-modified (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, bisphenol F EO-modified diacrylate, bisphenol A EO-modified diacrylate, dibromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl acrylate, tricyclodecane dimethylol di(meth)acrylate, bisphenoxyethanol fluorene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,Examples include dipentaerythritol hexa(meth)acrylate. Here, "EO" means "ethylene oxide."

[0136] Examples of (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-butyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-tolyl(meth)acrylamide, N-(hydroxyphenyl)(meth)acrylamide, N-(sulfamoylphenyl)(meth)acrylamide, N-(phenylsulfonyl)(meth)acrylamide, N-(tolylsulfonyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, and N-hydroxyethyl-N-methyl(meth)acrylamide.

[0137] Examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoate, vinyl t-butylbenzoate, vinyl chlorobenzoate, vinyl 4-ethoxybenzoate, vinyl 4-ethylbenzoate, vinyl 4-methylbenzoate, vinyl 3-methylbenzoate, vinyl 2-methylbenzoate, vinyl 4-phenylbenzoate, and vinyl pivalate.

[0138] Examples of styrenes include styrene, p-acetylstyrene, p-benzoylstyrene, 2-butoxymethylstyrene, 4-butylstyrene, 4-sec-butylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, dichlorostyrene, 2,4-diisopropylstyrene, dimethylstyrene, p-ethoxystyrene, 2-ethylstyrene, 2-methoxystyrene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, p-methylstyrene, p-phenoxystyrene, p-phenylstyrene, and divinylbenzene.

[0139] These radical polymerizable monomers may be used either alone or as a mixture of two or more kinds in any combination and ratio.

[0140] Any of the anionic polymerizable monomers and radical polymerizable monomers exemplified above may be used, or two or more of them may be used in combination. For example, in the case of a high refractive index optical lens or a holographic recording medium, it is preferable to use a radical polymerizable monomer as the other polymerizable compound to be used in combination with compound (1), because it is less likely to inhibit the reaction of forming a resin matrix.

[0141] 2-3. Other Additive Components Other components may be added to the polymerizable composition of the present invention as long as the effects of the present invention are not impaired.

[0142] Examples of other components include various additives such as solvents, antioxidants, plasticizers, ultraviolet absorbers, sensitizers, chain transfer agents, antifoaming agents, polymerization inhibitors, any fillers made of organic or inorganic substances, diffusing agents, pigments, and wavelength converting materials such as fluorescent substances.

[0143] The polymerizable composition of the present invention may contain a solvent to adjust the viscosity.

[0144] Specific examples of the solvent include, depending on the physical properties of the polymerizable composition, alcohols such as ethanol, propanol, isopropanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as hexane, pentane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform; chain ethers such as dimethyl ether and diethyl ether; cyclic ethers such as dioxane and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and ethyl butyrate; ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, and cyclohexanone; Examples of organic solvents include cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as methyl carbitol, ethyl carbitol and butyl carbitol; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono-n-butyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; N,N-dimethylformamide, N,N-dimethylacetamide, etc.), sulfoxides (amides such as dimethyl sulfoxide; nitriles such as acetonitrile and benzonitrile; and N-methylpyrrolidone.

[0145] These solvents can be used alone or as a mixed solvent. Depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.), water can also be used. When a solvent (or dispersion medium) is used, the amount thereof is not particularly limited, and it may be adjusted to obtain a polymerizable composition with a suitable viscosity depending on the polymerization method, processing method, and application.

[0146] In the present invention, in order to improve the heat yellowing resistance and weather resistance of the resulting polymer, it is preferable to incorporate an antioxidant and a light stabilizer as additives into the polymerizable composition.

[0147] Specific examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; and triphenyl phosphite, trisisodecyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, Examples of phosphorus-based antioxidants include tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, tris(nonylphenyl)phosphite, tristridecyl phosphite, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexan-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and tris(2,4-di-t-butylphenyl)phosphite. These can be used alone or in combination of two or more.

[0148] As the antioxidant, it is preferable to use a phenolic antioxidant in combination with a phosphorus-based antioxidant. A preferred combination of a phenolic antioxidant and a phosphorus-based antioxidant is a combination of at least one selected from tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane and n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate as the phenolic antioxidant and tris(2,4-di-t-butylphenyl)phosphite as the phosphorus-based antioxidant.

[0149] The content of the antioxidant in the polymerizable composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable composition, in terms of improving the heat yellowing resistance of the resulting polymer.

[0150] As the light stabilizer, a hindered amine light stabilizer (HALS) is preferably used. Specific examples of HALS include 2,2,6,6-tetramethyl-4-piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl)carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and ADK STAB L. A-68 (manufactured by ADEKA Corporation), Adekastab LA-63P (manufactured by ADEKA Corporation), butane-1,2,3,4-tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 249, TINUVIN 292, TINUVIN 5100 (all manufactured by BASF), and the like. These may be used alone or in combination of two or more.

[0151] The content of the light stabilizer in the polymerizable composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable composition, from the viewpoint of improving the heat yellowing resistance and weather resistance of the resulting polymer.

[0152] The antioxidants and light stabilizers may be used either alone or in combination of two or more thereof.

[0153] 2-4. Method for Producing Polymerizable Composition The polymerizable composition of the present invention may be produced by mixing the respective components, or by premixing the components other than the polymerization initiator and adding the polymerization initiator immediately before the polymerization reaction.

[0154] 2-5. Polymerization Method of Polymerizable Composition The polymerization method of the polymerizable composition of the present invention is not particularly limited, but includes a method of polymerizing by irradiation with active energy rays and a method of polymerizing by heating.

[0155] 2-5-1. Polymerization initiation method (active energy rays) When the polymerizable composition of the present invention is subjected to photoradical polymerization, the polymerization is carried out by irradiation with active energy rays. The active energy rays used are preferably electron beams or light in the wavelength range from ultraviolet to infrared. As the light source, for example, if the active energy rays are ultraviolet rays, an ultra-high pressure mercury light source or a metal halide light source can be used; if they are visible light, a metal halide light source or a halogen light source can be used; and if they are infrared rays, a halogen light source can be used. In addition to these, light sources such as lasers and LEDs can also be used.

[0156] The amount of active energy ray irradiation is appropriately set depending on the type of light source, the thickness of the coating film, etc., but is preferably set appropriately so that the reaction rate of the total amount of polymerizable functional groups of compound (1) and other polymerizable compounds is 80% or more, more preferably 90% or more. The reaction rate is calculated from the change in absorption peak intensity of the polymerizable functional groups before and after the reaction using infrared absorption spectroscopy. After polymerization by irradiation with active energy rays, the polymerization may be further promoted by heat treatment or annealing treatment as needed. The heating temperature in this case is preferably in the range of 80 to 200°C. The heating time is preferably in the range of 10 to 60 minutes.

[0157] 2-5-2. Polymerization initiation method (heating) When heat treatment is performed to polymerize 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 lower than 80° C., a longer heating time is required, which tends to be uneconomical, while if the heating temperature is higher than 200° C., it requires higher energy costs and takes longer to heat up and cool down, which tends to be uneconomical.

[0158] 3. Polymerizable Composition Suitable for Holographic Recording Media The polymerizable composition of the present invention can be suitably 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 containing, in addition to compound (1) and a polymerization initiator, a matrix resin, a radical scavenger, and other additives. Furthermore, it is preferable to use a photopolymerization initiator as the polymerization initiator. Hereinafter, the polymerizable composition suitable as a material for a holographic recording medium will be described in detail.

[0159] 3-1. Matrix Resin The polymerizable composition of the present invention preferably contains a matrix resin. In particular, the matrix resin constituting the recording layer of the holographic recording medium is an organic substance that does not undergo significant chemical or physical changes upon irradiation with light, and is mainly composed of a polymer of an organic compound.

[0160] Since the matrix resin constitutes the polymerizable composition of the present invention together with compound (1), a polymerization initiator, etc., it is strongly required that the matrix resin have excellent compatibility with compound (1), a polymerization initiator, etc. If the matrix resin has low compatibility with the other components, an interface will be formed between the materials, and light will be refracted or reflected at the interface, causing light to leak to unwanted areas. This can distort or break interference fringes, resulting in recording in inappropriate areas and potentially causing information degradation. The compatibility between the matrix resin and the other components can be evaluated based on the scattered light intensity obtained by placing a detector in a direction different from that of the transmitted light relative to the sample, as described in, for example, Japanese Patent No. 3737306.

[0161] The matrix resin may be a resin that is composed of a plurality of materials that are soluble in a solvent in the polymerizable composition and that is three-dimensionally crosslinked after being formed into a usable state, and examples of such a resin include thermoplastic resins, thermosetting resins, and photocurable resins, which will be described below.

[0162] Three-dimensionally crosslinked resins are solvent-insoluble and are cured products of the reaction between a polymerizable compound that is liquid at room temperature and a compound reactive with the polymerizable compound. The three-dimensionally crosslinked resin acts as a physical barrier, suppressing volumetric changes during recording. That is, after recording, the recording layer tends to expand in bright areas and contract in dark areas, resulting in unevenness on the surface of the holographic recording medium. To suppress this volumetric change, it is more preferable to use a polymerizable composition containing a three-dimensionally crosslinked resin matrix for the recording layer. Among these, thermosetting resins are preferred as matrix resins in terms of adhesion to the support. Resin materials that can be used as matrix resins are described in detail below.

[0163] 3-1-1. Thermoplastic Resin Specific examples of thermoplastic resin materials include chlorinated polyethylene, polymethyl methacrylate resin (PMMA), copolymers of methyl methacrylate and other alkyl acrylate esters, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate resin (PVAC), polyvinyl alcohol, polyvinyl formal, polyvinylpyrrolidone, cellulose resins such as ethyl cellulose and nitrocellulose, polystyrene resins, polycarbonate resins, etc. These may be used alone or in combination of two or more.

[0164] The solvent for these thermoplastic resins is not particularly limited as long as it dissolves them, and examples thereof include ketones such as acetone and methyl ethyl ketone, esters such as butyl acetate and propylene glycol methyl ether acetate, aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran and 1,2-dimethoxyethane, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, etc. These may be used alone or in combination of two or more.

[0165] 3-1-2. Thermosetting Resins When using a thermosetting resin as the matrix resin, the curing temperature varies depending on the type of crosslinker and catalyst. Typical examples of functional group combinations that cure at room temperature include epoxy and amine, epoxy and thiol, and isocyanate and amine. Typical examples of combinations that use a catalyst include epoxy and phenol, epoxy and acid anhydride, and isocyanate and polyol.

[0166] The former is simple because it reacts immediately upon mixing, but when molding, such as in a holographic recording medium, adjustments are difficult due to the limited time available. On the other hand, the latter allows for flexible control of the curing temperature and curing time by appropriately selecting the type and amount of catalyst used, making it suitable for curing while molding, such as in a holographic recording medium. A wide variety of resin raw materials, from low molecular weight to high molecular weight, are commercially available, so they can be selected while maintaining compatibility with polymerizable reactive compounds and photoinitiators, adhesion to the substrate, etc. Each raw material is explained below, but each raw material may be used alone or in combination of two or more types.

[0167] <Epoxy> Examples of the epoxy include polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerin; alicyclic epoxy compounds having a cyclic aliphatic group with a 4- to 7-membered ring such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and phenol or cresol novolac type epoxy compounds.

[0168] The epoxy preferably has two or more epoxy groups in one molecule, but the type is not particularly limited. If the number of epoxy groups is small, the hardness required for the matrix may not be obtained. There is no particular upper limit on the number of epoxy groups in one molecule, but it is usually 8 or less, and preferably 4 or less. If the number of epoxy groups is too large, it may take a long time to consume the epoxy groups, and the formation of the matrix resin may take too long.

[0169] <Amine> The amine may be one containing a primary amino group or a secondary amino group. Examples of such amines include aliphatic polyamines such as ethylenediamine, diethylenetriamine, and derivatives thereof, alicyclic polyamines such as isophoronediamine, menthanediamine, N-aminoethylpiperazine, and derivatives thereof, aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and derivatives thereof, polyamides such as condensates of dicarboxylic acids such as dimer acid with the above-mentioned polyamines, imidazole compounds such as 2-methylimidazole and derivatives thereof, and other compounds such as dicyandiamide and adipic dihydrazide.

[0170] <Thiol> Examples of thiols include thiol compounds such as dithiols such as 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzeneedithiol, 1,3-benzeneedithiol, 1,4-benzeneedithiol, 1,10-decanedithiol, 1,2-ethaneedithiol, 1,6-hexaneedithiol, and 1,9-nonanedithiol, and polythiols such as Thiokol (manufactured by Toray Fine Chemicals Co., Ltd.) and jER Cure QX40 (manufactured by Mitsubishi Chemical Corporation). Of these, commercially available fast-curing polythiols such as jER Cure QX40 are preferably used.

[0171] <Phenol> Examples of phenol include bisphenol A, novolac-type phenolic resins, and resol-type phenolic resins.

[0172] <Acid Anhydride> Examples of the acid anhydride include monofunctional acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride and derivatives thereof, and difunctional acid anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic anhydride and derivatives thereof.

[0173] <Amount of amine, thiol, phenol, or acid anhydride used> The amount of amine, thiol, phenol, or acid anhydride used is, in terms of the ratio to the number of moles of epoxy groups, usually 0.1 equivalents or more, preferably 0.7 equivalents or more, and usually 2.0 equivalents or less, preferably 1.5 equivalents or less. If the amount of amine, thiol, phenol, or acid anhydride used is too small or too large, the number of unreacted functional groups will be large, and storage stability may be impaired.

[0174] <Polymerization Initiator for Thermosetting Resin> As a catalyst for curing a thermosetting resin, an anionic polymerization initiator or a cationic polymerization initiator can be used depending on the curing temperature and curing time.

[0175] Anionic polymerization initiators generate anions upon exposure to heat or active energy rays, and examples thereof include amines. Examples of amines include amino group-containing compounds such as dimethylbenzylamine, dimethylaminomethylphenol, and 1,8-diazabicyclo[5.4.0]undecene-7, and derivatives thereof; imidazole compounds such as imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole, and derivatives thereof. These may be used alone or in combination depending on the curing temperature and curing time.

[0176] The cationic polymerization initiator generates cations when exposed to heat or active energy rays, and examples thereof include aromatic onium salts. Specific examples include SbF ６ -, BF ４ -, AsF ６ -, PF ６ -, CF ３ SO ３ -, B (C ６ F ５ ) ４Examples of suitable compounds include compounds comprising an anion component such as - and an aromatic cation component containing an atom such as iodine, sulfur, nitrogen, or phosphorus. Among these, diaryliodonium salts and triarylsulfonium salts are preferred. These can be used alone or in combination depending on the curing temperature and curing time.

[0177] The amount of these thermosetting resin polymerization initiators used is usually 0.001% by mass or more, preferably 0.01% by mass or more, and usually 50% by mass or less, preferably 10% by mass or less, based on the matrix resin. If the amount of these thermosetting resin polymerization initiators used is too small, the concentration of the thermosetting resin polymerization initiator will be too low, and the polymerization reaction may take too long. On the other hand, if the amount of thermosetting resin polymerization initiator used is too large, the polymerization reaction may not undergo a continuous ring-opening reaction.

[0178] <Isocyanate> The isocyanate is preferably one having two or more isocyanate groups per molecule, but the type is not particularly limited. If the number of isocyanate groups per molecule is small, the hardness required for a matrix resin may not be obtained. The upper limit of the number of isocyanate groups per molecule is not particularly limited, but is usually 8 or less, and preferably 4 or less. If the number of isocyanate groups per molecule is too large, it may take a long time to consume the isocyanate groups, and the formation of the matrix resin may take too long. The upper limit of the number of isocyanate groups per molecule is not particularly limited, but is usually about 20 or less.

[0179] Examples of isocyanates include aliphatic isocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate); aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and naphthalene-1,5'-diisocyanate; and oligomers thereof, of which trimers to heptamers are preferred.

[0180] Other examples include reaction products of the above-mentioned isocyanates with polyhydric alcohols such as water, trimethylolethane, and trimethylolpropane, and hexamethylene diisocyanate polymers or derivatives thereof. The molecular weight of the isocyanate is preferably 100 to 50,000 in number average molecular weight, more preferably 150 to 10,000, and even more preferably 150 to 5,000. If the number average molecular weight is too small, the crosslinking density increases, which can lead to excessive hardness of the matrix resin and reduced recording speed. If the number average molecular weight is too large, the compatibility with other components decreases or the crosslinking density decreases, which can lead to excessively low hardness of the matrix resin and the loss of recorded content.

[0181] <Polyol> Examples of polyols include polypropylene polyol, polycaprolactone polyol, polyester polyol, and polycarbonate polyol.

[0182] (Polypropylene Polyol) Polypropylene polyol is obtained by reacting propylene oxide with a diol or a polyhydric alcohol. Examples of diols or polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol. Commercially available polypropylene polyols include Sannix GP-400 and GP-1000 (all manufactured by Sanyo Chemical Industries, Ltd., trade names), and Adeka Polyether G400, G700, and G1500 (all manufactured by ADEKA Corporation, trade names).

[0183] (Polycaprolactone polyol) Polycaprolactone polyol is obtained by reacting a lactone with a diol or a polyhydric alcohol. Examples of lactones include α-caprolactone, β-caprolactone, γ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, and β-methyl-ε-caprolactone.

[0184] Examples of diols or polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol.

[0185] Commercially available polycaprolactone polyols obtained by the reaction of ε-caprolactone include PLACCEL 205, PLACCEL 205H, PLACCEL 205U, Examples of such products include PLACCEL 205UT, PLACCEL 210, PLACCEL 210N, PLACCEL 210CP, PLACCEL 220, PLACCEL 230, PLACCEL 230N, PLACCEL 240, PLACCEL 220EB, PLACCEL 220EC, PLACCEL 303, PLACCEL 305, PLACCEL 308, PLACCEL 309, PLACCEL 312, PLACCEL 320, PLACCEL 401, PLACCEL L205AL, PLACCEL L212AL, PLACCEL L220AL, PLACCEL L320AL, PLACCEL T2103, PLACCEL T2205, PLACCEL P3403, and PLACCEL 410 (all of which are trade names manufactured by Daicel Corporation).

[0186] (Polyester Polyol) Examples of polyester polyols include those obtained by polycondensing a dicarboxylic acid or an anhydride thereof with a polyol.

[0187] Examples of dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, maleic anhydride, isophthalic acid, terephthalic acid, and trimellitic acid.

[0188] Examples of polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol.

[0189] Examples of polyester polyols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, etc. Commercially available polyester polyols include the ADEKA New Ace F series, ADEKA New Ace Y series, and ADEKA New Ace NS series (trade names, manufactured by ADEKA Corporation), and Kuraray Polyol N-2010, P-4011, and P-1020 (trade names, all manufactured by Kuraray Co., Ltd.).

[0190] (Polycarbonate Polyol) Examples of polycarbonate polyols include those obtained by a dealcoholization condensation reaction between glycols and dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate, etc.), those obtained by a dephenolation condensation reaction between glycols and diphenyl carbonates, and those obtained by a glycol removal condensation reaction between glycols and carbonates (e.g., ethylene carbonate, diethyl carbonate, etc.).

[0191] Examples of glycols include aliphatic diols such as 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and neopentyl glycol, and alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol.

[0192] 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.

[0193] Commercially available polycarbonate polyols include Placcel CD CD205, Placcel CD CD210, and Placcel CD CD220 (all of which are trade names manufactured by Daicel Corporation), and Duranol T5651, Duranol T5652, and Duranol T5650J (all of which are trade names manufactured by Asahi Kasei Corporation).

[0194] (Molecular Weight of Polyol) The molecular weight of the polyol described above is preferably 100 to 50,000 in number average molecular weight, more preferably 150 to 10,000, and even more preferably 150 to 5,000. If the number average molecular weight is too small, the crosslinking density increases, which may cause the matrix resin to have too high hardness, resulting in a decrease in recording speed. On the other hand, if the number average molecular weight is too large, the compatibility with other components may decrease or the crosslinking density may decrease, which may cause the matrix resin to have too low hardness, resulting in the erasure of recorded content.

[0195] <Other Components> The matrix resin in the present embodiment may contain other components in addition to the above-described components, as long as it does not go against the spirit of the present invention.

[0196] Examples of such other components include compounds having a hydroxyl group, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, trimethylolpropane, polyethylene glycol, and polytetramethylene glycol, which are used for the purpose of changing the physical properties of the matrix resin.

[0197] <Urethane Polymerization Catalyst> A suitable urethane polymerization catalyst may be contained to promote the reaction of the isocyanate and the polyol. Examples of the urethane polymerization catalyst include onium salts such as bis(4-t-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-t-butylphenyl)iodonium p-toluenesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, (4-bromophenyl)diphenylsulfonium triflate, (4-t-butylphenyl)diphenylsulfonium trifluoromethanesulfonate, diphenyliodonium perfluoro-1-butanesulfonate, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and bis(alkylphenyl)iodonium hexafluorophosphonic acid; zinc chloride, tin chloride, iron chloride, aluminum chloride, and BF ３protonic 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-undecylimidazolylium trimellitate; bases such as sodium hydroxide, potassium hydroxide, and potassium carbonate; tin catalysts such as dibutyltin laurate, dioctyltin laurate, and dibutyltin octoate; bismuth catalysts such as tris(2-ethylhexanoate)bismuth and tribenzoyloxybismuth; and zirconium catalysts such as tetrakis(ethylacetoacetate)zirconium, 1,1'-isopropylidene zirconocene dichloride, and tetrakis(2,4-pentanedionato)zirconium.

[0198] Among these, bismuth catalysts and zirconium catalysts are preferred for improving storage stability.

[0199] The bismuth catalyst is not particularly limited as long as it is a catalyst containing bismuth element and is a compound that promotes the reaction between isocyanate and polyol. Examples of the bismuth catalyst include tris(2-ethylhexanoate)bismuth, tribenzoyloxybismuth, bismuth triacetate, tris(dimethyldicarbamate)bismuth, bismuth hydroxide, triphenylbismuth(V) bis(trichloroacetate), tris(4-methylphenyl)oxobismuth(V), and triphenylbis(3-chlorobenzoyloxy)bismuth(V).

[0200] Among these, trivalent bismuth compounds are preferred from the viewpoint of catalytic activity, and bismuth carboxylate, a compound represented by the general formula Bi(OCOR) ３ (R is a linear or branched alkyl group, a cycloalkyl group, or a substituted or unsubstituted aromatic group) is more preferred. The above bismuth catalysts may be used alone or in any combination and ratio of two or more.

[0201] The zirconium catalyst is not particularly limited as long as it is a catalyst containing zirconium element and is a compound that promotes the reaction of isocyanate and polyol. Examples thereof include cyclopentadienyl zirconium trichloride, decamethyl zirconocene dichloride, 1,1'-dibutyl zirconocene dichloride, 1,1'-isopropylidene zirconocene dichloride, tetrakis(2,4-pentanedionato)zirconium, tetrakis(trifluoro-2,4-pentanedionato)zirconium, tetrakis(hexafluoro-2,4-pentanedionato)zirconium, zirconium butoxide, zirconium Examples of the zirconium oxide include barium zirconium oxide, calcium zirconium oxide, zirconium bromide, zirconium chloride, zirconium fluoride, zirconium dichloride (indenyl) and zirconium carbonate.

[0202] Among these, compounds having an organic ligand are preferred in terms of compatibility with other components, and are more preferred than compounds having an alkoxide or acetylacetonate (2,4-pentanedionato) structure. Any one of the above zirconium compounds may be used alone, or two or more may be used in any combination and ratio.

[0203] The bismuth-based catalyst and the zirconium-based catalyst may be used alone or in combination.

[0204] The amount of the urethane polymerization catalyst used, in terms of the ratio to the matrix resin, is usually 0.0001% by mass or more, preferably 0.001% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. If the amount of the urethane polymerization catalyst used is too small, curing may take too long. On the other hand, if the amount used is too large, it may be difficult to control the curing reaction.

[0205] Although the composition can be cured at room temperature by using a urethane polymerization catalyst, it may also be cured at elevated temperatures, preferably between 40°C and 90°C.

[0206] 3-1-3. Photocurable resins When using photocurable resins as the matrix resin, they must be cured using a photoinitiator for the matrix resin that is appropriate for the wavelength used. Since curing during light irradiation can cause problems with molding and adhesion, it is desirable for the curing reaction to be stable around room temperature, which is the temperature at which the resin is primarily worked. Given this, catalytic curing using a photoinitiator for the matrix resin is the preferred choice.

[0207] Generally, photoinitiators for matrix resins generate either cationic or anionic active substrates upon irradiation with light. Therefore, it is considered best to select a material that undergoes curing via these active substrates and then cure it to form a matrix resin.

[0208] Examples of functional groups that react with cations such as protons include epoxy groups and oxetanyl groups. Specific examples of compounds containing these groups include polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerin, which contain epoxy groups; alicyclic epoxy compounds having a 4- to 7-membered cyclic aliphatic group such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; bisphenol A epoxy compounds, hydrogenated bisphenol A epoxy compounds, bisphenol F epoxy compounds, and phenol or cresol novolac epoxy compounds. Examples of compounds containing an oxetanyl group include 2-ethyl-2-oxetanyl ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetanyloxy)hexane. (Note that the term "(poly)ethylene glycol" refers to both "ethylene glycol" and its polymer, "polyethylene glycol.")

[0209] Examples of functional groups that react with anions include epoxy groups and episulfide groups. Specific examples of compounds having an episulfide group include phenyl episulfide and diepisulfide methyl ether of bisphenol A.

[0210] The amount of the matrix resin photoinitiator used when photocuring the matrix resin described above is typically 0.01% by mass or more, preferably 0.1% by mass or more, and typically 1% by mass or less, preferably 0.5% by mass or less, relative to the polymerizable compound. If the amount of matrix resin photoinitiator used is too small, curing may take too long. On the other hand, if the amount used is too large, it may be difficult to control the curing reaction.

[0211] Furthermore, particularly when used as a hologram recording material, it is important that the wavelength during curing is different from the wavelength during recording, since light is also irradiated during recording, and the wavelength difference is at least 10 nm, preferably 30 nm. The selection of a photoinitiator for the matrix resin can generally be predicted from the absorption wavelength of the initiator.

[0212] 3-2. Photopolymerization initiator The above-mentioned photoradical polymerization initiators can be used as the photopolymerization initiator. Among them, titanocene compounds, acylphosphine oxide compounds, and oxime ester compounds are preferred because they undergo polymerization reaction with light in the visible region.

[0213] 3-2-1. Titanocene Compound When a titanocene compound is used as a photopolymerization initiator, the type thereof is not particularly limited, and may be appropriately selected from the various titanocene compounds described in, for example, JP-A-59-152396 and JP-A-61-151197.

[0214] Specific examples of titanocene compounds include dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, and dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl. , dicyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyr-1-yl)-phenyl-1-yl, and the like.

[0215] 3-2-2. Acylphosphine oxide compounds Specific examples of acylphosphine oxide compounds include monofunctional initiators that have only one photocleavage site per molecule, and bifunctional initiators that have two photocleavage sites per molecule.

[0216] Examples of the monofunctional initiator include triphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide.

[0217] Examples of the bifunctional initiator include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, and bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide.

[0218] Specific examples of oxime ester compounds include 1-[4-(phenylthio)-2-(O-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, 4-(acetoximino)-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate, and 5-(9-ethyl-6-cyclohexanoyl-9H-carbazol-3-yl)-4-(O-acetyloxime)-5-oxopentanoate. , methyl 5-(9-ethyl-9H-carbazol-3-yl)-4-(O-acetyloxime)-5-oxopentanoate, 1-(9-ethyl-6-cyclohexanoyl-9H-carbazol-3-yl)-2-(O-acetyloxime)-1-heptanone, 1-(9-ethyl-9H-carbazol-3-yl)-1-(O-acetyloxime)-3-methylbutanoic acid, and the like.

[0219] 3-2-4. Amount of Photopolymerization Initiator Used Any one of the above-mentioned various photopolymerization initiators may be used alone, or two or more of them may be used in any combination and ratio.

[0220] The content of the photopolymerization initiator in the polymerizable composition of the present invention is preferably 0.5 μmol / g or more, more preferably 1 μmol / g or more, in terms of molar amount per unit weight of the polymerizable composition, and is preferably 100 μmol / g or less, more preferably 50 μmol / g or less, in terms of molar amount per unit weight of the polymerizable composition.

[0221] If the content of the photopolymerization initiator is too low, the amount of radicals generated will be small, which may slow down the photopolymerization rate and result in a decrease in the recording sensitivity of the holographic recording medium. On the other hand, if the content of the photopolymerization initiator is too high, the radicals generated by light irradiation will recombine with each other or undergo disproportionation, which may reduce their contribution to photopolymerization and also result in a decrease in the recording sensitivity of the holographic recording medium. When two or more photopolymerization initiators are used in combination, it is preferable that the total amount thereof satisfies the above range.

[0222] 3-3. Radical Scavenger In hologram recording, a radical scavenger may be added to accurately fix the interference light intensity pattern as a polymer distribution in the hologram recording medium. The radical scavenger preferably has both a functional group that captures radicals and a reactive group that is covalently fixed to the matrix resin. An example of a functional group that captures radicals is a stable nitroxyl radical group.

[0223] 3-3-1. Types of Radical Scavenger Reactive groups that can be covalently bonded to a matrix resin include hydroxyl groups, amino groups, isocyanate groups, and thiol groups. Examples of such radical scavengers include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (TEMPOL), 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxyl, 3-hydroxy-8-azabicyclo[3.2.1]octane N-oxyl, and 5-HO-AZADO: 5-hydroxy-2-azatricyclo[3.3.1.1]octane N-oxyl. ３，７ ] decane N-oxyl.

[0224] 3-3-2. Content of Radical Scavenger Any one of the above-mentioned various radical scavengers may be used alone, or two or more may be used in any combination and ratio. The content of the radical scavenger in the polymerizable composition of the present invention is preferably 0.5 μmol / g or more, more preferably 1 μmol / g or more, in terms of molar amount per unit weight of the polymerizable composition. The content of the radical scavenger in the polymerizable composition of the present invention is preferably 100 μmol / g or less, more preferably 50 μmol / g or less.

[0225] If the content of the radical scavenger is too low, the radical scavenging efficiency will be low, and the polymer with a low degree of polymerization will diffuse, tending to result in an increase in components that do not contribute to signals. On the other hand, if the content of the radical scavenger is too high, the polymer polymerization efficiency will be reduced, tending to make it impossible to record signals. When two or more radical scavengers are used in combination, it is preferable that their total amount satisfies the above range.

[0226] 3-4. Other Components Even when used as a holographic recording medium, the polymerizable composition of the present invention may contain other components in addition to the above-described components, as long as the other components do not deviate from the spirit of the present invention.

[0227] Other components include solvents, plasticizers, dispersants, leveling agents, antifoaming agents, adhesion promoters, etc. for preparing the polymerizable composition, and, particularly when used in holographic recording media, chain transfer agents, polymerization terminators, compatibilizers, reaction aids, sensitizers, etc. for controlling the recording reaction. Examples of additives that may be required for improving other properties include preservatives, stabilizers, antioxidants, UV absorbers, light stabilizers, etc. Any one of these components may be used alone, or two or more may be used in any combination and ratio.

[0228] <Sensitizer> A compound that controls the excitation of the photopolymerization initiator can be added to the polymerizable composition of the present invention. Examples of such compounds include a sensitizer and a sensitization aid.

[0229] The sensitizer can be selected from various known sensitizers, but generally, colored compounds such as dyes are used as sensitizers to absorb visible and ultraviolet laser light. When used in holographic recording media, the sensitizers vary depending on the wavelength of the laser light used for recording and the type of initiator used. In systems using green lasers, specific examples of preferred sensitizers include those described in JP-A-5-241338, JP-A-2-69, JP-B-2-55446, etc. In systems using blue lasers, specific examples of preferred sensitizers include those described in JP-A-2000-10277, JP-A-2004-198446, etc. These sensitizers may be used alone or in any combination and ratio of two or more.

[0230] When the resulting holographic recording medium is required to be colorless and transparent, it is preferable to use a cyanine dye as a sensitizer. Since cyanine dyes are generally easily decomposed by light, post-exposure, i.e., leaving the holographic recording medium under room light or sunlight for several hours to several days, decomposes the cyanine dye in the holographic recording medium, and the cyanine dye no longer absorbs in the visible range, thereby obtaining a colorless and transparent holographic recording medium.

[0231] The amount of sensitizer needs to be increased or decreased depending on the thickness of the recording layer to be formed, but it is preferable that the ratio to the aforementioned photopolymerization initiator is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. If the amount of sensitizer used is too small, the initiation efficiency may decrease and recording may take a long time. On the other hand, if the amount of sensitizer used is too large, the absorption of light used for recording and reproduction may increase, making it difficult for light to reach the depth direction. When two or more sensitizers are used in combination, the total amount thereof should be within the above range.

[0232] <Plasticizer> The polymerizable composition of the present invention may contain a plasticizer in order to improve the reaction efficiency and adjust the physical properties of the recording layer of the holographic recording medium.

[0233] Examples of the plasticizer include phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and diundecyl phthalate; adipates such as bis(2-ethylhexyl) adipate, diisononyl adipate, and di-n-butyl adipate; sebacates such as dioctyl sebacate and dibutyl sebacate; phosphates such as tricresyl phosphate; citric acid esters such as acetyl tributyl citrate; trimellitates such as trioctyl trimellitate; epoxidized soybean oil, chlorinated paraffin, alkoxylated (poly)alkylene glycol esters such as acetoxymethoxypropane; and terminally alkoxylated polyalkylene glycols such as dimethoxypolyethylene glycol.

[0234] It is also possible to use a plasticizer containing a fluorine element, such as those exemplified in Japanese Patent No. 6069294. Examples of the plasticizer containing a fluorine element include 2,2,2-trifluoroethyl butylcarbamate, bis(2,2,2-trifluoroethyl)-(2,2,4-trimethylhexane-1,6-diyl)biscarbamate, bis(2,2,2-trifluoroethyl)-[4-({[(2,2,2-trifluoroethoxy)carbonyl]amino}-methyl)octane-1,8-diyl]biscarbamate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl butylcarbamate, and 2,2,2-trifluoroethyl phenylcarbamate.

[0235] These plasticizers are used in an amount of usually 0.01% by mass to 50% by mass, preferably 0.05% by mass to 20% by mass, based on the total solid content of the polymerizable composition. If the plasticizer content is less than this range, the effects of improving reaction efficiency and adjusting physical properties will not be exhibited, whereas if it is more than this range, the transparency of the recording layer will decrease and bleeding out of the plasticizer will become significant.

[0236] <Leveling Agent> A leveling agent can be used in the polymerizable composition of the present invention. Examples of the leveling agent include sodium polycarboxylate, ammonium polycarboxylate, amine polycarboxylate, silicon-based leveling agents, acrylic leveling agents, ester compounds, ketone compounds, and fluorine compounds. Any one of these may be used alone, or two or more may be used in any combination and ratio.

[0237] <Chain Transfer Agent> A chain transfer agent can be used in the polymerizable composition of the present invention. Examples of the chain transfer agent include phosphinates such as sodium phosphite and sodium hypophosphite, mercaptans such as mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, and thiophenol, aldehydes such as acetaldehyde and propionaldehyde, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as trichloroethylene and perchloroethylene, terpenes such as terpinolene, α-terpinene, β-terpinene, and γ-terpinene, 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,4-cyclooctadiene, and 1,4-heptadiene. non-conjugated dienes such as thiadiene, 1,4-hexadiene, 2-methyl-1,4-pentadiene, 3,6-nonanedien-1-ol, and 9,12-octadecadienol; linolenic acids such as linoleic acid, γ-linolenic acid, methyl linolenate, ethyl linolenate, isopropyl linolenate, and linoleic acid anhydride; linoleic acids such as linoleic acid, methyl linoleate, ethyl linoleate, isopropyl linoleate, and linoleic acid anhydride; eicosapentaenoic acids such as eicosapentaenoic acid and ethyl eicosapentaenoate; and docosahexaenoic acids such as docosahexaenoic acid and ethyl docosahexaenoate.

[0238] The amount of these additives used is, in terms of the ratio to the total solid content of the polymerizable composition of the present embodiment, usually 0.001% by mass or more, and preferably 0.01% by mass or more, and usually 30% by mass or less, and preferably 10% by mass or less. When two or more additives are used in combination, the total amount thereof satisfies the above range.

[0239] 3-5. Compositional Ratio of Each Component in the Polymerizable Composition The content of each component in the polymerizable composition is arbitrary as long as it does not deviate from the gist of the present invention.

[0240] The content of the polymerizable compound including compound (1) of the present invention in the polymerizable composition of the present invention is preferably 5 μmol / g or more, more preferably 10 μmol / g or more, and even more preferably 100 μmol / g or more, based on the molar amount per unit mass of the polymerizable composition. The content of the polymerizable compound is preferably 1000 μmol / g or less, more preferably 500 μmol / g or less, and even more preferably 300 μmol / g or less. When the content of the polymerizable compound is equal to or more than the lower limit, sufficient diffraction efficiency can be obtained in the holographic recording medium. When the content of the polymerizable compound is equal to or less than the upper limit, compatibility with the resin matrix in the recording layer is maintained, and shrinkage of the recording layer due to recording tends to be kept low.

[0241] When an isocyanate and a polyol are used as the matrix resin in the polymerizable composition of the present invention, the total content thereof is usually 0.1% by mass or more, preferably 10% by mass or more, more preferably 35% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less. By setting this content to be equal to or greater than the above-mentioned lower limit, it becomes easy to form a recording layer.

[0242] 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, and usually 10.0 or less, preferably 2.0 or less. When this ratio is within the above range, there are fewer unreacted functional groups, and storage stability is improved.

[0243] The content of the urethane polymerization catalyst in the polymerizable composition is preferably determined in consideration of the reaction rate of the isocyanate and the polyol, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 1% by mass or less. The content of the urethane polymerization catalyst is preferably 0.003% by mass or more.

[0244] The total amount of other components in the polymerizable composition other than the above components may be 30% by mass or less, preferably 15% by mass or less, and more preferably 5% by mass or less.

[0245] 3-6. Method for Producing Polymerizable Composition In the present invention, the method for producing a polymerizable composition containing a polymerizable compound containing compound (1), a matrix resin, and a photopolymerization initiator is not particularly limited, and the order of mixing and the like can be adjusted as appropriate. Furthermore, when the polymerizable composition contains components other than those described above, the components may be mixed in any combination and in any order.

[0246] When an isocyanate and a polyol are used as the matrix resin, the polymerizable composition can be obtained, for example, by the following method, but the present invention is not limited to this. A photoreactive composition (liquid A) is obtained by mixing a polymerizable compound, a photopolymerization initiator, and all components other than the isocyanate and urethane polymerization catalyst. A mixture of the isocyanate and the urethane polymerization catalyst is obtained as liquid B. Alternatively, the photoreactive composition (liquid A) can be obtained by mixing a polymerizable compound and a photopolymerization initiator with all components other than the isocyanate.

[0247] It is preferable to dehydrate and degas each liquid. If dehydration and degassing are insufficient, bubbles may form during the production of the holographic recording medium, making it impossible to obtain a uniform recording layer. During this dehydration and degassing process, heating and decompression may be performed as long as the components are not damaged.

[0248] The preparation of the polymerizable composition by mixing liquid A and liquid B is preferably carried out immediately before molding the holographic recording medium. Conventional mixing techniques can also be used for this purpose. When mixing liquid A and liquid B, degassing may be performed as needed to remove residual gas. Furthermore, liquid A and liquid B are preferably subjected to a filtration step to remove foreign matter and impurities, either individually or after mixing, and it is more preferable to filter each liquid separately.

[0249] Also, an isocyanate-functional prepolymer obtained by reacting an isocyanate having an excess of isocyanate groups with a polyol can be used as the matrix resin. Furthermore, an isocyanate-reactive prepolymer obtained by reacting an isocyanate with a polyol having an excess of isocyanate-reactive functional groups can be used as the matrix resin.

[0250] 4. Polymer The polymer of the present invention obtained by polymerizing the polymerizable composition of the present invention will be described below.

[0251] 4-1. Refractive Index Generally, because the overall density increases through a polymerization reaction, the refractive index of a polymer tends to be higher than that of its precursor compound (called a monomer) before polymerization. By using a monomer with a high refractive index and allowing the polymerization reaction to proceed sufficiently, the refractive index of the resulting polymer can be increased, so it is considered important to improve the refractive index of a polymer by designing the molecular structure of the monomer.

[0252] The refractive index shows a large value when evaluated with irradiation light of a short wavelength, but a sample that shows a relatively large refractive index at a short wavelength also shows a relatively large refractive index at a long wavelength, and this relationship is not reversed. Therefore, by evaluating and comparing the refractive index at a constant wavelength, it is possible to compare the intrinsic refractive index of the material. In the present invention, the value at an irradiation light wavelength of 587 nm was used as the standard.

[0253] The refractive index of the compound (1) and the polymer of the present invention is preferably 1.60 or more, more preferably 1.63 or more, particularly preferably 1.65 or more, and most preferably 1.67 or more. There is no particular upper limit to the refractive index of the compound (1) and the polymer of the present invention, but it is usually 2.0 or less.

[0254] When compound (1) and the polymer of the present invention are used as recording layer materials for holographic recording media, the refractive index of compound (1) and the polymer of the present invention is usually in the range of 1.65 or more and 1.78 or less, preferably 1.77 or less. If the refractive index is less than 1.65, the diffraction efficiency is low and the multiplicity is insufficient. On the other hand, if the refractive index is more than 1.78, the difference in refractive index with the matrix resin becomes too large, resulting in increased scattering and reduced transmittance, and therefore requiring greater energy for recording and reproduction.

[0255] When compound (1) and the polymer of the present invention are used as optical materials such as lenses, a refractive index of less than 1.60 is undesirable because the central portion of the optical lens becomes thicker, which may impair the lightweight nature that is characteristic of plastics. Furthermore, in the development of precision optical components such as lenses, it is also important to combine optical materials with multiple refractive indices to achieve optical properties suitable for the components. From this perspective, monomers and polymers with a refractive index of more than 1.65 can be considered to be particularly useful materials for optical components.

[0256] 4-2. Glass Transition Temperature The glass transition temperature of the polymer of the present invention is preferably 90°C or higher, more preferably 100°C or higher, even more preferably 110°C or higher, particularly preferably 120°C or higher, and preferably 250°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower. If the glass transition temperature is below this range, the optical properties may change from the designed values ​​under the usage environment, and the practically required heat resistance may not be satisfied. If the glass transition temperature is above this range, the processability of the polymer may decrease, and a molded product with a good appearance and high dimensional accuracy may not be obtained. In addition, the polymer may become brittle, the mechanical strength may decrease, and the handleability of the molded product may deteriorate.

[0257] 5. Optical Materials and Optical Components The compound, polymerizable composition, and polymer of the present invention have properties such as a high refractive index, easy processability, and high chemical stability, and can therefore be applied to various optical materials and optical components.

[0258] Examples of optical materials include optical overcoats, hard coating agents, adhesives for optical components, resins for optical fibers, and acrylic resin modifiers.

[0259] Examples of optical components include lenses, filters, diffraction gratings, prisms, light guides, display cover glass, photosensors, photoswitches, LEDs, light-emitting elements, optical waveguides, light splitters, optical fiber adhesives, display element substrates, color filter substrates, touch panel substrates, polarizing plates, display backlights, light guide plates, anti-reflection films, viewing angle expansion films, optical recording, photolithography, and optical relief printing. They can also be used as layers of these. Examples include display protective films.

[0260] Among these, the compound (1) and the polymer of the present invention are particularly suitable for use in plastic lenses due to their high refractive index, including imaging lenses for cameras (such as vehicle-mounted cameras, digital cameras, PC cameras, mobile phone cameras, and surveillance cameras), eyeglass lenses, light beam focusing lenses, and light diffusing lenses.

[0261] Lenses using the compound (1) and polymer of the present invention can be subjected to physical or chemical treatments such as surface polishing, antistatic treatment, hard coating treatment, antireflective coating treatment, dyeing treatment, etc., in order to improve, if necessary, antireflection, impart high hardness, improve abrasion resistance, improve chemical resistance, impart antifogging property, or impart fashionability.

[0262] 6. Holographic Recording Medium The holographic recording medium of the present invention using the polymerizable composition of the present invention comprises a recording layer and, if necessary, a support or other layers. Typically, a holographic recording medium has a support, and the recording layer and other layers are laminated on this support to form the holographic recording medium. However, if the recording layer or other layers have the strength and durability required for the medium, the holographic recording medium does not need to have a support. Examples of other layers include a protective layer, a reflective layer, an antireflective layer (antireflective film), etc.

[0263] 6-1. Recording Layer The recording layer of the holographic recording medium of the present invention is a layer formed from the polymerizable composition of the present invention, and is the layer on which information is recorded. Information is usually recorded as a hologram. As will be described later in the section on recording method, the polymerizable compound (hereinafter referred to as polymerizable monomer) contained in the recording layer undergoes a chemical change, such as polymerization, in part upon holographic recording. Therefore, in the holographic recording medium after recording, part of the polymerizable monomer is consumed, and exists as a reacted compound, such as a polymer.

[0264] The thickness of the recording layer is not particularly limited and may be appropriately determined taking into consideration the recording method, etc., but is preferably 1 μm or more, more preferably 10 μm or more, and preferably 1 cm or less, more preferably 3 mm or less. By setting the thickness of the recording layer to the above-mentioned lower limit or more, selectivity of each hologram tends to be increased during multiplexed recording in the holographic recording medium, and the degree of multiplexed recording tends to be increased. By setting the thickness of the recording layer to the above-mentioned upper limit or less, it becomes possible to uniformly mold the entire recording layer, and multiplexed recording tends to be possible with uniform diffraction efficiency of each hologram and a high S / N ratio.

[0265] The shrinkage rate of the recording layer due to exposure during recording and reproduction of information is preferably 0.25% or less from the viewpoint of recording reproducibility.

[0266] 6-2. Support There are no particular limitations on the details of the support, and any support can be used as long as it has the strength and durability required for the holographic recording medium. There are no limitations on the shape of the support, but it is usually formed into a flat plate or film. There are also no limitations on the material that makes up the support, and it may be transparent or opaque.

[0267] Examples of transparent materials for the support include organic materials such as acrylic, polyethylene terephthalate, polyethylene naphthoate, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polystyrene, polycycloolefin, cellulose acetate, etc., and inorganic materials such as glass, silicon, quartz, etc. Among these, polycarbonate, acrylic, polyester, amorphous polyolefin, glass, etc. are preferred, and polycarbonate, acrylic, amorphous polyolefin, polycycloolefin, and glass are particularly more preferred.

[0268] Examples of opaque support materials include metals such as aluminum, and the above-mentioned transparent supports coated with metals such as gold, silver, and aluminum, or dielectrics such as magnesium fluoride and zirconium oxide.

[0269] The thickness of the support is not particularly limited, but is preferably in the range of 0.05 mm to 1 mm. If the thickness of the support is equal to or greater than the lower limit, the mechanical strength of the hologram recording medium can be ensured and warping of the substrate can be prevented. If the thickness of the support is equal to or less than the upper limit, advantages such as increased light transmittance and reduced weight and cost of the hologram recording medium can be obtained.

[0270] The surface of the support may be subjected to a surface treatment. This surface treatment is usually performed to improve the adhesion between the support and the recording layer. Examples of surface treatments include subjecting the support to a corona discharge treatment or forming an undercoat layer on the support in advance. Examples of compositions for the undercoat layer include halogenated phenols, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, etc.

[0271] The surface of the support may be treated for purposes other than improving adhesion. Examples of such treatments include a reflective coating treatment for forming a reflective coating layer made of a metal such as gold, silver, or aluminum, and a dielectric coating treatment for forming a dielectric layer made of magnesium fluoride, zirconium oxide, or the like. These layers may be formed as a single layer or as two or more layers.

[0272] These surface treatments may be performed for the purpose of controlling the gas and moisture permeability of the substrate. For example, the reliability of the holographic recording medium can be improved by providing the supports sandwiching the recording layer with a function of suppressing the gas and moisture permeability.

[0273] The support may be provided on either the upper or lower side of the recording layer of the holographic recording medium of the present invention, or on both sides. However, when supports are provided on both the upper and lower sides of the recording layer, at least one of the supports is configured to be transparent so as to transmit active energy rays (excitation light, reference light, reproduction light, etc.).

[0274] In the case of a holographic recording medium having a support on one or both sides of the recording layer, transmission or reflection holograms can be recorded, and in the case of a support having reflective properties on one side of the recording layer, reflection holograms can be recorded.

[0275] The support may be provided with a pattern for data addressing. In this case, the patterning method is not limited, but for example, the support itself may be provided with unevenness, a pattern may be formed on the reflective layer described later, or a combination of these methods may be used.

[0276] 6-3. Protective Layer The protective layer is a layer for preventing deterioration of the recording and reproduction characteristics of the recording layer. There are no restrictions on the specific configuration of the protective layer, and any known protective layer can be applied. For example, a layer made of a water-soluble polymer, organic / inorganic material, etc. can be formed as the protective layer.

[0277] The position where the protective layer is formed is not particularly limited, and may be formed, for example, on the surface of the recording layer, between the recording layer and the support, or on the outer surface side of the support. The protective layer may also be formed between the support and another layer.

[0278] 6-4. Reflective Layer The reflective layer is formed when the holographic recording medium is configured to be reflective. In the case of a reflective holographic recording medium, the reflective layer may be formed between the support and the recording layer, or may be formed on the outer surface of the support, but it is usually preferable that the reflective layer be between the support and the recording layer. Any known reflective layer can be used, and for example, a thin metal film or the like can be used.

[0279] 6-5. Antireflection Film For both transmission and reflection holographic recording media, an antireflection film may be provided on the side where the information light, reference light, and reproduction light enter and exit, or between the recording layer and the support. The antireflection film improves the light utilization efficiency and suppresses noise generation. Any known antireflection film can be used.

[0280] 6-6. Manufacturing Method of Holographic Recording Medium There are no limitations on the manufacturing method of the holographic recording medium of the present invention. For example, the holographic recording medium can be manufactured by applying the polymerizable composition of the present invention onto a support without a solvent to form a recording layer. In this case, any method can be used as the coating method. Specific examples include spraying, spin coating, wire bar coating, dipping, air knife coating, roll coating, blade coating, doctor roll coating, etc.

[0281] When forming a recording layer, particularly when forming a thick recording layer, a method of molding in a mold or a method of applying the composition to a release film and punching out a mold can be used. Alternatively, the recording layer can be produced by mixing the polymerizable composition of the present invention with a solvent or additives to prepare a coating liquid, applying this to a support, and drying the coating liquid to form a recording layer. In this case, any coating method can be used, and for example, the same methods as those described above can be used.

[0282] There are no limitations on the solvent used in the coating solution, but it is usually preferable to use one that has sufficient solubility for the components used, provides good coating properties, and does not attack supports such as resin substrates. A single solvent may be used, or two or more solvents may be used in any combination and ratio. There are also no limitations on the amount of solvent used, but from the standpoint of coating efficiency and handleability, it is preferable to prepare a coating solution with a solids concentration of about 1 to 100% by mass.

[0283] Examples of the solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; aromatic solvents such as toluene and xylene; alcohol-based solvents such as methanol, ethanol, propanol, n-butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; ketone alcohol-based solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; ether-based solvents such as tetrahydrofuran and dioxane; halogen-based solvents such as dichloromethane, dichloroethane, and chloroform; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol Examples of suitable solvents include propylene glycol solvents such as cholesteryl monobutyl ether acetate and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate ethyl 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; and mixed solvents thereof.

[0284] Examples of methods for producing a holographic recording medium include a method in which a polymerizable composition melted by heat is applied to a support, and then cooled and solidified to form a recording layer; a method in which a liquid polymerizable composition is applied to a support, and then thermally polymerized to harden the composition to form a recording layer; and a method in which a liquid polymerizable composition is applied to a support, and then photopolymerized to harden the composition to form a recording layer.

[0285] The holographic recording medium thus produced can be in the form of a free-standing slab or disc and can be used in three-dimensional image display devices, diffractive optical elements, large-capacity memories, and other applications. In particular, the holographic recording medium of the present invention using the polymerizable composition of the present invention has high refractive index modulation and is also useful as an AR glass light guide plate or an AR glass waveguide plate. Here, AR is an abbreviation for augmented reality.

[0286] 6-7. Uses of Holographic Recording Medium <Large Capacity Memory Use> Information is written (recorded) and read (reproduced) to the holographic recording medium of the present invention by irradiation with light.

[0287] When recording information, light capable of causing a chemical change in the polymerizable monomer, that is, its polymerization and concentration change, is used as object light (also called recording light).

[0288] For example, when recording information as a volume hologram, an object beam and a reference beam are irradiated onto the recording layer, causing the object beam and the reference beam to interfere with each other in the recording layer. This causes the polymerizable monomer in the recording layer to polymerize and change in concentration, resulting in interference fringes that cause a refractive index difference in the recording layer. The interference fringes recorded in the recording layer are then recorded as a hologram in the recording layer.

[0289] To reconstruct a volume hologram recorded in a recording layer, a predetermined reconstruction beam (usually a reference beam) is irradiated onto the recording layer. The irradiated reconstruction beam is diffracted in accordance with the interference fringes. This diffracted beam contains the same information as that in the recording layer, and so the information recorded in the recording layer can be reconstructed by reading the diffracted beam with an appropriate detection means.

[0290] The wavelength ranges of the object light, the reproduction light, and the reference light are arbitrary depending on the application, and may be in the visible light range or the ultraviolet range. Among these lights, preferred examples include ruby, glass, Nd-YAG, and Nd-YVO ４ diode lasers such as GaAs, InGaAs, and GaN; gas lasers such as helium-neon, argon, krypton, excimer, and CO2; and lasers with excellent monochromaticity and directivity, such as dye-containing dye lasers.

[0291] There is no limitation on the irradiation dose of the object beam, the reproduction beam, and the reference beam, and the irradiation dose may be any as long as recording and reproduction are possible. If the irradiation dose is extremely low, the chemical change of the polymerizable monomer may be incomplete, and the heat resistance and mechanical properties of the recording layer may not be fully exhibited. Conversely, if the irradiation dose is extremely high, the components of the recording layer (components of the polymerizable composition of the present invention) may be deteriorated. Therefore, the object beam, the reproduction beam, and the reference beam are usually set to 0.1 J / cm or less depending on the composition of the polymerizable composition of the present invention used to form the recording layer, the type and amount of the photopolymerization initiator, etc. ２ Above, 20J / cm ２ Irradiate within the following range:

[0292] Hologram recording methods include polarization collinear hologram recording, reference beam incident angle multiplexing hologram recording, etc. When the hologram recording medium of the present invention is used as a recording medium, good recording quality can be achieved with any of these recording methods.

[0293] <Application to AR Glass Light Guide Plate (Application to AR Glass Light Guide Plate)> A volume hologram can be recorded on the holographic recording medium of the present invention in the same manner as in the above-mentioned large-capacity memory application, and the resulting optical element can be used. This optical element is suitable for use in an AR glass light guide plate (AR light guide plate).

[0294] For a volume hologram recorded in the recording layer, a predetermined reproduction light is irradiated onto the recording layer. The irradiated reproduction light is diffracted in accordance with the interference fringes. In this case, even if the wavelength of the reproduction light does not match the wavelength of the recording light, diffraction will occur as long as the interference fringes and the Bragg condition are met. Therefore, if corresponding interference fringes are recorded according to the wavelength and incident angle of the reproduction light to be diffracted, diffraction can be caused for reproduction light over a wide wavelength range, thereby expanding the display color gamut of AR glasses.

[0295] By recording corresponding interference fringes according to the wavelength and diffraction angle of the reconstructed light, it is possible to guide the reconstructed light incident from outside the hologram recording medium into the hologram recording medium, to reflect, demultiplex, enlarge or reduce the reconstructed light that has been guided inside the hologram recording medium, or to emit the reconstructed light that has been guided inside the hologram recording medium to the outside of the hologram recording medium, thereby widening the viewing angle of the AR glasses.

[0296] The wavelength ranges of the object light and the reproduction light are arbitrary depending on the respective applications, and may be either the visible light range or the ultraviolet range. Among these light sources, the aforementioned laser and the like are preferred. The reproduction light is not limited to the laser and the like, and display devices such as a liquid crystal display (LCD) and an organic electroluminescence display (OLED) are also preferred.

[0297] There is no limitation on the irradiation dose of the object beam, the reproduction beam, and the reference beam, and the irradiation dose may be any as long as recording and reproduction are possible. If the irradiation dose is extremely low, the chemical change of the polymerizable monomer may be incomplete, and the heat resistance and mechanical properties of the recording layer may not be fully exhibited. Conversely, if the irradiation dose is extremely high, the components of the recording layer (components of the polymerizable composition of the present invention) may be deteriorated. Therefore, the object beam, the reproduction beam, and the reference beam are usually set to 0.1 J / cm or less depending on the composition of the polymerizable composition of the present invention used to form the recording layer, the type and amount of the photopolymerization initiator, etc. ２ Above, 20J / cm ２ Irradiate within the following range:

[0298] 6-8. Performance index of holographic recording media The performance of a holographic recording media is indexed by total Δn, which is calculated using the sum of the diffraction efficiencies across the entire multiplexed recording. In the case of a transmission hologram, the diffraction efficiency of the hologram is given by the ratio of the intensity of diffracted light to the sum of the intensity of transmitted light and the intensity of diffracted light. From the obtained diffraction efficiency, Δn is calculated using the following equation based on Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the sum across the entire multiplexed recording is taken as total Δn.

[0299]

[0300] Here, η is the diffraction efficiency, T is the thickness of the medium, λ is the wavelength of the reference light, and θ is the angle of incidence of the reference light on the recording surface.

[0301] In the case of large-capacity memories, a higher total Δn means that more information can be recorded per unit volume, which is preferable. Furthermore, in the case of AR glasses applications, a higher total Δn means that the projected image of the projector can be delivered to the pupil brightly, power consumption can be reduced, and the viewing angle can be widened, which is preferable. On the other hand, holographic recording media with a high total Δn can record unintended holograms called holographic scatter, which can cause a decrease in the reproduction quality of information in large-capacity memories and is treated as image noise in AR glasses applications. Holographic scatter is a phenomenon that is particularly pronounced in materials whose refractive index measured under the measurement conditions in the examples described below is 1.600 or higher. For this reason, a high total Δn and low holographic scatter are preferable.

[0302] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples as long as it does not deviate from the gist of the invention.

[0303] [Raw Materials Used] The raw materials for the compositions used in the Examples and Comparative Examples are as follows.

[0304] <Isocyanate> Duranate (registered trademark) TSS-100: hexamethylene diisocyanate-based polyisocyanate (NCO 17.6%) (manufactured by Asahi Kasei Corporation)

[0305] <Polyol> Placcel PCL-205U: Polycaprolactone diol (molecular weight 530) (manufactured by Daicel Corporation) Placcel PCL-305: Polycaprolactone triol (molecular weight 550) (manufactured by Daicel Corporation)

[0306] <Photopolymerization initiator> HLI02: methyl 5-(9-ethyl-6-cyclohexanoyl-9H-carbazol-3-yl)-4-(O-acetyloxime)-5-oxopentanoate HLI77: 1-(9-ethyl-6-cyclohexanoyl-9H-carbazol-3-yl)-2-(O-acetyloxime)-1-heptanone

[0307] <Radical Scavenger> TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0308] <Light stabilizer> Adekastab LA-63P (manufactured by ADEKA Corporation)

[0309] <Urethane polymerization catalyst> Octylic acid solution of tris(2-ethylhexanoate)bismuth (active ingredient amount: 56% by mass)

[0310] Example 1 Preparation of Compound M-1 Compound M-1 was prepared by the following synthesis method.

[0311]

[0312] 2,4-Dibromophenol (24.7 g) and sodium hydroxide (4.00 g) were added to 90 mL of water, and the solution was heated to 60°C. Epichlorohydrin (3.00 g) was slowly added dropwise to the reaction solution, and the reaction was carried out at 60°C. After the reaction was completed, the mixture was cooled to room temperature, and the precipitated solid was separated by filtration. The obtained solid was washed with water and ethanol. The solid was dried in a vacuum dryer, and 14.8 g of compound B-1 was obtained.

[0313] The NMR measurement data of Compound B-1 was as follows: １ H-NMR (400MHz, CDCl ３ , δ, ppm) 6.12 (d, Ar, 2H), 5.83 (dd, Ar, 2H), 5.29 (d, Ar, 2H), 2.94-2.85 (CH, 1H), 2.78-2.62 (d, CH2, 4H), 1.11 (d, HO, 1H)

[0314] Compound B-1 (3.39 g), phenanthrene-9-boronic acid (5.83 g), and sodium carbonate (1.41 g) were dissolved in 20 mL of toluene, 20 mL of ethanol, and 10 mL of water, and the solution was degassed by passing nitrogen gas through the solution. 0.67 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and the reaction solution was heated and stirred under reflux for 3 hours. After cooling to room temperature, 50 mL of toluene and 30 mL of water were added, and the mixture was separated. 4 g of diamine silica (manufactured by Fuji Silysia Chemical Ltd.) was added to the resulting organic layer, and the mixture was stirred for 30 minutes, filtered, and dried to obtain 5.36 g of compound S-1.

[0315] The NMR measurement data of the compound S-1 was as follows: １ H-NMR (400MHz, CDCl ３ , δ, ppm) 8.84-8.67 (Ar, 8H), 8.15-8.05 (Ar, 2H), 7.97-7.37 (Ar, 30H), 6.79-6.49 (Ar, 2H), 3.80-3.39 (CH, CH ２ , 5H), 1.50-1.41 (OH, 1H)

[0316] Compound S-1 (2.25 g), 2-isocyanatoethyl acrylate (0.558 g), and dichloromethane (50 mL) were mixed. Dibutyltin diacetate (20.8 mg) was added to the mixture and stirred for 14 days. After the reaction was completed, 2 g of diamine silica was added and stirred for 30 minutes, and then 1 g of neutral silica gel was added and stirred for 30 minutes in the same manner. Thereafter, the silica gel and solid components were filtered off, and the resulting organic layer was concentrated and then added dropwise to 50 mL of methanol that had been cooled to -10°C and had been supplemented with 10 mL of dichloromethane. The resulting solid was filtered, washed with a small amount of cold methanol, and then dried in a vacuum dryer to obtain 1.92 g of compound M-1.

[0317] The NMR measurement data of compound M-1 was as follows: １ H-NMR (400MHz, CDCl ３ , δ, ppm) 8.84-8.67 (Ar, 8H), 8.19-8.06 (Ar, 2H), 8.00-7.32 (Ar, 30H), 6.68-6.51 (Ar, 2H), 6.45-6.28 (CH=CH ２, 1H), 6.17-5.96 (CH=CH ２ , 1H), 5.89-5.75 (CH=CH ２ , 1H), 4.79-4.67 (CH, 1H), 4.38-2.33 (CH ２ , NH, 9H)

[0318] <Preparation of Holographic Recording Medium> 1.4287 g of Compound M-1 as a polymerizable monomer, 0.0532 g of a photopolymerization initiator HLI77, and 0.0195 g of a radical scavenger TEMPOL were dissolved in 3.3078 g of Duranate (registered trademark) TSS-100 and 0.5837 g of Takenate 600 to prepare Solution A. Separately, 3.6868 g of Capa 2047A and 0.9217 g of Placcel PCL-305 were mixed, and 0.68 mg of an octylic acid solution of tris(2-ethylhexanoate)bismuth was dissolved in the mixture to prepare Solution B.

[0319] After degassing each of solutions A and B under reduced pressure at room temperature or 45°C for 2 hours, solutions A and B were mixed by stirring and further degassed under vacuum for several minutes. Next, the vacuum-degassed mixture was poured onto a glass slide with 0.5 mm thick spacer sheets placed on two opposing edges, and a glass slide was placed on top of it, secured around the edges with clips, and heated at 80°C for 24 hours to produce a holographic recording medium as an evaluation sample. This evaluation sample had a 0.5 mm thick recording layer formed between the glass slides as covers.

[0320] <Hologram Recording and Evaluation> Using the hologram recording medium prepared as an evaluation sample, hologram recording and evaluation of the hologram recording performance of the hologram recording medium were carried out according to the procedures described below.

[0321] Hologram recording was performed using a semiconductor laser with a wavelength of 405 nm and an exposure power density of 10.2 mW / cm per beam. ２Using the exposure device shown in Figure 1, two-beam plane wave hologram recording was performed. The medium was rotated from -22.5° to 22.5°, and angle multiplexed recording was performed at the same location. The diffraction efficiency for each multiplexed recording was measured. Δn was calculated from the obtained diffraction efficiencies, and the sum of the entire multiplexed recording was taken as total Δn. This will be explained in detail below.

[0322] (Hologram Recording) Figure 1 is a structural diagram showing an overview of the device used for hologram recording. In Figure 1, S is a sample hologram recording medium, and M1 to M3 all represent mirrors. PBS represents a polarizing beam splitter, and L1 represents a laser light source for recording light that emits light with a wavelength of 405 nm (a single-mode laser manufactured by TOPTICA Photonics ("L1" in Figure 1) that can obtain light with a wavelength of around 405 nm). L2 represents a laser light source for reproducing light that emits light with a wavelength of 633 nm. PD1, PD2, and PD3 represent photodetectors. 1 represents an LED unit.

[0323] As shown in Figure 1, light with a wavelength of 405 nm was split by a polarizing beam splitter ("PBS" in the figure), and the two beams were made to intersect on the recording surface at an angle of 59.3°. At this time, the bisector of the angle between the two beams was set perpendicular to the recording surface, and further, the vibration plane of the electric field vectors of the two beams obtained by splitting was set perpendicular to the plane containing the two intersecting beams.

[0324] After the hologram was recorded, a He-Ne laser capable of producing light with a wavelength of 633 nm (V05-LHP151 manufactured by Melles Griot: "L2" in the figure) was used to irradiate the hologram recording medium with the light at an angle of 50.7°, and the diffracted light was detected using a photodiode and photosensor amplifier (S2281, C9329 manufactured by Hamamatsu Photonics: "PD1" in the figure) to determine whether the hologram was recorded correctly.

[0325] (Measurement of Diffraction Efficiency) The angle at which the sample was moved relative to the optical axis (the angle between the bisector of the interior angle at the point where the two beams, i.e., the incident light from mirrors M1 and M2 in Figure 1, intersect and the normal from the sample) was changed from -22.5° to 22.5° in 0.3° increments to perform 151 multiplexed recordings.

[0326] After multiplex recording, the LED unit (1 in the figure, central wavelength 405 nm) was turned on for a certain period of time to consume the remaining initiator and monomer. This process is called post-exposure. The LED power was 100 mW / cm. ２ The cumulative energy is 12 J / cm ２ The irradiation was carried out so that

[0327] The diffraction efficiency of a hologram is given by the ratio of the intensity of diffracted light to the sum of the intensity of transmitted light and the intensity of diffracted light. Light (wavelength 405 nm) from mirror M1 in Figure 1 was irradiated, and the diffraction efficiency was measured from angles of -23° to 23°. From 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 entire multiplexed recording was taken as total Δn.

[0328]

[0329] Here, η is the diffraction efficiency, T is the thickness of the medium, λ is the wavelength of the reference light, and θ is the angle of incidence of the reference light on the recording surface (29.65°).

[0330] Using multiple samples, evaluations were performed multiple times under different irradiation energy conditions, such as increasing or decreasing the irradiation energy at the beginning of recording and increasing or decreasing the total irradiation energy, to find the conditions under which the polymerizable monomer is almost completely consumed (total Δn reaches almost equilibrium during multiplex recording), and the total Δn was maximized. The obtained maximum value was then used as the total Δn of the medium.

[0331] (Holographic Scatter Intensity Ratio Measurement) Figure 2 is a schematic diagram of a measurement device for the holographic scatter intensity ratio. S in Figure 2 represents the holographic recording medium after the hologram has been recorded and reproduced. G-LD (532 nm) is a laser light source for measuring holographic scatter (JUNO532 single mode laser manufactured by Showa Optronics Co., Ltd.) that provides a wavelength of 532 nm. PD1 and PD2 represent photodetectors. The measurement light is incident on the sample S at an angle of incidence of approximately 5°. This angle of incidence is appropriately adjusted within a range of 5°±1° so that the holographic scatter light is most intensely incident on the photodetector PD2. The holographic scatter intensity ratio is calculated by the following formula (A), which is the ratio I of the intensity of the photodetector PD1 to the transmitted light intensity of the photodetector PD2: Ｈ The results were evaluated as a percentage. Ｈ = (PD1 intensity / PD2 transmitted light intensity) × 100 (A)

[0332] <Evaluation criteria> Holographic scatter intensity ratio I Ｈ Based on this, the following evaluation criteria were set. In the present invention, "○" was considered to be acceptable. ○: I Ｈ ≦0.10% △:0.10%<I Ｈ ≦0.20% ×: 0.20%<I Ｈ

[0333] The evaluation results are shown in Table 2 below.

[0334] Example 2 Compound M-2 was produced by the following synthesis method.

[0335]

[0336] Compound B-1 (2.80 g), 2-naphthylboronic acid (3.61 g), and sodium carbonate (1.17 g) were dissolved in 15 mL of toluene, 15 mL of ethanol, and 8 mL of water, and the solution was degassed by passing nitrogen gas through the solution. 0.35 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and the reaction solution was heated and stirred under reflux for 3 hours. After cooling to room temperature, 40 mL of toluene and 30 mL of water were added, and the layers were separated. 3 g of diamine silica was added to the resulting organic layer, and the mixture was stirred for 30 minutes, filtered, and dried to obtain 2.36 g of compound S-2.

[0337] The NMR measurement data of the compound S-2 was as follows: １ H-NMR (400MHz, CDCl ３ , δ, ppm) 8.11-7.42 (Ar, 32H), 6.93 (d, Ar, 2H), 4.25-4.13 (CH, 1H), 4.13-4.01 (CH ２ , 4H), 1.59-1.49 (OH, 1H)

[0338] Compound S-2 (3.03 g), 2-isocyanatoethyl acrylate (0.74 g), and dichloromethane (24 mL) were mixed. Dibutyltin diacetate (27.7 mg) was added to the mixture and stirred for 2 days. After the reaction was completed, 3 g of diamine silica was added and stirred for 30 minutes, and then 1 g of neutral silica gel was added and stirred for 30 minutes in the same manner. Thereafter, the silica gel and solid components were filtered off, and the resulting organic layer was concentrated and then added dropwise to 75 mL of methanol that had been cooled to -10°C and had been supplemented with 15 mL of dichloromethane. The resulting solid was filtered, washed with a small amount of cold methanol, and then dried in a vacuum dryer to obtain 2.12 g of compound M-2.

[0339] The NMR measurement data of the compound M-2 was as follows: １ H NMR (400 MHz, CDCl ３ , δ, ppm) 8.11-7.61 (Ar, 22H), 7.57-7.40 (Ar, 10H), 6.88 (d, Ar, 2H), 6.38 (dd, CH=CH ２ , 1H), 6.07(dd, CH=CH ２ , 1H), 5.80(dd, CH=CH ２, 1H), 5.32-5.21 (CH, 1H), 4.91-4.50 (NH, 1H), 4.26-3.73 (CH ２ , 6H), 3.40-2.90 (CH ２ , 2H)

[0340] 1.1306 g of Compound M-2 as a polymerizable monomer, 0.0516 g of photopolymerization initiator HLI77, and 0.0189 g of radical scavenger TEMPOL were dissolved in 3.3069 g of Duranate (registered trademark) TSS-100 and 0.5836 g of Takenate 600 to prepare Solution A. Separately, 3.6876 g of Capa 2047A and 0.9219 g of Placcel PCL-305 were mixed, and 0.68 mg of an octylic acid solution of tris(2-ethylhexanoate)bismuth was dissolved in the mixture to prepare Solution B.

[0341] Using the above-mentioned solutions A and B, holographic recording media were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[0342] Example 3 Compound M-3 was produced by the following synthesis method.

[0343]

[0344] Compound B-1 (5.05 g), 1-naphthylboronic acid (6.55 g), and sodium carbonate (2.13 g) were dissolved in 15 mL of toluene, 15 mL of ethanol, and 8 mL of water, and the solution was degassed by passing nitrogen gas through the solution. 0.64 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and the reaction solution was heated and stirred under reflux for 3 hours. After cooling to room temperature, 40 mL of toluene and 30 mL of water were added, and a separation operation was performed. 5 g of diamine silica was added to the obtained organic layer, and the mixture was stirred for 30 minutes, filtered, and dried to obtain 6.33 g of compound S-3.

[0345] The NMR measurement data of the compound S-3 was as follows: １ H-NMR (400MHz, CDCl ３ , δ, ppm) 8.12-8.02 (Ar, 2H), 7.96-7.79 (Ar, 8H), 7.76-7.27 (Ar, 22H), 6.84-6.56 (Ar, 2H), 3.78-3.41 (CH２ , 5H), 1.52 (d, OH, 1H)

[0346] Under a nitrogen atmosphere, compound S-3 (6.33 g), 2-isocyanatoethyl acrylate (1.8 g), and dichloromethane (48 mL) were mixed. Dibutyltin diacetate (67 mg) was added to the mixture and stirred for 2 days. After the reaction was completed, 6 g of diamine silica was added and stirred for 30 minutes, and then 2 g of neutral silica gel was added and stirred for 30 minutes in the same manner. Thereafter, the silica gel and solid components were filtered off, and the resulting organic layer was concentrated and then added dropwise to 150 mL of methanol that had been cooled to -10°C and had been supplemented with 30 mL of dichloromethane. The resulting solid was filtered, washed with a small amount of cold methanol, and then dried in a vacuum dryer to obtain 6.22 g of compound M-3.

[0347] The NMR measurement data of the compound M-3 was as follows: １ H-NMR (400MHz, CDCl ３ , δ, ppm) 8.14-8.02 (Ar, 2H), 7.96-7.79 (Ar, 8H), 7.77-7.22 (Ar, 22H), 6.77-6.61 (Ar, 2H), 6.47-6.36 (CH=CH ２ , 1H), 6.19-6.06 (CH=CH ２ , 1H), 5.89-5.81 (CH=CH ２ , 1H), 4.83-4.70 (CH, 1H), 4.50-3.96 (CH ２ , NH, 3H), 3.88-3.39 (CH ２ , 4H), 3.37-2.60 (CH ２ , 2H)

[0348] 1.1306 g of Compound M-3 as a polymerizable monomer, 0.0516 g of photopolymerization initiator HLI77, and 0.0189 g of radical scavenger TEMPOL were dissolved in 3.3078 g of Duranate (registered trademark) TSS-100 and 0.5837 g of Takenate 600 to prepare Solution A. Separately, 3.6868 g of Capa 2047A and 0.9217 g of Placcel PCL-305 were mixed, and 0.68 mg of an octylic acid solution of tris(2-ethylhexanoate)bismuth was dissolved in the mixture to prepare Solution B.

[0349] Using the above-mentioned solutions A and B, holographic recording media were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[0350] Comparative Example 1 Compound R-1 was produced by the following synthesis method.

[0351]

[0352] 4-Phenylphenol (16.6 g) and sodium hydroxide (3.89 g) were added to 90 mL of water, and the temperature was raised to 60°C. Epichlorohydrin (3.00 g) was slowly added dropwise to the reaction solution, and the reaction was carried out at 60°C. After the reaction was completed, the mixture was cooled to room temperature, and the precipitated solid was separated by filtration. The obtained solid was washed with a 1N aqueous sodium hydroxide solution, water, and ethanol. The solid was dried in a vacuum dryer, and 9.80 g of compound L-1 was obtained.

[0353] The NMR measurement data of compound L-1 was as follows: １ H NMR (400 MHz, CDCl ３ , δ, ppm) 7.64-7.48 (Ar, 8H), 7.48-7.37 (Ar, 4H), 7.37-7.28 (Ar, 2H), 7.08-6.95 (Ar, 4H), 4.51-4.40 (CH, 1H), 4.30-4.17 (CH ２ , 4H), 2.62 (d, OH, 1H)

[0354] Compound L-1 (9.80 g) and triethylamine (5.25 g) were added to dichloromethane (160 mL), and acryloyl chloride (4.03 g) was slowly added dropwise in an ice bath. After completion of the reaction, 100 mL of a 5% by mass aqueous solution of sodium bicarbonate was added to the reaction solution and stirred for 1 hour. The mixture was then extracted with 100 mL of dichloromethane, washed with 100 mL of saturated brine, dried over sodium sulfate, filtered, and concentrated. The resulting crude product was purified by column chromatography to obtain 6.02 g of compound R-1.

[0355] The NMR measurement data of compound R-1 was as follows: １ H NMR (400 MHz, CDCl ３, δ, ppm) 7.60-7.48 (Ar, 8H), 7.47-7.37 (Ar, 4H), 7.36-7.28 (Ar, 2H), 7.06-6.96 (Ar, 4H), 6.49 (dd, CH=CH ２ , 1H), 6.20(dd, CH=CH ２ , 1H), 5.90(dd, CH=CH ２ , 1H), 5.62 (quin, CH, 1H), 4.36 (d, CH ２ , 4H)

[0356] The preparation of a holographic recording medium was investigated in the same manner as in Example 1, except that compound R-1 was used as the polymerizable monomer. However, the solubility was low and it was not possible to prepare solution A, so evaluation of the holographic recording medium was not possible.

[0357] Comparative Example 2 Compound R-2 was produced by the following synthesis method.

[0358]

[0359] 2,4,6-Tribromophenol (2.3 g), phenanthrene-9-boronic acid (5.8 g), and sodium carbonate (3.5 g) were dissolved in 100 mL of dioxane and 25 mL of water, and the solution was degassed by passing nitrogen gas through it. 10 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through it for an additional 5 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 5 hours. After cooling to room temperature, 100 mL of ethyl acetate and 50 mL of water were added, and the mixture was separated. The resulting organic layer was washed with an aqueous sodium bicarbonate solution. After drying the organic layer, the resulting solid was washed with hexane. The solid was dried in a vacuum dryer, yielding 4.4 g of crude compound L-2.

[0360] The NMR measurement data of Compound L-2 was as follows: １ H-NMR (400MHz, CDCl ３ , δ, ppm) 8.84-8.66 (Ar, 6H), 8.32 (dd, Ar, 1H), 8.11 (dd, Ar, 1H), 8.07 (d d, Ar, 1H), 8.04-7.86 (Ar, 8H), 7.75-7.57 (Ar, 12H), 5.18-5.13 (OH, 1H)

[0361] Under a nitrogen atmosphere, compound L-2 (3.1 g), 2-isocyanatoethyl acrylate (1.1 g), and THF (20 mL) were mixed. To this mixture, diazabicycloundecene (0.02 g) was added and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 50 mL of an aqueous ammonium chloride solution, extracted with 100 mL of ethyl acetate, washed with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated. The resulting crude product was purified by column chromatography to obtain 2.2 g of compound R-2.

[0362] The NMR measurement data of compound R-2 was as follows: １ H NMR (400 MHz, CDCl ３ , δ, ppm) 8.82-8.66 (Ar, 6H), 8.33-8.25 (Ar, 1H), 8.15-8.01 (Ar, 2H), 7.99 -7.85 (Ar, 6H), 7.84-7.77 (Ar, 2H), 7.74-7.55 (Ar, 12H), 6.09-5.95 (CH=CH ２ , 1H), 5.69-5.53 (CH=CH ２ , 2H), 4.42-3.89 (NH, 1H), 3.29-2.80 (CH ２ , 2H), 2.79-2.13 (CH ２ , 2H)

[0363] 1.1230 g of Compound R-2 as a polymerizable monomer, 0.0515 g of photopolymerization initiator HLI77, and 0.0189 g of radical scavenger TEMPOL were dissolved in 3.3454 g of Duranate (registered trademark) TSS-100 and 0.5904 g of Takenate 600 to prepare solution A. Separately, 3.6514 g of Capa 2047A and 0.9129 g of Placcel PCL-305 were mixed, and 0.68 mg of an octylic acid solution of tris(2-ethylhexanoate)bismuth was dissolved in the mixture to prepare solution B.

[0364] Using the above-mentioned solutions A and B, holographic recording media were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[0365] Comparative Example 3 Compound R-3 was produced by the following synthesis method.

[0366]

[0367] Crude compound L-2 (4.0 g) and potassium carbonate (2.0 g) were added to DMF (40 mL), and the mixture was heated to 60°C, followed by dropwise addition of 2-bromoethanol (1.8 g). The reaction mixture was stirred for 8 hours, then returned to room temperature, ice-cold water was added, and the solid was filtered. The resulting solid was purified by column chromatography to obtain 1.95 g of compound L-3.

[0368] The NMR measurement data of compound L-3 was as follows: １ H NMR (400 MHz, CDCl ３ , δ, ppm) 8.83-8.69 (Ar, 6H), 8.33-8.26 (Ar, 1H), 8.18-8.08 (Ar, 2H), 8.03 -7.86 (Ar, 6H), 7.82-7.76 (d, Ar, 2H), 7.76-7.56 (Ar, 12H), 3.38-3.27 (CH ２ , 2H), 2.89-2.70 (CH ２ , 2H), 0.60, 0.51 (OH, 1H)

[0369] Under a nitrogen atmosphere, compound L-3 (1.92 g) and triethylamine (0.95 g) were added to THF (20 mL), and acryloyl chloride (0.78 g) was slowly added dropwise in an ice bath. After completion of the reaction, the reaction solution was poured into 20 mL of 1N aqueous sodium hydroxide solution, extracted with 50 mL of ethyl acetate, washed with 50 mL of saturated brine, dried over sodium sulfate, filtered, and concentrated. The obtained crude product was purified by column chromatography to obtain 580 mg of compound R-3.

[0370] The NMR measurement data of compound R-3 was as follows: １ H NMR (400 MHz, CDCl ３ , δ, ppm) 8.81-8.68 (Ar, 6H), 8.32-8.26 (Ar, 1H), 8.17-8.07 (Ar, 2H), 8.03-7.85 (Ar, 6H), 7.79-7.57 (Ar, 14H), 5.60-5.52 (CH=CH ２ , 1H), 5.23-5.16 (CH=CH ２ , 1H), 5.06-4.94 (CH=CH ２, 1H), 3.56-3.37 (CH ２ , 4H)

[0371] 0.9919 g of Compound R-3 as a polymerizable monomer, 0.0435 g of photopolymerization initiator HLI02, and 0.0155 g of radical scavenger TEMPOL were dissolved in 3.6022 g of Duranate (registered trademark) TSS-100 and 0.6357 g of Takenate 600 to prepare solution A. Separately, 3.8359 g of Capa 2047A and 0.4262 g of Placcel PCL-305 were mixed, and 0.68 mg of an octylic acid solution of tris(2-ethylhexanoate)bismuth was dissolved in the mixture to prepare solution B.

[0372] Using the above-mentioned solutions A and B, holographic recording media were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[0373] Comparative Example 4 Compound R-4 was produced by the following synthesis method.

[0374] Under a nitrogen atmosphere, compound L-3 (6.03 g), 2-isocyanatoethyl acrylate (1.53 g), and dichloromethane (36 mL) were mixed. To this mixture, diazabicycloundecene (1.38 g) was added and stirred for 1 hour. After completion of the reaction, 6 g of neutral silica gel was added to the reaction solution, which was stirred for 1 hour, filtered, and concentrated. Dichloromethane (30 mL) was added to the concentrate, which was then added dropwise to ice-cooled methanol (150 mL) and stirred for 1 hour. The precipitated solid was filtered and dried, yielding 5.76 g of compound R-4.

[0375] The NMR measurement data of compound R-4 was as follows: １ H NMR (400 MHz, CDCl ３ , δ, ppm) 8.83-8.68 (Ar, 6H), 8.34-8.25 (Ar, 1H), 8.20-8.08 (Ar, 2H), 8.0 4-7.95 (Ar, 4H), 7.94-7.85 (Ar, 2H), 7.79-7.58 (Ar, 14H), 6.40 (d, CH=CH ２ , 1H), 6.11(dd, CH=CH ２ , 1H), 5.87(d, CH=CH ２ , 1H), 3.89-3.80 (CH２ , 2H), 3.60-3.12 (CH ２ , NH, 5H), 2.92-2.78 (CH ２ , 2H)

[0376] 1.0645 g of Compound R-4 as a polymerizable monomer, 0.0434 g of the photopolymerization initiator HLI02, and 0.0154 g of the radical scavenger TEMPOL were dissolved in 3.5657 g of Duranate (registered trademark) TSS-100 and 0.6292 g of Takenate 600 to prepare Solution A. Separately, 3.8746 g of Capa 2047A and 0.4305 g of Placcel PCL-305 were mixed, and 0.68 mg of a solution of tris(2-ethylhexanoate)bismuth in octylic acid was dissolved in the mixture to prepare Solution B.

[0377] Using the above-mentioned solutions A and B, holographic recording media were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[0378] [Refractive Index of Polymerizable Monomer] The refractive index of the polymerizable monomers produced in the Examples and Comparative Examples was measured by the following method. The results are shown in Table 1. Test solutions were prepared by dissolving the sample in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate in a 4:1 mass ratio to obtain a predetermined concentration. Two types of test solutions were prepared: 10% by mass and 20% by mass. The refractive index of each test solution was measured using a Kalnew Precision Refractometer (Shimadzu Corporation, product name: KPR-2000). The test solution temperature was 23°C, and the measurement wavelength was the d-line of a helium lamp (587.6 nm). Based on the measurement results, a calibration curve showing the correlation between sample concentration and refractive index was created, and the refractive index at a sample concentration of 100% by mass was calculated from the resulting calibration curve and used as the refractive index of the sample. However, since compound R-1 of Comparative Example 1 did not dissolve in the test solution, the refractive index could not be measured.

[0379]

[0380] As can be seen from Table 1, the refractive indexes of the polymerizable monomers M-1 to M-3, which are compounds of the examples, are all 1.65 or more, and are equivalent to or higher than the compounds of the comparative examples, and therefore are excellent high refractive index materials.

[0381] [Solubility of Polymerizable Monomers] 100 mg of each of polymerizable monomers M-1 to M-3 and R-1 to R-4 was dissolved in 400 mg of Duranate (registered trademark) TSS-100, and the resulting solution was stored at room temperature for 5 days. The state of the solution was visually observed and evaluated as ○ (completely dissolved), △ (cloudy), or × (some undissolved solids remaining). The results are shown in Table 2.

[0382] [Heat resistance of polymerizable monomers] TG-DTA was measured using each polymerizable monomer, and the weight loss temperature at which the weight was reduced by 10% was determined as T ｄ10 The result was recorded as an index of heat resistance. ｄ10 The evaluation was made by assigning a value of x when the temperature was less than 350°C and a value of ◯ when the temperature was 350°C or higher. The results are shown in Table 2. The TG-DTA measurement conditions were as follows: TG-DTA measurement conditions Measurement device: STA200 (manufactured by HITACHI) Atmosphere: N ２ Temperature: 30-500℃ (10℃ / min)

[0383]

[0384] As shown in Examples 1 to 3 in Table 2, the polymerizable monomers M-1 to M-3, which are compounds of the present invention, have excellent solubility, heat resistance, holographic properties (Δn), and holographic scatter intensity ratio I Ｈ In particular, materials with a holographic performance Δn exceeding 0.030 exhibit excellent performance. Ｈ It is generally difficult to suppress the refractive index to 0.100 or less, but the compound of the present invention is excellent in these properties and has high heat resistance, making it a useful optical material.

[0385] When using AR glass light guide plates as optical elements, a higher total Δn of the holographic recording medium can brighten the projected image and widen the viewing angle. Furthermore, in memory applications, improving total Δn can improve recording capacity. On the other hand, holographic recording media require high transparency, and turbidity due to the inclusion or generation of insoluble matter can cause absorption and scattering of the recording light, leading to a decrease in the performance of the holographic recording medium. In particular, in AR glass waveguide applications, light scattering due to insoluble matter reduces light utilization efficiency and aesthetics. Furthermore, if insoluble matter precipitates in the waveguide over time, the absorption intensity of the guided light also changes over time, leading to a decrease in the performance stability of the waveguide. Therefore, by using the compound of the present invention, which combines a high total Δn with composition stability, particularly high solubility in the medium, it is possible to create an AR glass light guide plate with excellent light utilization efficiency, aesthetics, and long-term performance stability. From the above, it can be said that the compound of the present invention used in the examples is superior to the compound of the comparative example.

[0386] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2024-105184, filed on June 28, 2024, and is incorporated by reference in its entirety.

[0387] S Hologram recording medium M1, M2, M3 Mirrors L1 Semiconductor laser light source for recording light L2 Laser light source for reproducing light PD1, PD2, PD3 Photodetector PBS Polarizing beam splitter 1 LED unit G-LD Laser light source for holographic scattering measurement

Claims

1. A compound represented by the following formula (1): [In the formula, n represents an integer of 1 to 3. L represents an optionally branched (n+1)-valent linking group. Y 1 , Y 2 each independently represents an aromatic ring group having a total of 7 to 20 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. １ , Ar 2 each independently represents an aromatic hydrocarbon group. １ , Ar 2 are Y 1 , Y 2 Ar may have a substituent other than １ and Y 1 , Ar 2 and Y 2 p and q each independently represent an integer of 0 to 5, provided that p and q are not both 0. Y １ , Y ２ When there are multiple Y １ and Y ２ may be the same or different. １ represents a hydrogen atom or a methyl group. １ If there are multiple R １ may be the same or different.] 2. The Ar １ , Ar 2 and each independently represent an aromatic hydrocarbon group having 6 to 16 carbon atoms.

3. The above Y １ , Y ２ and each independently represent an aromatic hydrocarbon group having a total of 10 to 14 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms.

4. The above Y １ , Y ２ and each independently represent a naphthyl group or a phenanthryl group which may have a substituent.

5. The above Y １ and Y ２ is a naphthyl group which may have a substituent, and Y １ is a naphthyl group, Ar is at the 1st or 2nd position of the naphthyl group １ and Y ２ is a naphthyl group, Ar is at the 1st or 2nd position of the naphthyl group ２ The compound of claim 4, wherein 6. The above Y １ and Y ２ is a phenanthryl group which may have a substituent, and Y １ is a phenanthryl group, Ar is at the 9-position of the phenanthryl group １ and Y ２ is a phenanthryl group, Ar is at the 9-position of the phenanthryl group ２ The compound of claim 4, wherein 7. The compound of claim 1, wherein L is a group containing a urethane bond.

8. The above Y １ and Y ２ The compound of claim 1 , wherein 9. The Ar １ and Ar 2 The compound according to claim 1 , wherein the aromatic hydrocarbon groups of 10. The Ar １ and Ar 2 and each represent a benzene ring.

11. A polymerizable composition comprising the compound according to claim 1 and a polymerization initiator.

12. A polymerizable composition containing a compound represented by the following formula (1) and a polymerization initiator: [In the formula, n represents an integer of 1 to 3. L represents an optionally branched (n+1)-valent linking group. Y 1 , Y 2 each independently represents an aromatic ring group having a total of 7 to 20 carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. １ , Ar 2 each independently represents an aromatic hydrocarbon group. １ , Ar 2 are Y 1 , Y 2 Ar may have a substituent other than １ and Y 1 , Ar 2 and Y 2 p and q each independently represent an integer of 0 to 5, provided that p and q are not both 0. Y １ , Y ２ When there are multiple Y １ and Y ２ may be the same or different. １ represents a hydrogen atom or a methyl group. １ If there are multiple R １ may be the same or different.] 13. A holographic recording medium comprising the polymerizable composition according to claim 11 or 12.

14. A polymer obtained by polymerizing the polymerizable composition according to claim 11 or 12.

15. An optical material comprising the polymer of claim 14.

16. An optical component comprising the polymer of claim 14.

17. A large-capacity memory including the holographic recording medium according to claim 13.

18. An optical element obtained by holographically recording on the holographic recording medium according to claim 13.

19. An AR light guide plate comprising the optical element according to claim 18.

20. AR glasses comprising the optical element according to claim 18.

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