JP2010008470A - Composition for optical recording and holographic recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a holographic recording medium having small volume shrinkage and high storage stability of recording. <P>SOLUTION: The composition for optical recording contains a polyfunctional isocyanate, a polyfunctional alcohol and a compound expressed by general formula (I) and general formula (IV). In general formula (I), R<SB>1</SB>represents a hydrogen atom, alkyl group, hydroxyl group, amino group, carboxyl group, acid anhydride or isocyanate group; and Z<SB>1</SB>represents an atomic group that constitutes a cyclic structure with an adjoining carbon atom, a sulfur atom and a carbon atom bonded to the sulfur atom. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an optical recording composition, and more particularly to a holographic recording composition. More specifically, an optical recording composition capable of forming a holographic recording medium with low volume shrinkage and high storage stability of recording, and a holographic recording medium having a recording layer formed from the optical recording composition About.

  Conventionally, development of a holographic optical recording medium using a holographic principle has been advanced. Information is recorded on a holographic optical recording medium by superimposing information light containing image information and reference light in a recording layer made of a photosensitive composition, and writing interference fringes formed at that time on the recording layer. Done. On the other hand, when information is reproduced, reference light is incident on the recording layer on which information is recorded at a predetermined angle, whereby light diffraction of the reference light due to the formed interference fringes occurs and information light is reproduced.

  In recent years, volume holography, particularly digital volume holography, has been developed in practical use for ultra-high density optical recording and has attracted attention. Volume holography is a method of writing interference fringes in three dimensions by actively utilizing the thickness direction of the optical recording medium. Increasing the thickness increases the diffraction efficiency and increases the recording capacity by using multiple recording. There is a feature that can be achieved. Digital volume holography is a computer-oriented holographic recording method that uses a recording medium and a recording method similar to those of volume holography, but restricts image information to be recorded to a binarized digital pattern. In this digital volume holography, for example, image information such as an analog picture is once digitized, developed into two-dimensional digital pattern information, and recorded as image information. At the time of reproduction, the digital pattern information is read and decoded so that the original image information is restored and displayed. As a result, even if the S / N ratio (signal-to-noise ratio) is somewhat poor during reproduction, the original information can be reproduced with high fidelity by performing differential detection or performing error correction by encoding binary data. Can be reproduced (see Patent Document 1).

  The recording layer of the optical recording medium contains a monomer generally used for recording and storage called a matrix and a polymer for holding a photopolymerization initiator. For example, Patent Document 2 discloses the use of a urethane matrix in a photopolymer holographic optical recording medium. However, if the recording monomer is not sufficiently retained by the matrix, there is a problem that the brightness of the reproduction light is lowered after storage on the medium, and the recording sensitivity is lowered.

Patent Document 3 proposes to introduce a functional group that reacts with a matrix into a radically polymerizable compound as a means for improving the storage stability of recording.
Japanese Patent Laid-Open No. 11-311936 JP-T-2005-502918 JP 2007-86235 A

  Patent Document 3 discloses an acryloyl group, a methacryloyl group, an allyl group, and a styryl group as polymerizable groups in a radical polymerizable compound. However, these polymerizable groups have a large volume shrinkage after polymerization. Volume shrinkage causes a decrease in recording capacity. In addition, the volume shrinkage causes distortion of recording interference fringes, which causes an error during data input / output, resulting in a problem that recording / reproducing accuracy is lowered.

  Accordingly, an object of the present invention is to provide a holographic recording medium having a small volume shrinkage and a high storage stability of recording.

  As a result of intensive studies in order to achieve the above object, the present inventors have obtained a cyclic allyl sulfide compound represented by the following general formula (I) having a functional group capable of binding to a matrix and the following general formula having a small volume shrinkage. It has been found that by using the cyclic allyl sulfide compound represented by (IV) in combination, the storage stability of recording can be enhanced without causing a large volume change, and the present invention has been completed.

That is, the above object was achieved by the following means.
[1] An optical recording composition comprising a polyfunctional isocyanate, a polyfunctional alcohol, a compound represented by the following general formula (I), and a compound represented by the following general formula (IV).
[In the general formula (I), R ₁ represents a hydrogen atom, an alkyl group, a hydroxy group, an amino group, a carboxy group, an acid anhydride or an isocyanate group, and Z ₁ represents an adjacent carbon atom, a sulfur atom and the sulfur atom. It represents an atomic group that forms a ring structure with the carbon atoms to which it is bonded. At least _one of R ₁ and Z ₁ has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride, and an isocyanate group. ]
[In the general formula (IV), R ₆ represents a hydrogen atom or an alkyl group, and Z ₂ represents an atomic group forming a ring structure with the adjacent carbon atom, sulfur atom, and carbon atom bonded to the sulfur atom. ]
[2] The composition for optical recording according to [1], wherein in general formula (I), at least _one of R ₁ and Z ₁ has at least one group selected from the group consisting of a hydroxy group and an amino group.
[3] The optical recording composition according to [1] or [2], wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).
[In general formula (II), R ₁ has the same definition as in general formula (I), R ₂₂ represents a hydrogen atom, alkyl group, hydroxy group, amino group, carboxy group, acid anhydride or isocyanate group, R ₂₃ , R ₂₄ and R ₂₅ are each independently a hydrogen atom, alkyl group, hydroxy group, amino group, carboxy group, acid anhydride, isocyanate group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group Represents an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an acyl group or a halogen group, and m2 represents 0 or 1. At least one of R ₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride and an isocyanate group. ]
[4] In general formula (II), R ₁ and R ₂₂ each independently represent a hydrogen atom or a methyl group, and R ₂₃ , R ₂₄ and R ₂₅ each independently represent a hydrogen atom, an alkyl group, a hydroxy group, amino Represents a group, a carboxy group, an acid anhydride, an isocyanate group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, or an acyl group, and R ₂₃ , R ₂₄ and R The optical recording composition according to [3], wherein at least one of ₂₅ has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride, and an isocyanate group.
[5] In general formula (II), each of R ₁ and R ₂₂ represents a hydrogen atom, and R ₂₃ , R ₂₄ and R ₂₅ are each independently a hydrogen atom, an alkyl group, a hydroxy group, an amino group, or a carboxy group. , An acid anhydride, an isocyanate group, an aryl group, an alkoxy group, an aryloxy group or an acyloxy group, and at least one of R ₂₃ , R ₂₄ and R ₂₅ is a hydroxy group, an amino group, a carboxy group, an acid anhydride And at least one group selected from the group consisting of isocyanate groups, and m2 represents 1, the optical recording compound according to [4].
[6] The optical recording composition according to any one of [1] to [5], further containing a photoradical polymerization initiator.
[7] The optical recording composition according to any one of [1] to [6], which is a holographic recording composition.
[8] A holographic recording medium having a recording layer formed from the optical recording composition according to any one of [1] to [7].

  According to the present invention, it is possible to provide a holographic recording medium that is capable of high-sensitivity recording / reproduction with little volume shrinkage and that is excellent in storage stability of recording. The holographic recording medium of the present invention is suitable as a recording medium for digital volume holography, which can perform ultra-high density recording and can achieve volume holography, in particular, use of an inexpensive laser and shortening of writing time.

[Optical recording composition]
The optical recording composition of the present invention comprises a polyfunctional isocyanate, a polyfunctional alcohol, a cyclic allyl sulfide compound represented by the following general formula (I) and a cyclic allyl sulfide compound represented by the following general formula (IV), It can be used as a recording material in various recording methods for recording information by light irradiation. Among them, it is preferably used as a holographic recording composition, and particularly suitable as a volume holographic recording composition. As described above, holographic recording is information recording in which information light containing information and reference light are superimposed in a recording layer and information is recorded by writing an interference image formed at that time in the recording layer. Volume holographic recording is an information recording method in which an interference image is three-dimensionally written on a recording layer in holographic recording. In the present invention, “holographic recording” refers to recording interference fringes as refractive index modulation directly or indirectly by light irradiation for information recording.
When the cyclic allyl sulfide compound represented by the general formula (I) is present in a system in which a polyfunctional isocyanate and a polyfunctional alcohol are subjected to a curing reaction (matrix formation reaction), a hydroxy group, an amino group, a carboxy group, an acid anhydride, and A group selected from the group consisting of isocyanate groups can be immobilized on the matrix by reacting with the matrix-forming component. On the other hand, when the compound represented by the general formula (IV) undergoes a polymerization reaction by the action of radicals generated from the photopolymerization initiator by light irradiation, the compounds represented by the general formula (IV) are bonded to each other, and the matrix It can also bind to the compound represented by the general formula (I) immobilized on As a result, the polymer produced by the polymerization reaction can be immobilized on the matrix via the compound represented by the general formula (I), so that the storage stability of the recording can be improved. Furthermore, since the cyclic allyl sulfide compound represented by the general formula (I) and the cyclic allyl sulfide compound represented by the general formula (IV) have a small volume change (volume shrinkage) before and after the polymerization reaction, the volume shrinkage is large. The storage stability of the record can be improved without causing it.
Hereinafter, the optical recording compound of the present invention will be described in more detail.

Cyclic allyl sulfide compound represented by general formula (I) The optical recording composition of the present invention comprises a cyclic allyl sulfide compound represented by the following general formula (I).

In the general formula (I), R ₁ represents a hydrogen atom, an alkyl group, a hydroxy group, an amino group, a carboxy group, an acid anhydride or an isocyanate group, and Z ₁ is bonded to the adjacent carbon atom, sulfur atom and the sulfur atom. Represents an atomic group that forms a ring structure together with carbon atoms. At least _one of R ₁ and Z ₁ has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride, and an isocyanate group.
Hereinafter, the general formula (I) will be described in more detail.

In the compound represented by the general formula (I), at least _one of R ₁ and Z ₁ is a group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride and an isocyanate group (hereinafter referred to as “reaction”). At least one of them. As described above, by having the reactive group, it can be bonded to the matrix during the matrix formation reaction. The reactive group should just be contained at least 1 in 1 molecule, Preferably 1-2 are contained in 1 molecule. Further, it may be contained in at least _one of R ₁ and Z ₁ , but is preferably contained in Z ₁ from the viewpoint of storage stability of recording. When the reactive group is included in Z ₁ , it is included as a substituent of the ring structure formed by Z ₁ . On the other hand, if contained in R ₁ are included as substituents in the group represented by the group represented by R _1, or R _1.

  The amino group may be an unsubstituted amino group or a substituted amino group. As the substituted amino group, a monosubstituted amino group is preferable, and the carbon number thereof is preferably 1-30, and more preferably 1-20. Examples of such an amino group include an amino group, a methylamino group, and a phenylamino group. From the viewpoint of improving the storage stability of the record, an unsubstituted amino group is preferred.

  As the acid anhydride, an acid anhydride having 1 to 30 carbon atoms is preferable, and an acid anhydride having 1 to 20 carbon atoms is more preferable. Specifically, acetyloxycarbonyl group, ethylcarbonyloxycarbonyl group, n-propylcarbonyloxycarbonyl group, iso-propylcarbonyloxycarbonyl group, n-butylcarbonyloxycarbonyl group, iso-butylcarbonyloxycarbonyl group, n-pentyl An acid anhydride substituted with a carbonyloxycarbonyl group and the like can be mentioned, and an acid anhydride substituted with an acetyloxycarbonyl group, an ethylcarbonyloxycarbonyl group or the like is more preferable.

  Of the groups selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride, and an isocyanate group, a hydroxyl group and an amino group are preferred, and a hydroxyl group is more preferred from the viewpoint of reactivity with the matrix-forming component.

In the general formula (I), Z ₁ represents an atomic group that forms a ring structure with adjacent carbon atoms, sulfur atoms, and carbon atoms bonded to the sulfur atoms. Examples of the cyclic structure formed by Z ₁ include methylene carbon. In addition to methylene carbon, divalent organic linking groups such as a carbonyl group, a thiocarbonyl group, an oxygen atom, and a sulfur atom are also exemplified. These ring structures are constituted by a combination thereof. The number of ring members is preferably 6 to 9, more preferably 6 to 8, and particularly preferably 7 to 8. Moreover, it is preferable that methylene carbon number of the ring structure is 3-7, It is more preferable that it is 4-6, It is especially preferable that it is 4-5.

In the general formula (I), the alkyl group represented by R ₁ may be linear or branched, and may be unsubstituted or substituted. The number of carbon atoms is preferably 1-20, more preferably 1-10, and particularly preferably 1-3. In the present invention, the “carbon number” for a certain group means the carbon number of the portion not containing the substituent for the group having a substituent.

Examples of the alkyl group represented by R ₁ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, Examples include heptyl group, octyl group, tertiary octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, 2,3-dibromopropyl group, adamantyl group, benzyl group and 4-bromobenzyl group. These may further have a substituent.

In the general formula (I), when the group represented by R ₁ further has a substituent, examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryloxy, an alkylthio group, an alkoxycarbonyl group, an aryl Examples thereof include an oxycarbonyl group, an amino group, an acyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, a sulfonamide group, a cyano group, a carboxy group, a hydroxyl group, and a sulfonic acid group. Among these, a halogen atom, an alkoxy group, and an alkylthio group are particularly preferable. As described above, the group represented by R ₁ can also contain the reactive group as a substituent. Further, when the cyclic allyl sulfide compound of the general formula (I) is substituted as a substituent, it represents a polyfunctional compound.

In general formula (I), R ₁ represents a hydrogen atom or an alkyl group, and the ring structure formed with the carbon atom adjacent to Z ₁ , the sulfur atom, and the carbon atom bonded to the sulfur atom has a ring number of 6 to 9 and the atomic group represented by Z ₁ preferably contains a carbonyl group, an oxygen atom or a sulfur atom, or a combination thereof in addition to methylene carbon, and R ₁ represents a hydrogen atom or an alkyl group. And the number of ring members of the ring structure formed together with the carbon atom adjacent to Z ₁ , the sulfur atom and the carbon atom bonded to the sulfur atom is 6-8, and the atomic group represented by Z ₁ is methylene carbon In addition to the above, it is more preferable to include a combination of a carbonyl group and an oxygen atom, or a sulfur atom, R ₁ represents a hydrogen atom or an alkyl group, and a carbon atom adjacent to Z ₁ , a sulfur atom, and the sulfur It is particularly preferred that the ring structure formed together with the carbon atom bonded to the atom has 7 to 8 members and the atomic group represented by Z ₁ contains a sulfur atom in addition to methylene carbon. The compound represented by the general formula (I) is preferably a compound represented by the general formula (II) or the general formula (III), and is represented by the general formula (II) from the viewpoint of recording characteristics. More preferably, it is a compound.
Hereinafter, the compound represented by the general formula (II) and the compound represented by the general formula (III) will be described.

Compound represented by general formula (II)

In general formula (II), R ₁ has the same definition as in general formula (I), R ₂₂ represents a hydrogen atom, alkyl group, hydroxy group, amino group, carboxy group, acid anhydride or isocyanate group; ₂₃ , R ₂₄ and R ₂₅ are each independently a hydrogen atom, alkyl group, hydroxy group, amino group, carboxy group, acid anhydride, isocyanate group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, Represents an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an acyl group or a halogen group, and m2 represents 0 or 1. At least one of R ₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride and an isocyanate group.

In the general formula (II), the reactive group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride and an isocyanate group is represented by R ₁ , R ₂₂ , R ₂₃ , R ₂₄ and R _25. Or as a substituent of the group represented by R ₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ . In general formula (II), the reactive group is preferably contained in any one or more of R _{23 to} R ₂₅ , and more preferably in R ₂₅ .

In the general formula (II), details of the alkyl group represented by R ₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and the reactive group described above are the alkyl group and reactivity in the general formula (I) described above. This is the same as the explanation of the group.

In general formula (II), the aryl group represented by R ₂₃ , R ₂₄ , and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. These may further have a substituent.

In general formula (II), the heterocyclic group represented by R ₂₃ , R ₂₄ , or R ₂₅ is preferably a heterocyclic group having 4 to 14 carbon atoms, and is a heterocyclic group having 4 to 10 carbon atoms. It is more preferable that the heterocyclic group has 5 carbon atoms. Specific examples of the heterocyclic group represented by R ₂₃ , R ₂₄ and R ₂₅ include a pyridine ring, piperazine ring, thiophene ring, pyrrole ring, imidazole ring, oxazole ring and thiazole ring. These may further have a substituent. Of the heterocycles, a pyridine ring is particularly preferred.

In general formula (II), the alkoxy group represented by R ₂₃ , R ₂₄ , or R ₂₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxy groups include methoxy, ethoxy, normal propyloxy, isopropyloxy, normal butyloxy, isobutyloxy, tertiary butyloxy, pentyloxy, cyclopentyloxy, hexyloxy. Group, cyclohexyloxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, 2,3-dibromopropyloxy group, adamantyloxy group, Examples include benzyloxy group and 4-bromobenzyloxy group.

In general formula (II), the aryloxy group represented by R ₂₃ , R ₂₄ , and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenyloxy group, a naphthyloxy group, an anthranyloxy group, and the like.

In general formula (II), the alkylthio groups represented by R ₂₃ , R ₂₄ , and R ₂₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an alkylthio group include a methylthio group, an ethylthio group, a normal propylthio group, an isopropylthio group, a normal butylthio group, an isobutylthio group, a tertiary butylthio group, a pentylthio group, a cyclopentylthio group, a hexylthio group, Cyclohexylthio group, heptylthio group, octylthio group, tertiary octylthio group, 2-ethylhexylthio group, decylthio group, dodecylthio group, octadecylthio group, 2,3-dibromopropylthio group, adamantylthio group, benzylthio group, 4- Examples include a bromobenzylthio group.

In general formula (II), the arylthio groups represented by R ₂₃ , R ₂₄ and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenylthio group, a naphthylthio group, an anthranylthio group, and the like.

In general formula (II), the alkoxycarbonyl group represented by R ₂₃ , R ₂₄ , and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxycarbonyl groups include methyloxycarbonyl group, ethyloxycarbonyl group, normal propyloxycarbonyl group, isopropyloxycarbonyl group, normal butyloxycarbonyl group, isobutyloxycarbonyl group, tertiary butyloxycarbonyl group, pentyloxy Carbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, tertiary octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, decyloxycarbonyl group, dodecyloxycarbonyl group Groups and the like.

In general formula (II), the aryloxycarbonyl group represented by R ₂₃ , R ₂₄ , and R ₂₅ may be unsubstituted or substituted. The carbon number is preferably 7-30, and particularly preferably 7-20. As a specific example. For example, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, an anthranyloxycarbonyl group, etc. are mentioned.

In general formula (II), the acyloxy groups represented by R ₂₃ , R ₂₄ and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such acyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, normal propylcarbonyloxy group, isopropylcarbonyloxy group, normal butylcarbonyloxy group, isobutylcarbonyloxy group, tertiary butylcarbonyloxy group, pentylcarbonyloxy group. Group, cyclopentylcarbonyloxy group, hexylcarbonyloxy group, cyclohexylcarbonyloxy group, heptylcarbonyloxy group, octylcarbonyloxy group, tertiary octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group And benzoyloxy group.

In general formula (II), the acylamino groups represented by R ₂₃ , R ₂₄ and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acylamino group include a methylcarbonylamino group, an ethylcarbonylamino group, and a phenylcarbonylamino group.

In general formula (II), the sulfonylamino group represented by R ₂₃ , R ₂₄ and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such a sulfonylamino group include a methylsulfonylamino group, an ethylsulfonylamino group, and a phenylsulfonylamino group.

In general formula (II), the acyl groups represented by R ₂₃ , R ₂₄ and R ₂₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acyl group include an acetyl group and a benzoyl group.

In the general formula (II), examples of the halogen group represented by R ₂₃ , R ₂₄ , and R ₂₅ include a chloro group, a bromo group, and an iodo group, and a bromo group is preferable.

In the general formula (II), when the group represented by R ₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ further has a substituent, the substituent includes a halogen atom, an alkyl group, an alkenyl group, and an alkoxy group. , Aryloxy, alkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, acyl group, alkylaminocarbonyl group, arylaminocarbonyl group, sulfonamido group, cyano group, carboxy group, hydroxyl group, sulfonic acid group, etc. It is done. Among these, a halogen atom, an alkoxy group, and an alkylthio group are particularly preferable. As described above, the groups represented by R ₁ , R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ can include the reactive group as a substituent. When the cyclic allyl sulfide compound represented by the general formula (II) is substituted as a substituent, it represents a polyfunctional compound.

  In general formula (II), m2 represents an integer of 0 or 1. m2 is preferably 1.

In a preferred embodiment of the compound represented by the general formula (II), R ₁ and R ₂₂ each independently represent a hydrogen atom or a methyl group, and R ₂₃ , R ₂₄ and R ₂₅ each independently represent a hydrogen atom, an alkyl A group, a reactive group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, or an acyl group, and R ₂₃ , R ₂₄ and R ₂₅ Examples thereof include compounds in which at least one of them has at least one reactive group. In a more preferred embodiment, in general formula (II), R ₁ and R ₂₂ are each independently a hydrogen atom or a methyl group, and R ₂₃ and R ₂₄ are each independently a hydrogen atom, an alkyl group, the reactive group, aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an acyl group, R ₂₅ is a hydrogen atom, an alkyl group, the reactive group, aryl group, acyloxy group And a compound in which m2 is 0 or 1, and at least one of R ₂₃ , R ₂₄ and R ₂₅ has at least one reactive group. In a more preferred embodiment, in general formula (II), R ₁ and R ₂₂ are a hydrogen atom or a methyl group, R ₂₃ and R ₂₄ are each independently a hydrogen atom, a methyl group or the reactive group, and R ₂₅ is an alkyl group, the above reactive group or an acyloxy group, and m2 is 0 or 1, and at least one of R ₂₃ , R ₂₄ and R ₂₅ has at least one of the above reactive groups A compound can be mentioned. In a more preferred embodiment, in general formula (II), R ₁ and R ₂₂ are both hydrogen atoms, and R ₂₃ , R ₂₄ and R ₂₅ are each independently a hydrogen atom, an alkyl group, or the above reactive group. , An aryl group, an alkoxy group, an aryloxy group, or an acyloxy group, wherein m2 is 1, and at least one of R ₂₃ , R _24, and R ₂₅ has at least one reactive group Can be mentioned. In the most preferred embodiment, R ₁ and R ₂₂ are both hydrogen atoms, R ₂₃ and R ₂₄ are hydrogen atoms, R ₂₅ is an acyloxy group substituted by the reactive group, and m2 is 1 The compound which is can be mentioned.

Compound represented by general formula (III)

In general formula (III), R ₁ has the same definition as in general formula (I), and R ₃₃ , R ₃₄ and R ₃₅ are each independently a hydrogen atom, alkyl group, hydroxy group, amino group, carboxy group, acid Anhydride, isocyanate group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, sulfonylamino group, acyl group or halogen group M3 represents 0 or 1.

In the general formula (III), the reactive group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride and an isocyanate group is a group represented by R ₁ , R _{33 to} R ₃₅ , or R ₁ , included as a substituent of the group represented by R _{33 to} R ₃₅ . In general formula (III), the reactive group is preferably contained in any one or more of R _{33 to} R ₃₅ , and more preferably in R ₃₅ .

In the general formula (III), details of the alkyl group represented by R ₁ , R ₃₃ , R ₃₄ , R ₃₅ and the reactive group described above are the explanation of the alkyl group and reactive group in the general formula (I) described above. Is the same.

In the general formula (III), the aryl group represented by R ₃₃ , R ₃₄ , and R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. These may further have a substituent.

In general formula (III), the heterocyclic group represented by R ₃₃ , R ₃₄ , and R ₃₅ is preferably a heterocyclic group having 4 to 14 carbon atoms, and is a heterocyclic group having 4 to 10 carbon atoms. It is more preferable that the heterocyclic group has 5 carbon atoms. Specific examples of the heterocyclic group represented by R ₃₃ , R ₃₄ , and R ₃₅ include a pyridine ring, a piperazine ring, a thiophene ring, a pyrrole ring, an imidazole ring, an oxazole ring, and a thiazole ring. These may further have a substituent. Of the heterocycles, a pyridine ring is particularly preferred.

In the general formula (III), the alkoxy group represented by R ₃₃ , R ₃₄ , or R ₃₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxy groups include methoxy, ethoxy, normal propyloxy, isopropyloxy, normal butyloxy, isobutyloxy, tertiary butyloxy, pentyloxy, cyclopentyloxy, hexyloxy. Group, cyclohexyloxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, 2,3-dibromopropyloxy group, adamantyloxy group, Examples include benzyloxy group and 4-bromobenzyloxy group.

In general formula (III), the aryloxy group represented by R ₃₃ , R ₃₄ , or R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenyloxy group, a naphthyloxy group, an anthranyloxy group, and the like.

In general formula (III), the alkylthio group represented by R ₃₃ , R ₃₄ , or R ₃₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an alkylthio group include a methylthio group, an ethylthio group, a normal propylthio group, an isopropylthio group, a normal butylthio group, an isobutylthio group, a tertiary butylthio group, a pentylthio group, a cyclopentylthio group, a hexylthio group, Cyclohexylthio group, heptylthio group, octylthio group, tertiary octylthio group, 2-ethylhexylthio group, decylthio group, dodecylthio group, octadecylthio group, 2,3-dibromopropylthio group, adamantylthio group, benzylthio group, 4- Examples include a bromobenzylthio group.

In general formula (III), the arylthio group represented by R ₃₃ , R ₃₄ , or R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenylthio group, a naphthylthio group, an anthranylthio group, and the like.

In the general formula (III), the alkoxycarbonyl group represented by R ₃₃ , R ₃₄ , or R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxycarbonyl groups include methyloxycarbonyl group, ethyloxycarbonyl group, normal propyloxycarbonyl group, isopropyloxycarbonyl group, normal butyloxycarbonyl group, isobutyloxycarbonyl group, tertiary butyloxycarbonyl group, pentyloxy Carbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, tertiary octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, decyloxycarbonyl group, dodecyloxycarbonyl group Groups and the like.

In the general formula (III), the aryloxycarbonyl group represented by R ₃₃ , R ₃₄ , R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 7-30, and particularly preferably 7-20. As a specific example. For example, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, an anthranyloxycarbonyl group, etc. are mentioned.

In general formula (III), the acyloxy groups represented by R ₃₃ , R ₃₄ and R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such acyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, normal propylcarbonyloxy group, isopropylcarbonyloxy group, normal butylcarbonyloxy group, isobutylcarbonyloxy group, tertiary butylcarbonyloxy group, pentylcarbonyloxy group. Group, cyclopentylcarbonyloxy group, hexylcarbonyloxy group, cyclohexylcarbonyloxy group, heptylcarbonyloxy group, octylcarbonyloxy group, tertiary octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group And benzoyloxy group.

In general formula (III), the acylamino group represented by R ₃₃ , R ₃₄ , R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acylamino group include a methylcarbonylamino group, an ethylcarbonylamino group, and a phenylcarbonylamino group.

In the general formula (III), the sulfonylamino group represented by R ₃₃ , R ₃₄ , or R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such a sulfonylamino group include a methylsulfonylamino group, an ethylsulfonylamino group, and a phenylsulfonylamino group.

In general formula (III), the acyl groups represented by R ₃₃ , R ₃₄ and R ₃₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acyl group include an acetyl group and a benzoyl group.

In the general formula (III), examples of the halogen group represented by R ₃₃ , R ₃₄ , and R ₃₅ include a chloro group, a bromo group, and an iodo group, and a bromo group is preferable.

In the general formula (III), when the group represented by R ₁ , R ₃₃ , R ₃₄ , or R ₃₅ further has a substituent, examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, aryloxy Alkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, acyl group, alkylaminocarbonyl group, arylaminocarbonyl group, sulfonamido group, cyano group, carboxy group, hydroxyl group, sulfonic acid group and the like. Among these, a halogen atom, an alkoxy group, and an alkylthio group are particularly preferable. As described above, the reactive group may be included as a substituent. When the cyclic allyl sulfide compound represented by the general formula (III) is substituted as a substituent, it represents a polyfunctional compound.

  In general formula (III), m3 represents an integer of 0 or 1. m3 is preferably 0.

In a preferred embodiment of the compound represented by the general formula (III), R ₁ represents a hydrogen atom or a methyl group, and R ₃₃ , R ₃₄ and R ₃₅ are each independently a hydrogen atom, an alkyl group, or the above reactive group. , An aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, or an acyl group, wherein at least one of R ₃₃ , R _34, and R ₃₅ is the above Mention may be made of compounds having at least one reactive group. In a more preferred embodiment, in general formula (III), R ₁ is a hydrogen atom or a methyl group, and R ₃₃ and R ₃₄ are each independently a hydrogen atom, an alkyl group, the reactive group, an aryl group, an alkoxy group, An aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an acyl group, R ₃₅ is a hydrogen atom, an alkyl group, the above reactive group, an aryl group, or an acyloxy group, and m3 is 0. Or a compound that is 1, wherein at least one of R ₃₃ , R _34, and R ₃₅ has at least one reactive group. In a more preferred embodiment, in general formula (III), R ₁ is a hydrogen atom or a methyl group, R ₃₃ and R ₃₄ are each independently a hydrogen atom, a methyl group or the reactive group, and R ₃₅ is an alkyl group. A compound in which m3 is 0 or 1 and at least one of R ₃₃ , R ₃₄ and R ₃₅ has at least one of the above reactive groups, which is a group, an acyloxy group or the above reactive group be able to. In a more preferred embodiment, in general formula (III), R ₁ is a methyl group, and R ₃₃ , R ₃₄ and R ₃₅ are each independently a hydrogen atom, an alkyl group, the above reactive group, an aryl group, an alkoxy group. A compound that is a group, an aryloxy group, or an acyloxy group, and m3 is 0, in which at least one of R ₃₃ , R _34, and R ₃₅ has at least one reactive group. The most preferred embodiment is a compound in which R ₁ is a methyl group, R ₃₃ and R ₃₄ are hydrogen atoms, R ₃₅ is an acyloxy group substituted by the reactive group, and m3 is 0. be able to.

  Specific examples of the compound represented by the general formula (I) are shown below. However, the present invention is not limited to the following specific examples.

  Compounds represented by general formula (I) are, for example, Macromolecules. 1994, 27, 7935. Macromolecules, 1996, 29, 6983., Macromolecules, 2000, 33, 6722. and J. Po1ym. Sci .: Part A Polym Chem. 2001, 39, 202 and the like can be obtained by synthesizing the reactive group by a known method to the cyclic allyl sulfide compound synthesized by the method described in Chem.

The compound represented by the general formula (I) is fixed to the matrix at the time of the thermosetting reaction, and then bonded to the compound by polymerization reaction with the polymerizable compound by light irradiation, resulting in the polymerizable compound. Can be immobilized on the matrix. The optical recording composition of the present invention contains a cyclic allyl sulfide compound represented by the general formula (IV) as a polymerizable compound. Since the cyclic allyl sulfide compound represented by the general formula (I) and the cyclic allyl sulfide compound represented by the general formula (IV) are both small in volume shrinkage before and after polymerization, by using these two compounds together, Further, it is possible to improve the record retention without causing a large volume shrinkage.
Hereinafter, the compound represented by formula (IV) will be described.

In the general formula (IV), Z ₂ represents an atomic group that forms a ring structure with adjacent carbon atoms, sulfur atoms, and carbon atoms bonded to the sulfur atoms. Examples of the ring structure formed by Z ₂ include methylene carbon. In addition to methylene carbon, divalent organic linking groups such as a carbonyl group, a thiocarbonyl group, an oxygen atom, and a sulfur atom are also exemplified. These ring structures are constituted by a combination thereof. The number of ring members is preferably 6 to 9, more preferably 6 to 8, and particularly preferably 7 to 8. Moreover, it is preferable that methylene carbon number of the ring structure is 3-7, It is more preferable that it is 4-6, It is especially preferable that it is 4-5.

In the general formula (IV), R ₆ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ₆ may be linear or branched, and may be unsubstituted or may have a substituent. The number of carbon atoms is preferably 1-20, more preferably 1-10, and particularly preferably 1-3.

Examples of the alkyl group represented by R ₆ include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, Examples include heptyl group, octyl group, tertiary octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, 2,3-dibromopropyl group, adamantyl group, benzyl group and 4-bromobenzyl group. These may further have a substituent.

In the general formula (IV), when the group represented by R ₆ further has a substituent, the substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryloxy, an alkylthio group, an alkoxycarbonyl group, an aryloxy group. Examples thereof include a carbonyl group, an amino group, an acyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, a sulfonamide group, a cyano group, a carboxy group, a hydroxyl group, and a sulfonic acid group. Among these, a halogen atom, an alkoxy group, and an alkylthio group are particularly preferable. Further, when the cyclic allyl sulfide compound of the general formula (IV) is substituted as a substituent, it represents a polyfunctional compound.

In general formula (IV), R ₆ represents a hydrogen atom or an alkyl group, and the ring structure formed with the carbon atom adjacent to Z ₂ , the sulfur atom, and the carbon atom bonded to the sulfur atom has a ring number of 6 to 9 and the atomic group represented by Z ₂ preferably contains a carbonyl group, an oxygen atom or a sulfur atom, or a combination thereof other than methylene carbon, and R ₆ represents a hydrogen atom or an alkyl group. And the number of members of the ring structure formed together with the carbon atom adjacent to Z ₂ , the sulfur atom and the carbon atom bonded to the sulfur atom is 6-8, and the atomic group represented by Z ₂ is methylene carbon more preferably containing a carbonyl group combined with an oxygen atom or a sulfur atom, in addition, R ₆ represents a hydrogen atom or an alkyl group, and the carbon atom adjacent to Z _6, a sulfur atom and sulfuric Ring members of the ring structure formed together with the carbon atom bonded to the atom is 7-8, and atomic group represented by Z ₆ is particularly preferred that a sulfur atom in addition to methylene carbon. The compound represented by the general formula (IV) is preferably a compound represented by the general formula (V) or the general formula (VI), and is represented by the general formula (V) from the viewpoint of recording characteristics. More preferably, it is a compound.
Hereinafter, the compound represented by the general formula (V) and the compound represented by the general formula (VI) will be described.

In general formula (V), R ₆ has the same definition as in general formula (IV), R ₅₂ represents a hydrogen atom or an alkyl group, and R ₅₃ , R ₅₄ and R ₅₅ each independently represent a hydrogen atom or an alkyl group. , Aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, sulfonylamino group, amino group, acyl group or halogen group , M5 represents 0 or 1.

In the general formula (V), the details of the alkyl group represented by R ₆ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ are the same as those described above for the alkyl group in the general formula (IV).

In the general formula (V), the aryl group represented by R ₅₃ , R ₅₄ and R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. These may further have a substituent.

In general formula (V), the heterocyclic group represented by R ₅₃ , R ₅₄ , and R ₅₅ is preferably a heterocyclic group having 4 to 14 carbon atoms, and is a heterocyclic group having 4 to 10 carbon atoms. It is more preferable that the heterocyclic group has 5 carbon atoms. Specific examples of the heterocyclic group represented by R ₅₃ , R ₅₄ , and R ₅₅ include a pyridine ring, a piperazine ring, a thiophene ring, a pyrrole ring, an imidazole ring, an oxazole ring, and a thiazole ring. These may further have a substituent. Of the heterocycles, a pyridine ring is particularly preferred.

In general formula (V), the alkoxy group represented by R ₅₃ , R ₅₄ , or R ₅₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxy groups include methoxy, ethoxy, normal propyloxy, isopropyloxy, normal butyloxy, isobutyloxy, tertiary butyloxy, pentyloxy, cyclopentyloxy, hexyloxy. Group, cyclohexyloxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, 2,3-dibromopropyloxy group, adamantyloxy group, Examples include benzyloxy group and 4-bromobenzyloxy group.

In general formula (V), the aryloxy groups represented by R ₅₃ , R ₅₄ , and R ₅₅ may be unsubstituted or have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenyloxy group, a naphthyloxy group, an anthranyloxy group, and the like.

In general formula (V), the alkylthio group represented by R ₅₃ , R ₅₄ , or R ₅₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an alkylthio group include a methylthio group, an ethylthio group, a normal propylthio group, an isopropylthio group, a normal butylthio group, an isobutylthio group, a tertiary butylthio group, a pentylthio group, a cyclopentylthio group, a hexylthio group, Cyclohexylthio group, heptylthio group, octylthio group, tertiary octylthio group, 2-ethylhexylthio group, decylthio group, dodecylthio group, octadecylthio group, 2,3-dibromopropylthio group, adamantylthio group, benzylthio group, 4- Examples include a bromobenzylthio group.

In general formula (V), the arylthio group represented by R ₅₃ , R ₅₄ and R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenylthio group, a naphthylthio group, an anthranylthio group, and the like.

In general formula (V), the alkoxycarbonyl group represented by R ₅₃ , R ₅₄ , and R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxycarbonyl groups include methyloxycarbonyl group, ethyloxycarbonyl group, normal propyloxycarbonyl group, isopropyloxycarbonyl group, normal butyloxycarbonyl group, isobutyloxycarbonyl group, tertiary butyloxycarbonyl group, pentyloxy Carbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, tertiary octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, decyloxycarbonyl group, dodecyloxycarbonyl group Groups and the like.

In general formula (V), the aryloxycarbonyl group represented by R ₅₃ , R ₅₄ and R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 7-30, and particularly preferably 7-20. As a specific example. For example, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, an anthranyloxycarbonyl group, etc. are mentioned.

In general formula (V), the acyloxy groups represented by R ₅₃ , R ₅₄ and R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such acyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, normal propylcarbonyloxy group, isopropylcarbonyloxy group, normal butylcarbonyloxy group, isobutylcarbonyloxy group, tertiary butylcarbonyloxy group, pentylcarbonyloxy group. Group, cyclopentylcarbonyloxy group, hexylcarbonyloxy group, cyclohexylcarbonyloxy group, heptylcarbonyloxy group, octylcarbonyloxy group, tertiary octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group And benzoyloxy group.

In general formula (V), the acylamino groups represented by R ₅₃ , R ₅₄ and R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acylamino group include a methylcarbonylamino group, an ethylcarbonylamino group, and a phenylcarbonylamino group.

In general formula (V), the sulfonylamino group represented by R ₅₃ , R ₅₄ , or R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such a sulfonylamino group include a methylsulfonylamino group, an ethylsulfonylamino group, and a phenylsulfonylamino group.

In general formula (V), the amino group represented by R ₅₃ , R ₅₄ , or R ₅₅ may be a mono-substituted amino group or a di-substituted amino group, and a di-substituted amino group is preferable. . It may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an amino group include a dimethylamino group and a diphenylamino group.

In general formula (V), the acyl groups represented by R ₅₃ , R ₅₄ and R ₅₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acyl group include an acetyl group and a benzoyl group.

In the general formula (V), examples of the halogen group represented by R ₅₃ , R ₅₄ , and R ₅₅ include a chloro group, a bromo group, and an iodo group, and a bromo group is preferable.

In the general formula (V), when the group represented by R ₆ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ further has a substituent, the substituent includes a halogen atom, an alkyl group, an alkenyl group, and an alkoxy group. , Aryloxy, alkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, acyl group, alkylaminocarbonyl group, arylaminocarbonyl group, sulfonamido group, cyano group, carboxy group, hydroxyl group, sulfonic acid group, etc. It is done. Among these, a halogen atom, an alkoxy group, and an alkylthio group are particularly preferable. Moreover, when the cyclic allyl sulfide compound represented by general formula (V) substitutes as a substituent, it represents a polyfunctional compound.

  In general formula (V), m5 represents an integer of 0 or 1. m5 is preferably 1.

In a preferred embodiment of the compound represented by the general formula (V), R ₆ and R ₅₂ each independently represent a hydrogen atom or a methyl group, and R ₅₃ , R ₅₄ and R ₅₅ each independently represent a hydrogen atom, an alkyl And a compound representing a group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an amino group, or an acyl group. In a more preferred embodiment, in general formula (V), R ₆ and R ₅₂ are each independently a hydrogen atom or a methyl group, and R ₅₃ and R ₅₄ are each independently a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group. , an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an amino group, an acyl group, R ₅₅ is a hydrogen atom, an alkyl group, an aryl group, an acyloxy group, and m5 is 0 or The compound which is 1 can be mentioned. In a more preferred embodiment, in general formula (V), R ₆ and R ₅₂ are a hydrogen atom or a methyl group, R ₅₃ and R ₅₄ are each independently a hydrogen atom or a methyl group, and R ₅₅ is an alkyl group or The compound which is an acyloxy group and m5 is 0 or 1 can be mentioned. In a more preferred embodiment, in general formula (V), R ₆ and R ₅₂ are both hydrogen atoms, and R ₅₃ , R ₅₄ and R ₅₅ are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group. And a compound in which m5 is 1 is a group, an aryloxy group or an acyloxy group. The most preferred embodiment is a compound in which R ₆ and R ₅₂ are both hydrogen atoms, R ₅₃ and R ₅₄ are hydrogen atoms, R ₅₅ is an acyloxy group, and m5 is 1. .

In general formula (VI), R ₆ has the same definition as in general formula (IV), and R ₆₃ , R ₆₄ and R ₆₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, An aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an amino group, an acyl group, or a halogen group, and m6 represents 0 or 1.

In the general formula (VI), the details of the alkyl group represented by R ₆ , R ₆₃ , R ₆₄ and R ₆₅ are the same as _those described above for the alkyl group in the general formula (IV).

In general formula (VI), the aryl group represented by R ₆₃ , R ₆₄ and R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. These may further have a substituent.

In general formula (VI), the heterocyclic group represented by R ₆₃ , R ₆₄ , or R ₆₅ is preferably a heterocyclic group having 4 to 14 carbon atoms, and is a heterocyclic group having 4 to 10 carbon atoms. It is more preferable that the heterocyclic group has 5 carbon atoms. Specific examples of the heterocyclic group represented by R ₆₃ , R ₆₄ and R ₆₅ include a pyridine ring, piperazine ring, thiophene ring, pyrrole ring, imidazole ring, oxazole ring and thiazole ring. These may further have a substituent. Of the heterocycles, a pyridine ring is particularly preferred.

In general formula (VI), the alkoxy group represented by R ₆₃ , R ₆₄ , or R ₆₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxy groups include methoxy, ethoxy, normal propyloxy, isopropyloxy, normal butyloxy, isobutyloxy, tertiary butyloxy, pentyloxy, cyclopentyloxy, hexyloxy. Group, cyclohexyloxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, 2,3-dibromopropyloxy group, adamantyloxy group, Examples include benzyloxy group and 4-bromobenzyloxy group.

In general formula (VI), the aryloxy group represented by R ₆₃ , R ₆₄ , or R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenyloxy group, a naphthyloxy group, an anthranyloxy group, and the like.

In general formula (VI), the alkylthio groups represented by R ₆₃ , R ₆₄ , and R ₆₅ may be linear or branched, and may be unsubstituted or substituted. You may do it. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an alkylthio group include a methylthio group, an ethylthio group, a normal propylthio group, an isopropylthio group, a normal butylthio group, an isobutylthio group, a tertiary butylthio group, a pentylthio group, a cyclopentylthio group, a hexylthio group, Cyclohexylthio group, heptylthio group, octylthio group, tertiary octylthio group, 2-ethylhexylthio group, decylthio group, dodecylthio group, octadecylthio group, 2,3-dibromopropylthio group, adamantylthio group, benzylthio group, 4- Examples include a bromobenzylthio group.

In the general formula (VI), the arylthio group represented by R ₆₃ , R ₆₄ and R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples include a phenylthio group, a naphthylthio group, an anthranylthio group, and the like.

In general formula (VI), the alkoxycarbonyl group represented by R ₆₃ , R ₆₄ , R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such alkoxycarbonyl groups include methyloxycarbonyl group, ethyloxycarbonyl group, normal propyloxycarbonyl group, isopropyloxycarbonyl group, normal butyloxycarbonyl group, isobutyloxycarbonyl group, tertiary butyloxycarbonyl group, pentyloxy Carbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, tertiary octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, decyloxycarbonyl group, dodecyloxycarbonyl group Groups and the like.

In general formula (VI), the aryloxycarbonyl group represented by R ₆₃ , R ₆₄ , R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 7-30, and particularly preferably 7-20. Specific examples include a phenyloxycarbonyl group, a naphthyloxycarbonyl group, an anthranyloxycarbonyl group, and the like.

In general formula (VI), the acyloxy groups represented by R ₆₃ , R ₆₄ and R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such acyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, normal propylcarbonyloxy group, isopropylcarbonyloxy group, normal butylcarbonyloxy group, isobutylcarbonyloxy group, tertiary butylcarbonyloxy group, pentylcarbonyloxy group. Group, cyclopentylcarbonyloxy group, hexylcarbonyloxy group, cyclohexylcarbonyloxy group, heptylcarbonyloxy group, octylcarbonyloxy group, tertiary octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group And benzoyloxy group.

In general formula (VI), the acylamino groups represented by R ₆₃ , R ₆₄ and R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acylamino group include a methylcarbonylamino group, an ethylcarbonylamino group, and a phenylcarbonylamino group.
In the general formula (VI), the sulfonylamino group represented by R ₆₃ , R ₆₄ , or R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such a sulfonylamino group include a methylsulfonylamino group, an ethylsulfonylamino group, and a phenylsulfonylamino group.

In general formula (VI), the amino group represented by R ₆₃ , R ₆₄ , or R ₆₅ may be a mono-substituted amino group or a di-substituted amino group, and a di-substituted amino group is preferred. . It may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an amino group include a dimethylamino group and a diphenylamino group.

In the formula (VI), acyl group represented by R _63, R _64, R ₆₅ may be unsubstituted or may have a substituent. The carbon number is preferably 1-30, and more preferably 1-20. Examples of such an acyl group include an acetyl group and a benzoyl group.

In the general formula (VI), examples of the halogen group represented by R ₆₃ , R ₆₄ , and R ₆₅ include a chloro group, a bromo group, and an iodo group, and a bromo group is preferable.

In the general formula (VI), when the group represented by R ₁ , R ₆₃ , R ₆₄ , R ₆₅ further has a substituent, the substituent may be a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, aryloxy Alkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, acyl group, alkylaminocarbonyl group, arylaminocarbonyl group, sulfonamido group, cyano group, carboxy group, hydroxyl group, sulfonic acid group and the like. Among these, a halogen atom, an alkoxy group, and an alkylthio group are particularly preferable. Moreover, when the cyclic allyl sulfide compound represented by general formula (VI) substitutes as a substituent, it represents a polyfunctional compound.

  In general formula (VI), m6 represents an integer of 0 or 1. m6 is preferably 0.

In a preferred embodiment of the compound represented by the general formula (VI), R ₆ represents a hydrogen atom or a methyl group, and R ₆₃ , R ₆₄ and R ₆₅ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group. And a compound representing a group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an amino group, or an acyl group. In a more preferred embodiment, in general formula (VI), R ₆ is a hydrogen atom or a methyl group, and R ₆₃ and R ₆₄ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxy group. Examples include a carbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an amino group, and an acyl group, R ₆₅ is a hydrogen atom, an alkyl group, an aryl group, and an acyloxy group, and m6 is 0 or 1. be able to. In a more preferred embodiment, in general formula (VI), R ₆ is a hydrogen atom or a methyl group, R ₆₃ and R ₆₄ are each independently a hydrogen atom or a methyl group, and R ₆₅ is an alkyl group or an acyloxy group. And a compound in which m6 is 0 or 1. In a more preferred embodiment, in general formula (VI), R ₆ is a methyl group, and R ₆₃ , R ₆₄ and R ₆₅ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group. Alternatively, a compound that is an acyloxy group and m6 is 0 can be given. The most preferred embodiment includes a compound in which R ₆ is a methyl group, R ₆₃ and R ₆₄ are hydrogen atoms, R ₆₅ is an acyloxy group, and m6 is 0.

  Specific examples of the cyclic allyl sulfide compound represented by the general formula (IV) are shown below. However, the present invention is not limited to the following specific examples.

  For example, Macromolecules. 1994, 27, 7935. Macromolecules, 1996, 29, 6983., Macromolecules, 2000, 33, 6722. and J. Po1ym. Sci .: Part A Polym. Chem. 2001, 39, 202, etc. The details of the synthesis method can also refer to examples described later.

  The content of the compound represented by the general formula (I) in the optical recording composition of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of improving the storage stability of recording, 0.1-20 mass% is preferable, 0.5-10 mass% is more preferable, and 1-5 mass% is still more preferable. The content of the cyclic allyl sulfide compound represented by the general formula (IV) in the optical recording composition of the present invention is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and 2 to 20% by mass. Is more preferable. If the content is 50% by mass or less, the stability of the interference image can be easily secured, and if it is 1% by mass or more, desirable performance can be obtained in terms of diffraction efficiency. As for the compound represented by general formula (I) and the compound represented by general formula (IV), only 1 type may be used, and 2 or more types can also be used together.

Photoradical polymerization initiator The optical recording composition of the present invention is preferably used as a holographic recording composition, and particularly suitable as a volume holographic recording composition. When the optical recording composition of the present invention is used as a holographic recording composition, together with the compound represented by the general formula (I) and the compound represented by the general formula (IV), an optical radical polymerization initiator is used. Can be included. The radical photopolymerization initiator is not particularly limited as long as it has sensitivity to the recording light. Specific examples thereof include, for example, 2,2′-bis (o-chlorophenyl) -4,4. ', 5,5'-tetraphenyl-1,1'-biimidazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 (P-methoxyphenylvinyl) -1,3,5-triazine, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, 4,4′-di-t-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenylbenzenediazonium Hexafluorophosphate, benzoin, 2-hydroxy-2-methyl-1-phenyl group Pan-2-one, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide, triphenylbutyl borate tetraethylammonium, bis (η5-2,4-cyclopentadien-1-yl) bis [2,6 -Difluoro-3- (1H-pyrrol-1-yl) phenyltitanium] and the like. In the optical recording composition of the present invention, the radical photopolymerization initiator may be used alone or in combination of two or more. Moreover, you may use together the sensitizing dye mentioned later according to the wavelength of the light to irradiate.

  Suitable examples of the radical photopolymerization initiator include compounds represented by the following general formula (VII).

In general formula (VII), R ^a , R ^b and R ^c each independently represents an alkyl group, an aryl group or a heterocyclic group, and X represents an oxygen atom or a sulfur atom.
Details of the compound represented by the general formula (VII) will be described below.

In general formula (VII), R ^a , R ^b and R ^c each independently represents an alkyl group, an aryl group or a heterocyclic group.

The alkyl group represented by R ^a , R ^b and R ^c may be linear or branched, and may be unsubstituted or have a substituent. The carbon number is preferably 1-30, and more preferably 1-20.

Examples of the alkyl group represented by R ^a , R ^b and R ^c include, for example, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, cyclopentyl group, Hexyl group, cyclohexyl group, heptyl group, octyl group, tertiary octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, 2,3-dibromopropyl group, adamantyl group, benzyl group, 4-bromobenzyl group Etc. These may further have a substituent. Among these, a tertiary butyl group is most preferable from the viewpoint of stability to nucleophilic compounds such as water and alcohol.

In general formula (VII), the aryl group represented by R ^a , R ^b and R ^c may be unsubstituted or may have a substituent. The carbon number is preferably 6 to 30, and particularly preferably 6 to 20. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. These may further have a substituent. Among them, R ^a is 2-position an alkyl group, an aryl group, preferably denotes an aryl group having an alkoxy group or a halogen group, further, 2-position and 6-position alkyl group, an aryl group, an alkoxy group or a halogen group It is more preferable that the aryl group has. For example, R ¹¹ is preferably 2-methylphenyl group, 2,4,6-trimethylphenyl group, 2,6-dichlorophenyl group, 2,6-dimethoxyphenyl group, 2,6-trifluoromethylphenyl group, Particularly preferred are 2,4,6-trimethylphenyl group, 2,6-dichlorophenyl group and 2,6-dimethoxyphenyl group. The reason why it is preferable to have the above substituents at the 2-position or 2-position and 6-position is, for example, Jacobi, M .; Henne, A .; Polymers Paint Color Journal 1985, 175, 636. As described in the above, the stability to nucleophilic compounds such as water and alcohol is improved. Details such as preferred examples of the alkyl group and aryl group as the substituent are as described above for the alkyl group represented by R ^a , R ^b and R ^c .

In general formula (VII), the heterocyclic group represented by R ^a , R ^b and R ^c preferably has 4 to 8 ring members, more preferably 4 to 6 ring members, and particularly preferably 5 or 6 ring members. Specific examples include a pyridine ring, a piperazine ring, a thiophene ring, a pyrrole ring, an imidazole ring, an oxazole ring, and a thiazole ring. These may further have a substituent. Of the heterocycles, a pyridine ring is particularly preferred.

In the general formula (VII), when the groups represented by R ^a , R ^b and R ^c further have a substituent, examples of the substituent include a halogen group, an alkyl group, an alkenyl group, an alkoxy group, an aryloxy, an alkylthio group, an alkoxy group Examples include a carbonyl group, an aryloxycarbonyl group, an amino group, an acyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, a sulfonamido group, a cyano group, a carboxy group, a hydroxyl group, and a sulfonic acid group. Among these, a halogen group, an alkoxy group, and an alkylthio group are particularly preferable. Further, as described above, when R ^a is an aryl group, the aryl group preferably has the above substituents at the 2-position or 2-position and 6-position.

  In general formula (VII), X represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

In a preferred embodiment of the compound represented by the general formula (VII), R ^a is an aryl group having an alkyl group, an aryl group, an alkoxy group or a halogen group at the 2-position, R ^b is an aryl group, and R ^c A compound in which is an alkyl group and X is an oxygen atom or a sulfur atom. In a more preferred embodiment, R ^a is an aryl group having an alkyl group, an aryl group, an alkoxy group or a halogen group at the 2-position and the 6-position, R ^b is an aryl group, R ^c is an alkyl group, and X And a compound in which is an oxygen atom. In a more preferred embodiment, R ^a is a 2,6-dimethoxybenzoyl group or a 2,6-dichlorobenzoyl group, R ^b is a phenyl group, R ^c is an ethyl group or an isopropyl group, and X is an oxygen atom. The compound which is can be mentioned.

  Specific examples of the phosphorus compound represented by the general formula (VII) are shown below. However, the present invention is not limited to the following specific examples.

  The method for synthesizing the compound represented by the general formula (VII) described above is described in detail, for example, in DE2830927A1.

  The content of the photo radical polymerization initiator in the optical recording composition of the present invention is preferably 0.01 to 5% by mass, and more preferably 1 to 3% by mass. When the content is 0.01% by mass or more, an interference image can be secured with high sensitivity. When the content is 5% by mass or less, a recording layer that has a sufficient transmittance for recording light and can exhibit good recording sensitivity can be formed.

Matrix-forming component The recording layer of the optical recording medium contains a monomer generally referred to as a matrix for recording and storage and a polymer for holding a photopolymerization initiator. The matrix is used for the purpose of enhancing the effects of improving coating properties, film strength, and hologram recording characteristics. The optical recording composition of the present invention contains a polyfunctional isocyanate and a polyfunctional alcohol as a matrix forming component (matrix precursor). Since the above components are polyfunctional, a three-dimensional polyurethane matrix can be formed and recording retention is excellent. Further, in the present invention, the recording monomer can be immobilized on the matrix via the compound represented by the general formula (I). By these actions, the recording layer formed from the optical recording composition of the present invention can exhibit excellent recording retainability. In the present invention, “polyfunctional” means bifunctional or higher. For example, the polyfunctional isocyanate and polyfunctional alcohol can form a matrix by applying a curing treatment after being applied to the surface of the substrate and the like. The recording layer can be formed by using a solvent. The matrix-forming component is a thermosetting compound, and is superior in terms of recording characteristics as compared with a photocurable compound that is cured by light irradiation using a catalyst or the like.
Below, the said polyfunctional isocyanate and polyfunctional alcohol are demonstrated.

  Specific examples of the polyfunctional isocyanate include biscyclohexylmethane diisocyanate, hexamethylene diisocyanate, phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, and 1-methyl. Phenylene-2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4′-diisocyanate, 3 , 3'-dimethoxybiphenylene-4,4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate Anate, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, naphthylene-1,5-diisocyanate, cyclobutylene-1,3-diisocyanate, cyclo Pentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, 1-methylcyclohexylene-2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexane-1,3-bis (methylisocyanate), cyclohexane-1,4-bis (methylisocyanate), isophorone diisocyanate , Dicyclohexylmethane-2,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12- Diisocyanate, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, diphenylmethane-2,5,4'-triisocyanate, triphenylmethane-2,4 ', 4 "-triisocyanate Isocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, diphenylmethane-2,4,2', 4'-tetraisocyanate, diphenylmethane-2,5,2 ', 5'-tetraisocyanate, cyclohexane-1 , 3,5-Triisocy Nate, cyclohexane-1,3,5-tris (methyl isocyanate), 3,5-dimethylcyclohexane-1,3,5-tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5- Stoichiometric excess of tris (methyl isocyanate), dicyclohexylmethane-2,4,2′-triisocyanate, dicyclohexylmethane-2,4,4′-triisocyanine lysine diisocyanate methyl ester, or these organic isocyanate compounds And a bifunctional isocyanate prepolymer obtained by reaction with a polyfunctional active hydrogen-containing compound. Among these, biscyclohexylmethane diisocyanate and hexamethylene diisocyanate are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

  The polyfunctional alcohol may be only one kind of polyfunctional alcohol, or may be mixed with other polyfunctional alcohols. Polyfunctional alcohols include glycols such as ethylene glycol, triethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and neopentyl glycol; diols such as butanediol, pentanediol, hexanediol, heptanediol, and tetramethylene glycol Such as bisphenols, compounds obtained by modifying these polyfunctional alcohols with polyethyleneoxy chain or polypropyleneoxy chain, triols such as glycerin, trimethylolpropane, butanetriol, pentanetriol, hexanetriol, decanetriol, etc. Examples include compounds obtained by modifying functional alcohols with polyethyleneoxy chains or polypropyleneoxy chains.

  The content of the matrix forming component in the optical recording composition of the present invention is preferably 10 to 95% by mass, and more preferably 35 to 90% by mass. If the content is 10% by mass or more, a stable interference image can be easily obtained, and if it is 95% by mass or less, desirable performance can be obtained in terms of diffraction efficiency.

For example, by applying the optical recording composition of the present invention on a substrate and leaving it at a high temperature, a curing reaction (polymerization reaction) proceeds between the polyfunctional isocyanate and the polyfunctional alcohol, and the polyurethane binder becomes It is formed. In the above reaction, the compound represented by the general formula (I) can be immobilized on the matrix via the above-described reactive group by the presence of the compound represented by the general formula (I). The polyurethane binder forming component may be cured by heat, or may be cured using a catalyst or the like. Examples of the catalyst that can be used in the polymerization reaction include a tin catalyst, a nitrogen-containing heterocycle, and an amine. What is necessary is just to determine the usage-amount of a catalyst suitably.
Examples of the tin catalyst include dimethyl dilaurate tin, dibutyl dilactate tin, stannous octoate, and the like.
Examples of the nitrogen-containing heterocycle include imidazole, pyridine, pyrazole and the like.
Examples of the amine include triethylamine, trioctylamine, N-methylmorpholine, and the like.

Other Components A polymerization inhibitor and an antioxidant may be added to the optical recording composition of the present invention as necessary for the purpose of improving the storage stability of the optical recording composition.
Examples of the polymerization inhibitor or the antioxidant include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, 2,6-ditertiary butyl-p-cresol, 2,2′-methylenebis (4-methyl-6-tertiary- Butylphenol), trifel phosphite, trisnonylphenyl phosphite, phenothiazine, N-isopropyl-N'-phenyl-p-phenylenediamine and the like.
The addition amount of the polymerization inhibitor or antioxidant is preferably 3% by mass or less based on the total amount of the recording monomer. When the amount added exceeds 3% by mass, the polymerization may be slowed or may not be polymerized in some cases.

A sensitizing dye can be added to the optical recording composition of the present invention as necessary. Examples of the sensitizing dye include “Research Disclosure, Vol. 200, December 1980, Item 20036” and “sensitizer” (p.160 to p.163, Kodansha; Katsumi Tokumaru and Nobu Okawara, edited by 1987. ) And the like can be used.
Specific examples of the sensitizing dye include a 3-ketocoumarin compound described in JP-A-58-15603, a thiopyrylium salt described in JP-A-58-40302, and JP-B-59-28328. The naphthothiazole merocyanine compound described in JP-A-60-53300, the merocyanine compound described in JP-B-61-9621, JP-A-62-2842, JP-A-59-89303, and JP-A-60-60104 Can be mentioned.
Further, the dyes described in “Functional dye chemistry” (1981, CMC Publishing Co., p.393 to p.416), “Coloring materials” (60 [4] 212-224 (1987)), and the like are also included. be able to. Specific examples include a cationic methine dye, a cationic carbonium dye, a cationic quinoneimine dye, a cationic indoline dye, and a cationic styryl dye.
In addition, coumarin (including ketocoumarin or sulfonocoumarin) dyes, melostyryl dyes, oxonol dyes, hemioxonol dyes, etc .; non-ketopolymethine dyes, triarylmethane dyes, xanthene dyes, anthracene dyes, rhodamine dyes, acridine dyes Non-keto dyes such as aniline dyes and azo dyes; Non-ketopolymethine dyes such as azomethine dyes, cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes, hemicyanine dyes, styryl dyes; azine dyes, oxazine dyes, thiazines Dyestuffs, quinoline dyes, quinoneimine dyes such as thiazole dyes, and the like are also included in the spectral sensitizing dyes.
The said sensitizing dye may be used individually by 1 type, and may be used in combination of 2 or more type.

The optical recording composition of the present invention may contain a photothermal conversion material for the purpose of improving the sensitivity of the recording layer formed from the optical recording composition.
The photothermal conversion material is not particularly limited and can be appropriately selected depending on the intended function and performance. For example, it can be easily added to the recording layer together with a photopolymer, or can cause scattering of incident light. Organic dyes are preferred from the standpoint of the absence of properties, and infrared absorbing dyes are preferred in that they do not absorb or scatter light from the light source used for recording.
The infrared absorbing dye is not particularly limited and may be appropriately selected depending on the intended purpose. Cationic dyes, complex salt-forming dyes, quinone neutral dyes, and the like are preferable. The maximum absorption wavelength of the infrared absorbing dye is preferably in the range of 600 to 1,000 nm, and more preferably in the range of 700 to 900 nm.
The content of the infrared absorbing dye can be determined by the absorbance of the wavelength having the highest absorbance in the infrared region in the recording layer formed from the optical recording composition of the present invention. As this light absorbency, the range of 0.1-2.5 is preferable, and the range of 0.2-2.0 is more preferable.

  In the optical recording composition of the present invention, if necessary, a component that diffuses in the direction opposite to the polymerization component may be added to relieve the volume change during polymerization, or an acid cleavage structure may be added. You may add separately the compound which has it in addition to a polymer.

  The optical recording composition of the present invention can be used as various holographic recording compositions capable of recording information by irradiation with light containing information, and is particularly suitable as a volume holographic recording composition. It is. A recording layer can be formed by applying the optical recording composition of the present invention onto a substrate, for example. Since the optical recording composition of the present invention contains a thermosetting compound as described above, the matrix can be formed by advancing the curing reaction by placing it under heating after coating. What is necessary is just to determine a heating condition according to the thermosetting compound to be used. If the optical recording composition has a sufficiently low viscosity, the recording layer can be formed by casting. On the other hand, if the viscosity is too high to be cast, a recording layer is placed on the lower substrate using a dispenser, and the recording layer is spread over the entire surface by pressing on the recording layer so as to cover the upper substrate. be able to.

[Holographic recording media]
The holographic recording medium of the present invention has a recording layer formed from the optical recording composition of the present invention. For example, a recording layer comprising the optical recording composition of the present invention can be formed by the above-described method.

  The holographic recording medium of the present invention contains a cyclic allyl sulfide compound represented by the general formula (I) in the recording layer. Since the compound represented by the general formula (I) has the reactive group, it can be bonded to the matrix during the matrix formation reaction (curing reaction), thereby improving the storage stability of the recording as described above. . Furthermore, since the cyclic allyl sulfide compound represented by the general formula (I) has a small volume shrinkage, the storage stability of recording can be improved without greatly degrading the multiple recording characteristics and the recording sensitivity. As a method for confirming that the recording layer contains the compound represented by the general formula (I), the recording layer portion is extracted with tetrahydrofuran (THF) or dioxane, and gas chromatography (GC) is used. Thus, a method for detecting the peak of the compound represented by the general formula (I) can be used. In addition, as a method for confirming the compound represented by the general formula (I) immobilized on the matrix, the compound represented by the general formula (I) and the matrix can be obtained by treating the recording layer with an acid or a base. And a method of cleaving a urethane bond, a urea bond or an ester bond that binds to each other.

  The content of the compound represented by the general formula (I) in the recording layer is preferably 0.1 to 20% by mass, similar to the content in the optical recording composition of the present invention. 10 mass% is more preferable, and 1-5 mass% is still more preferable. Further, the content of the compound represented by the general formula (IV) in the recording layer is also preferably 1 to 50% by mass, similarly to the content in the optical recording composition of the present invention, and 1 to 30% by mass. % Is more preferable, and 2 to 20% by mass is still more preferable. Details of each component in the recording layer of the holographic recording medium of the present invention are as described above for the optical recording composition of the present invention.

  The holographic recording medium of the present invention includes the recording layer (holographic recording layer), and preferably includes a lower substrate, a filter layer, a holographic recording layer, and an upper substrate. And other layers such as a reflective film, a filter layer, a first gap layer, and a second gap layer.

  The holographic recording medium of the present invention is capable of recording / reproducing information using the principle of hologram, and is a volume for recording a large amount of information such as a relatively thin planar hologram or a three-dimensional image for recording information such as two dimensions. It may be a hologram, and may be either a transmission type or a reflection type. The holographic recording medium of the present invention is suitable as a volume holographic recording medium for which high recording density is required because high capacity information recording is possible.

  Further, the recording method of the hologram on the holographic recording medium of the present invention is not particularly limited, and for example, an amplitude hologram, a phase hologram, a blazed hologram, a complex amplitude hologram, or the like may be used. Among these, information recording in the volume holographic recording area is performed by irradiating the volume holographic recording area with information light and reference light as a coaxial light beam, and recording information by an interference pattern due to interference between the information light and the reference light. The so-called collinear method is particularly preferable.

  Below, the detail of the board | substrate and each layer which may be contained in the holographic recording medium of this invention is demonstrated one by one.

-Board-
There is no restriction | limiting in particular about the shape, a structure, a magnitude | size, etc., a board | substrate can be suitably selected according to the objective. Examples of the shape include a disk shape and a card shape, and a material that can ensure the mechanical strength of the holographic recording medium should be selected. In addition, when light used for recording and reproduction enters through the substrate, it is preferable that the light is sufficiently transparent in the wavelength region of the light used.

  As the substrate material, glass, ceramics, resin, and the like are usually used, and resin is particularly preferable from the viewpoint of moldability and cost. Examples of the resin include polycarbonate resin, acrylic resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer, polyethylene resin, polypropylene resin, silicone resin, fluorine resin, ABS resin, urethane resin, and the like. Among these, polycarbonate resin and acrylic resin are particularly preferable from the viewpoints of moldability, optical characteristics, and cost. As a board | substrate, what was synthesize | combined suitably may be used and a commercial item may be used.

  The substrate is usually provided with a plurality of address-servo areas as linearly extending positioning areas at predetermined angular intervals, and a sector-shaped section between adjacent address-servo areas is a data area. . In the address-servo area, information for performing focus servo and tracking servo by the sampled servo method and address information are recorded in advance by embossed pits (servo pits) or the like (preformat). Note that the focus servo can be performed using the reflective surface of the reflective film. As information for performing the tracking servo, for example, a wobble pit can be used. In the case where the holographic recording medium has a card shape, the servo pit pattern may be omitted.

  There is no restriction | limiting in particular as thickness of a board | substrate, According to the objective, it can select suitably, 0.1-5 mm is preferable and 0.3-2 mm is more preferable. If the thickness of the substrate is 0.1 mm or more, the distortion of the shape during storage of the disc can be suppressed, and if it is 5 mm or less, the mass of the entire disc increases and an excessive load is applied to the drive motor. It can be avoided.

-Recording layer-
The recording layer is formed from the optical recording composition of the present invention, and information can be recorded using holography. There is no restriction | limiting in particular as thickness of a recording layer, According to the objective, it can select suitably. If the thickness of the recording layer is in the range of 1 to 1,000 μm, a sufficient S / N ratio can be obtained even if shift multiplexing of 10 to 300 is performed, and if it is in the range of 100 to 700 μm, this is remarkable. This is advantageous.

-Reflective film-
The reflective film can be formed on the servo pit pattern surface of the substrate.
As a material for the reflective film, a material having a high reflectance with respect to information light and reference light is preferably used. When the wavelength of light used as information light and reference light is 400 to 780 nm, for example, it is preferable to use Al, Al alloy, Ag, Ag alloy, or the like. When the wavelength of light used as information light and reference light is 650 nm or more, it is preferable to use Al, Al alloy, Ag, Ag alloy, Au, Cu alloy, TiN, or the like.
In addition, by using an optical recording medium that reflects light and can be added or erased as a reflective film, for example, a DVD (digital video disk), it is possible to rewrite to what area the hologram has been recorded. It is also possible to additionally write and rewrite directory information such as in which part an error exists and how the alternation process was performed without affecting the hologram.

The method for forming the reflective film is not particularly limited and can be appropriately selected according to the purpose. Various vapor deposition methods such as vacuum deposition, sputtering, plasma CVD, photo CVD, ion plating An electron beam evaporation method or the like is used. Among these, the sputtering method is excellent in terms of mass productivity and film quality.
The thickness of the reflective film is preferably 50 nm or more, and more preferably 100 nm or more so that sufficient reflectance can be achieved.

-Filter layer-
The filter layer can be provided on the servo pits of the substrate, on the reflective layer, or on the first gap layer described later.
The filter layer has a wavelength selective reflection function that reflects only light of a specific wavelength from among a plurality of types of light rays, transmits the first light, and reflects the second light. In particular, even if the incident angle changes, the selective reflection wavelength does not shift, and the function of preventing irregular reflection from the reflection film of the recording medium by the information light and the reference light and the generation of noise are also provided. By laminating filter layers, optical recording with high resolution and excellent diffraction efficiency can be performed.
There is no restriction | limiting in particular as a filter layer, According to the objective, it can select suitably, For example, a dichroic mirror layer, a coloring material containing layer, a dielectric material vapor deposition layer, a single layer or two or more cholesteric layers, and as needed It is possible to form a laminate in which at least one of the other layers appropriately selected is laminated. Although the thickness is not specifically limited, For example, it is about 0.5-20 micrometers.
The filter layer may be directly laminated on the substrate together with the recording layer or the like, or may be laminated on a substrate such as a film to produce a filter layer, which may be laminated on the substrate.

-First gap layer-
The first gap layer is provided between the filter layer and the reflective film as necessary, and is formed for the purpose of smoothing the lower substrate surface. It is also effective for adjusting the size of the hologram generated in the recording layer. That is, since it is necessary for the recording layer to form an interference area for the recording reference light and the information light to a certain extent, it is effective to provide a gap between the recording layer and the servo pit pattern.

The first gap layer can be formed, for example, by applying a material such as an ultraviolet curable resin on the servo pit pattern by spin coating or the like and curing it. Moreover, when using what apply | coated and formed on the transparent base material as a filter layer, this transparent base material will work | function also as a 1st gap layer.
There is no restriction | limiting in particular as thickness of a 1st gap layer, According to the objective, it can select suitably, 1-200 micrometers is preferable.

-Second gap layer-
The second gap layer is provided between the recording layer and the filter layer as necessary.
There is no restriction | limiting in particular as a material of a 2nd gap layer, According to the objective, it can select suitably, For example, a triacetyl cellulose (TAC), a polycarbonate (PC), a polyethylene terephthalate (PET), a polystyrene (PS) Transparent resin films such as polysulfone (PSF), polyvinyl alcohol (PVA), polymethyl methacrylate = polymethyl methacrylate (PMMA), etc., or JSR brand name ARTON film or Nippon Zeon brand name ZEONOR Examples thereof include norbornene resin films. Among these, those having high isotropic properties are preferred, and TAC, PC, trade name ARTON, and trade name ZEONOR are particularly preferred.
There is no restriction | limiting in particular as thickness of a 2nd gap layer, According to the objective, it can select suitably, 1-200 micrometers is preferable.
Hereinafter, the holographic recording medium of the present invention will be described in more detail based on specific embodiments. However, the present invention is not limited to the following specific embodiments.

<First embodiment>
FIG. 1 is a schematic cross-sectional view showing the configuration of the holographic recording medium according to the first embodiment. In the holographic recording medium 21 according to the first embodiment, a servo pit pattern 3 is formed on a polycarbonate resin substrate or glass substrate 1, and the servo pit pattern 3 is coated with aluminum, gold, platinum, or the like to be a reflective film 2 is provided. In FIG. 1, the servo pit pattern 3 is formed on the entire surface of the lower substrate 1. However, the servo pit pattern may be formed periodically. The height of the servo pit pattern 3 is usually 1750 mm (175 nm), which is sufficiently smaller than the thicknesses of the substrate and other layers.

  The first gap layer 8 is formed by applying a material such as an ultraviolet curable resin on the reflective film 2 of the lower substrate 1 by spin coating or the like. The first gap layer 8 is effective for protecting the reflective film 2 and adjusting the size of the hologram generated in the recording layer 4. That is, providing a gap between the recording layer 4 and the servo pit pattern 3 is effective for forming a recording reference light and information light interference region in the recording layer 4 to a certain size.

  A filter layer 6 is provided on the first gap layer 8, and a holographic recording medium 21 is configured by sandwiching the recording layer 4 between the filter layer 6 and the upper substrate 5 (polycarbonate resin substrate or glass substrate).

In FIG. 1, the filter layer 6 transmits only red light and does not transmit light of other colors. Therefore, since the information light, the recording and reproduction reference light are green or blue light, the light does not pass through the filter layer 6 and does not reach the reflection film 2 but becomes return light and is emitted from the incident / exit surface A. Become.
The filter layer 6 is a multilayer deposited film in which high refractive index layers and low refractive index layers are alternately stacked.
The filter layer 6 made of this multilayer deposited film may be directly formed on the first gap layer 8 by vacuum deposition, or a film in which the multilayer deposited film is formed on the substrate is punched into a holographic recording medium shape. May be.

  The holographic recording medium 21 in the present embodiment may have a disk shape or a card shape. In the case of a card shape, there is no need for the servo pit pattern. In the holographic recording medium 21, the lower substrate 1 is 0.6 mm, the first gap layer 8 is 100 μm, the filter layer 6 is 2 to 3 μm, the recording layer 4 is 0.6 mm, and the upper substrate 5 is 0.6 mm. The total thickness is about 1.9 mm.

Next, an optical system that can be used for recording and reproducing information on the holographic recording medium 21 will be described with reference to FIG.
First, light (red light) emitted from the servo laser is reflected almost 100% by the dichroic mirror 13 and passes through the objective lens 12. The servo light is irradiated onto the holographic recording medium 21 by the objective lens 12 so as to focus on the reflective film 2. That is, the dichroic mirror 13 transmits light having a wavelength of green or blue, and reflects light having a wavelength of red almost 100%. The servo light incident from the light incident / exit surface A of the holographic recording medium 21 passes through the upper substrate 5, the recording layer 4, the filter layer 6, and the first gap layer 8, is reflected by the reflective film 2, and again The first gap layer 8, the filter layer 6, the recording layer 4, and the upper substrate 5 are transmitted through the incident / exit surface A. The returned return light passes through the objective lens 12, is reflected almost 100% by the dichroic mirror 13, and servo information is detected by a servo information detector (not shown). The detected servo information is used for focus servo, tracking servo, slide servo, and the like. If the hologram material constituting the recording layer 4 is not sensitive to red light, even if the servo light passes through the recording layer 4 or the servo light is irregularly reflected by the reflective film 2, Has no effect. Further, since the return light of the servo light reflected by the reflection film 2 is reflected almost 100% by the dichroic mirror 13, the servo light is detected by the CMOS sensor or the CCD 14 for detecting the reproduced image. In addition, there is no noise with respect to the reproduction light.

  The information light and the recording reference light generated from the recording / reproducing laser pass through the polarizing plate 16 to become linearly polarized light, pass through the half mirror 17 and pass through the quarter wavelength plate 15. It becomes circularly polarized light. Through the dichroic mirror 13, the objective lens 12 irradiates the holographic recording medium 21 with information light and recording reference light so as to generate an interference pattern in the recording layer 4. The information light and the recording reference light enter from the incident / exit surface A and interfere with each other in the recording layer 4 to generate an interference pattern there. Thereafter, the information light and the recording reference light pass through the recording layer 4 and enter the filter layer 6, but are reflected to the bottom surface of the filter layer 6 to become return light. That is, the information light and the recording reference light do not reach the reflective film 2. This is because the filter layer 6 is a multilayer deposited layer in which a plurality of high refractive index layers and low refractive index layers are alternately stacked, and has a property of transmitting only red light.

<Second Embodiment>
FIG. 2 is a schematic cross-sectional view showing the configuration of the holographic recording medium according to the second embodiment. In the holographic recording medium 22 according to the second embodiment, a servo pit pattern 3 is formed on a polycarbonate resin or glass substrate 1, and the surface of the servo pit pattern 3 is coated with aluminum, gold, platinum, etc. Is provided. The height of the servo pit pattern 3 is the same as that of the first embodiment in that it is normally 1750 mm (175 nm).

  The difference in structure between the second embodiment and the first embodiment is that the second gap layer 7 is provided between the filter layer 6 and the recording layer 4 in the holographic recording medium 22 according to the second embodiment. It is that. The second gap layer 7 has a point where information light and reproduction light are focused. If this area is filled with a photopolymer, excessive consumption of monomers due to overexposure occurs, resulting in a decrease in multiple recording capability. Therefore, it is effective to provide a non-reactive and transparent second gap layer.

  A filter layer 6, which is a multilayer deposited film in which a plurality of high refractive index layers and low refractive index layers are alternately stacked, is formed on the first gap layer 8 after the first gap layer 8 is formed. The thing similar to embodiment can be used.

  In the holographic recording medium 22 of the second embodiment, the lower substrate 1 is 1.0 mm, the first gap layer 8 is 100 μm, the filter layer 6 is 3 to 5 μm, the second gap layer 7 is 70 μm, and the recording layer 4. Is 0.6 mm, the upper substrate 5 is 0.4 mm thick, and the total thickness is about 2.2 mm.

  Next, when information is recorded or reproduced, red servo light and green information light and recording and reproduction reference light are applied to the holographic recording medium 22 of the second embodiment having the above-described structure. Is irradiated. The servo light enters from the incident / exit surface A, passes through the recording layer 4, the second gap layer 7, the filter layer 6, and the first gap layer 8 and is reflected by the reflective film 2 to become return light. The return light again passes through the first gap layer 8, the filter layer 6, the second gap layer 7, the recording layer 4, and the upper substrate 5 in this order, and is emitted from the incident / exit surface A. The emitted return light is used for focus servo, tracking servo, and the like. If the hologram material constituting the recording layer 4 is not sensitive to red light, even if the servo light passes through the recording layer 4 or the servo light is irregularly reflected by the reflective film 2, Has no effect. Green information light or the like enters from the incident / exit surface A, passes through the recording layer 4 and the second gap layer 7, is reflected by the filter layer 6, and becomes return light. The return light again passes through the second gap layer 7, the recording layer 4 and the upper substrate 5 in this order, and exits from the incident / exit surface A. Also during reproduction, not only the reproduction reference light but also the reproduction light generated by irradiating the reproduction reference light onto the recording layer 4 is emitted from the incident / exit surface A without reaching the reflection film 2. The optical operation in the vicinity of the holographic recording medium 22 (the objective lens 12, the filter layer 6, the CMOS sensor or the CCD 14 as a detector in FIG. 3) is the same as in the first embodiment, and a description thereof will be omitted.

  Next, a method for recording information on the holographic recording medium of the present invention will be described. The recording layer formed from the optical recording composition of the present invention is irradiated with information light and reference light to form an interference image on the recording layer, and then the recording layer on which the interference image is formed. The interference image can be fixed by irradiating the fixing light. In the holographic recording medium of the present invention, during the polymerization reaction by irradiation with the recording light, the compound represented by the general formula (I) immobilized on the matrix and the radical polymerizable monomer are polymerized and bonded to each other. The radically polymerizable monomer can be immobilized on the matrix via this, thereby improving the storage stability of the recording.

  As information light, coherent light can be used. An interference image generated by the interference between the information light and the reference light by irradiating the recording medium with the information light and the reference light so that the optical axis of the information light and the optical axis of the reference light are coaxial. Can be recorded on the recording layer. Specifically, the information light provided with a two-dimensional intensity distribution and the information light and a reference light having a substantially constant intensity are superposed inside the recording layer, and recording is performed using an interference pattern formed by them. Information can be recorded by creating a distribution of optical properties within the layer. The wavelengths of the information light and the reference light are preferably 400 nm or more, more preferably 400 to 2000 nm, and particularly preferably 400 to 700 nm.

  After performing information recording (interference image formation) by irradiation with information light and reference light, the interference image can be fixed by irradiating with fixing light. The wavelength of the fixing light is preferably less than 400 nm, more preferably 100 nm or more and less than 400 nm, and particularly preferably 200 nm or more and less than 400 nm.

  Information can be reproduced by irradiating the interference light formed by the above method with reference light. When reading (reproducing) the written information, the recording layer is irradiated with only the reference light in the same arrangement as during recording, and the reproduction light having an intensity distribution corresponding to the optical characteristic distribution formed inside the recording layer is obtained. The light is emitted from the recording layer.

Next, an optical recording / reproducing apparatus suitably used for recording and reproducing information on the holographic recording medium of the present invention will be described with reference to FIG.
The optical recording / reproducing apparatus 100 shown in FIG. 4 maintains a spindle 81 to which the holographic recording medium 20 is attached, a spindle motor 82 for rotating the spindle 81, and the rotational speed of the holographic recording medium 20 at a predetermined value. A spindle servo circuit 83 that controls the spindle motor 82 is provided.

  The optical recording / reproducing apparatus 100 records information by irradiating the holographic recording medium 20 with information light and recording reference light, and irradiates the holographic recording medium 20 with reproduction reference light. A pickup 31 for detecting reproduction light and reproducing information recorded on the holographic recording medium 20, and a drive device 84 that enables the pickup 31 to move in the radial direction of the holographic recording medium 20. I have.

  The optical recording / reproducing apparatus 100 uses a detection circuit 85 for detecting a focus error signal FE, a tracking error signal TE, and a reproduction signal RF from an output signal of the pickup 31, and a focus error signal FE detected by the detection circuit 85. Based on this, the actuator in the pickup 31 is driven to move the objective lens (not shown) in the thickness direction of the holographic recording medium 20 to perform focus servo, and the tracking error detected by the detection circuit 85. Based on the signal TE, an actuator in the pickup 31 is driven to move the objective lens in the radial direction of the holographic recording medium 20 to perform tracking servo, a tracking error signal TE and a controller to be described later. It controls the drive unit 84 based on a command from over La and a slide servo circuit 88 for performing a slide servo for moving the pickup 31 in the radial direction of the holographic recording medium 20.

  The optical recording / reproducing apparatus 100 further decodes the output data of the CMOS or CCD array in the pickup 31 to reproduce the data recorded in the data area of the holographic recording medium 20 or the reproduction signal from the detection circuit 85. A signal processing circuit 89 that reproduces a basic clock from RF and discriminates an address; a controller 90 that controls the entire optical recording / reproducing apparatus 100; and an operation unit 91 that gives various instructions to the controller 90. I have. The controller 90 inputs the basic clock and address information output from the signal processing circuit 89, and controls the pickup 31, spindle servo circuit 83, slide servo circuit 88, and the like. The spindle servo circuit 83 receives the basic clock output from the signal processing circuit 89. The controller 90 includes a CPU (Central Processing Unit), a ROM (Read Only Memory), and a RAM (Random Access Memory), and the CPU executes a program stored in the ROM using the RAM as a work area. The function of the controller 90 can be realized.

  Hereinafter, the present invention will be further described based on examples. However, this invention is not limited to the aspect shown in the Example.

(Synthesis example of radically polymerizable monomer represented by general formula (IV))
Exemplified compounds M-17, M-18, M-46, M-47 and M-34 were synthesized according to the following scheme. By changing the synthesis raw materials and the like, various cyclic allyl sulfide compounds represented by the general formula (IV) can be synthesized according to the following scheme.

The identification results of the exemplary compounds synthesized by the above scheme are shown below.
M-17; ¹ H NMR (300 MHz, CDCl ₃ ) δ2.00 (s, 3H), 3.05 (m, 4H), 3.21 (s, 4H), 4.95 (m, 1H), 5.20 (s, 2H)
M-18; ¹ H NMR (300 MHz, CDCl ₃ ) δ 3.16 (d, 2H), 3.18 (d, 2H), 3.23 (s, 4H), 5.20 (s, 2H), 5.20 (m, 1H) , 7.30 (m, 3H), 8.0 (m, 3H)
M-46; ¹ H NMR (300 MHz, CDCl ₃ ) δ 3.16 (d, 2H), 3.18 (d, 2H), 3.24 (s, 4H), 5.20 (s, 2H), 5.22 (m, 1H) , 7.36 (m, 2H), 7.79 (dd, 1H), 7.80 (dd, 1H)
M-47; ¹ H NMR (300 MHz, CDCl ₃ ) δ 3.16 (d, 2H), 3.18 (d, 2H), 3.24 (s, 4H), 5.20 (s, 2H), 5.20 (m, 1H) , 7.30 (dd, 1H), 7.48 (d, 1H), 7.79 (d, 1H)
M-44; ¹ H NMR (300 MHz, CDCl ₃ ) δ2.00 (s, 3H), 2.80-3.80 (m, 7H), 4.10-4.30 (m, 2H), 4.85 (d, 2H)
M-34; ¹ H NMR (300 MHz, CDCl ₃ ) δ2.95 (m, 2H), 2.36 (s, 2H), 4.50 (m, 2H), 5.60 (s, 1H), 5.85 (s, 1H)

(Synthesis example of the compound represented by the general formula (I))
Exemplary compounds (A-4) and (A-5) were obtained as synthesis intermediates of the radical polymerizable monomer. The identification results are shown below. Exemplary compounds (A-15), (A-18), and (A-20) were also synthesized according to the above method.
A-4; ¹ H NMR (300MHz, CDCl ₃ ) δ2.60-3.80 (m, 9H), 4.80 (s, 2H)
A-5; ¹ H NMR (300 MHz, CDCl ₃ ) δ 2.18 (d, 1H), 2.90 (dd, 2H), 3.05 (dd, 2H), 3.19 (q, 4H), 3.92 (sept, 1H), 5.21 (s, 2H)

Example 1
-Preparation of composition for holographic recording-
31.5 g of biscyclohexylmethane diisocyanate, 61.2 g of polypropylene oxide triol (mass average molecular weight 1,000), 2.5 g of tetramethylene glycol, 0.6 g of exemplary compound A-4, 3.1 g of exemplary compound M-18, photopolymerization initiator Bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Irgacure 784, manufactured by Ciba Specialty Chemicals) 0.69 g and 1.01 g of dibutyl dilaurate tin were mixed under a nitrogen stream to prepare a holographic recording composition.

(Example 2)
-Preparation of composition for holographic recording-
In Example 1, a holographic recording composition was prepared in the same manner as in Example 1 except that the exemplified compound A-5 was used instead of the exemplified compound A-4.

(Example 3)
-Preparation of composition for holographic recording-
In Example 1, a holographic recording composition was prepared in the same manner as in Example 1 except that the exemplified compound A-15 was used instead of the exemplified compound A-4.

Example 4
-Preparation of composition for holographic recording-
In Example 1, a holographic recording composition was prepared in the same manner as in Example 1 except that Example Compound A-18 was used instead of Example Compound A-4.

(Example 5)
-Preparation of composition for holographic recording-
In Example 1, a holographic recording composition was prepared in the same manner as in Example 1 except that Example Compound A-20 was used instead of Example Compound A-4.

(Comparative Example 1)
-Preparation of composition for holographic recording-
31.5 g of biscyclohexylmethane diisocyanate, 61.2 g of polypropylene oxide triol (mass average molecular weight 1,000), 2.5 g of tetramethylene glycol, 3.1 g of exemplary compound M-18, photopolymerization initiator (Irgacure 784, Ciba Specialty) A holographic recording composition was prepared by mixing 0.69 g of Chemicals) and 1.01 g of dibutyl dilaurate tin under a nitrogen stream.

(Comparative Example 2)
-Preparation of composition for holographic recording-
31.5 g of biscyclohexylmethane diisocyanate, 61.2 g of polypropylene oxide triol (mass average molecular weight 1,000), 2.5 g of tetramethylene glycol, 0.6 g of exemplified compound A-5, the following compound R-1 (2, 4, 6 -Tribromophenyl acrylate) 3.1 g, photopolymerization initiator (Irgacure 784, manufactured by Ciba Specialty Chemicals) 0.69 g, and dibutyl dilaurate tin 1.01 g were mixed under a nitrogen stream to prepare a composition for holographic recording. A product was prepared.

(Examples 6 to 10 and Comparative Examples 3 and 4)
-Production of optical recording media-
An antireflection treatment was performed on one surface of 0.5 mm thick glass so that the reflectance by incident light perpendicular to the wavelength of 532 nm was 0.1%, and a first substrate was produced.
An aluminum deposition process was performed on one surface of 0.5 mm thick glass so that the reflectance by incident light perpendicular to the wavelength of 532 nm was 90%, and a second substrate was produced.
Next, a transparent polyethylene terephthalate sheet having a thickness of 500 μm was provided as a spacer on the surface of the first substrate not subjected to the antireflection treatment.
Next, the holographic recording compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were each placed on the first substrate, and the aluminum-deposited surface of the second substrate was aired on the holographic recording composition. The first substrate and the second substrate were bonded to each other through a spacer so as not to get caught. Thereafter, the optical recording mediums of Examples 6 to 10 and Comparative Examples 3 and 4 were produced by leaving at 45 ° C. for 24 hours. The thickness of the formed recording layer was 200 μm.

<Recording on optical recording media and evaluation>
Using the collinear hologram recording / reproduction tester (SHOT-1000 manufactured by Pulstec Industrial Co., Ltd.), a series of multiple holograms with a recording spot diameter of 200 μm at the focal position of the recording hologram was written on each of the produced optical recording media. Thus, the sensitivity (recording energy), the volumetric shrinkage of the medium, and the record storage stability were measured. The results are shown in Table 1.

-Measurement of sensitivity-
The irradiation light energy (mJ / cm ² ) at the time of recording was changed, and the change in the error probability (BER: Bit Error Rate) of the reproduction signal was measured. Usually, the luminance of the reproduction signal increases with the increase of irradiation light energy, and the BER of the reproduction signal tends to gradually decrease. Here, the lowest irradiation light energy at which a substantially good reproduced image (BER <10 ⁻³ ) can be obtained is defined as the recording sensitivity of the optical recording medium. The wavelength of recording light and reference light was 532 nm, and the wavelength of reproduction light was 532 nm.

-Volumetric shrinkage of medium-
As a means for analyzing the shrinkage and expansion of a photopolymer, a method of calculating from changes in interference fringes due to plane wave two-beam interference is known. In the FPR (Fringe Plane Rotation) model, the shrinkage of the recording layer that occurs between recording and playback due to the difference between the recording angle of the Bragg grating recorded obliquely on the recording medium and the optimum playback angle after recording (or after fixing) Can be evaluated. FIG. 5 shows a conceptual diagram of this model. It is assumed that the shrinkage change that occurs before and after recording is only in the thickness direction.
The change in the inclination of the interference fringes by the FPR model is expressed by the following equation.

Here, Φ and Φ ^* are inclinations of interference fringes during recording and reproduction, respectively, and α is a change rate of the recording layer.

  An interference fringe (6 mmφ) with a weak diffraction efficiency (˜1%) is recorded on a recording medium at a predetermined angle Φ by a plane wave two-beam interferometer of a 532 nm laser, and then exposure or fixing light irradiation (365 nm laser, spot diameter) of the recording medium 10 mmφ), the photoreactive component of the recording medium was completely consumed, the reproduction angle dependency of the diffraction efficiency was measured, and the angle of the interference fringes was measured again. The shrinkage rate α of the recording medium was estimated based on the formula (1) based on the change in the interference fringe inclination angle during recording and after exposure or fixing.

-Hologram recording storability-
Each optical recording medium on which the hologram was written was left in an oven at 85 ° C. for 24 hours, and the brightness of the recording was evaluated again with a collinear hologram recording / reproduction tester (manufactured by Pulstec Industrial Co., Ltd., SHOT-1000). Assuming that the initial brightness is μ _ON 0h and μ _ON 24h after 24 hours, the storability of the recording is expressed as a remaining rate expressed by Equation 2 below.
<Formula 2>
Residual rate (%) = (μ _ON 24h / μ _ON 24h) × 100

  From the results of Table 1, the optical recording media of Examples 6 to 10 using the holographic recording compositions of Examples 1 to 5 are the light of Comparative Example 3 using the holographic recording composition of Comparative Example 1. It is recognized that the recording storability is higher than that of the recording medium. Further, it was found that all of them had excellent recording sensitivity, small volume shrinkage, and high record storage stability as compared with the optical recording medium of Comparative Example 4 using the holographic recording composition of Comparative Example 2. It is done.

  Since the optical recording composition of the present invention can perform higher density recording, it is suitable for production of various volume hologram type optical recording media capable of high density image recording.

It is a schematic sectional drawing which shows an example of the holographic recording medium concerning 1st embodiment. It is a schematic sectional drawing which shows an example of the holographic recording medium concerning 2nd embodiment. It is explanatory drawing which shows an example of the optical system which can be used for recording and reproduction | regeneration of the information to a holographic recording medium. It is a block diagram showing an example of the whole structure of the recording / reproducing apparatus used suitably for the recording and reproduction | regeneration of the information to the holographic recording medium of this invention. The conceptual diagram of a FPR model is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Lower substrate 2 Reflective film 3 Servo pit pattern 4 Recording layer 5 Upper substrate 6 Filter layer 7 Second gap layer 8 First gap layer 12 Objective lens 13 Dichroic mirror 14 Detector 15 1/4 wavelength plate 16 Polarizing plate 17 Half Mirror 20 Holographic recording medium 21 Holographic recording medium 22 Holographic recording medium 31 Pickup 81 Spindle 82 Spindle motor 83 Spindle servo circuit 84 Drive device 85 Detection circuit 86 Focus servo circuit 87 Tracking servo circuit 88 Slide servo circuit 89 Signal processing circuit 90 Controller 91 Operation unit 100 Optical recording / reproducing device A Input / output surface FE Focus error signal TE Tracking error signal RF reproduction signal

Claims (8)

An optical recording composition comprising a polyfunctional isocyanate, a polyfunctional alcohol, a compound represented by the following general formula (I), and a compound represented by the following general formula (IV).
[In the general formula (I), R ₁ represents a hydrogen atom, an alkyl group, a hydroxy group, an amino group, a carboxy group, an acid anhydride or an isocyanate group, and Z ₁ represents an adjacent carbon atom, a sulfur atom and the sulfur atom. It represents an atomic group that forms a ring structure with the carbon atoms to which it is bonded. At least _one of R ₁ and Z ₁ has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride, and an isocyanate group. ]
[In the general formula (IV), R ₆ represents a hydrogen atom or an alkyl group, and Z ₂ represents an atomic group forming a ring structure with the adjacent carbon atom, sulfur atom, and carbon atom bonded to the sulfur atom. ] 2. The optical recording composition according to claim 1, wherein in general formula (I), at least _one of R ₁ and Z ₁ has at least one group selected from the group consisting of a hydroxy group and an amino group. 3. The optical recording composition according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).
[In general formula (II), R ₁ has the same definition as in general formula (I), R ₂₂ represents a hydrogen atom, alkyl group, hydroxy group, amino group, carboxy group, acid anhydride or isocyanate group, R ₂₃ , R ₂₄ and R ₂₅ are each independently a hydrogen atom, alkyl group, hydroxy group, amino group, carboxy group, acid anhydride, isocyanate group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group Represents an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an acyl group or a halogen group, and m2 represents 0 or 1. At least one of R ₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride and an isocyanate group. ] In general formula (II), R ₁ and R ₂₂ each independently represent a hydrogen atom or a methyl group, and R ₂₃ , R ₂₄ and R ₂₅ each independently represent a hydrogen atom, an alkyl group, a hydroxy group, an amino group, a carboxy group Group, acid anhydride, isocyanate group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, or acyl group, and R ₂₃ , R ₂₄ and R ₂₅ 4. The optical recording composition according to claim 3, wherein at least one has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an acid anhydride, and an isocyanate group. In general formula (II), R ₁ and R ₂₂ both represent a hydrogen atom, and R ₂₃ , R ₂₄ and R ₂₅ are each independently a hydrogen atom, an alkyl group, a hydroxy group, an amino group, a carboxy group or an acid anhydride. An isocyanate group, an aryl group, an alkoxy group, an aryloxy group or an acyloxy group, and at least one of R ₂₃ , R ₂₄ and R ₂₅ is a hydroxy group, an amino group, a carboxy group, an acid anhydride and an isocyanate group The optical recording compound according to claim 4, wherein the compound has at least one group selected from the group consisting of: The composition for optical recording according to any one of claims 1 to 5, further comprising a radical photopolymerization initiator. It is a composition for holographic recording, The composition for optical recording of any one of Claims 1-6. The holographic recording medium which has a recording layer formed from the composition for optical recording of any one of Claims 1-7.