JPWO2008123302A1 - Photosensitive composition for fluorine-containing volume hologram recording, photosensitive medium for fluorine-containing volume hologram recording and fluorine-containing volume hologram using the same - Google Patents

Abstract

The present invention relates to a photosensitive composition for fluorine-containing volume hologram recording having a larger refractive index modulation amount (Δn) than that of the prior art, and a photosensitive medium for fluorine-containing volume hologram recording and a fluorine-containing volume hologram using the same. provide. A curable fluorine-containing polymer comprising a base polymer (a), a liquid monomer (b), a photopolymerization initiator (c) and an organic solvent (f), wherein the base polymer (a) has a fluorine content of 26 to 80% by mass. The liquid monomer (b) contains at least one kind, and the liquid monomer (b) contains at least one liquid monomer (b1) that initiates polymerization by the active species generated from the photopolymerization initiator (c), and the photopolymerization initiator (c) contains , A compound that is sensitive to light having excellent coherence and initiates polymerization of the liquid monomer (b1), and the refractive index of the liquid monomer (b) is such that the base polymer (a) and the photopolymerization initiator (c ) And a fluorine-containing volume hologram recording photosensitive composition, which is higher than the average refractive index of a mixture thereof.

Description

  The present invention relates to a photosensitive composition for fluorine-containing volume hologram recording which is excellent in high refractive index modulation using a fluorine-containing polymer as a base polymer, a photosensitive medium for fluorine-containing volume hologram recording and a fluorine-containing volume type using the same. It relates to holograms.

  In general, in a hologram recording mechanism in a volume hologram material using a photopolymer utilizing photopolymerization, when interference light is incident on the material, a polymerization initiator is activated in a region where the light intensity is strong, and photopolymerization is started. In the region where the light intensity is high, the monomer is consumed by polymerization, and conversely, the monomer in the weak region diffuses and moves to the strong region. As a result, it is said that a difference in density of monomers is caused by the intensity of light intensity, which becomes a difference in refractive index and forms a hologram (for example, Japanese Patent No. 3330854).

  For example, DuPont has proposed a photopolymer composed of a thermoplastic binder resin, a photo-radical polymerizable monomer, and a photopolymerization initiator system, and has been partially commercialized.

  This is because a hologram is formed by the difference in refractive index between the low refractive index binder resin and the high refractive index photopolymerizable monomer containing an aromatic ring, and as a result, shows hologram performance such as high diffraction efficiency.

  However, although the monomer easily moves during interference exposure and the refractive index modulation increases, problems with heat resistance, mechanical properties, and transparency have been pointed out because a thermoplastic resin having a low glass transition temperature is used.

  Further, studies have been made to increase the refractive index modulation amount by combining a high refractive index aromatic ring-containing binder polymer and a low refractive index fluorine-containing monomer. Known examples used are, in particular, Japanese Patent Application Laid-Open Nos. 5-210343, 5-210344, and 5-257416. However, in this combination, since the polymerization reactivity is not sufficient, the sensitivity at the time of interference exposure is not so high. Although the addition of a polyfunctional acrylate to increase the polymerizability of the fluorine-containing monomer is also described, this method impairs the low refractive index inherent in the fluorine-containing monomer. Furthermore, in this combination, the strongly exposed portion where a polymer of fluorine-containing monomer is present in a high proportion is mechanically brittle, and the use of an aromatic ring-containing base polymer causes problems such as easy yellowing. is there.

  Further, as a known example using a combination of a low refractive index base polymer composed of a fluorine-containing acrylic monomer and an acrylic monomer containing no fluorine, and a high refractive index aromatic ring-containing monomer, JP-A-6-67588 is disclosed. is there. However, even in this example, the low refractive index property of the fluorine-containing acrylic monomer is impaired by copolymerization with an acrylic monomer that does not contain fluorine, and further, yellowing is likely to occur due to the aromatic ring of the aromatic ring-containing monomer. There is.

  In addition, by using only a fluorine-containing material for the base polymer, for example, Japanese Patent No. 2625028 states that “the presence of fluorine in the binder reduces the refractive index of the polymer, thereby forming an image including a hologram. Refractive index modulation is achieved in later films, which increases with increasing fluorine content, but the amount of fluorine present is limited because it does not cause the film to become opaque. The amount is achieved even if the effect is at a low level, such as 1%, but is typically in the range of about 3-25% " Fluorine-based polymer materials have poor compatibility when the fluorine content is high, and the refractive index drop due to the introduction of fluorine into the base polymer, which is the original purpose, is insufficient. Can not contain a monomer, in order not to have a light-scattering and cross-linked gel structure by poor compatibility, heat resistance, sensitivity and mechanical properties, can be or have drawbacks such as transparency of failure are described.

  In addition, some examples of fluorine-containing polymers are known (Japanese Patent No. 3370762, Japanese Patent Laid-Open No. 8-24026, Japanese Patent Laid-Open No. 8-272284), but all have the same drawbacks. ing.

  As an index indicating the performance of the volume hologram, there is a refractive index modulation amount (Δn). This value is calculated by Kogelnik's coupled wave theory. As described above, various volume hologram recording materials are known, and the refractive index modulation amount (Δn) showing the hologram performance is about 0.06 at the maximum, and is applied to a new optical element or the like. At this time, further improvement of the refractive index modulation amount (Δn) is desired.

  Also, considering the application to a wide range of fields such as optical elements, not only hologram recording performance such as refractive index difference, sensitivity, transparency, but also various performances including physical properties such as film strength and heat resistance. A sufficiently satisfying material system is desired.

  The present invention has been completed in view of the above circumstances, and a first object of the present invention is to provide a photosensitive composition for fluorine-containing volume hologram recording having a refractive index modulation amount (Δn) larger than that of the prior art, and It is an object of the present invention to provide a fluorine-containing volume hologram recording photosensitive medium and a fluorine-containing volume hologram used.

  In addition, the second object of the present invention is not only the hologram recording performance such as refractive index difference, sensitivity and transparency, but also the fluorine-containing volume hologram recording photosensitive material excellent in physical properties such as film strength and heat resistance. It is an object to provide a photosensitive composition, a photosensitive medium for recording a fluorine-containing volume hologram and a fluorine-containing volume hologram using the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that hologram recording such as refractive index difference, sensitivity, and transparency is not made opaque even if the fluorine content is increased and the refractive index property of the base polymer is lowered. The present inventors have found that an ideal fluorine-containing volume hologram recording photosensitive composition excellent not only in performance but also in physical properties such as film strength and heat resistance can be obtained.

That is, the present invention comprises a base polymer (a), a liquid monomer (b), a photopolymerization initiator (c) and an organic solvent (f),
The base polymer (a) contains at least one curable fluorine-containing polymer having a fluorine content of 26 to 80% by mass,
The liquid monomer (b) contains at least one liquid monomer (b1) that initiates polymerization with active species generated from the photopolymerization initiator (c),
The photopolymerization initiator (c) is a compound that is sensitive to light having excellent coherence and initiates polymerization of the liquid monomer (b1).
And the refractive index of liquid monomer (b) is higher than the average refractive index of the mixture of a base polymer (a) and a photoinitiator (c), The photosensitive composition for fluorine-containing volume hologram recording characterized by the above-mentioned Related to things.

In the present invention, the base polymer (a) is
The fluorine content is 26 to 80% by mass,
Formula (1):

［式中、構造単位Ｍ１は式（２）：

[Wherein the structural unit M1 is represented by the formula (2):

（式中、Ｘ¹およびＸ²は同じかまたは異なり、いずれもＨまたはＦ；Ｘ³はＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ⁴およびＸ⁵は同じかまたは異なり、いずれもＨ、ＦまたはＣＦ₃；Ｒｆ¹は炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ¹（Ｙ¹は末端にヒドロキシル基を有する炭素数０〜１０の１価の有機基、エチレン性炭素−炭素二重結合を有する炭素数２〜１０の１価の有機基または水素原子がフッ素原子で置換されていてもよい架橋性環状エーテル構造を１〜５個有する炭素数２〜１００の１価の有機基）が１〜３個結合している有機基；ａは０〜３の整数；ｂおよびｃは同じかまたは異なり、いずれも０または１である）
で示される含フッ素エチレン性単量体に由来する構造単位、
構造単位Ａ１は式（２）で示される含フッ素エチレン性単量体と共重合可能な単量体に由来する構造単位である］
で示され、
構造単位Ｍ１を０．１〜１００モル％および構造単位Ａ１を０〜９９．９モル％含み、数平均分子量が１００００より大きく、１００００００以下である硬化性含フッ素ポリマー、
式（３）：

(Wherein X ¹ and X ² are the same or different, both are H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and both are H, F Or CF ₃ ; Rf ¹ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms, Y ¹ (Y ¹ is a carbon atom having 0 to 10 carbon atoms having a hydroxyl group at the terminal) A monovalent organic group, a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond, or a crosslinkable cyclic ether structure in which a hydrogen atom may be substituted with a fluorine atom. An organic group in which 1 to 3 monovalent organic groups having 2 to 100 carbon atoms are bonded; a is an integer of 0 to 3; b and c are the same or different and both are 0 or 1 )
A structural unit derived from a fluorine-containing ethylenic monomer represented by:
The structural unit A1 is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (2)]
Indicated by
A curable fluorinated polymer containing 0.1 to 100 mol% of the structural unit M1 and 0 to 99.9 mol% of the structural unit A1 and having a number average molecular weight of more than 10,000 and 1,000,000 or less,
Formula (3):

［式中、構造単位Ｍ１は前記式（２）と同じ構造単位、
構造単位Ａ２は式（４）：

[In the formula, the structural unit M1 is the same structural unit as the formula (2),
The structural unit A2 is represented by the formula (4):

（式中、Ｘ⁶、Ｘ⁷およびＸ⁸は同じかまたは異なり、いずれもＨまたはＦ；Ｘ⁹はＨ、ＦまたはＣＦ₃；ｄは０〜２の整数；ｅは０または１；Ｒｆ²は炭素数１〜４０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を有する含フッ素アルキレン基；Ｚ¹は−ＯＨ、−ＣＨ₂ＯＨ、−ＣＯＯＨ、カルボン酸誘導体、−ＳＯ₃Ｈ、スルホン酸誘導体、エポキシ基、シアノ基、オキセタニル基、不飽和エステル基またはアミノ基である）
で示される構造単位、
構造単位Ａ３は式（５）：

(Wherein X ⁶ , X ⁷ and X ⁸ are the same or different, and all are H or F; X ⁹ is H, F or CF ₃ ; d is an integer of 0 to 2; e is 0 or 1; Rf ² Is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; Z ¹ is —OH, —CH ₂ OH, —COOH, a carboxylic acid derivative, —SO ₃ H, A sulfonic acid derivative, an epoxy group, a cyano group, an oxetanyl group, an unsaturated ester group or an amino group)
A structural unit represented by
The structural unit A3 is represented by the formula (5):

（式中、Ｘ¹⁰、Ｘ¹¹、Ｘ¹³は同じかまたは異なり、いずれもＨまたはＦ；Ｘ¹²はＨ、ＦまたはＣＦ₃、ｆ、ｇおよびｈは同じかまたは異なり、いずれも０または１；Ｚ²はＨ、ＦまたはＣｌ；Ｒｆ³は炭素数１〜２０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を含む含フッ素アルキレン基である）
で示される構造単位である］
で示され、
構造単位Ｍ１を０〜９０モル％、構造単位Ａ２を０〜１００モル％および構造単位Ａ３を０〜９９．９モル％含み、かつ構造単位Ｍ１と構造単位Ａ２を合計０．１〜１００モル％含み、数平均分子量が１００００より大きく、１００００００以下である硬化性含フッ素ポリマー、ならびに
式（６）：

(Wherein X ¹⁰ , X ¹¹ and X ¹³ are the same or different, all are H or F; X ¹² is H, F or CF ₃ , f, g and h are the same or different, and each is 0 or 1 ; Z ² is H, F or Cl; Rf ³ is a fluorine-containing alkylene group containing an ether bond or a fluorine-containing alkylene group having 2-100 carbon atoms of 1 to 20 carbon atoms)
Is a structural unit represented by
Indicated by
The structural unit M1 is 0 to 90 mol%, the structural unit A2 is 0 to 100 mol%, the structural unit A3 is 0 to 99.9 mol%, and the structural unit M1 and the structural unit A2 are 0.1 to 100 mol% in total. A curable fluorinated polymer having a number average molecular weight of greater than 10,000 and no greater than 1,000,000, as well as formula (6):

［式中、構造単位Ｍ２は式（７）：

[Wherein the structural unit M2 is represented by the formula (7):

（式中、Ｘ¹⁴およびＸ¹⁵は同じかまたは異なり、いずれもＨまたはＦ；Ｘ¹⁶はＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ¹⁷およびＸ¹⁸は同じかまたは異なり、いずれもＨ、ＦまたはＣＦ₃；Ｒｆ⁴は炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ²（Ｙ²は、
式（８）：

Wherein X ¹⁴ and X ¹⁵ are the same or different, both H or F; X ¹⁶ is H, F, CH ₃ or CF ₃ ; X ¹⁷ and X ¹⁸ are the same or different and both H, F or CF _3; Rf ⁴ is Y ² (Y ² to a fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group or a 2 to 100 carbon atoms 1 to 40 carbon atoms,
Formula (8):

（式中、Ｒ¹およびＲ²は同じかまたは異なり、いずれもフッ素原子で置換されていてもよい炭素数１〜７の２価の有機基；Ｘ¹⁹はＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ²⁰およびＸ²¹は同じかまたは異なり、いずれもＨまたはＦ；ｌおよびｍは同じかまたは異なり、いずれも０または１である）
で示される炭素数３〜１０の有機基、
式（９）：

(In the formula, R ¹ and R ² are the same or different, and each is a C 1-7 divalent organic group optionally substituted with a fluorine atom; X ¹⁹ is H, F, CH ₃ or CF _3. X ²⁰ and X ²¹ are the same or different, both H or F; and l and m are the same or different, both are 0 or 1);
An organic group having 3 to 10 carbon atoms represented by:
Formula (9):

（式中、Ｘ²²およびＸ²³は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数２〜１００の有機基、
式（１０）：

(In the formula, X ²² and X ²³ are the same or different, and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
An organic group having 2 to 100 carbon atoms and having 1 to 5 crosslinkable cyclic ether structures represented by:
Formula (10):

（式中、Ｑは炭素数３〜１００の単環構造、複環構造または複素環構造の水素原子が前記Ｘ²²またはＸ²³で置換されていてもよい１価または２価の有機基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基、
式（１１）：

(In the formula, Q is a monovalent or divalent organic group in which a hydrogen atom of a monocyclic structure, a polycyclic structure or a heterocyclic structure having 3 to 100 carbon atoms may be substituted with X ²² or X ^23. )
An organic group having 3 to 100 carbon atoms and having 1 to 5 crosslinkable cyclic ether structures represented by:
Formula (11):

（式中、Ｘ²⁴〜Ｘ²⁸は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基、または
式（１２）：

(Wherein, X ^{24 to} X ²⁸ are the same or different, and all are H, F, a C 1-6 alkyl group or a C 1-6 fluorinated alkyl group)
An organic group having 3 to 100 carbon atoms having 1 to 5 crosslinkable cyclic ether structures represented by formula (12):

（式中、Ｘ²⁹〜Ｘ³²は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基である）が１〜３個結合している有機基；ｉは０〜３の整数；ｊおよびｋは同じかまたは異なり、いずれも０または１である）
で示される含フッ素エチレン性単量体に由来する構造単位、
構造単位Ａ４は該式（７）で示される含フッ素エチレン性単量体と共重合可能な単量体に由来する構造単位である］
で示され、構造単位Ｍ２を０．１〜１００モル％および構造単位Ａ４を０〜９９．９モル％含み、数平均分子量が１００００より大きく、１００００００以下である硬化性含フッ素ポリマー
よりなる群から選ばれた少なくとも１種の硬化性含フッ素ポリマーを含むことが好ましい。

(In the formula, X ^{29 to} X ³² are the same or different and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
An organic group having 1 to 5 crosslinkable cyclic ether structures represented by the above formula and having 3 to 100 carbon atoms), i is an integer of 0 to 3; j and k are the same Or both are 0 or 1)
A structural unit derived from a fluorine-containing ethylenic monomer represented by:
Structural unit A4 is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (7)]
The structural unit M2 is 0.1 to 100 mol% and the structural unit A4 is 0 to 99.9 mol%, and the number average molecular weight is greater than 10,000 and less than 1,000,000. It is preferable to include at least one selected curable fluorine-containing polymer.

  Moreover, it is preferable that the liquid monomer (b) includes two or more types of monomers, and at least one of the monomers has a polyether structure and has a molecular weight of 1000 or less.

  Furthermore, it is preferable that the liquid monomer (b) contains two or more monomers, and at least one of the monomers is a polyfunctional monomer.

  The composition of the present invention may further contain a polyfunctional unsaturated compound (d) that undergoes a crosslinking reaction with the crosslinking site in the base polymer (a) by heat.

  The composition of the present invention may further contain a dye sensitizer (e).

  The present invention is also a fluorine-containing volume hologram recording photosensitive medium in which an optical recording layer is formed on a substrate film, and the optical recording layer is formed from the fluorine-containing volume hologram recording photosensitive composition. The present invention relates to a fluorine-containing volume hologram recording photosensitive medium which is an optical recording layer having a thickness of 1 to 180 μm.

  Furthermore, the present invention is a fluorine-containing volume hologram in which an optical recording layer is formed on a substrate film, and the optical recording layer is formed from the photosensitive composition for fluorine-containing volume hologram recording with a thickness of 1 The present invention also relates to a fluorine-containing volume hologram which is an optical recording layer of ˜180 μm.

In this invention, it is a schematic explanatory drawing of the transmission type hologram optical system apparatus used in order to measure the refractive index modulation amount.

  The composition of the present invention is used for a fluorine-containing volume hologram recording photosensitive material used for recording interference fringes generated by light interference having excellent coherence as fringes having different refractive indexes. It contains a polymer (a), a liquid monomer (b), a photopolymerization initiator (c) and an organic solvent (f).

  Light with excellent coherence is light obtained by passing monochromatic light such as laser light or sodium lamp light through a pinhole, but it is light with very high coherence both spatially and temporally. From the viewpoint, laser light is preferable.

  The base polymer (a) contains a fluorine-containing monomer as a structural unit from the viewpoint that the difference in refractive index from other monomers can be increased. In addition, the base polymer (a) has excellent compatibility with other monomers, photopolymerization initiators, and dye sensitizers even when the fluorine content is high, and can improve the refractive index difference, sensitivity, and transparency. From the point, it is an amorphous polymer and is different from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and the like.

  The fluorine content of the base polymer (a) is 26 to 80% by mass, preferably 30 to 65% by mass. If the fluorine content of the base polymer (a) is small, there is a problem that the difference in refractive index is small and the diffraction efficiency and sensitivity are lacking. If it is large, uniform hologram interference fringes cannot be formed, and each hologram composition is phase-separated. Or there is a problem that light scattering occurs.

  The base polymer (a) may be a polymer having a cross-linked site or a polymer having no cross-linked site. However, the base polymer (a) is cross-linked from the viewpoint of excellent sensitivity, hologram stability, light resistance, and mechanical strength. Polymers having sites are preferred.

［式中、構造単位Ｍ１は式（２）：

（式中、Ｘ¹およびＸ²は同じかまたは異なり、いずれもＨまたはＦ；Ｘ³はＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ⁴およびＸ⁵は同じかまたは異なり、いずれもＨ、ＦまたはＣＦ₃；Ｒｆ¹は炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ¹（Ｙ¹は末端にヒドロキシル基を有する炭素数０〜１０の１価の有機基、エチレン性炭素−炭素二重結合を有する炭素数２〜１０の１価の有機基または水素原子がフッ素原子で置換されていてもよい架橋性環状エーテル構造を１〜５個有する炭素数２〜１００の１価の有機基）が１〜３個結合している有機基；ａは０〜３の整数；ｂおよびｃは同じかまたは異なり、いずれも０または１である）
で示される含フッ素エチレン性単量体に由来する構造単位、構造単位Ａ１は該式（２）で示される含フッ素エチレン性単量体と共重合可能な単量体に由来する構造単位である］
で示され、
構造単位Ｍ１を０．１〜１００モル％および構造単位Ａ１を０〜９９．９モル％含み、数平均分子量が１００００〜１００００００である硬化性含フッ素ポリマーがあげられる。Specific examples of preferable base polymer (a) include, for example, formula (1):

[Wherein the structural unit M1 is represented by the formula (2):

(Wherein X ¹ and X ² are the same or different, both are H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and both are H, F Or CF ₃ ; Rf ¹ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms, Y ¹ (Y ¹ is a carbon atom having 0 to 10 carbon atoms having a hydroxyl group at the terminal) A monovalent organic group, a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond, or a crosslinkable cyclic ether structure in which a hydrogen atom may be substituted with a fluorine atom. An organic group in which 1 to 3 monovalent organic groups having 2 to 100 carbon atoms are bonded; a is an integer of 0 to 3; b and c are the same or different and both are 0 or 1 )
The structural unit derived from the fluorine-containing ethylenic monomer represented by the formula, the structural unit A1 is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (2). ]
Indicated by
Examples thereof include a curable fluorinated polymer containing 0.1 to 100 mol% of the structural unit M1 and 0 to 99.9 mol% of the structural unit A1 and having a number average molecular weight of 10,000 to 1,000,000.

（式中、Ｘ¹〜Ｘ⁵、Ｒｆ¹、ａ〜ｃは式（２）と同じである）
で示される含フッ素エチレン性単量体に由来する構造単位である。The structural unit M1 is represented by the formula (13):

(Wherein, X ^{1 to} X ⁵ , Rf ¹ and a to c are the same as those in the formula (2))
Is a structural unit derived from a fluorine-containing ethylenic monomer represented by

  That is, a homopolymer of a fluorine-containing ethylenic monomer having a hydroxyl group curable by reaction and an ethylenic carbon-carbon double bond in the side chain, or the fluorine-containing ethylenic monomer as an essential component. As a copolymer.

At least one of Y ¹ is preferably bonded to the end of Rf ¹ .

（式中、Ｘ¹〜Ｘ⁵、Ｒｆ¹、ａおよびｃは式（２）と同じである）
で示される構造単位である。In the base polymer represented by the formula (1), the structural unit M1 is preferably M1-1, and M1-1 is represented by the formula (14):

(Wherein, X ^{1 to} X ⁵ , Rf ¹ , a and c are the same as those in formula (2))
Is a structural unit represented by

（式中、Ｘ¹〜Ｘ⁵、Ｒｆ¹、ａおよびｃは式（２）と同じである）
で示される含フッ素エチレン性単量体に由来する構造単位である。The structural unit M1-1 is represented by the formula (15):

(Wherein, X ^{1 to} X ⁵ , Rf ¹ , a and c are the same as those in formula (2))
Is a structural unit derived from a fluorine-containing ethylenic monomer represented by

（式中、Ｘ¹〜Ｘ⁵、ａおよびｃは式（２）と同じ；Ｒｆ^1'は炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ³（Ｙ³は末端にヒドロキシル基または、エチレン性炭素−炭素二重結合を有する炭素数２〜１０の１価の有機基である）が１〜３個結合している有機基である）
で示される含フッ素不飽和化合物であって、Ｙ³が式（１７）：
−（Ｏ）_n−（Ｃ＝Ｏ）−Ｙ⁴
（式中、Ｙ⁴は末端にヒドロキシル基または、エチレン性炭素−炭素二重結合を有する炭素数２〜５のアルケニル基または含フッ素アルケニル基；ｎは０または１である）
で示される有機基である含フッ素不飽和化合物などもあげられる。Among the fluorine-containing unsaturated compounds represented by the formula (15), the formula (16):

(Wherein, X ^{1 to} X ⁵ , a and c are the same as those in formula (2); Rf ^{1 ′} is a fluorine-containing alkyl group having 1 to 40 carbon atoms or an ether bond having 2 to 100 carbon atoms. Y ³ (Y ³ is a hydroxyl group or a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond) at the terminal is an organic group having 1 to 3 bonded thereto. )
In which Y ³ is represented by the formula (17):
-(O) _n- (C = O) -Y ⁴
(In the formula, Y ⁴ is a hydroxyl group or an alkenyl group having 2 to 5 carbon atoms or a fluorine-containing alkenyl group having an ethylenic carbon-carbon double bond at the end; n is 0 or 1)
And a fluorine-containing unsaturated compound which is an organic group represented by

  The polymer containing the structural unit M1-1 has a particularly low refractive index, and in particular, even in a polymer having a composition obtained by increasing the M1-1 homopolymer or M1-1, the refractive index can be lowered. is there.

（式中、Ｒｆ¹は式（２）と同じである）
で示される構造単位である。Furthermore, a more preferable specific example of M1-1 is the structural unit M1-2, and the structural unit M1-2 is represented by the formula (18):

(Wherein Rf ¹ is the same as in formula (2))
Is a structural unit represented by

（式中、Ｒｆ¹は式（２）と同じである）
で示される含フッ素エチレン性単量体に由来する構造単位である。なお、式（１９）で示される含フッ素不飽和化合物のなかで、式（２０）：

（式中、Ｒｆ^1'は式（１６）と同じである）
で示される含フッ素不飽和化合物などもあげられる。The structural unit M1-2 is represented by the formula (19):

(Wherein Rf ¹ is the same as in formula (2))
Is a structural unit derived from a fluorine-containing ethylenic monomer represented by Among the fluorine-containing unsaturated compounds represented by the formula (19), the formula (20):

(Wherein Rf ^{1 ′} is the same as in formula (16))
And a fluorine-containing unsaturated compound represented by the formula:

  That is, the above-mentioned M1-2 is a structural unit of a fluorine-containing allyl ether having a hydroxyl group or an ethylenic carbon-carbon double bond at the end, and not only has a low refractive index but also has a good polymerizability, The polymerizability and the copolymerizability with the fluorine-containing ethylene monomer are favorable, which is preferable.

（式中、Ｒｆ¹は式（２）と同じである）
で示される構造単位である。Another preferred specific example of M1 is the structural unit M1-3, and the structural unit M1-3 is represented by the formula (21):

(Wherein Rf ¹ is the same as in formula (2))
Is a structural unit represented by

（式中、Ｒｆ¹は式（２）と同じである）
で示される含フッ素エチレン性単量体に由来する構造単位である。なお、式（２２）で示される含フッ素不飽和化合物のうち、式（２３）：

（式中、Ｒｆ^1'は式（１６）と同じである）
で示される含フッ素不飽和化合物などもあげられる。The structural unit M1-3 is represented by the formula (22):

(Wherein Rf ¹ is the same as in formula (2))
Is a structural unit derived from a fluorine-containing ethylenic monomer represented by Of the fluorine-containing unsaturated compounds represented by the formula (22), the formula (23):

(Wherein Rf ^{1 ′} is the same as in formula (16))
And a fluorine-containing unsaturated compound represented by the formula:

  The M1-3 is a structural unit of a fluorine-containing vinyl ether having a hydroxyl group or an ethylenic carbon-carbon double bond at the end, can have a low refractive index, and is copolymerizable with a fluorine-containing ethylene monomer. It is preferable in that it is good.

In the base polymer (a) represented by the formula (1), Y ¹ contained in the structural units M1, M1-1, M1-2, and M1-3 is a monovalent C 0-10 having a hydroxyl group at the terminal. An organic group or an organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond.

That is, the hydroxyl group in Y ¹ has the ability to cause urethane reaction, epoxy reaction, hydrosilation reaction, etc., and the carbon-carbon double bond performs polycondensation reaction, cyclization reaction, addition reaction, etc. It has the ability to raise, and can obtain a cured (crosslinked) body. Specifically, for example, between the curable fluorine-containing polymer molecules of the present invention by contact with isocyanates, radicals, cations, and amides, or between the curable fluorine-containing polymer and a curing (crosslinking) agent added as necessary. A cured (crosslinked) product can be obtained by causing a polymerization reaction, a condensation reaction, and an addition reaction.

In the curable fluorine-containing polymer represented by the formula (1), Y ¹ is preferably a formula (24):
-(O) _o- (C = O) _p -Y ⁵
(In the formula, Y ⁵ is a hydroxyl group at the terminal, or an alkenyl group having 2 to 5 carbon atoms or a fluorine-containing alkenyl group having an ethylenic carbon-carbon double bond; o and p are the same or different, and both are 0 or 1)
Y ⁵ is preferably represented by formula (25):
-CX ³³ = CX ³⁴ X ³⁵
(Wherein X ³³ is H, F, CH ₃ or CF ₃ ; X ³⁴ and X ³⁵ are the same or different and both are H or F)
Or -OH
It has a high curing reactivity due to contact with isocyanates, radicals, cations, and amides.

Y ⁴ in the base polymer (a) represented by the formulas (17), (20) and (23) is preferably the same as Y ⁵ described above.

Preferred examples of Y ⁴ and Y ⁵ include, for example, —CH═CH ₂ , —CF═CH ₂ , —C (CH ₃ ) ═CH ₂ , —CF═CF ₂ , —C (CF ₃ ) ═CH _{2, -CH = CHF, -CH 2} -OCOCH = CH 2, such as -CH ₂ -OH and the like.

As preferred specific examples of Y ¹ and Y ³ , for example, formula (26):
-OCOCX ³³ = CX ³⁴ X ³⁵
(Wherein X ^{33 to} X ³⁵ are the same as in formula (25)),
formula:
—CH ₂ —OCOCH═CH ₂
In particular, it is preferable in terms of higher curing reactivity due to contact with radicals, and is preferable in that a cured product can be easily obtained by photocuring or the like.

More preferred examples of the Y ¹ and Y ^3, for _{example, -OCOCH = CH 2, -OCOC (} CH 3) = CH 2, -OCOCF = CH 2, -OCOC (CF 3) = CH 2, -OCOCF ═CF ₂ , —CH ₂ —OCOCH═CH _{2 and the} like.

Other examples of Y ¹ include -CH = CH ₂ , -CH ₂ CH = CH ₂ , -OCH ₂ CH = CH ₂ , -OCH = CH ₂ , -OCF = CF ₂ , -COOCH = CH ₂ ,- COOCH ₂ CH═CH ₂ , —CH (OH) CH ₂ OCOCX ³⁶ ═CH ₂ (X ³⁶ : H, F or CH ₃ ), —CH (OCOCX ³⁷ ═CH ₂ ) CH ₂ OCOCX ³⁸ ═CH ₂ (X ³⁷ , X ^38: H, F or _{CH 3), - CH (OH} ) CH 2 OCH 2 CH = CH 2, -CH (OCH 2 CH = CH 2) CH 2 OCH 2 CH = CH 2, -CH 2 -OCOCH ═CH _{2 and the} like.

Other examples of Y ³ include —COCH═CH ₂ , —CH (OH) CH ₂ OCOCX ³⁹ ═CH ₂ (X ³⁹ : H, F or CH ₃ ), —CH (OCOCX ⁴⁰ ═CH ₂ ) CH ₂ OCOCX ⁴¹ ═CH ₂ (X ⁴⁰ , X ⁴¹ : H, F or CH ₃ ).

Among them, those having a structure of —OCOCF═CH ₂ , —CH ₂ —OCOCH═CH ₂ , —CH ₂ —OH can lower the refractive index, and further have a particularly high curing (crosslinking) reactivity and efficiently produce a cured product. It is preferable in that it can be obtained.

  In the photosensitive composition for fluorine-containing volume hologram optical recording of the present invention, the curable fluorine-containing polymer in which the side chain terminal of the base polymer (c) is acrylic-modified with α-fluoroacrylates or acrylic isocyanates, It has a mechanism for trapping radicals derived from photopolymerization initiators, and can suppress curing shrinkage during photoreaction.

In the base polymer (a) represented by the formula (1), preferred organic groups other than Rf ¹ , Rf ^{1 ′} , Y ¹ , Y ³ , Y ⁴ , Y ⁵ are particularly functional groups Y ¹ , Y ³ , If Y ⁵ is one, the number 1 to 40 of a fluorine-containing alkylene group having a carbon is a fluorine-containing alkylene group having ether bond having 2-100 carbon atoms. These organic groups only need to have a fluorine atom bonded to the carbon atom contained, and are generally a fluorine-containing alkylene group in which a fluorine atom and a hydrogen atom or a chlorine atom are bonded to a carbon atom, or a fluorine-containing alkylene group having an ether bond. However, those containing more fluorine atoms (high fluorine content) are preferred, and the fluorine content is 50% or more, preferably 70% or more, relative to the molecular weight excluding oxygen atoms of the organic group excluding the functional group, More preferred is a perfluoroalkylene group or a perfluoroalkylene group having an ether bond. By these, it becomes possible to lower the refractive index of the curable fluorine-containing polymer, and it is preferable because the refractive index can be kept low even if the degree of curing (crosslinking density) is increased for the purpose of increasing the hardness of the cured product.

  If the number of carbon atoms is too large, in the case of a fluorine-containing alkylene group, the compatibility with the hologram component may be reduced, or the transparency of the hologram may be reduced. In addition, in the case of a fluorine-containing alkylene group having an ether bond, the polymer This is not preferable because it may reduce the hardness and mechanical properties of itself and its cured product. Carbon number of a fluorine-containing alkylene group becomes like this. Preferably it is 1-20, More preferably, it is 1-10. The carbon number of the fluorine-containing alkylene group having an ether bond is preferably 2 to 30, more preferably 2 to 20.

（Ｘ⁴²、Ｘ⁴³：ＦまたはＣＦ₃；Ｘ⁴⁴、Ｘ⁴⁵：ＨまたはＦ；ｔ＋ｕ＋ｖ：１〜３０の整数；ｗ：０または１；ｘ、ｙ：０または１）
などがあげられる。As a preferable specific example, for example,

(X ^42, X ^43: F or _{^{CF 3; X 44, X 45}} : H or F; t + u + v: 1~30 integer; w: 0 or 1; x, y: 0 or 1)
Etc.

  The structure of the structural unit M1 constituting the base polymer (a) used in the present invention and specific examples of the base polymer (a) will be described.

Preferable specific examples of the monomer that gives the structural unit M1-2 include, for example, CH ₂ ═CFCF ₂ OCF (CF ₃ ) Y ¹ , CH ₂ ═CFCF ₂ OCF (CF ₃ ) CH ₂ Y ¹ , CH ₂ = CFCF ₂ OCF (CF ₃ ) CH ₂ OY ¹ , CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _z CF (CF ₃ ) Y ¹ , CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF _{2 O) z CF (CF 3} ) CH 2 Y 1, CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) z CF (CF 3) CH 2 OCH 2 CHY 1 CH 2 Y 1, CH 2 = CFCF ₂ O (CF ₂ CF ₂ O) _z CF ₂ Y ¹ , CH ₂ = CFCF ₂ O (CF ₂ CF ₂ O) _z CF ₂ CH ₂ Y ¹ , CH ₂ = CFCF ₂ O (CF ₂ CF ₂ CF ₂ O) _z CF ₂ CF ₂ Y ¹ , CH ₂ = CFCF ₂ O (CF ₂ CF ₂ CF ₂ O) _z CF ₂ CF ₂ CH ₂ Y ¹ , CH ₂ = CFCF ₂ O (CH ₂ CF ₂ CF ₂ O) _z CH ₂ CF ₂ Y ¹ , CH ₂ = CFCF ₂ O (CH ₂ CF ₂ CF ₂ O) _z CH ₂ CF ₂ CH ₂ Y ¹ , CH ₂ = CFCF ₂ O (CF ₂ CF ₂ ) _z Y ¹ , CH ₂ = CFCF ₂ O (CF ₂ CF (CF ₃ )) _z CH ₂ Y ¹ (z: integer from 1 to 30) More specifically, CH ₂ ═CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _z CF (CF ₃ ) CH ₂ OCOCX ⁴⁶ ═CH ₂ , CH ₂ ═CFCF ₂ O (CF (CF _{3) CF 2 O) z CF} (CF 3) CH 2 OCH 2 CH (OCOCX 46 = CH 2) CH 2 OCOCX 46 = CH 2, CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) z CF _{(CF 3) CH 2 OCH =} CH 2, CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) z CF _{CF 3) CH 2 OCH 2 CH} (OCH = CH 2) OCH = CH 2, CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) z CF = CF 2, CH 2 = CFCF 2 O (CF ( CF ₃ ) CF ₂ O) _z CF (CF ₃ ) COOCH═CH ₂ , CH ₂ ═CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _z CF (CF ₃ ) CH ₂ OCH ₂ CH═CH ₂ , CH _{2 = CFCF 2 O (CF (} CF 3) CF 2 O) z CF (CF 3) CH 2 OCH 2 CH (OCH 2 CH = CH 2) CH 2 OCH 2 CH = CH 2, CH 2 = CFCF 2 O ( _{CF (CF 3) CF 2 O} ) z CF (CF 3) CRf 5 Rf 6 OCOCX 46 = CH 2, CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) z CF (CF 3) C (CH ₂ CH═CH ₂ ) ₂ OCOCX ⁴⁶ ═CH ₂ (X ⁴⁶ : H, CH ₃ , F or CF ₃ , Rf ⁵ , Rf ⁶ : a C 1-5 perfluoroalkyl group, z: an integer of 0-30, and the like.

Preferred examples of the base polymer (a) represented by the formula (20) include those in which Y ¹ is replaced with Y ³ in the examples of the monomer that gives the structural unit M1-2.

More specifically, CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _z CF (CF ₃ ) CH ₂ OCOCX ⁴⁶ = CH ₂ , CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _{z CF (CF 3) CH 2} OCH 2 CH (OCOCX 46 = CH 2) CH 2 OCOCX 46 = CH 2, CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) z CF (CF 3) CRf 5 _{^{Rf 6 OCOCX 46 = CH 2,}} CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) z CF (CF 3) C (CH 2 CH = CH 2) 2 OCOCX 46 = CH 2 (X 46, Rf ⁵ , Rf ⁶ , z: the same as above).

Preferable specific examples of the monomer that gives the structural unit M1-3 include, for example, CF ₂ = CFOCF ₂ CF ₂ Y ¹ , CF ₂ = CFOCF ₂ CF ₂ CH ₂ Y ¹ , CF ₂ = CFOCF ₂ CF ₂ CH _{2 ^{OCH 2 CHCH 2 Y 1, CF}} 2 = CFOCF 2 CF 2 CH 2 OCH 2 CHY 1 CH 2 -Y 1, CF 2 = CFO (CF 2 CF (CF 3)) α Y 1, CF 2 = CFO (CF 2 _{CF (CF 3) O) α} CF 2 CF 2 CH 2 Y 1, CF 2 = CFO (CF 2 CF (CF 3) O) α CF 2 CF 2 CH 2 OCH 2 CHY 1 CH 2 Y 1 (α: 1 _{~30), CF 2 = CFO (} CF 2) 3 Y 1, CF 2 = CFO (CF 2) 3 CH 2 Y 1, CF 2 = CFOCF 2 CF 2 OCF 2 Y 1, CF 2 = CFOCF 2 CF 2 OCF ^{_{2 CH 2 Y 1, CF 2}} = CFOCF 2 CF 2 OCF 2 Such as ^{_{H 2 OCH 2 CHY 1 CH 2}} Y 1, CF 2 = CFOCF 2 CF 2 CH 2 OCF 2 CF 2 Y 1, CF 2 = CFOCF 2 CF 2 CH 2 OCF 2 CF 2 CH 2 Y 1 and the like.

（Ｒｆ⁵、Ｒｆ⁶、Ｘ⁴⁶：前記と同じ；β：０〜３０；γ：１〜３）
などがあげられる。For more details,

(Rf ⁵ , Rf ⁶ , X ⁴⁶ : same as above; β: 0 to 30; γ: 1 to 3)
Etc.

Preferred examples of the base polymer (a) of the formula (23) include those in which Y ¹ is replaced with Y ³ in the examples of the monomer that gives the structural unit M1-3.

（Ｘ⁴⁶、Ｒｆ⁵、Ｒｆ⁶、β、γ：前記と同じ）
などがあげられる。More details

(X ⁴⁶ , Rf ⁵ , Rf ⁶ , β, γ: same as above)
Etc.

Preferable specific examples of the monomer constituting the structural unit M1 of the curable fluorinated polymer of the present invention other than M1-2 and M1-3 include, for example, CF ₂ = CFCF ₂ ORf ⁷ Y ¹ , CF ₂ = CFCF ₂ ORf ⁷ CH ₂ CHCH ₂ Y ¹ , CF ₂ = CFRf ⁷ Y ¹ , CF ₂ = CFRf ⁷ CH ₂ CHCH ₂ Y ¹ , CH ₂ = CHRf ⁷ Y ¹ , CH ₂ = CHRf ⁷ CH ₂ CHCH ₂ Y ¹ , CH ₂ = CHORf ⁷ Y ¹ , CH ₂ = CHORf ⁷ CH ₂ CHCH ₂ Y ¹ (Rf ⁷ : perfluoroalkyl group having 1 to 5 carbon atoms) and the like.

More specifically, for _{example, CF 2 = CFCF 2 OCF 2} CF 2 CF 2 Y 1, CF 2 = CFCF 2 OCF 2 CF 2 CF 2 CH 2 Y 1, CF 2 = CFCF 2 OCF 2 CF (CF 3) Y ¹ , CF ₂ = CFCF ₂ OCF ₂ CF (CF ₃ ) CH ₂ Y ¹ , CF ₂ = CFCF ₂ OCF ₂ CFCH ₂ OCH ₂ CHCH ₂ Y ¹ , CF ₂ = CFCF ₂ Y ¹ , CF ₂ = CFCF ₂ CH ₂ Y ¹ , CF ₂ = CFCF ₂ CH ₂ OCH ₂ CHCH ₂ Y ¹ , CH ₂ = CHCF ₂ CF ₂ CH ₂ CH ₂ Y ¹ , CH ₂ = CHCF ₂ CF ₂ Y ¹ , CH ₂ = CHCF ₂ CF ₂ CH ₂ Y ¹ , CH ₂ = CHCF ₂ CF ₂ CF ₂ CF ₂ Y ¹ , CH ₂ = CHCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ Y ¹ , CH ₂ = CHCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ OCH ₂ CHY ¹ CH ₂ Y ¹ , CH ₂ = CHOCH ₂ CF ₂ CF ₂ Y ¹ , CH ₂ = CHOCH ₂ CF ₂ CF ₂ CH ₂ Y ^{1 and the} like.

In the base polymer (a) of the formula (16) of the present invention, examples of the fluorine-containing unsaturated compound other than the formula (20) and the formula (23) include the structural units M1 other than the structural units M1-2 and M1-3. A preferred specific example in which Y ¹ is replaced by Y ³ in a preferable specific example of the monomer to be provided is also exemplified.

  In the base polymer (a) represented by the formula (1), the structural unit A1 is an optional component and is particularly a monomer that can be copolymerized with the structural unit M1, M1-1, M1-2, or M1-3. It is not limited, What is necessary is just to select suitably according to the target base polymer (a).

  For example, the following structural units can be exemplified.

（式中、Ｘ⁶、Ｘ⁷およびＸ⁸は同じかまたは異なり、いずれもＨまたはＦ；Ｘ⁹はＨ、ＦまたはＣＦ₃；ｄは０〜２の整数；ｅは０または１；Ｒｆ²は炭素数１〜４０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を有する含フッ素アルキレン基；Ｚ¹は−ＯＨ、−ＣＨ₂ＯＨ、−ＣＯＯＨ、カルボン酸誘導体、−ＳＯ₃Ｈ、スルホン酸誘導体、エポキシ基、シアノ基、オキセタニル基、不飽和エステル基、アミノ基、式：

または式：

である）で示される構造単位であり、なかでも、式（２８）：

（式中、Ｒｆ²およびＺ¹は式（２７）と同じである）
で示される構造単位が好ましい。(1) Structural unit derived from a fluorine-containing ethylenic monomer having a functional group (A1-1)
These are preferable because they can improve diffraction efficiency, hologram sensitivity, hologram stability, light resistance, and mechanical strength while maintaining the refractive index of the base polymer (a) low. It is preferable at the point which can provide. The structural unit of a preferred fluorine-containing ethylenic monomer having a functional group is represented by the formula (27):

(Wherein X ⁶ , X ⁷ and X ⁸ are the same or different, and all are H or F; X ⁹ is H, F or CF ₃ ; d is an integer of 0 to 2; e is 0 or 1; Rf ² Is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; Z ¹ is —OH, —CH ₂ OH, —COOH, a carboxylic acid derivative, —SO ₃ H, Sulfonic acid derivative, epoxy group, cyano group, oxetanyl group, unsaturated ester group, amino group, formula:

Or the formula:

A structural unit represented by formula (28):

(Wherein Rf ² and Z ¹ are the same as in formula (27))
Is preferred.

More specifically, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol),
(CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH),
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 2 CF (CF 3) CH 2 OH),
(CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) ₃ CF (CF ₃ ) CH ₂ OH),
(CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOH,
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 2 CF (CF 3) COOH,
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 3 CF (CF 3) COOH,
(CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CN,
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 2 CF (CF 3) CN,
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 3 CF (CF 3) CN,
_{(CH 2 = CFCF 2 OCF (} CF 3) CF 2 OCF (CF 3) H,
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 2 CF (CF 3) H,
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 3 CF (CF 3) H,
_{(CH 2 = CFCF 2 OCF (} CF 3) CF 2 OCF (CF 3) CH 2 COOCH 3
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 2 CF (CF 3) CH 2 COOCH 3
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 3 CF (CF 3) CH 2 COOCH 3
_{(CH 2 = CFCF 2 OCF (} CF 3) CF 2 OCF (CF 3) CH 2 OCH 2 CHOCH 2
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 2 CF (CF 3) CH 2 OCH 2 CHOCH 2
_{(CH 2 = CFCF 2 O (} CF (CF 3) CF 2 O) 3 CF (CF 3) CH 2 OCH 2 CHOCH 2
CH ₂ = CFCF ₂ OCF (CF ₃ ) Z ¹ , CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) Z ¹ , CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) ₂ CF (CF ₃ ) Z ¹ , CH ₂ = CFCF ₂ OCH ₂ CF ₂ Z ¹ , CH ₂ = CFCF ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) Z ¹ , CH ₂ = CFCF ₂ OCF ₂ A structural unit derived from a fluorine-containing ethylenic monomer such as CF ₂ OCF ₂ Z ¹ or CH ₂ ═CFCF ₂ O (CF ₂ CF ₂ O) ₂ CF ₂ Z ¹ is preferred.

（式中、Ｒｆ²およびＺ¹は式（２７）と同じである）
で示される構造単位も好ましく例示でき、より具体的には、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ（ＣＦ₃）ＯＣＦ₂ＣＦ₂ＣＨ₂Ｚ¹、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃Ｚ¹、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃ＣＨ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂ＣＨ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂ＣＨ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ（ＣＦ₃）ＯＣＦ₂ＣＦ₂ＣＨ₂Ｚ¹、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃Ｚ¹、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃ＣＨ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂ＣＨ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂Ｚ¹、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂ＣＨ₂Ｚ¹などの単量体から誘導される構造単位などがあげられる。Moreover, Formula (29):

(Wherein Rf ² and Z ¹ are the same as in formula (27))
The structural unit represented by can also be preferably exemplified, and more specifically, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ Z ¹ , CF ₂ = CFO (CF ₂ ) ₃ Z ¹ , CF ₂ = _{CFO (CF 2) 3 CH 2} Z 1, CF 2 = CFOCF 2 CF 2 OCF 2 Z 1, CF 2 = CFOCF 2 CF 2 OCF 2 CH 2 Z 1, CF 2 = CFOCF 2 CF 2 CH 2 OCF 2 CF 2 _{^{Z 1, CF 2 = CFOCF 2}} CF 2 CH 2 OCF 2 CF 2 CH 2 Z 1, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 CH 2 Z 1, CF 2 = CFO (CF 2) 3 Z ¹ , CF ₂ = CFO (CF ₂ ) ₃ CH ₂ Z ¹ , CF ₂ = CFOCF ₂ CF ₂ OCF ₂ Z ¹ , CF ₂ = CFOCF ₂ CF ₂ OCF ₂ CH ₂ Z ¹ , CF ₂ = CFOCF ₂ CF ₂ CH ₂ OCF ₂ CF ₂ Z ¹ , CF ₂ = CFOCF Such as _{2 CF 2 CH 2 OCF 2 CF} 2 CH 2 structural units derived from monomers such as Z ¹ and the like.

Other functional group-containing fluorine-containing ethylenic monomers include, for example, CF ₂ = CFCF ₂ ORf ¹ Z ¹ , CF ₂ = CFRf ¹ Z ¹ , CH ₂ = CHRf ¹ Z ¹ , CH ₂ = CHORf ¹ Z ^1. (Rf ¹ : the same as formula (2)) and the like. More specifically, CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ Z ¹ , CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ CH ₂ Z ¹ , CF ₂ = CFCF ₂ OCF ₂ CF (CF ₃ ) Z ¹ , CF ₂ = CFCF ₂ OCF ₂ CF (CF ₃ ) CH ₂ Z ¹ , CF ₂ = CFCF ₂ Z ¹ , CF ₂ = CFCF ₂ CH ₂ Z ^{_{1, CH 2 = CHCF 2 CF}} 2 CH 2 CH 2 Z 1, CH 2 = CHCF 2 CF 2 Z 1, CH 2 = CHCF 2 CF 2 CH 2 Z 1, CH 2 = CHCF 2 CF 2 CF 2 CF 2 Z ^{_{1, CH 2 = CHCF 2 CF}} 2 CF 2 CF 2 CH 2 Z 1 Such as _{CH 2 = CHOCH 2 CF 2 CF} 2 Z 1, CH 2 = CHOCH 2 CF 2 CF 2 CH 2 Z 1 and the like.
(2) Structural unit derived from a fluorine-containing ethylenic monomer containing no functional group (A1-2)
These are preferable in that the refractive index of the base polymer (a) can be kept low, and further in that hologram sensitivity can be improved and light resistance can be imparted. In addition, by selecting a monomer, the viscosity characteristics and glass transition point of the base polymer (a) can be adjusted, and particularly, the glass transition point can be increased by copolymerization with the structural unit M1, which is preferable.

（式中、Ｘ¹⁰、Ｘ¹¹、Ｘ¹³は同じかまたは異なり、いずれもＨまたはＦ；Ｘ¹²はＨ、ＦまたはＣＦ₃；ｆ、ｇおよびｈは同じかまたは異なり、いずれも０または１；Ｚ²はＨ、ＦまたはＣｌ；Ｒｆ³は炭素数１〜２０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を含む含フッ素アルキレン基である）
で示されるものが好ましい。The structural unit of the fluorine-containing ethylenic monomer is represented by the formula (30):

(Wherein X ¹⁰ , X ¹¹ and X ¹³ are the same or different, all are H or F; X ¹² is H, F or CF ₃ ; f, g and h are the same or different, and all are 0 or 1 ; Z ² is H, F or Cl; Rf ³ is a fluorine-containing alkylene group containing an ether bond or a fluorine-containing alkylene group having 2-100 carbon atoms of 1 to 20 carbon atoms)
Is preferred.

As specific examples, for example, CF ₂ = CF ₂ , CF ₂ = CH ₂ , CF ₂ = CFCl, CF ₂ = CFCF ₃ , CF ₂ = C (CF ₃ ) ₂ , CF ₂ = CFO (CF ₂ ) _δ F (Δ: integer of 1 to 5), CH ₂ = C (CF ₃ ) ₂ , CF ₂ = CFH, CF ₂ = CCl ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) OC ₃ F ₇ , CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _ε CFHCF ₃ (ε: 0 to 10), CH ₂ = CF (CF ₂ ) _ε Z ² (Z ² is the same as formula (30), ε: 1 to 10 ), CH ₂ = CHOCH ₂ (CF ₂ ) _ε Z ² (Z ² is the same as in formula (30), ε: 1 to 10), CH ₂ = CHOCH ₂ (CF ₂ ) _ε Z ² (Z ² is the formula ( A structural unit derived from a monomer such as ε: 1 to 10), which is the same as 30), is preferred.

(3) Aliphatic cyclic structural unit having fluorine (A1-3)
By introducing these structural units, transparency can be increased, a lower refractive index can be achieved, a fluorine-containing polymer having a high glass transition point can be obtained, and further high-sensitivity recording can be expected for holograms. preferable.

（式中、Ｘ⁴⁷、Ｘ⁴⁸、Ｘ⁵¹、Ｘ⁵²、Ｘ⁵³およびＸ⁵⁴は同じかまたは異なり、いずれもＨまたはＦ；Ｘ⁴⁹およびＸ⁵⁰は同じかまたは異なり、いずれもＨ、Ｆ、ＣｌまたはＣＦ₃；Ｒｆ⁷は炭素数１〜１０の含フッ素アルキレン基または炭素数２〜１０のエーテル結合を有する含フッ素アルキレン基；ｎ２は０〜３の整数；ｎ１、ｎ３、ｎ４およびｎ５は同じかまたは異なり、いずれも０または１である）
で示されるものが好ましい。As the fluorine-containing aliphatic cyclic structural unit, the formula (31):

^Wherein X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ and X ⁵⁴ are the same or different, both H or F; X ⁴⁹ and X ⁵⁰ are the same or different, and all are H, F, Cl or CF ₃ ; Rf ⁷ is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 10 carbon atoms; n2 is an integer of 0 to 3; n1, n3, n4 and n5 are The same or different, both 0 or 1)
Is preferred.

（式中、Ｒｆ⁷、Ｘ⁴⁹、Ｘ⁵⁰は前記と同じ）
で示される構造単位などがあげられる。For example, equation (32):

(Wherein Rf ⁷ , X ⁴⁹ and X ⁵⁰ are the same as above)
The structural unit indicated by

などがあげられる。In particular,

Etc.

(4) Structural unit derived from an ethylenic monomer that does not contain fluorine A structure derived from an ethylenic monomer that does not contain fluorine as long as the refractive index of the fluorine-containing base polymer is not deteriorated (higher refractive index) Units may be introduced.

  As a result, the compatibility with the monomer is further improved, and photopolymerization initiators, dyes, additives such as sensitizers, plasticizers, heat stabilizers, brighteners, UV absorbers, polymerization inhibitors, and continuous agent transfer. It is preferable because the compatibility with the agent, bleaching agent, and crosslinking agent added as necessary can be improved.

など
アクリル系またはメタクリル系単量体：
アクリル酸、メタクリル酸、アクリル酸エステル類、メタクリル酸エステル類のほか、無水マレイン酸、マレイン酸、マレイン酸エステル類などがあげられる。Specific examples of non-fluorinated ethylenic monomers include
α-olefins:
Vinyl ether or vinyl ester monomers such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride:
Allyl monomers such as CH ₂ = CHOR, CH ₂ = CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms):
Allyl ether monomers such as CH ₂ = CHCH ₂ Cl, CH ₂ = CHCH ₂ OH, CH ₂ = CHCH ₂ COOH, CH ₂ = CHCH ₂ Br, etc .:
_{CH 2 = CHCH 2 OR (R} : hydrocarbon group having 1 to 20 carbon _{atoms), CH 2 = CHCH 2 OCH} 2 CH 2 COOH,

Acrylic or methacrylic monomers such as:
In addition to acrylic acid, methacrylic acid, acrylic esters and methacrylic esters, maleic anhydride, maleic acid, maleic esters and the like can be mentioned.

(5) Structural unit derived from alicyclic monomer As the copolymer component of structural unit M1, more preferably structural unit M1 and the above-mentioned fluorine-containing ethylenic monomer or non-fluorine ethylenic monomer (described above) In addition to the structural units of (3) and (4)), an alicyclic monomer structural unit may be introduced as the third component, thereby increasing the glass transition point and increasing the viscosity. preferable.

（式中：ｍは０〜３の整数、Ａ、Ｂ、ＣおよびＤは同じかまたは異なり、いずれもＨ、Ｆ、Ｃｌ、ＣＯＯＨ、ＣＨ₂ＯＨまたは炭素数１〜５のパーフルオロアルキル基である）
で示されるノルボルネン誘導体、

などの脂環式単量体や、これらに置換基を導入した誘導体などがあげられる。As a specific example of the alicyclic monomer, for example,

(In the formula: m is an integer of 0 to 3, A, B, C and D are the same or different, and each is H, F, Cl, COOH, CH ₂ OH or a C 1-5 perfluoroalkyl group. is there)
A norbornene derivative represented by:

And alicyclic monomers such as these, and derivatives obtained by introducing substituents into these.

  In the base polymer (a), the combination and composition ratio of the structural unit M1 (M1-1, M1-2, M1-3) and the structural unit A1 are the intended use and physical properties (especially the glass transition point, Various selections can be made depending on the function (sensitivity, light resistance, transparency), etc.

  The base polymer (a) contains the structural unit M1 (M1-1, M1-2, M1-3) as an essential component, and the structural unit M1 itself maintains a low refractive index and imparts transparency. It has the feature of combining a refractive index difference, transparency, sensitivity, light resistance, and mechanical strength to a photosensitive medium for fluorine-containing volume hologram recording by function and hologram recording. Therefore, the crosslinkable fluorine-containing polymer that is the base polymer of the present invention can maintain the physical properties even if it is a polymer containing a large amount of the structural unit M1, that is, a polymer composed of only the structural unit M1 (100 mol%). At the same time, a photosensitive medium for hologram recording having a high curing (crosslinking) density can be obtained, which is preferable in that a photosensitive medium for hologram recording excellent in high recording sensitivity, light resistance, hologram stability, and mechanical strength can be obtained.

  Furthermore, in the case of a copolymer comprising a structural unit A1 of a monomer that can be copolymerized with the structural unit M1 of the present invention, by selecting the structural unit A1 from the above-mentioned examples, a higher viscosity (high glass transition Point) and a polymer that provides a photosensitive medium for hologram recording excellent in transparency.

  In the copolymer of the structural unit M1 and the structural unit A1, the content ratio of the structural unit M1 may be 0.1 mol% or more with respect to all monomers constituting the base polymer (a). In order to obtain a photosensitive medium for hologram recording having a high viscosity, high recording sensitivity, excellent light resistance, and excellent hologram stability and mechanical strength by crosslinking, 2.0 mol% or more, preferably 5 mol% or more, More preferably, it is 10 mol% or more.

  In the present invention, since transparency is required, a crosslinkable fluoropolymer having a combination and composition in which the combination of the structural unit M1 and the structural unit A1 can be amorphous is preferable.

で示されるものがあげられる。
式（３）中の構造単位Ｍ１は、前述のヒドロキシル基または、エチレン性炭素−炭素二重結合を側鎖に有する構造単位であり、式（Ｍ１−１）、（Ｍ１−２）、（Ｍ１−３）で示した前記の好ましい具体例と同様のものが適用できる。Among these, as a preferred form of the fluorine-containing polymer for the fluorine-containing volume hologram recording photosensitive composition having high recording sensitivity and aiming at hologram stability and mechanical strength, the formula (3):

What is indicated by.
The structural unit M1 in the formula (3) is a structural unit having the aforementioned hydroxyl group or ethylenic carbon-carbon double bond in the side chain, and is represented by the formulas (M1-1), (M1-2), (M1). The same thing as the said preferable specific example shown by -3) is applicable.

（式中、Ｘ⁶、Ｘ⁷およびＸ⁸は同じかまたは異なり、いずれもＨまたはＦ；Ｘ⁹はＨ、ＦまたはＣＦ₃；ｄは０〜２の整数；ｅは０または１；Ｒｆ²は炭素数１〜４０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を有する含フッ素アルキレン基；Ｚ¹は−ＯＨ、−ＣＨ₂ＯＨ、−ＣＯＯＨ、カルボン酸誘導体、−ＳＯ₃Ｈ、スルホン酸誘導体、エポキシ基、シアノ基、オキセタニル基、不飽和エステル基またはアミノ基である）
で示される構造単位であり、前述の官能基を有する含フッ素エチレン性単量体から誘導される構造単位Ａ１の具体例が同様に好ましく適用できる。The structural unit A2 is a structural unit derived from a fluorine-containing ethylenic monomer having a functional group in the side chain. Specifically, the structural unit A2 is represented by the formula (4):

(Wherein X ⁶ , X ⁷ and X ⁸ are the same or different, and all are H or F; X ⁹ is H, F or CF ₃ ; d is an integer of 0 to 2; e is 0 or 1; Rf ² Is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; Z ¹ is —OH, —CH ₂ OH, —COOH, a carboxylic acid derivative, —SO ₃ H, A sulfonic acid derivative, an epoxy group, a cyano group, an oxetanyl group, an unsaturated ester group or an amino group)
Specific examples of the structural unit A1 derived from the fluorine-containing ethylenic monomer having the functional group described above can be similarly applied.

（式中、Ｘ¹⁰、Ｘ¹¹、Ｘ¹³は同じかまたは異なり、いずれもＨまたはＦ；Ｘ¹²はＨ、ＦまたはＣＦ₃;ｆ、ｇおよびｈは同じかまたは異なり、いずれも０または１；Ｚ²はＨ、ＦまたはＣｌ；Ｒｆ³は炭素数１〜２０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を含む含フッ素アルキレン基である）
で示される構造単位が好ましい。The structural unit A3 is a structural unit derived from a fluorine-containing ethylenic monomer having no functional group. Specifically, the structural unit A3 is represented by the formula (5):

(Wherein X ¹⁰ , X ¹¹ and X ¹³ are the same or different, and each is H or F; X ¹² is H, F or CF ₃ ; f, g and h are the same or different, and each is 0 or 1 ; Z ² is H, F or Cl; Rf ³ is a fluorine-containing alkylene group containing an ether bond or a fluorine-containing alkylene group having 2-100 carbon atoms of 1 to 20 carbon atoms)
Is preferred.

  Respective proportions of the structural units M1, A2 and A3 are M1 = 0 to 90 mol%, A2 = 0 to 100 mol% and A3 = 0 to 99.9 mol%, and M1 + A2 = 0.1 to 100 It is preferably a mol%. That is, a single polymer of the structural unit A2 can also be used.

  If the number of structural units M1 is too small, shrinkage after hologram recording tends to increase, and light resistance tends to be insufficient. When A2 is too small, the compatibility with each compound in the hologram composition, the recording sensitivity, etc. tend to be insufficient. When A3 is too small, transparency tends to be insufficient.

  The base polymer (a) composed of these structural units M1, A2, and A3 has high recording sensitivity and can provide high-density recording and light resistance due to the crosslinkable portion of the structural unit M1. Moreover, compatibility with each compound in the hologram composition and recording sensitivity can be imparted by the functional group of the structural unit A2. Furthermore, the structural unit A3 can impart further good transparency to the photosensitive composition for volume hologram recording and the medium.

  The molecular weight of the base polymer (a) can be selected from the range of, for example, greater than 10,000 and 1,000,000 or less in number average molecular weight, but is preferably selected from the range of 50,000 to 500,000, particularly 70000 to 200,000.

  If the molecular weight is too low, the viscosity is low even after hologram recording, the interference fringes are disturbed or the interference fringes tend to contract, and the hologram stability tends to be lacking. If the molecular weight is too high, the compatibility with each compound in the photosensitive composition for hologram recording and the recording sensitivity are deteriorated, and the film forming property and leveling property are liable to be deteriorated particularly when a hologram medium or a hologram foil is formed.

  The base polymer (a) can be variously determined depending on the type and content of the structural unit M1, and the type of the copolymer structural unit A1 used as necessary, but the refractive index of the base polymer (a) itself (before hologram recording) is It is preferably 1.45 or less, more preferably 1.40 or less, and particularly preferably 1.38 or less. Although it varies depending on the type of the substrate and the substrate, maintaining the low refractive index and allowing curing (crosslinking) can be preferable as a photosensitive composition for volume hologram recording and a base polymer of a medium.

で示され、構造単位Ｍ２を０．１〜１００モル％および構造単位Ａ４を０〜９９．９モル％含み、数平均分子量が１００００より大きく、１００００００以下であるものもあげられる。In addition, the base polymer (a) used in the present invention is represented by the formula (6):

The structural unit M2 is 0.1 to 100 mol% and the structural unit A4 is 0 to 99.9 mol%, and the number average molecular weight is more than 10,000 and less than 1,000,000.

（式中、Ｘ²²およびＸ²³は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数２〜１００の有機基や、式（１０）：

（式中、Ｑは炭素数３〜１００の単環構造、複環構造または複素環構造の水素原子が前記Ｘ²²またはＸ²³で置換されていてもよい１価または２価の有機基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基や、式（１１）：

（式中、Ｘ²⁴〜Ｘ²⁸は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基や、式（１２）：

（式中、Ｘ²⁹〜Ｘ³²は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基で置換したものも好ましく利用できる。また、構造単位Ａ４は、前述の構造単位Ａ１〜Ａ３と同様のものが好ましく利用できる。In the base polymer (a) represented by the formula (6), specific examples of the structural unit M2 include a site Y ¹ containing a carbon-carbon double bond corresponding to each of the specific examples of the structural unit M1 described above. the objects or structures that put the solution into the site Y ⁶ containing OH groups, the formula (9):

(In the formula, X ²² and X ²³ are the same or different, and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
Or an organic group having 2 to 100 carbon atoms having 1 to 5 crosslinkable cyclic ether structures represented by formula (10):

(In the formula, Q is a monovalent or divalent organic group in which a hydrogen atom of a monocyclic structure, a polycyclic structure or a heterocyclic structure having 3 to 100 carbon atoms may be substituted with X ²² or X ^23. )
An organic group having 3 to 100 carbon atoms having 1 to 5 crosslinkable cyclic ether structures represented by formula (11):

(Wherein, X ^{24 to} X ²⁸ are the same or different, and all are H, F, a C 1-6 alkyl group or a C 1-6 fluorinated alkyl group)
An organic group having 3 to 100 carbon atoms having 1 to 5 crosslinkable cyclic ether structures represented by formula (12):

(In the formula, X ^{29 to} X ³² are the same or different and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
What substituted by the C3-C100 organic group which has 1-5 crosslinkable cyclic ether structures shown by these can also be utilized preferably. As the structural unit A4, the same structural units as those described above for the structural units A1 to A3 can be preferably used.

  As the base polymer (a) used in the present invention, in addition to those mentioned above, for example, those having a crosslinking site are used, and the composition for fluorine-containing volume hologram optical information recording material of the present invention is used. However, it can also contain a polyfunctional unsaturated compound (d) that undergoes a crosslinking reaction with the crosslinking site by heat.

  As a combination of the base polymer (a) having such a crosslinking site and the polyfunctional unsaturated compound (d), a compound having an isocyanate group and a compound having a hydroxyl group, a compound having an isocyanate group and a compound having an amino group, A compound having a carbodiimide group and a compound having a carboxyl group, a compound having an unsaturated ester group and a compound having an amino group, a compound having an unsaturated ester group and a compound having a mercaptan group, a compound having a vinyl group and a silicon hydride group A combination of a base polymer (a) having at least one combination selected from a compound having a compound having a cationic reactive group and a compound having a cationic reactive group and a polyfunctional unsaturated compound (d) is selected as appropriate. Furthermore, the combination The combination is more preferably the base polymer (a) having a polyfunctional unsaturated compound having an isocyanate group that can be polymerized or crosslinked under mild conditions in the Align (d) and a hydroxyl group.

The polyfunctional unsaturated compound (d) having an isocyanate group that can be used in the present invention can be used without any particular limitation. However, the hologram recording is sufficiently maintained after the production of the photosensitive medium for fluorine-containing volume hologram optical recording. In order to improve the recording sensitivity, a polyfunctional unsaturated compound (d) having two or more isocyanate groups in the molecule is more preferable. Specific examples of such compounds having an isocyanate group include For example, 1,8-diisocyanate-4-isocyanatomethyl-octane, 2-isocyanatoethyl-2,6-diisocyanate caproate, benzene-1,3,5-triisocyanate, 1-methylbenzene-2,4, 6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate Diphenylmethane-2,4,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, bis (isocyanatotolyl) phenylmethane, dimethylene diisocyanate, tetramethylene diisocyanate, hexanemethylene diisocyanate, 2, 2-dimethylpentane diisocyanate, 2,2,4-trimethylpentane diisocyanate, decane diisocyanate, ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,2-dimethylcyclohexane diisocyanate, ω, ω-diisocyanate-1,4-diethylbenzene, isophorone diisocyanate, 1-methylcyclohexyl-2,4-diisocyanate, ω, ω′-diisocyanate-1,5-dimethylnaphthalene ω, ω′-diisocyanate-n-propylbiphenyl, 1,3-phenylene diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1,3-dimethylbenzene-2,6-diisocyanate, naphthalene-1,4-diisocyanate 1,1′-dinaphthyl-2,2′-diisocyanate, biphenyl-2,4′-diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, 2, 2′-dimethyldiphenylmethane-4,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-diethoxydiphenylmethane-4,4 '-Diisocyanate, Tolylene diisocyanate , 1,5-naphthylene diisocyanate, cyclohexylmethane-4,4′-diisocyanate, xylylene diisocyanate, tetramethylene xylylene diisocyanate, and the like, and dimer or trimer of each of the above isocyanate compounds. Adducts (eg, 2 moles of hexamethylene diisocyanate, 3 moles of hexamethylene diisocyanate, 2 moles of 2,4-tolylene diisocyanate, 3 moles of 2,4-tolylene diisocyanate), these isocyanates And adducts of two or more different isocyanates selected from the group consisting of these isocyanates and divalent or trivalent polyalcohols such as diethylene glycol, polyethylene glycol, Adducts (eg, adducts of tolylene diisocyanate and trimethylol propane, adducts of hexamethylene diisocyanate and trimethylol propane) and the like. In addition, you may use these isocyanate compounds individually by 1 type or in combination of 2 or more types.
As the polyfunctional unsaturated compound (d) having an isocyanate group that can be used in the present invention, a crosslinking reaction catalyst can be further used. Examples of the crosslinking reaction catalyst include dibutyltin laurate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, dioctyltin maleate polymer, and organic tin compounds such as tin octylate. These crosslinking reaction catalysts may be used alone or in combination of two or more.

  In addition, the fluorine-containing volume type used in the state where the optical recording is performed on the photosensitive medium for fluorine-containing volume hologram recording in which the recording photosensitive layer composed of the photosensitive composition for fluorine-containing volume hologram recording is laminated and the recording is completed. The photosensitive medium for holographic recording has a possibility that the ambient temperature under the fluorescent lamp, the window side, or the neglected environment may be variously similar to the CD and DVD. Accordingly, those which suppress the coloring of the recording photosensitive layer under various conditions are preferable. In order to suppress the coloring as described above, an aliphatic isocyanate compound is more preferable among the compounds having an isocyanate group.

  In the present invention, when a compound having an isocyanate group is used, the binder may be formed by self-crosslinking of the compound having an isocyanate group. However, in order to cause the binder formation to be performed under mild conditions, it is described in detail above. It is preferable to form a binder by a cross-linking reaction with a compound having a functional group that reacts with the isocyanate group of the isocyanate compound in the molecule, and examples of the compound capable of reacting with such an isocyanate compound include a compound having a hydroxyl group in the molecule. And compounds having a primary or secondary amino group, as well as compounds having an enamine structure. However, all the information is recorded on the photosensitive medium for fluorine-containing volume hologram recording in which the recording photosensitive layer composed of the photosensitive composition for fluorine-containing volume hologram recording of the present invention is laminated, and used in a state where this recording is completed. In order to suppress coloring of the photosensitive medium for fluorine-containing volume hologram recording, the base polymer (a) having a hydroxyl group as a compound capable of reacting with an isocyanate compound among the above-mentioned compounds is preferred, and further an alcoholic hydroxyl group is used. A base polymer (a) having one or more molecules in the molecule is more preferable.

（式中、Ｒｆ²は式（２７）と同じである）
で示される構造単位が好ましい。As the base polymer (a) having one or more alcoholic hydroxyl groups in the molecule, for example,

(Wherein Rf ² is the same as in formula (27))
Is preferred.

More _{specifically, CH 2 = CFCF 2 OCF (} CF 3) OH, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) OH, CH 2 = CFCF 2 O (CF (CF 3) CF ₂ O) ₂ CF (CF ₃ ) OH, CH ₂ = CFCF ₂ OCH ₂ CF ₂ OH, CH ₂ = CFCF ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) OH, CH ₂ = CFCF ₂ OCF ₂ CF ₂ OCF _{2 OH, CH 2 = CFCF 2} O (CF 2 CF 2 O) 2 CF 2 OH, CH 2 = CFCF 2 OCF (CF 3) CH 2 OH, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF ₃ ) CH ₂ OH, CH ₂ ═CFCF ₂ O (CF (CF ₃ ) CF ₂ O) ₂ Structural units derived from fluorine-containing ethylenic monomers such as CF (CF ₃ ) CH ₂ OH are preferred. .

（式中、Ｒｆ²は式（２７）と同じである）
で示される構造単位も好ましく例示でき、より具体的には、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ（ＣＦ₃）ＯＣＦ₂ＣＦ₂ＣＨ₂ＯＨ、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃ＯＨ、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃ＣＨ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂ＣＨ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂ＣＨ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ（ＣＦ₃）ＯＣＦ₂ＣＦ₂ＣＨ₂ＯＨ、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃ＯＨ、ＣＦ₂＝ＣＦＯ（ＣＦ₂）₃ＣＨ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＯＣＦ₂ＣＨ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂ＯＨ、ＣＦ₂＝ＣＦＯＣＦ₂ＣＦ₂ＣＨ₂ＯＣＦ₂ＣＦ₂ＣＨ₂ＯＨなどの単量体から誘導される構造単位などがあげられる。Also,

(Wherein Rf ² is the same as in formula (27))
The structural unit represented by can also be preferably exemplified, and more specifically, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ OH, CF ₂ = CFO (CF ₂ ) ₃ OH, CF ₂ = CFO ( _{CF 2) 3 CH 2 OH,} CF 2 = CFOCF 2 CF 2 OCF 2 OH, CF 2 = CFOCF 2 CF 2 OCF 2 CH 2 OH, CF 2 = CFOCF 2 CF 2 CH 2 OCF 2 CF 2 OH, CF 2 = _{CFOCF 2 CF 2 CH 2 OCF 2} CF 2 CH 2 OH, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 CH 2 OH, CF 2 = CFO (CF 2) 3 OH, CF 2 = CFO (CF 2 ) ₃ CH ₂ OH, CF ₂ = CFOCF ₂ CF ₂ OCF ₂ OH, CF ₂ = CFOCF ₂ CF ₂ OCF ₂ CH ₂ OH, CF ₂ = CFOCF ₂ CF ₂ CH ₂ OCF ₂ CF ₂ OH, CF ₂ = CFOCF Examples thereof include structural units derived from monomers such as ₂ CF ₂ CH ₂ OCF ₂ CF ₂ CH ₂ OH.

Other functional group-containing fluorine-containing ethylenic monomers include, for example, CF ₂ = CFCF ₂ ORf ¹ OH, CF ₂ = CFRf ¹ OH, CH ₂ = CHRf ¹ OH, CH ₂ = CHORf ¹ OH (Rf ¹ : And more specifically, CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ OH, CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ CH ₂ OH, CF ₂ = CFCF _{2 OCF 2 CF (CF 3)} OH, CF 2 = CFCF 2 OCF 2 CF (CF 3) CH 2 OH, CF 2 = CFCF 2 OH, CF 2 = CFCF 2 CH 2 OH, CH 2 = CHCF 2 CF 2 CH ₂ CH ₂ OH, CH ₂ = CHCF ₂ CF ₂ OH, CH ₂ = CHCF ₂ CF ₂ CH ₂ OH, CH ₂ = CHCF ₂ CF ₂ CF ₂ CF ₂ OH, CH ₂ = CHCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ OH _{CH 2 = CHOCH 2 CF 2 CF} 2 OH, such as _{CH 2 = CHOCH 2 CF 2 CF} 2 CH 2 OH , and the like.

Among detailed the base polymer (a) _{or, CH 2 = CFCF 2 OCF (} CF 3) CH 2 OH, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CH 2 OH, CH 2 _{= CFCF 2 O (CF (CF} 3) CF 2 O) 2 CF (CF 3) CH 2 OH are preferred.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the refractive index of the base polymer (a) is 1.350 to 1 from the viewpoint of increasing the refractive index difference and improving the sensitivity and diffraction efficiency. .385 is preferable, and 1.360 to 1.370 is more preferable.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the content of the base polymer (a) is 20 to 20 from the viewpoint of sensitivity, diffraction efficiency and hologram stability, improvement of mechanical strength, and light resistance. 80 mass% is preferable and 25-60 mass% is more preferable.

  The liquid monomer (b) used in the present invention contains at least one liquid monomer (b1) that initiates polymerization by an active species generated from a photopolymerization initiator (c) described later.

  Specific examples of such a liquid monomer (b1) include compounds having a fluoroacryloyl group. Specific examples having a fluoroacryloyl group include the following.

（ＸはＨ、ＣＨ₃またはＦ、Ｒｆは炭素数２〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基）で表わされる化合物が好ましい。

A compound represented by (X is H, CH ₃ or F, and Rf is a fluorine-containing alkyl group having 2 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms) is preferable.

などがあげられる。In particular,

Etc.

（Ｒｆは、炭素数１〜４０の含フッ素アルキル基である）、

（Ｒｆは、炭素数１〜４０の含フッ素アルキル基である）、

（Ｒｆは、炭素数１〜４０の含フッ素アルキル基またはエーテル結合を含む含フッ素アルキル基、ＲはＨまたは炭素数１〜３のアルキル基である）、

（Ｒｆ’は、炭素数１〜４０の含フッ素アルキル基またはエーテル結合を含む含フッ素アルキレン基である）、

（Ｒｆ’は、炭素数１〜４０の含フッ素アルキル基またはエーテル結合を含む含フッ素アルキレン基である）、

（Ｒｆ’は、炭素数１〜４０の含フッ素アルキル基またはエーテル結合を含む含フッ素アルキレン基、ＲはＨまたは炭素数１〜３のアルキル基である）
などの一般式で示される含フッ素多価アルコール類の２個以上のヒドロキシル基をアクリレート基、メタクリレート基またはα−フルオロアクリレート基に置き換えた構造のものが好ましくあげられる。Besides, for example,

(Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms),

(Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms),

(Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group containing an ether bond, R is H or an alkyl group having 1 to 3 carbon atoms),

(Rf ′ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkylene group containing an ether bond),

(Rf ′ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkylene group containing an ether bond),

(Rf ′ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkylene group containing an ether bond, and R is H or an alkyl group having 1 to 3 carbon atoms)
Preferred are those having a structure in which two or more hydroxyl groups of fluorine-containing polyhydric alcohols represented by the general formulas such as are replaced with acrylate groups, methacrylate groups or α-fluoroacrylate groups.

  In addition, for example, styrene, α-methylstyrene, 2-bromostyrene, vinyl acetate, methyl vinyl ketone, acrylonitrile, N-vinyl carbazole, N-vinyl pyrrolidone, acrylate, methyl acrylate, n-butyl acrylate, lauryl acrylate, 2 -Ethylhexyl acrylate, dicyclopentanyl acrylate, phenyl acrylate, o-biphenyl acrylate, 2-naphthyl acrylate, ethylene oxide phenol acrylate, phenoxy diethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, nonyl phenol ethylene oxide acrylate, bisphenol A ethylene oxide diacrylate, ethylene oxide tetrabromo Bisphenol A Diacryle Ethylene oxide bisphenol A diacrylate, propylene oxide bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate, dimethylol-tricyclodecane diacrylate, propylene oxide trimethylol propane triacrylate, urethane acrylate, ε-caprolactone acid tris- ( 2-acryloxyethyl) isocyanurate, methoxypolyethylene glycol acrylate, polypropylene glycol 400 diacrylate, octoxypolyethylene glycol-polypropylene glycol monoacrylate, trimethylolpropane triacrylate, tribromophenyl acrylate, ethylene oxide tribromophenyl acrylate, phenylphenol glycol Siji Ether acrylate, 2-methyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl acrylate, 1-adamantyl acrylate, phenylethyl acrylate, 2-phenylethyl acrylate, 2-phenoxyethyl acrylate, 2- (9-carbazolyl) ethyl acrylate , Methylphenoxyethyl acrylate, triphenylmethylthioacrylate, 2- (p-chlorophenoxy) ethyl acrylate, nonylphenoxyethyl acrylate, phenol ethoxylate monoacrylate, p-chlorophenyl acrylate, 2- (1-naphthyloxy) ethyl acrylate, 2 , 4,6-tribromophenyl acrylate, isobornyl acrylate, hydroxyethyl acrylate, 2-hydroxy- -Phenoxypropyl acrylate, 2,3-dibromopropyl acrylate, 2- (tricyclo [5,2,102.6] dibromodecylthio) ethyl acrylate, tetramethylene glycol diacrylate, ethylene glycol diacrylate, diethylene dithioglycol diacrylate , Triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, phenoxy polyethylene glycol acrylate, propylene glycol diacrylate, methoxypropylene glycol acrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, hexanediol Diacrylate, 1,4-cyclohexanediol diacrylate, trimethyl Propane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate Sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, 2-ethylhexyl carbitol acrylate, S- (1-naphthylmethyl) thioacrylate, β-acryloxyethyl hydrogen phthalate, ethoxylated bisphenol A di Acrylate, itaconic acid, male Acid, N-acryloylmorpholine, methyl α-cyanoacrylate, vinyl-2-chloroethyl ether, vinyl-n-butyl ether, triethylene glycol divinyl ether, trimethylolethane trivinyl ether, 1,4-cyclohexanedimethanol divinyl ether , Trimethylolpropane tri (acryloyloxypropyl) ether, (2-acryloxyethyl) ether of bisphenol A, bis (4-acryloxydiethoxyphenyl) methane, bis (4-acryloxyethoxy-3,5-dibromophenyl) ) Methane, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxy-3,5- (Dibromophenyl) Lopan, 2,3-naphthalenedicarboxylic acid (acryloxyethyl) monoester, 2,3-naphthalene dicarboxylic acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diester, 4,5-phenanthrenedicarboxylic Acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diester, diphenic acid (2-methacryloxyethyl) monoester, diphenic acid (2-acryloxyethyl) (3-acryloxypropyl-2 -Hydroxy) diester, 1,3-bis [2-acryloxy-3- (2,4,6-tribromophenoxy) propoxy] benzene, bis (4-acryloxyethoxyphenyl) sulfone, bis (4-acryloxydi) Ethoxyphenyl) sulfone, bis (4-acryloxypropoxyphenyl) sulfone, bis (4 -Acryloxyethoxy-3,5-dibromophenyl) sulfone, 4,4'-bis (β-acryloyloxyethylthio) diphenylsulfone, 9,9-bis (4-acryloxydipropoxyphenyl) fluorene, 9,9 -Bis (4-acryloxyethoxy-3,5-dimethyl) fluorene, 9,9-bis (4-acryloxytriethoxyphenyl) fluorene, 9,9-bis (4-acryloxyethoxy-3-methylphenyl) Fluorene, 9,9-bis (4-acryloxyethoxy-3-ethylphenyl) fluorene, 9,9-bis (4-acryloxydiethoxyphenyl) fluorene, 2,4-bis (β-acryloyloxyethylthio) Diphenyl ketone, 4,4′-bis (β-acryloyloxyethylthio) diphenyl ketone, 4 , 4′-bis (β-acryloyloxyethylthio) diphenyl ketone, tri (acryloyloxyethyl) isocyanurate, acrylamide, methylenebisacrylamide, diacetone acrylamide, cyclohexene oxide, dendrimer (2nd generation) acrylate, and acrylate in the above Examples include compounds changed to methacrylate.

（式中、Ｘ²²およびＸ²³は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数２〜１００の有機基や、式（１０）：

（式中、Ｑは炭素数３〜１００の単環構造、複環構造または複素環構造の水素原子が前記Ｘ²²またはＸ²³で置換されていてもよい１価または２価の有機基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基を有するものなども使用できる。その具体例としては、たとえば、
式（１１）：

（式中、Ｘ²⁴〜Ｘ²⁸は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基や、式（１２）：

（式中、Ｘ²⁹〜Ｘ³²は同じかまたは異なり、いずれもＨ、Ｆ、炭素数１〜６のアルキル基または炭素数１〜６の含フッ素アルキル基である）
で示される架橋性環状エーテル構造を１〜５個有する炭素数３〜１００の有機基を有するものなども使用することができる。Other examples of the liquid monomer (b1) include the formula (9):

(In the formula, X ²² and X ²³ are the same or different, and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
Or an organic group having 2 to 100 carbon atoms having 1 to 5 crosslinkable cyclic ether structures represented by formula (10):

(In the formula, Q is a monovalent or divalent organic group in which a hydrogen atom of a monocyclic structure, a polycyclic structure or a heterocyclic structure having 3 to 100 carbon atoms may be substituted with X ²² or X ^23. )
Those having 1 to 5 crosslinkable cyclic ether structures represented by the above and having an organic group having 3 to 100 carbon atoms can also be used. For example, for example,
Formula (11):

(Wherein, X ^{24 to} X ²⁸ are the same or different, and all are H, F, a C 1-6 alkyl group or a C 1-6 fluorinated alkyl group)
An organic group having 3 to 100 carbon atoms having 1 to 5 crosslinkable cyclic ether structures represented by formula (12):

(In the formula, X ^{29 to} X ³² are the same or different and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
Those having 1 to 5 crosslinkable cyclic ether structures represented by the formula (1) and having an organic group having 3 to 100 carbon atoms can also be used.

  Specific examples thereof include the following as specific examples.

（ＲはＨまたはＣＨ₃）、

(R is H or CH ₃ ),

（ＲはＨまたはＣＨ₃；Ｒ^6cは炭素数１〜２００の２価以上の含フッ素有機基）、

(R is H or CH ₃ ; R ^6c is a divalent or higher valent fluorine-containing organic group having 1 to 200 carbon atoms),

（ｎは１〜８の整数）、

(N is an integer from 1 to 8),

（Ｒ⁷は炭素数３〜２０の２価の有機基；Ｒ⁸およびＲ⁹は同じかまたは異なり、ＨまたはＣ₃；ｎは２〜１００の整数）で示されるオリゴマーなどがあげられる。

(R ⁷ is a divalent organic group having 3 to 20 carbon atoms; R ⁸ and R ⁹ are the same or different and H or C ₃ ; n is an integer of 2 to 100).

  In addition, for example, allyl glycidyl ether, vinyl glycidyl ether, p-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ester, di-2,3-epoxycyclopentyl ether, ethylene glycol-bis (3,4-epoxycyclohexanecarboxyl) Rate), polyethylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyalkylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycerol polyglycidyl ether, diglycerol tri Glycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, trimer Roll propane polyglycidyl ether, 1,6-dimethylol perfluorohexane diglycidyl ether, phenyl glycidyl ether, resorcin diglycidyl ether, glycerin triglycidyl ether, diglycidyl hexahydrophthalate, orthophthalic acid diglycidyl ester, dibromophenyl glycidyl ether, Bisphenol A diglycidyl ether, 4,4′-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl) -3 ', 4'-epoxy-1,3-dioxane-5-spirocyclohexane, 4', 5'-epoxy-2'-methylcyclohexylmethyl- 4,5-epoxy-2-methylcyclohexanecarboxylate, bis- (3,4-epoxycyclohexylmethyl) adipate, 1,2,5,6-diepoxy-4,7-methanoperhydroindene, 1,2-ethylene Dioxy-bis (3,4-epoxycyclohexylmethane), 3,4-epoxycyclohexyloxirane, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, 1,2,7,8-diepoxy And octane.

  The liquid monomer (b1) is not limited to those exemplified, and a radical polymerizable compound and a cationic polymerizable compound can also be used. From the viewpoint, those having an α-fluoroacryloyl group or an acryloyl group are preferred. Moreover, as a cationically polymerizable compound, what has the organic group shown by Formula (9) or Formula (10) from the point of shrinkage | contraction rate or hologram stability is preferable.

  The liquid monomer (b1) is preferably a polyfunctional monomer from the viewpoint of light resistance and stability.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the molecular weight of the liquid monomer (b1) is preferably 50 to 1000, more preferably 100 to 800, from the viewpoint of recording sensitivity, shrinkage rate, and diffraction efficiency.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the refractive index of the liquid monomer (b1) is preferably 1.40 to 1.70 from the viewpoint of refractive index difference, recording sensitivity or diffraction efficiency. .45 to 1.68 is more preferable.

  In addition, the refractive index of the liquid monomer (b1) is adjusted so that the refractive index modulation degree of the volume hologram to be obtained is increased, a base polymer (a), a photopolymerization initiator (c) described later, and a plasticizer as necessary. It is necessary to be higher than the average refractive index of the mixture with (b2).

  In the fluorine-containing volume hologram recording photosensitive composition of the present invention, the content of the liquid monomer (b1) is preferably 30 to 90% by mass from the viewpoint of recording sensitivity, hologram stability, and diffraction efficiency. 80 mass% is more preferable.

  Furthermore, the liquid monomer (b1) is not limited to these exemplified single use, and two or more kinds can be selected and used.

  In particular, the combination of the liquid monomers (b1) includes a combination of a liquid monomer having an α-fluoroacryloyl group or an acryloyl group and a liquid monomer having a methacryloyl group or a vinyl group, and organic compounds represented by the formulas (9) and (10). A combination of a liquid monomer having a group and a liquid monomer having an organic group represented by formula (11) or formula (12), a liquid monomer having an α-fluoroacryloyl group or an acryloyl group, or a liquid monomer having a methacryloyl group or a vinyl group And combinations of liquid monomers having an organic group represented by formula (9), formula (10), formula (11), or formula (12), etc. From the viewpoint of liquidity having an α-fluoroacryloyl group or an acryloyl group. A combination of a monomer and a liquid monomer having a methacryloyl group or a vinyl group, a liquid monomer having an organic group represented by formula (9) or formula (10), and a liquid having an organic group represented by formula (11) or formula (12) A combination of monomers is preferred.

  As the liquid monomer (b), in addition to the liquid monomer (b1) described above, it is usually preferable to add and use a plasticizer (b2) from the viewpoint of improving sensitivity and diffraction efficiency.

  Examples of the plasticizer (b2) include phthalates represented by dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, dioctyl phthalate; dimethyl adipate, diethyl adipate, dibutyl adipate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate Aliphatic dibasic acid esters typified by Kate and diethylsuccinate; Orthophosphoric acid esters typified by trimethyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate; typified by glyceryl triacetate and 2-ethylhexyl acetate Acetic acid esters; inactive compounds such as phosphites represented by triphenyl phosphite and dibutyl hydrogen phosphite, acetic acid-2-eth Shiechiru are exemplified.

Also, the following formula (33):
R ³ (CH ₂ CH ₂ O) _ζ R ⁴
(In the formula, R ³ and R ⁴ are the same or different and both are alkyl groups having 1 to 5 carbon atoms, hydroxyl groups or acetyl groups; ζ is an integer of 1 to 5)
An alkylene glycol alkyl ether represented by the following formula can also be used.

  Representative alkylene glycol alkyl ethers that can be used include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene Glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, cellosolve acetate, ethylene glycol diacetyl ether, ethylene glycol monoacetyl ether, diethylene glycol diacetyl ether, diethylene glycol monoacetyl ether, triethylene glycol diacetyl ether, triethylene glycol Examples include monoacetyl ether.

  Further, polyethylene glycol or silicone oil having a weight average molecular weight of 10,000 or less can be used as the plasticizer (b2).

  As the plasticizer (b2), it is preferable to select a plasticizer whose refractive index is as close as possible compared with the refractive index of the base polymer (a).

  As the plasticizer (b2), the above exemplary compounds may be used alone or in combination of two or more. The plasticizer (b2) is not limited to those exemplified, and 2-ethoxyethyl acetate, diethyl sebacate, and diethyl adipate are particularly preferable from the viewpoint of recording sensitivity and shrinkage.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the molecular weight of the plasticizer (b2) is preferably 100 to 1000, and preferably 200 to 800 from the viewpoint of the viscosity, sensitivity, shrinkage rate and diffraction efficiency of the composition. Is more preferable.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the refractive index of the plasticizer (b2) is preferably 1.40 to 1.50, and preferably 1.42 to 1.50 from the viewpoint of sensitivity and diffraction efficiency. 45 is more preferred.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the content of the plasticizer (b2) is preferably 10 to 80% by mass from the viewpoint of the viscosity, sensitivity, shrinkage rate and diffraction efficiency of the composition, 20-60 mass% is more preferable.

  The photopolymerization initiator (c) used in the present invention is a compound that is sensitive to light having excellent coherence and starts polymerization of the liquid monomer (b1).

  As the photopolymerization initiator (c), He-Ne (wavelength 633 nm), Ar (wavelength 515, 488 nm), Nd-YAG or Nd: YVO4 (wavelength 532 nm), He-Cd (wavelength 442 nm), AlGaN or InGaN ( It is preferable to generate radicals by absorbing laser light such as a wavelength of 405 ± 5 nm and a YAG triple wave (wavelength of 355 nm).

  Examples of the photo radical polymerization initiator that can be used as the photo polymerization initiator (c) include, for example, US Pat. No. 4,766,055, US Pat. No. 4,868,092, US Pat. No. 4,965,171, and JP-A No. 54-151024. JP-A-58-15503, JP-A-58-29803, JP-A-59-189340, JP-A-60-76735, JP-A-1-28715 and “Proceedings of・ Conference on Radiation Curing Asia (PROCEEDINGS OF CONFERENCE ON RADIATION CURING ASIA) ”(P.461-477, 1988) etc. can be used, but as long as this Absent.

  Specific examples of the radical photopolymerization initiator that can be used as the photopolymerization initiator (c) include, for example, diaryliodonium salts as described in JP-A-58-29803 and JP-A-1-287105, Or 2,4,6-substituted-1,3,5-triazines and organic peroxides. When high photosensitivity is required, the use of diaryliodonium salts is particularly preferred.

  Specific examples of the diaryl iodonium salts include, for example, diphenyl iodonium, 4,4′-dichlorodiphenyl iodonium, 4,4′-dimethoxydiphenyl iodonium, 4,4′-ditertiary butyl diphenyl iodonium, 3,3′-dinitro. Examples include chlorides such as diphenyliodonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, and the like.

  Specific examples of 2,4,6-substituted-1,3,5-triazines include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,4 6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 (P-methoxyphenylvinyl) -1,3,5-triazine, 2- (4′-methoxy-1′-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, benzoic acid -4- [4,6-bis (trichloromethyl) -1,3,5-triazin-2-yl] -methyl ester, benzoic acid-4- [4,6-bis (trichloromethyl) -1,3 5-Triazin-2-yl], 1,3,5-to Azine-2,4-bis (trichloromethyl) -6- [4- (trifluoromethyl) phenyl], 1,3,5-triazine-2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) ), 1,3,5-triazine-2- [4- (methylthio) phenyl] -4,6-bis (trichloromethyl), N-1606, a photopolymerization initiator manufactured by ADEKA, and the like.

  Specific examples of organic peroxides include 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, “3,3-bismethoxycarbonyl-4,4-bis-tert- Butylperoxycarbonylbenzophenone, 3,4-bismethoxycarbonyl-4,3-bis-tert-butylperoxycarbonylbenzophenone, 4,4-bismethoxycarbonyl-3,3-bis-tert-butylperoxycarbonylbenzophenone "mixture, di -Tert-butyl peroxyisophthalate, benzophenone and the like are exemplified.

  The cationic photopolymerization initiator that can be used as the photopolymerization initiator (c) is an initiator that generates a Bronsted acid or a Lewis acid in response to light and polymerizes the cationic polymerizable compound. That's fine. As such a photocationic polymerization initiator, for example, “UV Curing; Science and Technology (UV CURING; SCIENCE AND TECHNOLOGY)” [pp. 23-76, S.M. Edited by S. PETER PAPPAS, A TECHNOLOGY MARKING PUBLICATION] and "Comments Inorg. Chem." [B. Klingelt, M.M. Reedy Car and A. Rolov (B. KLINGERT, M. RIEDICER and A. ROLOFF), Vol. 3, pp109-138 (1988)], etc., and one or more of these may be used.

  Preferable photocationic polymerization initiators that can be used as the photopolymerization initiator (c) include initiators containing diaryliodonium salts, triarylsulfonium salts, and the like.

  Preferred examples of the diaryl iodonium salts as the photocationic polymerization initiator include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, iodonium described in the photoradical polymerization initiator, 9,10-dimethoxyanthracene-2-sulfonate and the like.

  Preferred triarylsulfonium salts include triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, 4-thiophenyltriphenylsulfonium, and the like. Examples include sulfonium tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, and one or more of these may be used.

At least one of the cationic polymerizable liquid monomer (b1) and the radical polymerizable liquid monomer (b1) is partially exposed to light used in pre-exposure having a wavelength different from that of light used in interference fringe exposure. It is also possible to polymerize. At that time, the photopolymerization initiator (c) used is sensitized to light having a wavelength different from the wavelength of the laser beam used in the interference fringe exposure in the exposure, and the cationic polymerizable liquid monomer (b1) and radical It is an initiator that acts as a radical photopolymerization initiator and / or a cationic photopolymerization initiator on at least one of the polymerizable liquid monomer (b1). At least one of the cationic polymerizable liquid monomer (b1) and the radical polymerizable liquid monomer (b1) is partially polymerized by the action of the photopolymerization initiator in the pre-exposure. As used herein, “partially polymerized” refers to a cationically polymerizable liquid monomer (b1) and / or a radically polymerizable liquid monomer (b1) in an unreacted compound state. It means a state in which at least one of b1) and the radical polymerizable liquid monomer (b1) is polymerized. In particular,
When the cationic polymerizable liquid monomer (b1) is substantially completely polymerized and the radical polymerizable liquid monomer (b1) is not polymerized or partially polymerized,
When the radical polymerizable liquid monomer (b1) is substantially completely polymerized and the cationic polymerizable liquid monomer (b1) is not polymerized or partially polymerized,
When only a part of the cationic polymerizable liquid monomer (b1) is polymerized and the radical polymerizable liquid monomer (b1) is not polymerized,
When only a part of the radically polymerizable liquid monomer (b1) is polymerized and the liquid monomer (b1) of the cationically polymerizable compound is not polymerized, and ・ The cationically polymerizable liquid monomer (b1) and radically polymerizable The case where both of the liquid monomers (b1) are partially polymerized is included. By such polymerization by pre-exposure, when the photosensitive layer made of the photosensitive composition is left in a horizontal state, the composition is cured to such an extent that the solidity is maintained without flowing out. Preferably, the polymerizable compound polymerized by pre-exposure is a polymerizable compound different from the polymerizable compound polymerized by subsequent interference fringe exposure, and in this case, better interference fringe recording can be obtained.

  Among such photopolymerization initiators (c), examples of compounds that act as photoradical polymerization initiators when exposed to the light used in the pre-exposure include, for example, the photopolymerization initiators, titanocene compounds, mono Examples include acylphosphine oxide, bisacylphosphine oxide, and a combination of bisacylphosphine oxide and α-hydroxyketone.

  Of the photopolymerization initiator (c), examples of the compound that is sensitive to the light used in the pre-exposure and acts as a photocationic polymerization initiator include iron arene complexes. One of these may be used as the photopolymerization initiator (c), or two or more may be used in combination. These are compounds having an absorption maximum wavelength mainly in the range from the near ultraviolet to the visible region.

  All titanocene compounds known as titanocene compounds can be used. For example, the titanocene compounds described in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705 are disclosed. can give. Specific examples include bis (cyclopentadienyl) -di-chloro-titanium, bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -bis (2,3,4,5). , 6-pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluorophenyl) titanium, bis (methylcyclopentadienyl) -bis (2,3,4,5,6-penta Fluorophenyl) titanium, bis (methylcyclopentadienyl) -bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr) -1-yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-((1-pyr- -Yl) methyl) phenyl] titanium, bis (methylcyclopentadienyl) -bis [2,6-difluoro-3-((1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) ) -Bis [2,6-difluoro-3-((2,5-dimethyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro- 3-((3-trimethylsilyl-2,5-dimethyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-((2, 5-bis (morpholinomethyl) -1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-4-((2,5- Methyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methyl-4- (2- (1-pyr-1-yl) Ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1-methyl-2- (1-pyr-1-yl) ethyl) phenyl] titanium, bis (cyclopenta Dienyl) -bis [2,6-difluoro-3- (6- (9-carbazol-9-yl) hexyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (4,5,6,7-tetrahydro-2-methyl-1-indol-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro- 3-((acetylamino) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (propionylamino) ethyl) phenyl] titanium, bis (cyclopentadienyl) ) -Bis [2,6-difluoro-3- (4- (bivaloylamino) butyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (2, 2-dimethylpentanoylamino) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (benzoylamino) propyl) phenyl] titanium, bis (cyclopentadienyl) ) -Bis [2,6-difluoro-3- (2- (N-allylmethylsulfonylamino) ethyl) phenyl] titani Arm, bis (cyclopentadienyl) - bis (2,6-difluoro-3- (1-pill-1-yl) phenyl) such as titanium and the like.

  Any known monoacylphosphine oxide can be used as the monoacylphosphine oxide. Examples thereof include monoacylphosphine oxide compounds described in Japanese Patent Publication No. 60-8047 and Japanese Patent Publication No. 63-4077. Specific examples include isobutyryl-tylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid methyl ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p. -Toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenylphosphinic acid methyl ester, p-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, acryloyl-phenylphosphinic acid Methyl ester, isobutyryl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, o-tolu Ru-diphenylphosphine oxide, p-tertiary butylbenzoyl-diphenylphosphine oxide, 3-pyridylcarbonyl-diphenylphosphine oxide, acryloyl-diphenylphosphine oxide, benzoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid vinyl ester, adipoyl-bis- Diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, 4- (tertiarybutyl) -benzoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, 2-methylbenzoyl-diphenylphosphine oxide, versatoyl -Diphenylphosphine oxide, 2-methyl-2-ethyl Examples include ruhexanoyl-diphenylphosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, and SP-246, a photopolymerization initiator manufactured by ADEKA. It is done. Any known bisacylphosphine oxide can be used as the bisacylphosphine oxide. Examples thereof include bisacylphosphine oxide compounds described in JP-A-3-101686, JP-A-5-345790, and JP-A-6-298818. Specific examples include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl). -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-di Chlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis ( 2,6-dichlorobenzoyl) -decylphos Zinc oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5 -Dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxy Benzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis ( 2-Methyl-1-naphthoyl) -2- Butylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methoxy-1) -Naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine And oxides.

  Examples of α-hydroxy ketones include 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl. -Propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone and the like.

Examples of iron arene complexes include ferrocene, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (II) ⁻ , (η ⁶ -toluene) (η ⁵ -cyclopentadienyl) iron (II) ^−. , (Η ⁶ -cumene) (η ⁵ -cyclopentadienyl) iron (II) ⁻ , (η ⁶ -naphthalene) (η ⁵ -cyclopentadienyl) iron (II) ⁻ , (η ⁶ -anthracene) ( chlorides such as η ⁵ -cyclopentadienyl) iron (II) ⁻ , (η ⁶ -pyrene) (η ⁵ -cyclopentadienyl) iron (II) ⁻ , bromide, sulfonate, tetrafluoroborate, hexafluorophosphate, Hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, etc., and derivatives having one or more substituents on the ligand of these compounds And the like. In addition, N-1919 and N-1717, which are photopolymerization initiators manufactured by ADEKA, are listed.

  In the composition for a fluorine-containing volume hologram optical information recording material of the present invention, the content of the photopolymerization initiator (c) is preferably 5 to 90% by weight (particularly 8 to 80% by weight). The photopolymerization initiator (c) may contain any one of (c-1) a photoradical polymerization initiator and (c-2) a photocationic polymerization initiator, depending on the interference fringe exposure process to be used, or A photopolymerization initiator containing both of them may be used as a polymerization initiator in a post-exposure step performed as necessary. Furthermore, you may use the compound which acts as both (c-1) photoradical polymerization initiator and (c-2) photocationic polymerization initiator as a photoinitiator (c). When different compounds are used in combination as (c-1) photoradical polymerization initiator and (c-2) photocationic polymerization initiator, (c-1) photoradical polymerization initiator is used with respect to the total amount of photopolymerization initiator. 5 to 70% by weight (especially 8 to 40% by weight), and (c-2) a photopolymerization initiator containing a cationic photopolymerization initiator in an amount of 5 to 70% by weight (especially 8 to 40% by weight) is used. Is preferred.

  The dye sensitizer (e) is a component that generally absorbs light, and a combination of the photopolymerization initiator (c) and the dye sensitizer (e) in order to sensitize the photopolymerization initiator (c). Are preferably used. As the dye sensitizer (e), a compound that does not substantially absorb light of the light source wavelength used in the pre-exposure or has little absorption of this light is used. As the dye sensitizer (e), a colored compound such as a dye is often used to absorb visible laser light.

  The dye sensitizer may be any one that absorbs light in the visible region. In addition to the above, for example, cyanine derivatives, merocyanine derivatives, phthalocyanine derivatives, xanthine derivatives, thioxanthene derivatives, acridine derivatives, porphyrin derivatives, coumarin derivatives Base styryl derivatives, ketocoumarin derivatives, quinolone derivatives, stilbene derivatives, oxazine derivatives, thiazine-based dyes, squarylium derivatives, and metal-containing squarylium derivatives, etc. can also be used. Kodansha, 1986), “Chemistry of functional pigments” (Nobu Okawara et al., CMC 1983), “Special functional materials” (Tadasaburo Ikemori et al., CMC, 1986) A dye can also be used. When the final volume hologram recording layer is required to be colorless and transparent, cyanine as described in JP-A-58-29803 and JP-A-1-287105 is used as a dye sensitizer. It is preferred to use a system dye. Since cyanine dyes are generally easily decomposed by light, the dyes in the volume hologram are decomposed and absorbed in the visible region by being left exposed for several hours to several days under post-exposure or indoor light or sunlight in the present invention. A colorless and transparent volume hologram can be obtained.

  Specific examples of the cyanine dye include anhydro-3,3′-dicarboxymethyl-9-ethyl-2,2′-thiacarbocyanine betaine, anhydro-3-carboxymethyl-3 ′, 9-diethyl-2, 2'-thiacarbocyanine betaine, 3,3 ', 9-triethyl-2,2'-thiacarbocyanine iodine salt, 3,9-diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine Iodine salt, 3,3 ′, 9-triethyl-2,2 ′-(4,5,4 ′, 5′-dibenzo) thiacarbocyanine iodine salt, 2- [3- (3-ethyl-2-benzo Thiazolidene) -1-propenyl] -6- [2- (3-ethyl-2-benzothiazolidene) ethylideneimino] -3-ethyl-1,3,5-thiadiazolium iodine salt, 2- [[3-ants -4-oxo-5- (3-n-propyl-5,6-dimethyl-2-benzothiazolidene) -ethylidene-2-thiazolinylidene] methyl] -3-ethyl-4,5-diphenylthiazolinium Iodine salt, 1,1 ′, 3,3,3 ′, 3′-hexamethyl-2,2′-indotricarbocyanine / iodine salt, 3,3′-diethyl-2,2′-thiatricarbocyanine Perchlorate, anhydro-1-ethyl-4-methoxy-3′-carboxymethyl-5′-chloro-2,2′-quinothiocyanine betaine, anhydro-5,5′-diphenyl-9-ethyl-3 , 3′-disulfopropyloxacarbocyanine hydroxide triethylamine salt, YT-245, GPX-102 and TY-235 which are photosensitizing dyes manufactured by ADEKA, It may be used one or more of these.

  Further, when the finally obtained volume hologram does not have to be colorless and transparent, an acene as described in JP-A-6-184111, JP-A-6-317907 and JP-T-2000-513102. Or a coumarin dye as described in JP-A-63-180946 can be used.

  Specific examples of the acene dye include anthracene, 9-anthracenemethanol, 1,4-dimethoxyanthracene, 9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9-phenoxymethylanthracene, 9,10-bis (n -Butylethynyl) anthracene, 9,10-bis (n-trimethylsilylethynyl) anthracene, 1,8-dimethoxy-9,10-bis (phenylethynyl) anthracene, 5,12-bis (phenylethynyl) -naphthacene It is done. These compounds have an effect of sensitizing the photopolymerization initiator to light having a wavelength of 514 nm from an argon ion laser and a double wave of 532 nm from a YAG laser. 1,8-dimethoxy-9,10-bis (phenylethynyl) anthracene and 5,12-bis (phenylethynyl) -naphthacene can be preferably used as sensitizers.

  Specific examples of coumarin dyes and ketocoumarin dyes include, for example, 7-dimethylamino-3- (2-thenoyl) coumarin, 7-diethylamino-3- (2-furoyl) coumarin, 7-diethylamino-3- (2 -Thenoyl) coumarin, 7-pyrrolidinyl-3- (2-thenoyl) coumarin, 7-pyrrolidinyl-3- (2-benzofuroyl) coumarin, 7-diethylamino-3- (4-dimethylaminocinnamoyl) coumarin, 7-diethylamino -3- (4-diethylaminocinnamoyl) coumarin, 7-diethylamino-3- (4-diphenylaminocinnamoyl) coumarin, 7-diethylamino-3- (4-dimethylaminocinnamylideneacetyl) coumarin, 7-diethylamino- 3- (4-Diethylaminocinnamylidene acetylene ) Coumarin, 7-diethylamino-3- (4-diphenylaminocinnamylideneacetyl) coumarin, 7-diethylamino-3- (2-benzofuroyl) coumarin, 7-diethylamino-3- [3- (9-julolidyl) acryloyl] Coumarin, 3,3′-carbonylbis (7-methoxycoumarin), 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (6-methoxycoumarin), 3,3 ′ -Carbonylbis (7-dimethylaminocoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3,3'carbonylbis-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 3, 3'-carbonylbis (7-dibutylaminocoumarin), 3-carbethoxy-7- Diethylamino) coumarin, 3- (2-benzothiazolyl) -7-diethylamino) coumarin, 3- (2-benzothiazolyl) -7-dibutylamino) coumarin, 3- (2-benzothiazolyl) -7-dioctylamino) coumarin, 3 -(2-Benzimidazolyl) -7-diethylamino) coumarin, 10 [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1, 7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one and the like.

  For example, 2- [p- (dimethylamino) styryl] benzothiazole, 2- [p- (dimethylamino) styryl] naphtho [1,2-d] thiazole, 2-[(m- Hydroxy-p-methoxy) styryl] benzothiazole and the like.

  As the merocyanine derivative, for example, 3-ethyl-5-[(3-ethyl-2- (3H) -benzothiazolylidene) ethylidene] -2-thioxo-4-oxazolidinone-5-[(1,3 -Dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) ethylidene] -3-ethyl-2-thioxo-4-oxazolidinone.

  Furthermore, since the squarylium derivative and the metal-containing squarylium derivative have optical constants suitable for recording and reproduction with laser light in a short wavelength region of 300 nm to 530 nm, the optical recording composition for recording and reproduction with a short wavelength laser is used. It is extremely useful as a dye sensitizer to be used.

For example, the maximum absorption wavelength (hereinafter referred to as “λmax”) of 3-hydroxy-4- (4-methoxy-2-methyl-phenyl) -cyclobut-3-ene-1,2-dione, which is a squarylium compound, in methanol. (Hitachi High-Technologies, U-3500) was 330 nm, and the extinction coefficient at λmax was 75.4 l · g ⁻¹ cm ⁻¹ .

  Further, as a result of differential thermal analysis (Seiko Instruments Inc., TG / DTA6300), the decomposition point was 430 ° C. Further, the obtained squarylium compound was dissolved in tetrafluoropropanol to 2 wt%, and a thin film was formed on a flat polycarbonate disk by a spin coating method. As a result, the absorption spectrum of this coating film was λmax of 350 nm (transmission method) )Met.

  This squarylium compound and the metal squarylium compound that is a nickel complex thereof have light absorption in the wavelength region of 300 to 530 nm and have a high extinction coefficient.

  Specific examples of the squarylium compound include 3-hydroxy-4- (4-methoxy-2-methyl-phenyl) -cyclobut-3-ene-1,2-dione, 3-amino-4- [2,6-dimethyl. -3- (2-phenyl-propoxy) -phenyl] -cyclobut-3-ene-1,2-dione, N- [2- (3-ethoxy-5-fluoro-phenyl) 3,4-dioxo-cyclobuta- 1-enyl] -C, C, C-trifluoro-methanesulfonamide,

  Further, specific examples of these metal-containing squaryliums include 3-hydroxy-4- (4-methoxy-2-methyl-phenyl) -cyclobut-3-ene-1,2-dione-nickel complex (metal-containing squarylium compound). 3-amino-4- [2,6-dimethyl-3- (2-phenyl-propoxy) -phenyl] -cyclobut-3-ene-1,2-dione-zinc complex, N- [2- (3- Ethoxy-5-fluoro-phenyl) 3,4-dioxo-cyclobut-1-enyl] -C, C, C-trifluoro-methanesulfonamide-cobalt complex.

  Specific examples of the organic peroxide-dye sensitizer combination include 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone or “3,3-bismethoxycarbonyl-4, 4-bis-tert-butylperoxycarbonylbenzophenone, 3,4-bismethoxycarbonyl-4,3-bis-tert-butylperoxycarbonylbenzophenone, 4,4-bismethoxycarbonyl-3,3-bis-tert-butylperoxy "Carbonyl benzophenone" mixture or di-tert-butylperoxyisophthalate and photosensitizing dyes (dye sensitizers) manufactured by Nippon Photosensitive Dye Laboratories, Inc. NKX653, NKX3883, NKX188150, NKX1253, NKX1595, NKX1658, NKX1695 NK4256, NK1886, NK1473, NK1474, NK4795, NK4276, NK4278, NK91, NK1046, NK1237, NK1420, NK1538, combination of such NK3590 is preferred.

  Specific examples of 2,4,6-substituted-1,3,5-triazines-dye sensitizer combinations include 2,4,6-tris (trichloromethyl) -1,3,5-triazine, or 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine or 2,4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine NKX653, NKX3883, NKX188150, NKX1253, NKX1595, NKX1658, NKX1695, NK4256, NK1886, NK1473, NK1475, NK4295, 42, NK91, NK1046, NK1237, NK1420, NK1538, NK3 Preferably in combination with, such as 90.

  Further, a combination of “B-CIM” manufactured by Hodogaya Chemical Co., Ltd. as a bisimidazole derivative, a chain transfer agent such as 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and the above-described dye sensitizer can also be used suitably. .

  Specific examples of the carbonyl compound-dye sensitizer combination include benzyl-mihiraketone and benzyl-acridine yellow. Moreover, as a dye sensitizer combined with an amine compound, decarboxylated rose bengal is preferable. As the dye sensitizer combined with the borate compound, cyanine dyes such as cyanines, isocyanines and pseudocyanines are preferable.

  In the photosensitive composition for fluorine-containing volume hologram recording of the present invention, the content of the dye sensitizer (e) is 0.01 to 15% by weight (particularly 0. 15%) from the viewpoints of sensitivity, diffraction efficiency and shrinkage. In an amount of 03 to 10% by weight).

Furthermore, you may use a photosensitizer for the composition used for the recording layer of the volume hologram of this invention.
Preferred photosensitizers include Michler's ketone, acridine yellow, merocyanine, methylene blue, camphorquinone, eosin, 2,5-bis [(4-diethylamino) -2-methylbenzylidene] cyclopentanone, decarboxylated rose bengal, etc. Used for.

  In addition, the fluorine-containing volume hologram recording photosensitive composition of the present invention and its medium include additives such as plasticizers, heat stabilizers, brighteners, ultraviolet absorbers, polymerization inhibitors, continuous agent transfer agents, It is preferable to add a bleaching agent and, if necessary, ultrafine particles.

  Specific examples of the ultrafine particles include, but are not particularly limited to, for example, inorganic compound fine particles and colloidal sol, but an inorganic oxide having a refractive index of 1.70 or less is preferable.

Specifically, ultrafine particles such as colloidal silica (refractive index 1.45) and colloidal zirconia (refractive index 1.55) and colloidal sol are desirable. The particle diameter (volume average particle diameter) of the ultrafine particles and colloidal sol is desirably sufficiently smaller than the wavelength of visible light in order to ensure the transparency of the low refractive index material. Specifically, it is preferably 100 nm or less, particularly 10 nm or less.
The volume average particle size of the fine particles can be dispersed at room temperature by dispersing in an organic solvent such as ethanol using a particle size distribution measuring device using a laser diffraction scattering method (for example, a particle size distribution measuring device 9320HRA manufactured by Microtrack). To measure.

  When using inorganic compound fine particles, it should be used in the form of an organic sol dispersed in advance in an organic dispersion medium in order not to lower the dispersion stability in the composition and the hologram recording stability in the material. desirable. Furthermore, in order to improve the dispersion stability of the inorganic compound fine particles in the composition, the surface of the inorganic fine particle compound can be modified in advance using various coupling agents. Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony or mixtures thereof; salts of organic acids; coordination compounds bonded to coordination compounds, and the like. .

  In addition to the above, the fluorine-containing volume hologram optical recording composition of the present invention and the volume hologram thereof include additives such as polymerization non-shrink materials, expansion materials, organometallic compounds, deterioration inhibitors, An extender for blocking prevention, a filler such as a resin, a surfactant, an antifoaming agent, a leveling agent, and a thixotropic agent may be added as necessary.

  The following etc. are illustrated as a polymerization non-shrink material and an expansion material.

In the photosensitive composition for fluorine-containing volume hologram optical recording of the present invention and the method for producing the volume hologram, the volume shrinkage rate upon curing is 15% or less. Here, “volume shrinkage ratio upon curing” means that the liquid specific gravity of the fluorine-containing volume hologram optical recording photosensitive composition before curing containing a polymerizable liquid monomer is D1, and the solid specific gravity after curing is D2. Then, it is a value given by the following formula.
[(D2-D1) / D2] × 100

  In general, a large number of polymerizable monomers are known to cause volume shrinkage because the distance between molecules becomes short when polymerized or cured through radical polymerization reaction or cationic polymerization reaction. On the other hand, the volume shrinkage due to the curing in the ring-opening polymerization of cyclic ethers is relatively small and can be preferably used in the present invention.

  Some compounds having a plurality of cyclic ether structures in one molecule expand in volume with polymerization, and these compounds can also be used in the present invention. For example, spiro orthoesters of epoxy compounds are high in density because of the large interaction between molecules before polymerization, and even when cured through ring-opening polymerization, the change in the distance between molecules is small or may expand. Known (for example, “Japanese Patent Publication No. 61-038931”, “Precision Polymer Design by Ring-Opening Polymerization”, Toshikazu Takada, Nobuhiro Kihara, Kobunka Kako, Vol. 47, No. 11 (1998) pp. 482-488. "Functional polymer synthesis utilizing spiro compounds", Takeshi Endo, Toshikazu Takada, Journal of Petroleum Society, Vol. 32, No. 5 (1989), pp. 237-247).

  In the present invention, since a spiro orthoester of an epoxy compound is used as the matrix material of the recording layer, volume change during polymerization can be suppressed, and warpage of the substrate and peeling of the recording layer can be prevented.

  Moreover, what is synthesize | combined by reaction of an epoxy compound and lactone can be used suitably as spiro orthoester of an epoxy compound. These compounds are relatively easy to synthesize.

  Examples of epoxy compounds include phenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 2,3-epoxy-1-propanol, styrene oxide, 1, 2: 8,9 -Diepoxy limonene, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,2,7,8-diepoxyoctane, hydroquinone diglycidyl Ether, diglycidyl terephthalate, N-glycidyl phthalimide, resorcinol diglycidyl ether, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A, 3,4-epoxycyclohexenylmethyl-3 ′ , 4'-epoxycyclohexenecarboxylate, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylylenediamine, tetraglycidylbisaminomethylcyclohexane and epoxypropoxypropyl terminated poly Examples thereof include dimethylsiloxane.

Examples of lactones include γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprolactone, γ-laurolactone, γ-palmilactone, γ-stearolactone, crotolactone, α-angelica lactone, β- Examples thereof include angelica lactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, coumarin, and a macrocyclic lactone represented by the following general formula (1).

  The spiro orthoester of an epoxy compound is prepared by dissolving a lactone and a catalyst such as BF3OEt3 in methylene chloride or carbon tetrachloride and adding a solution obtained by dissolving the epoxy compound in an appropriate solvent dropwise while controlling the reaction rate. The reaction temperature at this time is generally in the range of 0 to 30 ° C. The charging ratio of lactone and epoxy compound is usually a ratio of 1 equivalent or more of lactone to 1 equivalent of epoxy group.

Examples of the spiro orthoester obtained by reacting an epoxy compound with a lactone include the following compounds. Compound (2) can be obtained by reacting glycidyl ether of bisphenol A with γ-butyrolactone. Compound (3) can be obtained by reacting an alicyclic epoxy with ε-caprolactone.

  In order to promote the ring-opening polymerization reaction of the spiro orthoester, it is preferable to add a cationic polymerization accelerator. Examples of the cationic polymerization accelerator include known sulfonium salts, ammonium salts, onium salts such as phosphonium salts, and aluminum silanol complexes.

  As disclosed in Japanese Examined Patent Publication No. 62-15083, spiro orthoesters synthesized from epoxy compounds and lactones undergo ring-opening polymerization even with organic acid curing agents. Therefore, spiro orthoesters and organic acid curing agents are used in combination. Thus, a matrix may be formed. Examples of organic acid curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), Maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene tetracarboxylic anhydride, polyadipic acid Anhydrides, polyazeline acid anhydrides, polysebacic acid anhydrides and the like can be mentioned.

  In order to shorten the curing time, a curing accelerator may be added as necessary. Examples of the curing accelerator include tertiary amines, organic phosphine compounds, imidazole compounds and derivatives thereof. Specifically, triethanolamine, piperidine, N, N′-dimethylpiperazine, 1,4-diazadicyclo [2.2.2] octane, pyridine, picoline, dimethylcyclohexylamine, dimethylhexylamine, benzyldimethylamine, 2- (Dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), DBU phenol salt, trimethylphosphine, triethylphosphine , Tributylphosphine, triphenylphosphine, tri (p-methylphenyl) phosphine, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyli Imidazole, such as 2-hepta-imidazole, and the like. A catalyst such as boron trifluoride amine complex, dicyandiamide, organic acid hydrazide, diaminomaleonitrile and derivatives thereof, melamine and derivatives thereof, and amine imide may be used.

  The organometallic compound is in a gel or sol form, and the liquid monomer (a) or base polymer (b) in the liquid phase is uniformly dispersed with good compatibility in the organometallic compound.

  The organometallic compound has at least two kinds of metal (M), oxygen, and an aromatic group (Ar), and two aromatic groups (Ar) are directly bonded to one metal (M). It has an organometallic unit (Ar-M-Ar). Metals (M) are bonded through oxygen atoms. Here, the metal (M) is arbitrarily selected from the group consisting of Si, Ti, Zr, Ge, Sn, Al, and Zn, for example. Of the two or more selected metals, only one type of metal may constitute the organometallic unit, or other types of metals may constitute separate organometallic units. When the organometallic compound contains two or more kinds of metals as constituent metals, it is easy to control characteristics such as a refractive index, and the material design of the recording material is facilitated. The organometallic compound is a so-called sol / gel hydrolysis and polymerization reaction using two or more corresponding metal (M) alkoxide compounds and a metal (M) diaryl alkoxide compound constituting the organometallic unit. Formed by reaction.

  First, the organometallic compound is prepared by hydrolysis and polymerization reaction such as sol / gel method. For example, by using a diphenyl alkoxide compound of Si and an alkoxide compound of Ti as raw materials, both raw materials are hydrolyzed and polymerized, Si and Ti are used as constituent metals, and the organometallic has various molecular weights including diphenylsilane units. A composition of the compound is obtained.

  This hydrolysis and polymerization reaction can be carried out under the same operation and conditions as in the known sol / gel method. For example, a predetermined proportion of a metal alkoxide compound raw material (Si diphenyl alkoxide compound and Ti alkoxide compound) is dissolved in an appropriate good solvent to form a homogeneous solution, and an appropriate acid catalyst is dropped into the solution, and in the presence of water. The reaction can be carried out by stirring the solution.

  Examples of such solvents include water; alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; ethers such as diethyl ether, dioxane, dimethoxyethane, and tetrahydrofuran; N-methylpyrrolidone, acetonitrile, dimethylformamide, and dimethyl. Examples include acetamide, dimethyl sulfoxide, acetone, benzene and the like. What is necessary is just to select suitably from these. Or it can also be set as these mixed solvents. Although the quantity of a solvent is not limited, It is good to set it as 10-1000 weight part with respect to 100 weight part of the whole metal alkoxide compound.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, and the like. Organic acids and the like.

  Although it depends on the reactivity of the metal alkoxide compound, the hydrolysis polymerization reaction can generally be performed at room temperature, and can be performed at a temperature of about 0 to 150 ° C., preferably at a temperature of about room temperature to 50 ° C. The reaction time may be appropriately determined in relation to the reaction temperature, but is about 0.1 to 240 hours. The reaction may be performed under an inert atmosphere such as nitrogen gas, or may be performed under reduced pressure of about 0.5 to 1 atm while removing alcohol generated by the polymerization reaction.

  Before or after the hydrolysis, the liquid monomer (a) or the base polymer (b) and the mixture of the liquid monomer (a) and the base polymer (b) are mixed. The liquid monomer (a) or base polymer (b) and the metal alkoxide compound raw material may be mixed after hydrolysis, or may be mixed before hydrolysis. When mixing after hydrolysis, in order to mix uniformly, it is preferable to add and mix the liquid monomer (a) or the base polymer (b) while the sol / gel reaction system containing the organometallic compound is in a sol state. . The photopolymerization initiator (c) can also be mixed before or after the hydrolysis.

  Thus, a fluorine-containing volume hologram recording photosensitive composition in which the liquid monomer (a) or the base polymer (b) and the organometallic compound in the sol state are uniformly mixed is obtained.

  The photosensitive composition for fluorine-containing volume hologram recording of the present invention can be applied to a substrate without solvent, but it is solubilized in an organic solvent (f) for the purpose of controlling the film thickness, and is solvent-based. It is applied in the form of a composition.

  As the organic solvent (f) to be used, for example, at least one general-purpose organic solvent such as a ketone solvent, an acetate solvent, an alcohol solvent, an aromatic solvent, or a mixed solvent containing at least one of these general-purpose solvents Can be given.

  Solubilization in organic solvents, especially general-purpose organic solvents, is preferable because it is excellent in film formability and homogeneity when it is formed on a wide variety of transparent substrates, especially for coating applications, especially from 1 μm thin film to about 180 μm coating film formation. It is also advantageous in terms of productivity, and is suitable for producing a fluorine-containing volume hologram recording photosensitive medium and a fluorine-containing volume hologram.

  The organic solvent (f) is particularly suitable as long as the fluorine-containing volume hologram recording photosensitive composition and additives such as a crosslinking agent, a leveling agent, a light stabilizer and the like are uniformly dissolved or dispersed as required. Although there is no restriction | limiting, Especially the thing which melt | dissolves the fluorine-containing volume type hologram recording photosensitive composition uniformly is preferable. The mode of using this solvent is particularly preferable in the field where a thin layer coating (about 1 μm to 20 μm) is required, such as for optical elements, and is highly transparent and capable of obtaining a uniform coating with good productivity.

  Examples of the organic solvent (f) include cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, acetic acid Ester solvents such as butyl, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Propylene glycol solvents such as ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol System solvents; aromatic hydrocarbons such as toluene and xylene, or a mixed solvent of two or more of these.

  Furthermore, in order to improve the solubility of the base polymer (a), a fluorine-based organic solvent may be used as necessary.

などのフッ素系アルコール類、ベンゾトリフルオライド、パーフルオロベンゼン、パーフルオロ（トリブチルアミン）、ＣｌＣＦ₂ＣＦＣｌＣＦ₂ＣＦＣｌ₂などがあげられる。Examples of fluorine-based organic solvents include CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2-butyltetrahydrofuran). ), Methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene,

And fluorinated alcohols such as benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), and ClCF ₂ CFClCF ₂ CFCl ₂ .

  These fluorinated solvents may be used singly or as a mixed solvent of fluorinated solvents or one or more of non-fluorinated and fluorinated solvents.

  Of these, ketone solvents, acetate solvents, alcohol solvents, aromatic solvents, and the like are preferable in terms of paintability and coating productivity.

  In addition, when the fluorine-containing volume hologram recording photosensitive composition is dissolved and applied, the present inventors mix a fluorine-containing alcohol solvent together with these general-purpose solvents to form a base of the photosensitive composition film after coating and drying. It has been found that leveling properties for the material are improved.

  This leveling improvement effect is high for resin base materials, particularly acrylic resins, cellulosic resins, polyethylene terephthalate, polycarbonate, and polyolefin, and particularly remarkable for polyethylene terephthalate base materials.

などが好ましい具体例である。The fluorine-containing alcohol to be added may be any one having a boiling point of 50 ° C. or higher, preferably 80 ° C. or higher and capable of dissolving and applying the fluorine-containing volume hologram recording photosensitive composition. For example,

Etc. are preferable specific examples.

  The fluorinated alcohol may be used as an organic solvent by itself, but it is also effective when used in addition to general-purpose solvents such as the above-mentioned ketone solvents, acetate solvents, non-fluorine alcohol solvents, and aromatic solvents. Is.

  When used in combination, the addition amount is 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 10 to 30% by weight, based on the whole solvent.

  The proportion of the organic solvent (f) in the solvent-type composition of the present invention varies depending on the coating method, drying conditions (temperature, humidity), etc., but is preferably 1% by weight or more, more preferably 5% by weight or more of the entire composition. It is preferably 95% by weight or less, more preferably 90% by weight or less.

  Hologram recording methods that can be employed in the present invention include a polarization collinear hologram recording (including coaxial recording) method, a reference light incident angle multiplex hologram recording (including polytopic recording) method, and the like. When a photosensitive medium for recording is used as a recording medium, the reference collinear hologram recording (including coaxial recording) method is also available because the reference light and information light are coaxial and can be positioned with high accuracy and vibration measures are easy. preferable.

  In the photosensitive medium for fluorine-containing volume hologram recording, the thickness of the photosensitive recording layer formed from the photosensitive composition for fluorine-containing volume hologram recording is 1 from the viewpoint of adhesion to the substrate and flexibility. ˜180 μm is preferable, and 1 to 150 μm is more preferable.

  The photosensitive medium for fluorine-containing volume hologram recording of the present invention is a suitable base material by a method such as a spin coater, gravure coater, comma coater, bar coater, etc. It can manufacture by apply | coating to and forming a photosensitive recording layer.

  The substrate film used for the photosensitive medium for fluorine-containing volume hologram recording or the fluorine-containing volume hologram of the present invention has transparency and is not particularly limited. For example, a polyethylene film, Polypropylene film, Polyethylene fluoride film, Polyvinylidene fluoride film, Polyvinyl chloride film, Polyvinylidene chloride film, Ethylene-vinyl alcohol film, Polyvinyl alcohol film, Polymethyl methacrylate film, Polyether sulfone film, Polyether ether ketone film, Polyamide film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film, triacetyl cellulose film (TAC), amorphous polyolefin, Polyester films such as triethylene terephthalate film (PET), are exemplified resin such as a polyimide film, as the film thickness from the viewpoint of strength and flexibility of the substrate is preferably 2 to 200 .mu.m, 10 to 50 [mu] m is more preferable.

In order to improve the optical properties of the fluorine-containing volume hologram optical recording photosensitive composition and the volume hologram, a functionalized layer may be introduced between the fluorine-containing volume hologram optical recording layer and the substrate. Is possible.
Materials for the functionalized layer include glass, quartz, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polyethylene fluoride, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polymethyl Examples include methacrylates, polyether sulfones, polyether ether ketones, polyamides, polyesters such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, polyesters such as polyethylene terephthalate, polyimides, and non-fluorine hard coating agents. It can be formed by depositing a plurality of thin film materials on a transparent support substrate by vapor deposition (EB vapor deposition), sputtering, or the like. The thin film material may be an organic multilayer film having a different refractive index, an organic multilayer film containing an inorganic substance, or an inorganic multilayer film. Examples of the inorganic multilayer film include a dielectric multilayer film. In this case, it can be formed at a lower cost by coating, laminating or the like. This dielectric multilayer _{film, TiO 2 / SiO 2 / ...} / SiO 2 / TiO 2 becomes 29 layered multilayer film, yet, like the multi-layer film composed of TiO ₂ / SiO ₂ as an example of a dielectric multilayer film by the foregoing However, it is preferable to select the material as appropriate for the wavelength of the target light.

For example, for visible light and infrared light,
- as high refractive index material (1.8 or more material having a refractive index _{generally), TiO 2, CeO 2,} Ta 2 O 5, ZrO 2, Sb 2 O 3, HfO 2, La 2 O 3, NdO 3, Y ₂ O ₃ , ZnO, Nb ₂ O ₅
As a relatively high refractive index material (material having a refractive index of approximately 1.6 to 1.8), MgO, Al ₂ O ₃ , CeF ₃ , LaF ₃ , NdF ₃
As a low refractive index material (a material having a refractive index of about 1.5 or less), SiO ₂ , AlF ₃ , MgF ₂ , Na ₃ AlF ₆ , NaF, LiF, CaF ₂ , BaF ₂
Etc. are preferable.

For ultraviolet rays
As a high refractive index material (a material having a refractive index of about 1.8 or more), ZrO ₂ , HfO ₂ , La ₂ O ₃ , NdO ₃ , Y ₂ O ₃ , TiO ₂ , Ta ₂ O ₅ , ZrO ₂ ( (However, the wavelength of light is approximately 360 to 400 nm)
-As a relatively high refractive index material (material having a refractive index of approximately 1.6 to 1.8), MgO, Al ₂
O ₃ , LaF ₃ , NdF ₃
- as low refractive index material (1.5 below material having a refractive index _{generally), SiO 2, AlF 3,} MgF 2, Na 3 AlF 6, NaF, LiF, CaF 2
Can be given.

  Further, the functionalized layer may have a color material-containing layer containing a color material of at least one of a pigment and a dye. Furthermore, the functionalized layer may be a laminate in which two or more cholesteric liquid crystal layers are laminated. The functionalized layer having a colorant-containing layer, a cholesteric liquid crystal layer, and a photoreactive chiral compound has a photoreactive chiral compound, and the photoreactive chiral compound has a chiral site and a photoreactive group. The chiral moiety may be selected from an isosorbide compound, an isomannide compound, and a binaphthol compound. There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, it forms with the laminated body of a dielectric vapor deposition layer, a single layer or two or more cholesteric liquid crystal layers, and also other layers as needed. Moreover, you may have a color material content layer. The dielectric vapor deposition layer is made by laminating a plurality of dielectric thin films having different refractive indexes. In order to obtain a functionalized layer, a high refractive index dielectric thin film and a low refractive index dielectric thin film are alternately arranged. Although it is preferable to laminate a plurality of layers, it is not limited to two types, and may be more types. Moreover, when providing a color material content layer, it is desirable to form under a dielectric vapor deposition layer.

  In addition to fluorine-containing volume holograms, applications or application fields of photosensitive compositions for optical recording of fluorine-containing volume holograms include optical elements, display / design impartment, interference measurement, optical information processing, and optical information recording. .

  Specific examples of the optical element include a diffraction grating, a POS scanner, an optical head for a CD / DVD player, a beam splitter, an interference filter, an aircraft / car head up display, optical switching, a waveguide, and the like.

  Specific examples of display and design features include 3D display, hologram art, interior and exterior decorations, art and craft records, educational materials, book and magazine covers and illustrations, securities, ID cards, credit cards and cash. For example, decoration of cards / telephone cards, anti-counterfeiting, and stereoscopic viewing of CT images.

  Specific examples of interference measurement include measurement of displacement / deformation of an object, measurement of vibration of an object, measurement of accuracy of an optical surface (computer hologram), and the like.

  Specific examples of optical information processing include pattern recognition using a holographic matched filter, fingerprint matching, and the like.

  Specific examples of optical information recording include (high-definition or digital) television broadcasting, video camera video, surveillance camera video image recording, information retrieval recording, graphic character input device, holographic associative memory, and the like.

  Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Example 1
(1) Preparation of photosensitive composition for fluorine-containing volume hologram recording As a base polymer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanone Nol) (CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH) as a structural unit only, and a fluorine-containing polymer having a hydroxyl group at the end of the side chain (tetrahydrofuran [ [THF] measured by GPC analysis using a solvent as a solvent, 2 g of number average molecular weight 70,000, weight average molecular weight 150,000; fluorine content 60.1%), 2 g of ethylene oxide bisphenol A diacrylate as a liquid monomer, and light 0.2 g of 2,4,6-tris (trichloromethyl) -1,3,5-triazine as a polymerization initiator, color As a sensitizer, 10 [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 0.00441 g of 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one was added to prepare a uniform photosensitive composition for fluorine-containing volume hologram recording. The refractive index of the liquid monomer was 1.519, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.373.

(2) Preparation of photosensitive medium for fluorine-containing volume hologram recording The photosensitive composition for fluorine-containing volume hologram recording obtained in (1) above was coated on a 188 μm thick polyethylene terephthalate film (300 × 210 mm square) with a bar coater. The photosensitive composition for fluorine-containing volume hologram recording was applied so as to have a thickness of 10 μm. At that time, in order to adjust the film thickness, the photosensitive composition for fluorine-containing volume hologram recording was diluted with a cyclohexanone solvent (solid content concentration: 20% by weight) to prepare a photosensitive medium for fluorine-containing volume hologram recording. .

(3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium The transmission hologram shown in FIG. 7 as a schematic explanatory diagram of the fluorine-containing volume hologram recording photosensitive medium obtained in (2) above at 25 ° C. A transmission hologram was recorded by the optical system apparatus, and the refractive index modulation amount of the recording medium was measured. The recording conditions are as follows.

(Recording conditions)
Recording information light source: Full color compatible Nd: YVO4 CW laser (532 nm)
AlGaN or InGaN (405 nm)
He-Ne CW laser (634nm)
Light intensity: 6 mW / cm ²
Measurement light source: He-Ne CW laser (634 nm)
Exposure amount: 1 to 5000 mJ / cm ²

  In FIG. 1, 1 is a laser light source, 2 is a beam splitter, 3 is a mirror, 4 is a lens, and 5 is a recording photosensitive medium.

(4) Measurement of coating film properties of fluorine-containing volume hologram recording photosensitive medium The fluorine-containing volume hologram recording photosensitive medium obtained in (2) above was subjected to dynamic ultrafine hardness at 25 ° C. DUH-201 (manufactured by Shimadzu Corp., trade name), heat resistance is DSC-50 (manufactured by Shimadzu Corp., trade name), and transparency is spectrophotometer U-4100 (manufactured by Hitachi, Ltd.). (Trade name). The results are shown in Table 1.

  This recording medium had the same performance after being left for one week at room temperature (25 ° C.). In addition, this hologram can be easily recorded and fixed by whole surface exposure with natural light, UV light or LED light (532 nm), the hologram recording is kept stable, and there is no problem even if these light sources are used.

Example 2
In Example (1), a fluorine-containing volume hologram was similarly used except that 0.045 g of cyclohexylmethane-4,4′-diisocyanate was added as a crosslinking agent and 0.0003 g of dibutyltin laurate was added as a crosslinking reaction catalyst. A photosensitive composition for recording was prepared. The refractive index of the liquid monomer was 1.519, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.373. Then, in the same manner as in Example 1, (2) Preparation of photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium, (4) Fluorine-containing The physical properties of the coating film of the photosensitive medium for volume hologram recording were measured. The results are shown in Table 1.

Example 3
Perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF as a base polymer (CF ₃ ) Fluoropolymer comprising only a homopolymer having a structural unit of CH ₂ OH and having a hydroxyl group at the end of the side chain (number average molecular weight measured by GPC analysis using tetrahydrofuran [THF] as a solvent, 33, 000, weight average molecular weight 75,000; fluorine content 60.1%), 2 g of ethylene oxide bisphenol A diacrylate, 1 g of N-acryloylmorpholine, 2 g of propoxylated ethoxylated dimethacrylate, and light 2,4,6-Tris (trichloromethyl) -1,3,5-tria as a polymerization initiator 0.1405 g of gin, 10 [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7 as a dye sensitizer -0.00441 g of tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one was added to prepare a uniform photosensitive composition for fluorine-containing volume hologram recording. The refractive index of the liquid monomer is 1.519 for ethylene oxide bisphenol A diacrylate, 1.506 for N-acryloylmorpholine, 1.456 for propoxylated ethoxylated dimethacrylate, and a mixture of base polymer and photoinitiator. The average refractive index of (2) was (373) a photosensitive medium for fluorine-containing volume hologram recording by the same method as in Example 1. (3) Measurement of the hologram characteristics of the fluorine-containing volume hologram recording photosensitive medium, and (4) Measurement of the coating film properties of the fluorine-containing volume hologram recording photosensitive medium. Show.

Example 4
In Example 3, the number average molecular weight and weight average molecular weight of the base polymer were changed to 70,000 and 150,000, respectively, except that the number average molecular weight was 10,500 and the weight average molecular weight was 15,000. Similarly, a photosensitive composition for fluorine-containing volume hologram recording was prepared. The refractive index of the liquid monomer is ethylene oxide bisphenol A diacrylate 1.519, N-acryloylmorpholine 1.506, propoxylated ethoxylated dimethacrylate 1.456, and the average refractive index of the mixture of base polymer and photoinitiator Was 1.373. Then, in the same manner as in Example 1, (2) Preparation of photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium, (4) Fluorine-containing The physical properties of the coating film of the photosensitive medium for volume hologram recording were measured. The results are shown in Table 2.

Example 5
6 g of trimethylolpropane diallyl ether () and 1.6 g of trimethylolpropane tris-3-mercaptopropionate (TMPTP) as a cross-linking agent were added to the fluorine-containing volume hologram recording photosensitive composition of Example 3. , 0.3 g of 2,4,6-tris (trichloromethyl) -1,3,5-triazine as a photopolymerization initiator, and 10 [3- [4- (dimethylamino) phenyl] -1- Oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11 -0.0441 g of ON was added and then left at room temperature for 2 days.

  As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. The refractive index of the liquid monomer used other than Example 1 was 1.451 for trimethylolpropane diallyl ether, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.373. Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) Fluorine-containing The film properties of the volume hologram recording photosensitive medium were measured. The results are shown in Table 2.

Example 6
6.7 g of pentaerythritol triallyl ether and 0.9 g of trimethylolpropane tris-3-mercaptopropionate (TMPTP) as a cross-linking agent were added to the photosensitive composition for fluorine-containing volume hologram recording of Example 3. , 0.3 g of 2,4,6-tris (trichloromethyl) -1,3,5-triazine as a photopolymerization initiator and 10 [3- [4- (dimethylamino) phenyl] -1 as a dye sensitizer -Oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine- 0.0441 g of 11-one was added and then left at room temperature for 2 days.

  As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. The refractive index of the liquid monomer other than Example 1 was 1.454 for pentaerythritol triallyl ether, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.373. Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) Fluorine-containing The film properties of the volume hologram recording photosensitive medium were measured. The results are shown in Table 2.

Example 7
Perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF as a base polymer (CF ₃ ) a fluorine-containing polymer consisting only of a homopolymer having a structural unit of CH ₂ OH and having a hydroxyl group at the end of the side chain (number average molecular weight 70 measured by GPC analysis using tetrahydrofuran [THF] as a solvent, 000, weight average molecular weight 150,000; fluorine content 60.1%) 3.5 g, liquid monomer, 2 g of ethylene oxide bisphenol A diacrylate, 2 g of propylene oxide (PO) modified trimethylolpropane triacrylate, propoxylated 2g of ethoxylated bisphenol A diacrylate and as a cross-linking agent 3 g of Limethylolpropane polyglycidyl ether (TMPPE), 3.5 g of Epolite 1500NP (EP) (manufactured by Kyoeisha Chemical Co., Ltd.), and Sun-Aid SI-60 (manufactured by Sanshin Chemical Industry Co., Ltd.) as a curing catalyst were reduced to 0.0. 1 g, 0.3 g of 2,4,6-tris (trichloromethyl) -1,3,5-triazine as a photopolymerization initiator, and 10 [3- [4- (dimethylamino) phenyl]-as a dye sensitizer 1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine 0.0441 g of -11-one was added and then left at 60 ° C. for 6 hours.

  As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. The refractive index of the liquid monomer used other than in Example 1 is 1.459 for PO-modified trimethylolpropane triacrylate, 1.461 for propoxylated ethoxylated bisphenol A diacrylate, and the base polymer and photopolymerization initiator The average refractive index of the mixture was 1.373. Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) Fluorine-containing The film properties of the volume hologram recording photosensitive medium were measured. The results are shown in Table 2.

Example 8
In Example 7, it carried out by the same operation except having used ethoxylated bisphenol A dimethacrylate instead of 2 g of ethylene oxide bisphenol A diacrylate.

  As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. The refractive index of the liquid monomer used other than in Example 7 was 1.501 for ethoxylated bisphenol A dimethacrylate, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.373. . Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) Fluorine-containing The film properties of the volume hologram recording photosensitive medium were measured. The results are shown in Table 3.

Example 9
In Example 7, the base polymer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) Measured by GPC analysis using a fluorine-containing polymer (tetrahydrofuran [THF]) as a solvent consisting only of a homopolymer having a structural unit of CF ₂ OCF (CF ₃ ) CH ₂ OH and having a hydroxyl group at the end of the side chain. (Number average molecular weight 70,000, weight average molecular weight 150,000; fluorine content 60.1%) 3.8 g, as liquid monomer, 2 g of ethylene oxide bisphenol A diacrylate, 0.8 g of PO-modified trimethylolpropane triacrylate, 3.3 g of propoxylated ethoxylated bisphenol A diacrylate, propoxylated 1.7 g of xylated dimethacrylate, 5.3 g of trimethylolpropane polyglycidyl ether (TMPPE) as a crosslinking agent, 2.5 g of Epolite 1600 (EP) (manufactured by Kyoeisha Chemical Co., Ltd.), trimethylolpropane tris 1.3 g of 3-mercaptopropionate, 0.1 g of tetraethylammonium chloride as a curing catalyst, 0.3 g of 2,4,6-tris (trichloromethyl) -1,3,5-triazine as a photopolymerization initiator 10 [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl- as a dye sensitizer 0.0441 g of 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one was added, and then at room temperature. Left for 5 days.

  As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. The refractive index of the liquid monomer used other than in Example 7 was 1.456 for propoxylated ethoxylated dimethacrylate, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.373. It was. Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) Fluorine-containing The film properties of the volume hologram recording photosensitive medium were measured. The results are shown in Table 3.

Example 10
In Example 9, 1.3 g of N-acryloylmorpholine was used instead of 2 g of ethylene oxide bisphenol A diacrylate, and 3 g of ethoxylated bisphenol A dimethacrylate was used instead of 1.7 g of propoxylated ethoxylated dimethacrylate. The same operation was performed.

  As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. The refractive index of the liquid monomer used other than Example 9 is 1.510 for N-acryloylmorpholine, 1.501 for ethoxylated bisphenol A dimethacrylate, and the average refraction of the mixture of the base polymer and the photopolymerization initiator. The rate was 1.373. Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) Fluorine-containing The film properties of the volume hologram recording photosensitive medium were measured. The results are shown in Table 3.

Example 11
In Example 3, 0.05 g of dicyclohexylmethane diisocyanate (DHMDI) was added as a crosslinking agent, and 0.0001 g of dibutyltin laurate was added as a curing catalyst.

  As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) Fluorine-containing The film properties of the volume hologram recording photosensitive medium were measured. The results are shown in Table 3.

Example 12
In Example 11, before adding 0.05 g of dicyclohexylmethane diisocyanate (DHMDI) as a crosslinking agent and 0.0001 g of dibutyltin as a curing catalyst, perfluoro- (1,1,9,9-tetrahydro 2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH 1. Fluoropolymer having a hydroxyl group at the chain end (number average molecular weight 70,000, weight average molecular weight 150,000 measured by GPC analysis using tetrahydrofuran [THF] as a solvent; fluorine content 60.1%) to 5g, acryloyl isocyanate as a crosslinking agent _{(NCO-CH 2 CH 2 OCOCH} = CH 2 ) And 0.0017 g of dibutyltin as a reaction catalyst were added to acryloyl-modify the side chain terminal.
Otherwise, it was prepared in the same manner as in Example 11, and then allowed to stand at room temperature for 2 days. The average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.383. Then, in the same manner as in Example 1, (2) Preparation of photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium, (4) Fluorine-containing The physical properties of the coating film of the photosensitive medium for volume hologram recording were measured. The results are shown in Table 3.

Example 13
In Example 3, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) Example 3 except that the side chain end of CF ₂ OCF (CF ₃ ) CH ₂ OH was changed to an ester form (CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ COOCH ₃ As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1. Then, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, and (3) Hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording were obtained. Constant, (4) were measured for film properties of the fluorine-containing volume hologram recording photosensitive medium. The results are shown in Table 4.

Example 14
In Example 3, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) The same as in Example 3 except that the side chain end of CF ₂ OCF (CF ₃ ) CH ₂ OH is changed to fluoride (CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) H As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.384. Next, in the same manner as in Example 1, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4 ) Including foot It was measured film properties of the volume hologram recording photosensitive medium. The results are shown in Table 4.

Example 15
In Example 3, the base polymer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) The same method as in Example 3 except that the side chain end of CF ₂ OCF (CF ₃ ) CH ₂ OH is changed to a cyano compound (CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CN) As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.387. (2) Preparation of fluorine-containing volume hologram recording photosensitive medium, (3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium in the same manner as in Example 1, (4) Containing It was measured physical properties of the coating film containing a volume hologram recording photosensitive medium. The results are shown in Table 4.

Example 16
In Example 3, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) The same as in Example 3 except that the side chain end of CF ₂ OCF (CF ₃ ) CH ₂ OH is changed to carboxylic acid form (CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOH As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.381. (2) Preparation of a fluorine-containing volume hologram recording photosensitive medium in the same manner as in Example 1, (3) Measurement of hologram characteristics of the fluorine-containing volume hologram recording photosensitive medium, ) Was measured film properties of the fluorine-containing volume hologram recording photosensitive medium. The results are shown in Table 4.

を１ｇ添加した以外は、実施例１、３、４、１１、１２と同様の方法にてそれぞれ調製した。その結果、均一かつ透明な含フッ素体積型ホログラム記録用感光性組成物が得られた。ついで実施例１と同様の方法にて（２）含フッ素体積型ホログラム記録用感光性媒体の調製、（３）含フッ素体積型ホログラム記録用感光性媒体のホログラム特性の測定、（４）含フッ素体積型ホログラム記録用感光性媒体の塗膜物性の測定を行った。結果を表４および表５に示す。Examples 17-21
In Examples 1, 3, 4, 11, and 12, spiroester derivatives:

Was prepared in the same manner as in Examples 1, 3, 4, 11, and 12 except that 1 g of was added. As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. Then, in the same manner as in Example 1, (2) Preparation of photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium, (4) Fluorine-containing The physical properties of the coating film of the photosensitive medium for volume hologram recording were measured. The results are shown in Tables 4 and 5.

を１ｇ添加した以外は実施例１、３、４、１１、１２と同様の方法にてそれぞれ調製した。その結果、均一かつ透明な含フッ素体積型ホログラム記録用感光性組成物が得られた。ついで実施例１と同様の方法にて（２）含フッ素体積型ホログラム記録用感光性媒体の調製、（３）含フッ素体積型ホログラム記録用感光性媒体のホログラム特性の測定、（４）含フッ素体積型ホログラム記録用感光性媒体の塗膜物性の測定を行った。結果を表５および表６に示す。Examples 22-26
In Examples 1, 3, 4, 11, and 12, spiroester derivatives:

Were prepared in the same manner as in Examples 1, 3, 4, 11, and 12 except that 1 g of was added. As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. Then, in the same manner as in Example 1, (2) Preparation of photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium, (4) Fluorine-containing The physical properties of the coating film of the photosensitive medium for volume hologram recording were measured. The results are shown in Tables 5 and 6.

Examples 27-31
In Examples 17-21, the base polymer perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) (CH ₂ ═CFCF ₂ OCF (CF ₃ ) Instead of CF ₂ OCF (CF ₃ ) CH ₂ OH,
_{(CH 2 = CFCF 2 OCF (} CF 3) CF 2 OCF (CF 3) CH 2 OCH 2 CHOCH 2
Each was prepared in the same manner as in Examples 17 to 21 except that was used. As a result, a uniform and transparent photosensitive composition for fluorine-containing volume hologram recording was obtained. The average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.383. Then, in the same manner as in Example 1, (2) Preparation of photosensitive medium for fluorine-containing volume hologram recording, (3) Measurement of hologram characteristics of fluorine-containing volume hologram recording photosensitive medium, (4) Fluorine-containing The physical properties of the coating film of the photosensitive medium for volume hologram recording were measured. The results are shown in Table 6 and Table 7.

Comparative Example 1
Fluorine-containing volume hologram recording was carried out in the same manner except that 1 g of polystyrene (weight average molecular weight 230,000 measured by GPC analysis using tetrahydrofuran [THF] as a solvent) was used instead of the base polymer prepared in Example 1. A photosensitive composition was prepared. The refractive index of the liquid monomer was 1.519, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.503. Next, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording in Example 1, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) For fluorine-containing volume hologram recording The physical properties of the coating film of the photosensitive medium were measured. The results are shown in Table 8.

Comparative Example 2
Instead of the base polymer prepared in Example 1, 1 g of polystyrene (weight average molecular weight 230,000 measured by GPC analysis using tetrahydrofuran [THF] as a solvent) and 2.5 g of the plasticizer diethyl sebacate were used. Similarly, a photosensitive composition for fluorine-containing volume hologram recording was prepared. The refractive index of the liquid monomer was 1.475, and the average refractive index of the mixture of the base polymer and the photopolymerization initiator was 1.503. Next, (2) Preparation of a photosensitive medium for fluorine-containing volume hologram recording in Example 1, (3) Measurement of hologram characteristics of the photosensitive medium for fluorine-containing volume hologram recording, (4) For fluorine-containing volume hologram recording The physical properties of the coating film of the photosensitive medium were measured. The results are shown in Table 8.

  According to the present invention, a photosensitive composition for fluorine-containing volume hologram recording having a larger refractive index modulation amount (Δn) than the conventional one, a photosensitive medium for fluorine-containing volume hologram recording and a fluorine-containing volume type using the same. A hologram can be provided.

  Further, according to the present invention, the photosensitive composition for fluorine-containing volume hologram recording is excellent not only in hologram recording performance such as refractive index difference, sensitivity and transparency, but also in physical properties such as film strength and heat resistance. And a fluorine-containing volume hologram recording photosensitive medium and a fluorine-containing volume hologram using the same.

Claims (8)

Comprising a base polymer (a), a liquid monomer (b), a photopolymerization initiator (c) and an organic solvent (f),
The base polymer (a) contains at least one curable fluorine-containing polymer having a fluorine content of 26 to 80% by mass,
The liquid monomer (b) contains at least one liquid monomer (b1) that initiates polymerization with active species generated from the photopolymerization initiator (c),
The photopolymerization initiator (c) is a compound that is sensitive to light having excellent coherence and initiates polymerization of the liquid monomer (b1).
And the refractive index of liquid monomer (b) is higher than the average refractive index of the mixture of a base polymer (a) and a photoinitiator (c), The photosensitive composition for fluorine-containing volume type hologram recording characterized by the above-mentioned object. The base polymer (a) is
The fluorine content is 26 to 80% by mass,
Formula (1):

[Wherein the structural unit M1 is represented by the formula (2):

(Wherein X ¹ and X ² are the same or different, both are H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and both are H, F Or CF ₃ ; Rf ¹ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms, Y ¹ (Y ¹ is a carbon atom having 0 to 10 carbon atoms having a hydroxyl group at the terminal) A monovalent organic group, a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond, or a crosslinkable cyclic ether structure in which a hydrogen atom may be substituted with a fluorine atom. An organic group in which 1 to 3 monovalent organic groups having 2 to 100 carbon atoms are bonded; a is an integer of 0 to 3; b and c are the same or different and both are 0 or 1 )
A structural unit derived from a fluorine-containing ethylenic monomer represented by:
The structural unit A1 is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (2)]
Indicated by
A curable fluorinated polymer containing 0.1 to 100 mol% of the structural unit M1 and 0 to 99.9 mol% of the structural unit A1 and having a number average molecular weight of more than 10,000 and 1,000,000 or less,
Formula (3):

[In the formula, the structural unit M1 is the same structural unit as the formula (2),
The structural unit A2 is represented by the formula (4):

(Wherein X ⁶ , X ⁷ and X ⁸ are the same or different, and all are H or F; X ⁹ is H, F or CF ₃ ; d is an integer of 0 to 2; e is 0 or 1; Rf ² Is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; Z ¹ is —OH, —CH ₂ OH, —COOH, a carboxylic acid derivative, —SO ₃ H, A sulfonic acid derivative, an epoxy group, a cyano group, an oxetanyl group, an unsaturated ester group or an amino group)
A structural unit represented by
The structural unit A3 is represented by the formula (5):

(Wherein X ¹⁰ , X ¹¹ and X ¹³ are the same or different, all are H or F; X ¹² is H, F or CF ₃ ; f, g and h are the same or different, and all are 0 or 1 ; Z ² is H, F or Cl; Rf ³ is a fluorine-containing alkylene group containing an ether bond or a fluorine-containing alkylene group having 2-100 carbon atoms of 1 to 20 carbon atoms)
Is a structural unit represented by
Indicated by
The structural unit M1 is 0 to 90 mol%, the structural unit A2 is 0 to 100 mol%, the structural unit A3 is 0 to 99.9 mol%, and the structural unit M1 and the structural unit A2 are 0.1 to 100 mol% in total. A curable fluorinated polymer having a number average molecular weight of greater than 10,000 and no greater than 1,000,000, as well as formula (6):

[Wherein the structural unit M2 is represented by the formula (7):

Wherein X ¹⁴ and X ¹⁵ are the same or different, both H or F; X ¹⁶ is H, F, CH ₃ or CF ₃ ; X ¹⁷ and X ¹⁸ are the same or different and both H, F or CF _3; Rf ⁴ is Y ² (Y ² to a fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group or a 2 to 100 carbon atoms 1 to 40 carbon atoms,
Formula (8):

(In the formula, R ¹ and R ² are the same or different, and each is a C 1-7 divalent organic group optionally substituted with a fluorine atom; X ¹⁹ is H, F, CH ₃ or CF _3. X ²⁰ and X ²¹ are the same or different, both H or F; and l and m are the same or different, both are 0 or 1);
An organic group having 3 to 10 carbon atoms represented by:
Formula (9):

(In the formula, X ²² and X ²³ are the same or different, and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
An organic group having 2 to 100 carbon atoms and having 1 to 5 crosslinkable cyclic ether structures represented by:
Formula (10):

(In the formula, Q is a monovalent or divalent organic group in which a hydrogen atom of a monocyclic structure, a polycyclic structure or a heterocyclic structure having 3 to 100 carbon atoms may be substituted with X ²² or X ^23. )
An organic group having 3 to 100 carbon atoms and having 1 to 5 crosslinkable cyclic ether structures represented by:
Formula (11):

(Wherein, X ^{24 to} X ²⁸ are the same or different, and all are H, F, a C 1-6 alkyl group or a C 1-6 fluorinated alkyl group)
An organic group having 3 to 100 carbon atoms having 1 to 5 crosslinkable cyclic ether structures represented by formula (12):

(In the formula, X ^{29 to} X ³² are the same or different and all are H, F, an alkyl group having 1 to 6 carbon atoms, or a fluorine-containing alkyl group having 1 to 6 carbon atoms)
An organic group having 1 to 5 crosslinkable cyclic ether structures represented by the above formula and having 3 to 100 carbon atoms), i is an integer of 0 to 3; j and k are the same Or both are 0 or 1)
A structural unit derived from a fluorine-containing ethylenic monomer represented by:
Structural unit A4 is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (7)]
The structural unit M2 is 0.1 to 100 mol% and the structural unit A4 is 0 to 99.9 mol%, and the number average molecular weight is greater than 10,000 and less than 1,000,000. The composition according to claim 1, comprising at least one selected curable fluorine-containing polymer. The composition according to claim 1 or 2, wherein the liquid monomer (b) comprises two or more monomers, and at least one of the monomers is a liquid monomer having a polyether structure and a molecular weight of 1000 or less. object. The composition according to any one of claims 1 to 3, wherein the liquid monomer (b) contains two or more monomers, and at least one of the monomers is a polyfunctional monomer. The composition according to any one of claims 1 to 4, further comprising a polyfunctional unsaturated compound (d) that undergoes a crosslinking reaction with the crosslinking site in the base polymer (a) by heat. The composition according to any one of claims 1 to 5, further comprising a dye sensitizer (e). A fluorine-containing volume hologram recording photosensitive medium having an optical recording layer formed on a base film, wherein the optical recording layer is a fluorine-containing volume according to any one of claims 1 to 6. A fluorine-containing volume hologram recording photosensitive medium, which is an optical recording layer having a thickness of 1 to 180 μm formed from a photosensitive composition for recording type hologram recording. 7. A fluorine-containing volume hologram in which an optical recording layer is formed on a substrate film, wherein the optical recording layer is a photosensitive for fluorine-containing volume hologram recording according to any one of claims 1 to 6. A fluorine-containing volume hologram, which is an optical recording layer having a thickness of 1 to 180 μm, formed from a conductive composition.

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