201106104 六、發明說明 【發明所屬之技術領域】 本發明有關能作爲使折射率調制結構（refraction indexmodulation structure)形成於材料中之光學製品，特 別是能作爲全像圖記錄媒體（hol〇gram recording medium) 很適合使用之感光性材料，其前驅物以及製造方法。 【先前技術】 經將因同調性（coherent)的光的干擾（optical interference)所產生之明暗的干擾型樣（interference pattern)，作爲折射率的調制結構而記錄於感光性材料之 相位型全像圖（phase type hologram)，係較振幅型全像圖 (amplitude type hologram)爲能獲得更高的穿透率 (permeability)或繞射效率（diffraction efficency)，而具有 能有效利用入射光能量（incident light energy)之特徵。有 人利用此種特徵而在硏究對全像圖記錄媒體（hologram record medium)、或濾光器（optical filter)、射束分裂器 (beam splitter)、頭戴顯示器（headmount display)般的全像 式光學元件（holographic optical element(HOE))等光學製 品的應用，並其中一部分已經實用化。 近年來，有人在硏究利用三次元全像微影術（3-dimensional holographic lithography)之光電子結晶結構 (photonic crystal stracture)的形成（例如，非專利文獻 1)，或利用三次元直接描畫（direct -write)光微影術 -5- 201106104 (photolithography)之光波導（light wane guide)的形成（例 如’非專利文獻2)等，使感光性材料中形成所需要的折 射率分佈結構（r e f r a c t i ο n i n d e X d i s t r i b u t i ο n s t r u c t u r e)之 光學製品的製造方法。 前述感光性材料而言，如考慮當製造前述光學製品時 的簡便性，原料選擇的多樣性，所製造之光學製品的安全 性等時’則採用感光性樹脂（以下，簡稱光聚合物 (photopolymer)較爲有利。 當進行光聚合物之感光（exposure to light)時，一般會 發生因單體的聚合反應所引起之體積收縮（volume shrinkage)(以下，簡稱收縮）。此種收縮亦成爲對前述調 制結構或分佈結構上引起變形（strain)或錯位（shear)之原 因，特別是當光聚合物採用爲前述光學製品時，則會成爲 嚴重的問題》 例如，當光聚合物作爲全像圖記錄媒體使用之情形， 如因記錄或定影（fixation)時的光照射所發生之收縮大 時，則因前述調制結構的變形（strain)或錯位（shear)而能 符合再生基準光（regenerative reference light)的旗標條件 (flag condition)之入射角或波長即會變化，其結果，當再 生所記錄之資訊時，有不能獲得足夠的繞射光強度 (diffnaction light strength)之問題。如此種收縮係僅止於 某種程度且屬於各向同性（isotropic)者時，則尙能以光學 式方式加以補償（compensation)，惟仍在系統側需要再生 基準光的入射角調整或波長調整等的控制，以致有產生再 201106104 生操作（regeneration operation)會複雜化之問題。另一方 面，如收縮係屬於各向異性（an isotropic)的情形，則即使 採用如前述的系統控制（system control)仍然難於加以補 償，結果難以正確再生所記錄之資訊。 於專利文獻1中，揭示有經利用因聚合反應所發生之 收縮較小的陽離子開環聚合（cation ring opening polymerization)之技術。具體而言，揭示有含有光引發酸 產生劑（light-induced acid initiator)、黏合聚合物（binder polymer)、具有特定的構造之二官能性及多官能性環氧化 物單體或低聚物（oligomer)之全像圖記錄媒體。此種技 術，係將因聚合反應所發生之收縮較自由基聚合者爲小的 陽離子開環聚合作爲光記錄（optical record)時的聚合反應 利用者。然而，仍然未能達成收縮率十分低的程度，又， 陽離子聚合內含有所生成之聚合物的分子量控制困難之問 題，因而亟待一種更經改良之材料之開發。 於專利文獻2中，揭示有經倂用解理反應（cleavage reaction)之技術。具體而言，揭示有具備含有光引發酸產 生劑、介由能在酸的存在下解理之官能基而聚合性取代基 經結合於支鏈之聚合物之記錄層之記錄媒體。此種技術， 係在光記錄時倂用聚合物支鏈的解理反應、與源自解理支 鏈之聚合性化合物的聚合反應，藉由使因前述解理反應所 發生之膨脹與因前述聚合反應所發生之收縮互相抵銷以達 成收縮率的降低者。但，在製作記錄媒體時需要採用溶 劑，而在均勻的記錄層之製作上，有厚度的限制之問題。 201106104 又’前述聚合物的分子量係爲能維持溶劑可溶性而不僅受 實質上的限制之外，尙因光記錄時的支鏈解理而會更小之 故，可能有記錄後的穩定性（歸檔壽命（archival life)之問 題。 於專利文獻3中，揭示有經使用有機-無機混雜基材 (hybrid matrix)之技術。具體而言，揭示有至少含有：具 有特定結構之有機金屬化合物、及單官能聚合性化合物之 全像圖記錄材料。此種技術，係藉由具有較剛硬（rigid)的 結構單元之有機-無機混雜基材、與難於因聚合反應而形 成橋聯結構（bridged structure)之單官能聚合性化合物之組 合’而謀求收縮率的降低者。然而，與專利文獻2的情形 同樣，當製作記錄材料時需要使用溶劑，以致在均勻的記 錄層之製造上，有厚度上之限制之問題。 於專利文獻4中，揭示有經於製造過程（原地（in_situ)) 中所形成之二次兀橋聯聚合物基材（3-dimensional bridged polymer matrix)中分散有光聚合性化合物所成之光學製 品。在此，三次元橋聯聚合物基材，可推測爲除對前述光 學製品賦與物理強度以保持形狀之角色之外，尙能發揮抑 制光聚合性化合物的過度的移動（migration)，又，降低因 光聚合性化合物的聚合反應所發生之體積收縮之角色（非 專利文獻3)。利用此種技術所獲得之光學製品的收縮 率，雖然，有達成0.3%的報告（專利文獻4，實施例4)， 惟仍留有改善的餘地。 又，爲滿足能獲得前述光學製品必備的高透明度所需 201106104 相溶性的條件而言，前述三次元橋聯聚合物基材與前述光 聚合性化合物或其聚合物的組合有其限制，以致不能採取 大的折射率差之問題。 於非專利文獻4中，有經將從点-環糊精（万-cyclo dextrin)與雙胺基末端丙二醇所調製之假聚旋型環 (Pseudo-Pol yrotaxane)作爲起始物質（starting material)使 用，以降低熱硬化性環氧樹脂組成物的硬化收縮之硏究例 之報告。此種技術係經利用來自前述假聚旋型環之/3-環 糊精的熱解離（thermal dissociation)者，硬化物成爲白濁 時，則表示/3-環糊精已解離之證據。因此，難於將此種 技術適用於透明性爲必需條件之光學製品。 如上所述，雖然感光性材料，特別是將用於全像圖記 錄媒體等光學製品之感光性材料，係經由種種方法謀求性 能的改善，惟仍然不足夠，尙需要開發一種感光時的體積 收縮小，透明性優異的感光性材料。 [先前技術文獻] [專利文獻Π日本專利特表2001 -523 842號公報 [專利文獻2]日本專利特開2005-1 〇3 78號公報 [專利文獻3]日本專利特開2007- 1 5 645 1號公報.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical article capable of forming a refractive index modulation structure in a material, particularly as a hologram recording medium (hologram communication medium) ) Photosensitive materials, precursors and methods of manufacture that are well suited for use. [Prior Art] A phase-type hologram of a photosensitive material is recorded as a modulation structure of a refractive index by an interference pattern generated by coherent light interference (optical interference) Phase type hologram, which is an amplitude type hologram that can achieve higher permeability or diffraction efficiency, and has the ability to effectively utilize incident light energy (incident Light energy). Some people use this feature to study the hologram record medium, or optical filter, beam splitter, headmount display. The application of optical products such as holographic optical elements (HOE), and some of them have been put into practical use. In recent years, there has been a study on the formation of a photonic crystal stracture using a three-dimensional holographic lithography (for example, Non-Patent Document 1), or by using a three-dimensional direct drawing (direct -write) Formation of a light gamma guide of light lithography-5-201106104 (photolithography) (for example, 'Non-Patent Document 2), etc., to form a desired refractive index distribution structure in a photosensitive material (refracti ο Ninde X distributi ο nstructure). The photosensitive material is a photosensitive resin (hereinafter referred to as a photopolymer) in consideration of the simplicity in the production of the optical article, the diversity of raw material selection, and the safety of the manufactured optical product. It is advantageous. When exposing to light of a photopolymer, volume shrinkage (hereinafter referred to as shrinkage) caused by polymerization of a monomer generally occurs. The reason for causing strain or shear on the aforementioned modulation structure or distribution structure, especially when the photopolymer is used as the aforementioned optical article, becomes a serious problem. For example, when the photopolymer is used as a hologram In the case where the recording medium is used, if the contraction due to light irradiation at the time of recording or fixing is large, the regenerative reference light (regenerative reference light) can be satisfied due to the strain or the shear of the aforementioned modulation structure. The incident angle or wavelength of the flag condition changes, and as a result, when the recorded information is reproduced, there is The problem of sufficient diffraction light strength can be obtained. When such a shrinkage system is only a certain degree and is isotropic, then it can be compensated optically. Still, on the system side, it is necessary to control the incident angle adjustment or the wavelength adjustment of the regenerated reference light, so that there is a problem that the regeneration operation is complicated. On the other hand, if the contraction system is anisotropic (an isotropic) In the case of the system control, as described above, it is still difficult to compensate, and as a result, it is difficult to correctly reproduce the recorded information. In Patent Document 1, it is revealed that the shrinkage due to the polymerization reaction is small. a technique of cation ring opening polymerization. Specifically, it discloses a light-induced acid initiator, a binder polymer, a bifunctional structure having a specific structure, and A hologram recording medium of a polyfunctional epoxide monomer or oligomer. The technique is to use a cationic ring-opening polymerization in which the shrinkage caused by the polymerization reaction is smaller than that of the radical polymerizer as a polymerization reaction in the optical record. However, the shrinkage rate is still not very low. Further, the cationic polymerization contains a problem that the molecular weight of the produced polymer is difficult to control, and thus development of a more improved material is urgently required. Patent Document 2 discloses a technique in which a cleavage reaction is employed. Specifically, a recording medium comprising a recording layer containing a photoinitiating acid generator, a functional group capable of being cleaved in the presence of an acid, and a polymerizable substituent bonded to a branched polymer is disclosed. This technique is a cleavage reaction of a polymer branch in the optical recording, and a polymerization reaction with a polymerizable compound derived from a cleavage branch, by the expansion due to the aforementioned cleavage reaction and the aforementioned The shrinkage that occurs in the polymerization reaction cancels each other to achieve a reduction in shrinkage. However, a solvent is required in the production of a recording medium, and there is a problem of thickness limitation in the production of a uniform recording layer. 201106104 Further, the molecular weight of the above polymer is not only limited by the fact that it can maintain solvent solubility, but is also less stable due to branch cleavage during optical recording, and may have stability after recording (archived) The problem of the life of the archival life. Patent Document 3 discloses a technique using an organic-inorganic hybrid matrix. Specifically, it discloses that at least: an organometallic compound having a specific structure, and a single A hologram recording material of a functional polymerizable compound, which is formed by an organic-inorganic hybrid substrate having a relatively rigid structural unit, and which is difficult to form a bridged structure by polymerization. In the case of the combination of the monofunctional polymerizable compounds, the reduction in shrinkage ratio is sought. However, as in the case of Patent Document 2, it is necessary to use a solvent when producing a recording material, so that in the production of a uniform recording layer, there is a thickness. The problem of limitation. In Patent Document 4, a secondary ruthenium bridged polymer substrate formed in a manufacturing process (in_situ) is disclosed. An optical product in which a photopolymerizable compound is dispersed in a (3-dimensional bridged polymer matrix). Here, a three-dimensional bridged polymer substrate is presumed to have a role of imparting physical strength to the shape of the optical article to maintain a shape. In addition, 尙 can suppress the excessive migration of the photopolymerizable compound and reduce the volume shrinkage caused by the polymerization reaction of the photopolymerizable compound (Non-Patent Document 3). The shrinkage rate of the optical article, although having reached a report of 0.3% (Patent Document 4, Example 4), leaves room for improvement. In addition, in order to satisfy the high transparency necessary for obtaining the aforementioned optical article, 201106104 phase is required. In the case of the solubility, the combination of the aforementioned ternary bridged polymer substrate and the aforementioned photopolymerizable compound or polymer thereof is limited so that a large refractive index difference cannot be taken. In Non-Patent Document 4, A pseudo-polycyclic ring (Pseudo-Pol yrotaxane) prepared from point-cyclodextrin (wan-cyclodextrin) and bis-amino terminal propylene glycol is used as a starting material (sta Rting material) A report of an example of use to reduce the hardening shrinkage of a thermosetting epoxy resin composition. This technique utilizes thermal dissociation using /3-cyclodextrin from the aforementioned pseudo-polycyclic ring. In the case where the hardened material becomes cloudy, it indicates evidence that /3-cyclodextrin has dissociated. Therefore, it is difficult to apply this technique to an optical product in which transparency is an essential condition. As described above, although a photosensitive material is particularly It is a photosensitive material which is used for an optical product such as an hologram recording medium, and the performance is improved by various methods. However, it is still insufficient, and it is necessary to develop a photosensitive material which is small in volume shrinkage and excellent in transparency. [Prior Art Document] [Patent Document Π Japanese Patent Laid-Open Publication No. 2001-523 842 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-1 〇3 78 [Patent Document 3] Japanese Patent Laid-Open No. 2007- 1 5 645 Bulletin No. 1.
[專利文獻4]日本專利特開平1 1 -3 5 23 03號公報 [非專利文獻]M.Campbell，D.N.Sharp，M.T.Harrison， R.G.Denning, and A.J.Turberfield 等人著，爲可見光譜利 用全像微影術之光電子結晶之成形加工，自然雜誌，第 404 卷，第 53 至 56 頁（2000 年出版）（Fabrication of -9 - 201106104 photonic crystals for the visible spectrum by holographic lithography,Nature,vol.404,pp.53-56(2000)) ° [非專利文獻 2]A.C.Sullivan，M.W.Grabowski，and R.R.McLeod等人著，對光聚合物之三次元直接描畫微影 術，應用光學，第46冊.，第295至301頁（2007年出 版)(Three-dimensional direct-write lithography into photopolymer，Applied Optics,vol.46，pp.295-30 1 (2007)) o [非專利文獻 3]T.J.Trentler，J.E.Boyd and V.L.Colvin 等人著，爲體積全像術用之環氧樹脂-光聚合物複合物， 材料化學，第 12冊，第 1431至 1438頁（2000年出 版)(Epoxy Resin-Photopolymer Composites for Volume Holography,Chemistry of Materials,Vol.12,pp.1431-1438(2000)) ° [非專利文獻 4]Y.Isobe，A.Sudo,and T.Endo 等人著， 環氧-胺熟化系統中作爲超分子收縮遏抑劑用之能熱解離 假聚旋型環，聯合物科學雜誌：A輯："聚合物化學"，第 46 冊，第 23 05 至 203 8 頁（2008 年出版）（Thermally Dissociable Pseudo-Polyrotaxane as a Supr amo 1 ecul ar Shrinkage Suppressor for Epoxy-Amine Curing System,Journal of Polymer Science : Part A : Polymer Chemistry，vol.46，pp.2305-2308(2008)) ° 【發明內容】 [發明所欲解決之課題] -10- 201106104 本發明之目的在於提供一種能作爲使折射率調制結構 形成於材料中之光學製品，特別是能作爲全像圖記錄媒體 很適合使用之感光時的體積收縮小，透明性優異的感光性 材料。 爲達成上述目的，本發明係有關一種感光性材料，其 特徵爲：具有 含有環狀低聚醣（ring type oligosaccharide)衍生物作 爲構成單元之聚合物基材、及 自由基聚合性單體以及光引發自由基聚合起始劑 (light-induced radical polymerization starter) 〇 本發明人等，爲達成上述目的而專心進行硏究。其結 果發現含有環狀低聚醣衍生物作爲聚合物基材的構成單 元，則可在使上述感光性材料感光以製造光學製品時，能 抑制前述感光性材料的體積收縮，並提升透明性之事實。 因而，如採用上述感光性材料，則可提供一種特別能作爲 全像圖記錄媒體很適合使用之感光時的體積收縮小，透明 性優異的感光性材料。 再者，含有作爲聚合物基材的構成單元之環狀低聚醣 衍生物，即可製得感光性材料在感光時的體積收縮小，且 透明性優異的感光性材料之理由則尙不明瞭，惟可推測爲 例如，因環狀低聚醣衍生物之剛硬性所產生之耐收縮性， 源自聚合性單體包藏（inclusion)作用之收縮緩和，源自體 積大之低結晶性等在發揮功用。 再者，上述感光性材料係準備一種感光性材料前驅 -11 - 201106104 物，其特徵爲具備含有環狀低聚醣衍生物之聚合物基材形 成成分，及自由基聚合性單體及光引發自由基聚合起始 劑，而前述聚合物基材形成成分係藉由光引發自由基聚合 反應以外之反應進行聚合，以形成前述聚合物基材者，並 如前所述，使該感光性材料前驅物發生藉由光引發自由基 聚合反應以外之反應而聚合形成前述聚合物基材，則可製 得。 又，本發明之感光性材料的聚合物基材，較佳爲作爲 構成單元而含有可以化學式（1)表示之自由基聚合性化合 物。同樣，本發明之感光性材料前驅物的聚合物基材形成 成分，較佳爲含有同樣可以化學式（1)表示之自由基聚合 性化合物。[Patent Document 4] Japanese Patent Laid-Open Publication No. Hei No. 1 1 - 3 5 23 03 [Non-Patent Document] M. Campbell, DNS Harp, MT Harrison, RGDenning, and AJ Turberfield, et al. Forming and Processing of Photonic Electronic Crystallization, Nature Journal, Vol. 404, pp. 53-56 (published in 2000) (Fabrication of -9 - 201106104 photonic crystals for the visible spectrum by holographic lithography, Nature, vol.404, pp .53-56(2000)) ° [Non-Patent Document 2] ACSullivan, MW Grabowski, and RRMcLeod et al., Direct Dielectric Imaging of Photopolymers, Applied Optics, Book 46. 295-301 (2007) (Three-dimensional direct-write lithography into photopolymer, Applied Optics, vol. 46, pp. 295-30 1 (2007)) o [Non-Patent Document 3] TJTrentler, JEBoyd and VLColvin et al., Epoxy Resin-Photopolymer Composites for Volume Holography, Volume Epoxy Resin-Photopolymer Composites, Materials Chemistry, Vol. 12, pp. 1431 to 1438 (2000). Chemistr Y of Materials, Vol. 12, pp. 1431-1438 (2000)) ° [Non-Patent Document 4] Y. Isobe, A. Sudo, and T. Endo et al., as a supramolecule in an epoxy-amine maturation system The use of a heat-dissociating pseudo-polycyclic ring for shrinkage inhibitors, Journal of Joint Science: Series A: "Polymer Chemistry", Book 46, pp. 23 05-203 8 (2008) (Thermally Dissociable Pseudo -Polyrotaxane as a Supr amo 1 ecul ar Shrinkage Suppressor for Epoxy-Amine Curing System, Journal of Polymer Science : Part A : Polymer Chemistry, vol. 46, pp. 2305-2308 (2008)) ° [Summary of the Invention] [Invention] Problem to be Solved] -10- 201106104 An object of the present invention is to provide an optical article which can be used as a material for forming a refractive index modulation structure, and particularly has a small volume shrinkage when used as a hologram recording medium. A photosensitive material excellent in transparency. In order to achieve the above object, the present invention relates to a photosensitive material characterized by having a polymer substrate containing a ring type oligosaccharide derivative as a constituent unit, and a radical polymerizable monomer and light. The light-induced radical polymerization starter is invented by the inventors of the present invention to achieve the above object. As a result, it has been found that when the cyclic oligosaccharide derivative is contained as a constituent unit of the polymer substrate, when the photosensitive material is exposed to light to produce an optical product, volume shrinkage of the photosensitive material can be suppressed, and transparency can be improved. fact. Therefore, by using the above-mentioned photosensitive material, it is possible to provide a photosensitive material which is small in volume shrinkage and excellent in transparency when used as a hologram recording medium. Further, the cyclic oligosaccharide derivative which is a constituent unit of the polymer substrate can produce a photosensitive material having a small volume shrinkage at the time of light-sensing, and the photosensitive material having excellent transparency is unclear. However, it is presumed that, for example, the shrinkage resistance due to the rigidity of the cyclic oligosaccharide derivative is derived from the shrinkage relaxation of the inclusion of the polymerizable monomer, and the low crystallinity derived from the bulk is large. Play a role. Further, the photosensitive material is prepared as a photosensitive material precursor -11 - 201106104, which is characterized by having a polymer substrate forming component containing a cyclic oligosaccharide derivative, and a radical polymerizable monomer and photoinitiator a radical polymerization initiator, wherein the polymer substrate forming component is polymerized by a reaction other than photoinitiated radical polymerization to form the polymer substrate, and the photosensitive material is as described above The precursor can be produced by polymerization of a polymer substrate formed by a reaction other than photoinitiated radical polymerization. In addition, the polymer base material of the photosensitive material of the present invention preferably contains a radical polymerizable compound represented by the chemical formula (1) as a constituent unit. Similarly, the polymer substrate of the photosensitive material precursor of the present invention forms a component, and preferably contains a radical polymerizable compound which can also be represented by the formula (1).
—C—CH2-~*L1—~ Ar—L1—CH2—C-~L2—C—CH2-~*L1—~ Ar—L1—CH2—C—~L2
(式中，Ar表示具有芳香環1個以上之之2價基， R1、R2分別表示氫原子或甲基，L1表示氧原子、硫原子 或- (OR3)nO-，R3爲伸烷基，η爲1至4的數，L2表示可 具有芳香環之2價基。）再者，伸烷基的碳數較佳爲1至 6，更佳爲1至4，特佳爲1至3。 在此情形，由於聚合物基材中存在有芳香環，即使在 採用分子中具有芳香環之高折射率的自由基聚合性單體之 情形，仍然相溶性高且難於產生混濁之故，能增大聚合物 -12- 201106104 基材與自由基聚合性單體或其聚合物之間的折射率差，結 果亦可提高感光性材料的折射率調制度。又，由於在感光 性材料的感光時，自由基聚合性單體的至少一部分能與存 在於聚合物基材中之自由基聚合性基進行反應而共聚合之 故，相溶性增高，透明性提升之同時，可使所形成之折射 料 材 性 。 光 化感 定之 穩述 構上。 結，用 制又使 調好 率很 體 媒 錄 記 圖 像 全 爲 作 是 別 特 [發明之效果] 以上，如採用本發明，則可提供一種能作爲使折射率 調制結構形成於材料中之光學製品，特別是能作爲全像圖 記錄媒體很適合使用之感光時的體積收縮小，透明性優異 的感光性材料》 [發明之最佳實施形態] 以下，就本發明之詳細內容以及其他特徵及優點，依 據實施形態之下加以說明。 本發明中，爲作爲聚合物基材的構成單元或聚合物基 材形成成分所含有之環狀低聚醣衍生物，可採用周知的環 狀低聚醣的各種衍生物。周知之環狀低聚醣而言，可例 舉：環糊精（cyclodextrin)(由α-1，4連接所成之環狀葡萄 基低聚醣 （cyclo-gluco-oligose)、 環葡聚糖 (cyclodextran)(由α-1，6連接所成之環狀葡萄基低聚醣）、 201106104 環甘露聚醜（cyclomannin)(由β -1，4-連接所成之環狀甘露 基低聚醣 （cyclo-manno-oligose))、 環阿卓糖 (cycloaltrin)(由α -1,4-連接所成之環狀阿卓糖基低聚酿 (cyclo-altro-oligose))、cycloawaodrin(由 α -1,4-連接所成 之環狀鼠李糖基低聚醣（cyclo-rhamno-oligose))、等。 於前述環狀低聚醣之中，從取得容易性或成本的觀點 來看，較佳爲環糊精衍生物，更佳爲α-環糊精衍生物或 /3-環糊精衍生物》環糊精，係複數個葡萄糖（glucose)經 按α-1，4連接以形成環狀結構之低聚醣（oligose)的一種， 而於前述環狀構造的內部具有空穴（vacancy)。一般周知， 此種空穴具有能收納適當大小的分子之包藏作用之事實， 而利用此種性質，產業上已經廣泛利用於對難水溶性的醫 藥品的.水溶性之賦與、食品中的揮發成分的穩定化、於生 活環境中之除臭等作法。 前述衍生物而言，從與構成本發明之感光性材料之成 分的相溶性的觀點來看，環狀低聚醣所具有之複數個羥基 之至少一部分，較佳爲經變換爲烷氧基之烷基化衍生物、 經變換爲羥烷氧基之羥烷基化衍生物，經變換爲乙醯氧基 之乙醯基化衍生物。 環狀低聚醣衍生物的含有率而言，對聚合物基材（如 係感光性材料前驅物的情形，則爲聚合物基材形成成分全 體），較佳爲1至40重量％、更佳爲5至3 5重量％、再佳 爲10至30重量％。如前述環狀低聚醣衍生物的含量率過 高時，則可能感光性材料前驅物的黏度增高以致感光性材 -14 - 201106104 料的製造變成煩雜、或者感光性材料的彈性率或玻璃化溫 度升高以致形成折射率調制結構的敏感度降低。另一方 面，如前述環狀低聚醣衍生物的含有率過低時，則可能難 於獲得充分的效果·» 對作爲聚合物基材的構成單元而含有環狀低聚醣衍生 物，即可製得感光性材料在感光時的體積收縮小，且透明 度優異的感光性材料之理由則尙不明瞭，惟可推測爲例 如，因環狀低聚醣衍生物的剛硬性所產生之耐收縮性、源 自聚合性單體包藏作用之收縮緩和、源自體積大之低結晶 性、等在發揮功用。可由因作爲聚合物基材的構成單元而 含有環狀低聚醣衍生物所期待之其他效果而言，尙可舉： 對感光性材料的生物降解性（1^〇£^§^(1&1^1丨17)之賦與。 [聚合物基材及聚合物基材形成成分] 於本發明中，聚合物基材，係對感光性材料前驅體中 之聚合物基材形成成分，較佳爲使其發生藉由除光引發自 由基聚合反應以外的反應之聚合而形成者。較佳爲，前述 聚合物基材，能在感光性材料的製造過程（原地（in-situ)中 使其形成爲宜。在此情形，於感光性材料前驅物中之聚合 物基材形成成分，即在自由基聚合性單體及光引發自由基 聚合起始劑之共存下進行聚合，結果可形成聚合物基材。 此時’如前述自由基聚合物單體或前述光引發自由基聚合 起始劑經反應而減少’則由於作爲感光性材料之性能會降 低之故’較佳爲按儘量不要使其減少之方式形成聚合物基 t S ] -15- 201106104 材。 再者’於本發明中之"藉由除光引發自由基聚合反應 以外之聚合"，係指除不飽和基能參與之聚合之外，尙包 含縮合（condensation)、加成聚合（polyaddition)，而單體 (作爲單體之化合物），則包含能顯示聚合性之低聚物。 具體而言，可例舉：縮聚反應或異氰酸酯-羥基加成 聚合反應（形成聚胺基甲酸酯）、異氰酸酯-胺加成聚合反 應（形成聚脲）、異氰酸酯-硫醇加成聚合反應、環氧-胺加 成聚合反應、環氧·硫醇加成聚合反應、表硫醚 (episulfide)-胺加成聚合反應、表硫醚·硫醇加成聚合反應 等。較佳爲異氰酸酯、羥基加成聚合反應。 爲實質上不使自由基聚合性單體或光引發自由基聚合 起如劑、或者如下所說明之可以化學式（1)表示之自由基 聚合性化合物減少之下形成聚合物基材起見，較佳爲作成 按除光引發自由基聚合以外之其他反應形態下之聚合能優 先發生之方式調配反應觸媒等，或調整反應溫度。 爲實質上不使自由基聚合性單體或光引發自由基聚合 起始劑、或者如可以化學式（1)表示之自由基聚合性化合 物減少之下形成聚合物基材之用的反應，如採用適當的觸 媒則可促進其反應。例如，異氰酸酸酯-羥基加成聚合反 應的觸媒而言，可採用：二甲基錫二月桂酸酯、二丁基錫 月桂酸酯等錫化合物，1,4-重氮二環[2,2,2]辛烷 (DABCO)、2,4,6-參（二甲基胺基甲基）苯酚、N，N-二甲基 苄基胺等三級胺化合物等。此等觸媒，可以單獨1種使用 -16- 201106104 亦可以組合2種以上之方式使用。 如以異氰酸酯-羥基加成聚合反應所得聚胺基甲酸_ 成爲聚合物基材之情形爲例加以說明時，則異氰酸酯化合 物與羥基化合物將成爲聚合物基材。在此情形，環狀低聚 醣衍生物，即作爲聚合物基材的構成單元或聚合物基材形 成成分而含於其中。 前述異氰酸酯化合物而言，可使用於1分子中具有2 個以上的異氰酸酯基之異氰酸酯化合物或其混合物。可例 舉：甲苯二異氰酸酯（TDI)、二苯基甲烷-4，4’-二異氰酸酯 (MDI)、伸苯二甲基二異氰酸酯（XDI)、四甲基伸苯二甲基 二異氰酸酯（TMXDI)、萘1,5-二異氰酸酯（NNI)、三苯基 甲烷-4,4，’4”-三異氰酸酯、二環己基甲烷_4,4’-二異氰酸 酯（H12MDI)、氫化伸苯二甲基二異氰酸酯（Η6Χ〇Ι)、六亞 甲基二異氰酸酯（HDI)、三甲基六亞甲基二異氰酸醋 (TMHDI) '異佛爾酮二異氰酸酯（IPDI)、降冰片烷二異氰 酸酯（NBDI)、環己烷- l，3,5-三異氰酸酯以及從此等異氰酸 酯化合物所得之三聚物（trimer)、縮二脲物（biuret)、加成 物（adduct)'預聚合物（prep〇lymer)等。此等異氰酸醋化合 物，可以單獨1種使用，亦可以組合2種以上之方式使 用。 前述羥基化合物而言，可使用1分子中具有2個以上 的羥基之羥基化合物或其混合物。可例舉.：聚醚型聚多元 醇類、聚酯型聚多元醇類 '聚碳酸酯型二元醇類等。此等 羥基化合物，可以單獨1種使用，亦可組合2組以上之方f -17- 201106104 式使用。 又，聚合物基材及聚合物基材形成成分中，可含有可 以化學式（1)表示之自由基聚合性化合物》藉此，可獲得 如下述之優點。亦即，如聚合物基材中存在有芳香環時， 即使採用分子中具有芳香環之高折射率的自由基聚合性單 體的情形，仍然相溶性高且由於難以產生混濁之故，可增 大聚合物基材與自由基聚合性單體或其聚合物間的折射率 差，而可提高感光性材料的折射率調制度。 又，在感光性材料的感光時，由於自由基聚合性單體 的至少一部分即與聚合物基材中所存在之自由基聚合性基 進行反應而共聚合之故，相溶性將增高而提升透明性之同 時可使所形成之折射率調制構造穩定化。 再者’如聚合物基材形成成分含有可以化學式（1)表 示之自由基聚合性化合物時，較佳爲實質上不致於減少前 述自由基聚合性基之下’使其參與聚合物基材之形成。爲 此，可以化學式（1)表示之化合物，除具有自由基聚合性 基之外’尙具有其他聚合性官能基爲宜。其他聚合性官能 基抵要是非爲自由基聚合性基即可，又，如以酯鍵（ester linkage)聚合之情形一樣，亦可按—方具有oh基，另— 方具有羧酸基或其衍生物之方式由2種以上的化合物所 成。 可以化學式（1)表示之自由基聚合性化合物的含有率 而言’對聚合物基材（如係感光性材料前驅物的情形，則 爲聚合物基材形成成分全體），較佳爲〇·5至2〇重量％、 -18- 201106104 更佳爲1至1 0重量％、特佳爲2至6重量％。如以化學式 (1)表示之自由基聚合性化合物的含有率過高時，則可能 損及藉由環狀低聚醣衍生物所得之收縮降低效果。另一方 面’如不含有可以化學式（1)表示之自由基聚合性化合物 或含有率過低時，則聚合物基材與自由基聚合性單體或其 聚合牧ϊ Ρ邊的相溶性將降低，以致有感光性材料中產生混濁 之情形。 W以化學式（1)表示之自由基聚合性化合物而言，可 以化學式（2)至（5)表示之化合物很好使用。 【化2】(wherein Ar represents one or more valent groups having an aromatic ring, R1 and R2 each represent a hydrogen atom or a methyl group, and L1 represents an oxygen atom, a sulfur atom or -(OR3)nO-, and R3 is an alkylene group. η is a number from 1 to 4, and L2 represents a divalent group which may have an aromatic ring. Further, the alkyl group has a carbon number of preferably from 1 to 6, more preferably from 1 to 4, particularly preferably from 1 to 3. In this case, since an aromatic ring is present in the polymer substrate, even in the case of using a radically polymerizable monomer having a high refractive index of an aromatic ring in the molecule, the compatibility is high and it is difficult to cause turbidity, and it can be increased. Large polymer-12-201106104 The refractive index difference between the substrate and the radical polymerizable monomer or its polymer, and as a result, the refractive index modulation degree of the photosensitive material can also be improved. In addition, at least a part of the radical polymerizable monomer can be copolymerized with the radical polymerizable group present in the polymer substrate to cause copolymerization during the photosensitive light-sensitive material, so that the compatibility is increased and the transparency is improved. At the same time, the formed refractive material can be made. The stabilizing effect of the sensitization of light. The use of the system and the adjustment rate are very good for the physical media recording image. [Effect of the invention] As described above, according to the present invention, it is possible to provide a refractive index modulation structure in the material. An optical product, particularly a photosensitive material which is small in volume shrinkage at the time of light-sensing, which is suitable for use as an hologram recording medium, and a photosensitive material which is excellent in transparency. [Best Embodiment of the Invention] Hereinafter, the details and other features of the present invention will be described. And the advantages are explained below according to the embodiment. In the present invention, various derivatives of the known cyclic oligosaccharides can be used as the cyclic oligosaccharide derivative contained in the constituent unit of the polymer substrate or the polymer substrate forming component. As the known cyclic oligosaccharide, cyclodextrin (cyclo-gluco-oligose, cycloglucan formed by α-1,4 linkage) can be exemplified. (cyclodextran) (cyclic glucosyl oligosaccharide formed by α-1,6 linkage), 201106104 cyclomannin (cyclic mannose oligosaccharide formed by β-1,4-linkage) (cyclo-manno-oligose), cycloaltrin (cyclo-altro-oligose formed by α-1,4-linkage), cycloawaodrin (by α - 1,4-connected cyclo-rhamno-oligose), etc. Among the above-mentioned cyclic oligosaccharides, from the viewpoint of availability or cost, Preferably, it is a cyclodextrin derivative, more preferably an α-cyclodextrin derivative or a /3-cyclodextrin derivative, cyclodextrin, in which a plurality of glucoses are linked by α-1,4 to form One type of oligoose having a cyclic structure, and having a vacancy inside the cyclic structure. It is generally known that such a hole has a occlusion function for accommodating a molecule of an appropriate size. In fact, the use of this property has been widely used in industries such as water-soluble pharmaceuticals, stabilization of volatile components in foods, and deodorization in living environments. From the viewpoint of compatibility with the components constituting the photosensitive material of the present invention, at least a part of the plurality of hydroxyl groups of the cyclic oligosaccharide is preferably an alkyl group converted into an alkoxy group. a derivative, a hydroxyalkylated derivative converted to a hydroxyalkoxy group, converted to an ethoxylated derivative of an ethoxylated ethoxy group. The content of the cyclic oligosaccharide derivative, the polymer The substrate (for example, in the case of a photosensitive material precursor, the entire polymer substrate forming component), preferably 1 to 40% by weight, more preferably 5 to 5% by weight, still more preferably 10 to 30% by weight. If the content of the cyclic oligosaccharide derivative is too high, the viscosity of the photosensitive material precursor may be increased so that the production of the photosensitive material-14 - 201106104 becomes complicated, or the elastic modulus of the photosensitive material or The glass transition temperature rises to form The sensitivity of the radiation rate modulation structure is lowered. On the other hand, when the content of the cyclic oligosaccharide derivative is too low, it may be difficult to obtain a sufficient effect, and the ring is contained as a constituent unit of the polymer substrate. The oligosaccharide derivative can produce a photosensitive material with a small volume shrinkage at the time of light sensation, and the reason for the photosensitive material having excellent transparency is unclear, but it can be presumed to be, for example, a cyclic oligosaccharide derivative. The shrinkage resistance by the rigidity, the shrinkage relaxation derived from the occlusion of the polymerizable monomer, the low crystallinity derived from the bulk, and the like. Other effects expected from the inclusion of a cyclic oligosaccharide derivative as a constituent unit of a polymer substrate include: biodegradability to a photosensitive material (1^〇£^§^(1& [1,1丨17). [Polymer substrate and polymer substrate forming component] In the present invention, the polymer substrate is formed by forming a component on the polymer substrate in the photosensitive material precursor. Preferably, it is formed by polymerization of a reaction other than photoinitiated radical polymerization. Preferably, the polymer substrate can be used in the process of producing a photosensitive material (in-situ). In this case, the polymer substrate forming component in the photosensitive material precursor, that is, the polymerization in the coexistence of the radical polymerizable monomer and the photoinitiated radical polymerization initiator, can be carried out. Forming a polymer substrate. At this time, 'as described above, the radical polymer monomer or the photoinitiated radical polymerization initiator is reduced by reaction', since the performance as a photosensitive material is lowered, it is preferable to Don't make it a way to reduce it Further, in the present invention, "polymerization other than photo-initiated radical polymerization" means, in addition to polymerization in which unsaturated groups can participate, 尙A condensation polymerization or a polyaddition is included, and a monomer (a compound as a monomer) contains an oligomer which exhibits polymerizability. Specifically, a polycondensation reaction or an isocyanate-hydroxy group addition may be mentioned. Polymerization (formation of polyurethane), isocyanate-amine addition polymerization (formation of polyurea), isocyanate-thiol addition polymerization, epoxy-amine addition polymerization, epoxy·thiol addition Polymerization reaction, episulfide-amine addition polymerization reaction, episulfide-thiol addition polymerization reaction, etc., preferably isocyanate or hydroxyl addition polymerization reaction. The photopolymer or photoinitiated radical polymerization initiator, or the radical polymerizable compound represented by the chemical formula (1), as described below, can be formed by a photopolymerization radical polymerization. In the other reaction forms, the polymerization can be preferentially generated to adjust the reaction catalyst, etc., or to adjust the reaction temperature. The radical polymerization polymerizable monomer or photoinitiated radical polymerization initiator is not substantially made, or 1) A reaction for forming a polymer substrate under the reduction of a radical polymerizable compound, such as a suitable catalyst to promote the reaction. For example, an isocyanate-hydroxyaddition polymerization catalyst For the purpose, a tin compound such as dimethyltin dilaurate or dibutyltin laurate may be used, 1,4-diazobicyclo[2,2,2]octane (DABCO), 2,4,6 a tertiary amine compound such as dimethylaminomethyl phenol or N,N-dimethylbenzylamine. These catalysts can be used in a single type -16- 201106104 or two or more types can be used in combination. When the polyaminocarbamic acid obtained by the isocyanate-hydroxy addition polymerization reaction is used as a polymer substrate as an example, the isocyanate compound and the hydroxy compound will become a polymer substrate. In this case, the cyclic oligosaccharide derivative is contained as a constituent unit of the polymer substrate or a polymer substrate forming component. The above isocyanate compound can be used for an isocyanate compound having two or more isocyanate groups in one molecule or a mixture thereof. For example, toluene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI), benzoyl diisocyanate (XDI), tetramethyl benzoyl diisocyanate (TMXDI) , naphthalene 1,5-diisocyanate (NNI), triphenylmethane-4,4,'4"-triisocyanate, dicyclohexylmethane-4,4'-diisocyanate (H12MDI), hydrogenated benzoic acid Diisocyanate (Η6Χ〇Ι), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI) 'isophorone diisocyanate (IPDI), norbornane diisocyanate (NBDI), cyclohexane-l,3,5-triisocyanate, and trimer, biuret, adduct' prepolymer (prep) obtained from such isocyanate compounds异 mer ) 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 A mixture thereof can be exemplified. Polyether type poly polyols, polyester type poly polyols An acid ester type diol, etc. These hydroxy compounds may be used alone or in combination of two or more groups of formula f -17- 201106104. Further, the polymer substrate and the polymer substrate are formed into a component. It may contain a radically polymerizable compound represented by the formula (1), whereby an advantage as follows may be obtained, that is, if an aromatic ring is present in the polymer substrate, even if the molecule has an aromatic ring In the case of a radically polymerizable monomer having a refractive index, the compatibility is high, and since it is difficult to cause turbidity, the refractive index difference between the polymer substrate and the radical polymerizable monomer or its polymer can be increased. The refractive index modulation degree of the photosensitive material is increased. Further, at the time of light-sensing of the photosensitive material, at least a part of the radical polymerizable monomer reacts with the radical polymerizable group present in the polymer substrate to copolymerize Therefore, the compatibility is increased to enhance the transparency, and the formed refractive index modulation structure can be stabilized. Further, if the polymer substrate forming component contains a chemical formula (1) In the case of a base polymerizable compound, it is preferred that the radical polymerizable group is not substantially reduced to participate in the formation of a polymer substrate. For this purpose, the compound represented by the formula (1) may have a radical polymerization. It is preferable that the other group has other polymerizable functional groups. Other polymerizable functional groups are preferably non-radical polymerizable groups, and, as in the case of ester linkage polymerization, - The compound having a OH group and having a carboxylic acid group or a derivative thereof is formed of two or more kinds of compounds. The content of the radically polymerizable compound represented by the chemical formula (1) is - The material (in the case of a photosensitive material precursor, the polymer substrate forming component as a whole), preferably 〇·5 to 2〇% by weight, -18-201106104, more preferably 1 to 10% by weight, Preferably it is 2 to 6% by weight. When the content of the radically polymerizable compound represented by the chemical formula (1) is too high, the shrinkage reducing effect by the cyclic oligosaccharide derivative may be impaired. On the other hand, if the radical polymerizable compound represented by the chemical formula (1) is not contained or the content is too low, the compatibility of the polymer substrate with the radical polymerizable monomer or the polymerized mash thereof is lowered. Therefore, there is a case where turbidity occurs in the photosensitive material. In the case of the radically polymerizable compound represented by the chemical formula (1), the compound represented by the chemical formulas (2) to (5) can be preferably used. [Chemical 2]
-19- 201106104 【化4】-19- 201106104 【化4】
於化學式（2)至（5)中，R1分別表示氫原子或甲基，R4 分別表示獨立之氫原子或碳數1至4的烷基，R5表示氫 原子、鹵素原子、碳數1至4的烷基或碳數1至4的烷氧 基。L1表示氧原子、硫原子或_(〇R3)n〇_，L3表示氧原 子、硫原子、-C(0)0-或-N(R6)-，L4表示單鍵、氧原子、 硫原子、硫醯基或伸烷基。又，η表示1至4之數，R3表 示伸烷基，R6表示氫原子或碳數1至4的烷基。再者， 伸烷基的碳數較佳爲1至6，更佳爲1至4，特佳爲1至 3 〇 可以化學式（2)表示之化合物而言，可例舉：9,9-雙 (4-羥基苯基）莽二縮水甘油基醚的（甲基）丙烯酸加成物、 9,9-雙（4-羥基-3-甲基苯基）莽二縮水甘油基醚的（甲基）丙 烯酸加成物、9,9-雙（4_(2_羥基乙氧基）苯基）苐二縮水甘油 基醚的（甲基）丙烯酸加成物等。 可以化學式（3)表示之化合物而言，可例舉：9,9_雙 (4-經基苯基）葬二縮水甘油基醚的乙烯基安息香酸加成 -20- 201106104 物、同樣乙烯基苯酚加成物、同樣乙烯基苯硫酚、同樣乙 烯基苯胺加成物、9,9-雙（4-羥基-3-甲基苯基）莽二縮水甘 油基醚的乙烯基安息香酸加成物、同樣乙烯基苯酚加成 物、同樣乙烯基苯硫酚加成物、同樣乙烯基苯胺加成物、 9,9-雙（4-(2-羥基乙氧基）苯基）兼二縮水甘油基醚的乙烯基 安息香酸加成物、同樣乙烯基苯酚加成物、同樣乙烯基苯 硫酚加成物、同樣乙烯基苯胺加成物等。 可以化學式（4)表示之化合物而言，可例舉：雙酚A 型環氧樹脂的（甲基）丙烯酸加成物、雙酚F型環氧樹脂的 (甲基）丙烯酸加成物等。 可以化學式（5)表示之化合物而言，可例舉：雙酚A 型環氧樹脂的乙烯基安息香酸加成物、同樣乙烯基苯酚加 成物、同樣乙烯基苯硫酚加成物、同樣乙烯基苯胺加成 物、同樣雙酚F型環氧樹脂的乙烯基安息香酸加成物、同 樣乙烯基苯酹加成物、同樣乙烯基硫苯酚加成物、同樣乙 烯基苯胺加成物等。 可以前述式（1)或（2)至（5)表示之化合物，可以單獨i 種使用’亦可以組合2種以上之方式使用。 [自由基聚合性單體] 本發明之感光性材料，可作爲於材料中形成折射率調 制結構之光學製品’特別是作爲全像圖記錄媒體很適合使 用。前述光學製品，一般而言，較佳爲折射率調制度高 者’爲此，如儘量增大聚合物基材與自由基聚合性單體或 -21 - 201106104 其聚合物間的折射率差則較爲有利。例如，將更低折射率 的聚合物基材、與更高折射率的自由基聚合性單體加以組 合，即可增大折射率差。 本發明之感光性材料或其前驅物中所調配之自由基聚 合性單體而言，祗要是同業者所周知者則並不特別加以限 制’惟較佳爲採用分子中具有芳香環之高折射率的自由基 聚合性單體。 此種分子中具有芳香環之高折射率的自由基聚合性單 體而言，可例舉：苯乙烯、氯苯乙烯、溴苯乙烯、α-甲 基苯乙烯、二乙烯基苯、乙烯基萘、二乙烯基萘、乙烯基 聯苯、二乙烯基聯苯、乙烯基聯三苯、乙烯基芘、茚 (indene)、危稀萘（acenaphthylene)、二苯并富燒 (dibenzofulvene)、苯基（乙烯基苯基）硫醚、苄基（乙烯基 节基）硫酸、N-乙燃基昨哩（vinylcarbazole)、苯基（甲基） 丙烯酸酯、苄基（甲基）丙烯酸酯、苯氧乙基（甲基）丙烯酸 酯、萘氧基乙基（甲基）丙烯酸酯、三溴苯基（甲基）丙烯酸 酯、三溴苯氧基乙基（甲基）丙烯酸酯、氧化烷烯改性雙酚 A的二（甲基）丙烯酸酯、9,9-雙（4-羥基苯基）蔣的二（甲基） 丙烯酸酯、9,9-雙（4-羥基-3-甲基苯基）弗的二（甲基）丙烯 酸酯、9,9-雙（4-(2-羥基乙氧基）苯基）苐的二（甲基）丙烯酸 酯、雙（4-甲基丙醯硫苯基）硫醚、雙（4—乙烯基硫苯基）硫 醚等。此等自由基聚合性單體，可以單獨1種使用，亦可 以組合2種以上之方式使用。 前述自由基聚合性單體的調配量，係對感光性材料或 -22- 201106104 感光性材料前驅物全體，較佳爲1至3〇重量％、更佳爲2 至25重量％、特佳爲3至20重量％。 [光弓丨發自由基聚合起始劑（iight-induced radical polymerization starter)] 本發明之感光性材料或其前驅物中所調配之光引發自 由基聚合起始劑而言，可採用同業者所周知之各種光引發 自由基聚合起始劑，而可按照所使用之光的波長適當加以 選擇使用》 較佳的光引發聚合起始劑可例舉：雙（5_2,4_環戊二 烯-1-基）雙（2,6-二氟代-3-(1^1-吡咯-1-基）苯基）鈦、雙 (2,4,6-三甲基苯醯基）苯基氧化膦、2,4,6-三甲苯醯基二苯 基氧化膦、2-苄基-2-(二甲基胺基）-1-[4-嗎啉-4-基）苯基] 丁烷-1-酮、2-(二甲基胺基）-2-(4-甲基苄基）-1-[4-(嗎啉-4-基）苯基]丁烷-1-酮、2_甲基-1-[4-(甲硫基）苯基]-2-(嗎啉-4-基）丙烷-1-酮、2,2-二甲氧-1，2-二苯基乙烷-1-酮、（1-羥 基環己基）苯基酮等。 前述光引發自由基聚合起始劑的調配量係由於因所使 用之光引發自由基聚合起始劑的種類，自由基聚合性單體 的調配量而有所異之故不能一槪而決定，惟對感光性材料 或感光性材料前驅物全體，較佳爲在〇·〇5至20重量％的 範圍、更佳爲在0.1至10重量％的範圍、特佳爲在0.2至 5重量％的範圍。 再者，本發明之感光性材料及感光性材料前驅物中， -23- 201106104 需要時，尙可含有可塑性、相溶化劑、鏈轉移劑（chain t r a n s f e r a g e n t)、聚合促進劑 '聚合抑制劑、表面活性劑、 消泡劑、剝離劑、穩定化劑、抗氧劑、阻燃劑等添加劑。 [感光性材料之製造] 就本發明之感光性材料的製造方法加以說明。首先， 準備本發明之感光性材料前驅物，亦即，具有聚合物基材 形成成分、自由基聚合性單體以及光引發自由基聚合起始 劑，並作爲前述聚合物基材形成成分而含有環狀低聚醣衍 生物之感光性材料前驅物。接著，對前述聚合物基材形成 成分，使其發生藉由除光引發自由基聚合反應以外的反應 之聚合以形成聚合物基材。在此情形，聚合物基材，係藉 由聚合物基材形成成分在自由基聚合性單體及光引發聚合 起始劑的共存下進行聚合而形成者。 較佳爲，前述聚合物基材，能在感光性材料的製造過 程（原地（in-situ)中使其形成爲宜。在此情形，將前述感光 性材料前驅物塗佈於玻璃、聚碳酸酯、聚甲基丙烯酸甲酯 或環烯烴聚合物等透明的基材或注入於基材間，然後，使 其發生藉由光引發自由基聚合反應以外的反應之聚合即可 形成聚合物基材。 由此，可製得以構成單元而含有環狀低聚醣衍生物之 聚合物基材中含有自由基聚合性單體及光引發自由基聚合 起始劑所成之感光性材料。 再者，於前述基材與前述感光性材料之間，以隔斷氧 -24- 201106104 氣或水分爲目的，而設置有保護層。爲保護層，可採用例 如與前述基材同等者’或者聚烯烴、聚氯化乙烯、聚二氯 亞乙烯、聚乙烯醇、聚對苯二甲酸乙二醇酯或聚乙烯_2,6· 萘二羧酸酯等的軟片或玻璃等。 [感光性材料之應用] 本發明之感光性材料’係很適合採用爲將因同調的光 的干擾所產生之明暗的干擾型樣作爲折射率調制結構而記 錄之體積相位型全像圖gS錄媒體（volume phase type hologram record medium)、或濾光器 '射束分裂器、頭戴 顯示器般的全像式光學元件（HOE)、由三次元全像微影術 所製作之光電子結晶光學元件、或者利用三次元直接描畫 (direct-write)光微影術等所製作之光波導等用途。 【實施方式】 [實施例] 以下，將藉由實施例而具體說明本發明內容，惟本發 明係並不因此等實施例而有所限定者。 (實施例1) [感光性材料前驅物之調製] 於聚合物基材形成成分之中，作爲環狀低聚醣衍生物 而調配甲基化環糊精（東京化成工業（股）製，羥基當量 367_4g/eq.(當量））10.0重量份（對聚合物基材形成成分全體& -25- 201106104 爲12.3重量％)’作爲以化學式（1)表示之自由基聚合性化 合物而調配9,9-雙（4-羥基苯基）蒔二縮水甘油基醚的丙烯 酸加成物（新日鐵化學（股）製，ASF-400)(折射率 nD=1.616)4.0重量份、六亞甲基二異氰酸酯（東京化成工 業（股）製）22.4重量份，聚醚型三元醇（三洋化成工業（股） 製、GP-600、平均分子量597)44.9重量份），作爲聚合物 基材形成觸媒而調配二丁基錫二月桂酸酯（東京化成工業 (股）製）〇.〇4 5重量份，作爲自由基聚合性單體而調配苯基 (4-乙烯基苯基）硫醚（新日鐵化學（股）製）（折射率 nD=1.648) 1 5.0重量份，作爲光引發聚合起始劑而調配雙 (7? 5-2,4-環戊二烯-1-基）-雙（2,6-二氟代-3-(1^吡咯-1-基） 苯基）鈦（千葉•特殊化學品製、伊爾加裘亞784) 1.2重量 份，作爲鏈轉移劑而調配2,4-二苯基-4-甲基-1-戊烯（東京 化成工業（股）製）2.5重量份，以調製感光性材料前驅物。 [含有感光性材料之全像圖記錄媒體之製作] 接著，將如上述方式所調製之感光性材料前驅體，導 入於經介由矽膠膜間隔片（silicon film spacer)(厚度 0.2mm)而貼合2片玻璃基板（30mmx30mm、厚度1.2mm)的 空隙，並於氮氣氣氛下，在60°C之下加熱處理5小時以 形成聚合物基材，製得含有感光性材料之穿透型全像圖記 錄媒體（permeation type hologram record medium) ° [含有感光性材料之全像圖記錄媒體之評價] -26- 201106104 接著’採用脈衝科技工業（股）製的二光束干擾型平面 波試驗器（double beam interference type plane wave tester)SHOT-5 00G進行如上述方式所得穿透型全像圖記錄 媒體（Permeati〇n type hologram record medium)之評價。 爲全像圖的記錄•再生（recording · regeneration)，則採 用連續振盪（continuos waves(CW))全固體雷射（total solid laser)(波長：532nm) » 將記錄光（recording light)在記錄媒 體上的光學強度（optical strength)(二光束的合計）作成 7mW(毫瓦特）/cm2，按總曝光量能成爲 5000mJ(毫焦 耳）/cm2之方式實施角度多路傳送記錄（angle multiplex recording)(49多路傳送）。所記錄之全像圖的繞射效率 (diffraction efficiency)，係採用經以光學動力計（optical power meter)讀取再生時的繞射光（diffraction light)及透 射光（transmitted light)的各強度，依下式加以算出。 繞射效率（％) =[繞射光強度/(透射光強度+繞射光強度）]xl00 採用該繞射效率的値，作爲全像圖記錄媒體之指標， 依下式算出M/#(M數）。於本實施例中之全像圖記錄媒體 的 M/#，爲 2.3。 Μ/# = Σ / (繞射效率） 又’隨著記錄時所發生之收縮率（shrinkage)，係從全 像圖記錄時的角度與再生時的繞射光峯値頂點角度（peak top angle)的差（失調角度（detuning angie)作爲表觀收縮率 -27- 201106104 (apparent shrinkage)加以算出者。本實施例中之全像圖記 錄媒體的收縮率，爲0.2%。又，本實施例中之全像圖記 錄媒體，在記錄前後均爲透明者。 (實施例2) 除作爲環狀低聚醣衍生物而採用甲基化-α環糊精 (Cycl〇Ub.Ltd.(賽克樂試驗所（股））製，羥基當量 273.4g/eq.)10.0重量份（對聚合物基材形成成分全體，爲 12.3重量％)，並將六亞甲基二異氰酸酯（東京化成工業（股） 製）作成22.9重量份、聚醚型三元醇（三洋化成工業（股）製 GP-600、平均分子量597)作成44.3重量份以外，其餘則 按與實施例1同樣方式製作含有感光性材料之穿透型全像 圖記錄媒體，並加以評價。所得全像圖記錄媒體的M/#爲 3.1，收縮率爲〇.2%。再者，本實施例中之全像圖記錄媒 體，在記錄前後均爲透明者。 (比較例1 ) 除不使用環狀低聚醣衍生物，並將六亞甲基二異氰酸 酯（東京化成工業（股）製）作成23.7重量份、將聚醚型三元 醇（三洋化成工業（股）製、GP-600、平均分子量597)作成 5 3 · 5重量份以外，其餘則按與實施例1同樣方式調製感光 性材料前驅物。採用所得感光性材料前驅物，按與實施例 1同樣方式製作穿透型全像圖記錄媒體，並加以評價。所 得全像圖記錄媒體的M/#爲2.0、收縮率爲0.3%。再者， -28- 201106104 本比較例中之全像圖記錄媒體’雖然在記錄前爲透明者 惟在記錄後產生有輕微的混濁》 (實施例3) 於聚合物基材形成成分之中，作爲環狀低聚醣衍生物 而調配甲基化環糊精（東京化成工業（股）製、羥基當量 3 67_4g/eq.)l5.0重量份（對聚合物基材形成成分全體爲 1 7.7重量％)，作爲以代學式（丨）表示之自由基聚合性化合 物而調配9,9-雙（4-羥基苯基）蕗二縮水甘油基醚的丙烯酸 加成物（新日鐵化學（股）製、ASF-400)(折射率 nD=l .6 1 6)4.0重量份、六亞甲基二異氰酸酯（東京化成工 業（股）製）20.1重量份、聚醚型三元醇（AdeKA(股）製、G-700、平均分子量740)45.7重量份，作爲聚合物基材形成 觸媒而調配二丁基錫二月桂酸酯（東京化成工業（股） 製）〇.〇3重量份’作爲自由基聚合性單體而調配苯基（4-乙 烯基苯基）硫醚（新日鐵化學（股）製）（折射率nD=1.648)l2.0 重量份’作爲光引發自由基聚合起始劑而調配雙（7? 5-2， 4-環戊二烯-1-基）-雙（2,6-二氟代_3-(1^吡咯-1-基）-苯基） 鈦（千葉特殊化學品製、伊爾加裘亞784) 1.2重量份，作爲 鍵轉移劑而調配2,4-二苯基-4-甲基-1-戊烯（東京化成工業 (股）製）2.0重量份，以調製感光性材料前驅物。採用所得 感光性材料前驅物，按與實施例丨同樣方式製作穿透型全 像圖記錄媒體’並加以評價。所得全像圖記錄媒體的M/# 爲3.1、收縮率爲0.2%。再者，本實施例中之全像圖記錄 -29 - 201106104 媒體，在記錄前後均爲透明者。 (實施例4) 除將甲基化-y3 -環糊精（東京化成工業（股）製，羥基當 量367.4g/eq.)作成20.0重量份（對聚合物基材形成成分全 體爲23_6重量％)、將六亞甲基二異氰酸酯（東京化成工業 (股）製）作成19.7重量份、將聚醚型三元醇（ADEKA(股） 製、G-700 '平均分子量740)作成41.1重量份以外，其餘 則按與實施例3同樣方式以調製感光性材料前驅物。採用 所得感光性材料前驅物，按與實施例1同樣方式以製作穿 透型全像圖記錄媒體，並加以評價。所得全像圖記錄媒體 的M/#爲3.0、收縮率爲0·2%。再者，本實施例中之全像 圖記錄媒體，在記錄前後均爲透明者。 (實施例5) 於聚合物基材形成成分之中，作爲環狀低聚醣衍生物 而調配甲基化環糊精（東京化成工業（股）製、羥基當量 367.4g/eq.)20.0重量份（對聚合物基材形成成分全體爲 24.1重量％)，作爲以化學式（1)表示之自由基聚合性化合 物而調配9,9-羥（4-羥基苯基）苐二縮水甘油基醚的丙烯酸 加成物（新日鐵化學（股）製、ASF-400)(折射率 nD=1.616)4.0重量份、六亞甲基二異氰酸酯（東京化成工 業（股）製）19.2重量份、聚醚型三元醇（ADEKA(股）製、G-700、平均分子量740)39.7重量份，作爲聚合物基材形成 -30- 201106104 觸媒而調配二丁基錫月桂酸酯（東京化成工業（股）製）0.04 重量份，作爲自由基聚合性單體而調配苯基（4-乙烯基苯 基）硫醚（新日鐵化學（股）製）（折射率nD=l.648)4.0重量 份，作爲光引發自由基聚合起始劑而調配雙（7； 5-2,4-環戊 二烯-1-基）-雙（2,6-二氟代-3-(111-吡咯-1-基）-苯基）鈦（千 葉特殊化學品製，伊爾加裘亞784) 1.2重量份，作爲鏈轉 移劑而調配2，4-二苯基-4-甲基-1-戊烯（東京化成工業（股） 製）1·〇重量份，作爲可塑劑而調配碳酸丙烯（東京化成工 業（股）製）10.8重量份，以調製感光性材料前驅物。 採用所得之感光性材料前驅物，按與實施例1同樣方 式製作穿透型全像圖記錄媒體，並加以評價。所得全像圖 記錄媒體的Μ/#爲1.7、收縮率爲0.1%。再者，本實施例 中之全像圖記錄媒體，在記錄前後均爲透明者。 (實施例6) 除作爲自由基聚合物而採用2-乙烯基萘（新日鐵化學 (股）製）（折射率nD=l.655)以外，其餘則按與實施例5同樣 方式製作穿透型全像圖記錄媒體，並加以評價。所得全像 圖記錄媒體的M/#爲1.7、收縮率爲0.09%。再者，本實 施例中之全像圖記錄媒體，在記錄前後均爲透明者。 (實施例7) 除作爲自由基聚合性單體而採用苊烯萘（新曰鐵化學 (股）製）（折射率nD=l ·67 8)以外，其餘則按與實施例5同樣e -31 - 201106104 方式以製作穿透型全像圖記錄媒體，並加以評價。所得全 像圖記錄圖記錄媒體的M/#爲1_8、收縮率爲0.07%。再 者，本實施例中之全像圖記錄媒體，在記錄前後均爲透明 者。 (比較例2) 除不使用環狀低聚醣衍生物，並將六亞甲基二異氰酸 酯（東京化成工業（股）製）作成20.9重量份，將聚醚型三元 醇（ADEKA(股）製、G-700、平均分子量740)作成58.1重 量份以外，其餘則按與實施例5同樣方式調製感光性材料 前驅物。採用所得感光性材料前驅物，按與實施例1同樣 方式製作穿透型全像圖記錄媒體，並加以評價。所得全像 圖記錄媒體的M/#爲1.0、收縮率爲0.2%。再者，本比較 例中之全像圖記錄媒體，雖然在記錄前爲透明者，惟在記 錄3日後產生有輕微的混濁。 從實施例及比較例中可知，依照本發明之實施例中所 得之感光性材料，係較與本發明相異而不含有環狀低聚醣 衍生物之感光性材料，爲體積收縮率小，並經確認在記錄 前後的透明性亦價異之事實。又，經確認全像圖記錄媒體 的M/#亦相對地較高之事實。 以上，係依據上述具體例將本發明之內容詳細加以說 明者，惟本發明並不因上述具體例而有所限定，祗要是不 脫逸本發明之要旨之範圍內，仍能加以各種變更或變形》 -32-In the chemical formulae (2) to (5), R1 represents a hydrogen atom or a methyl group, respectively, and R4 represents an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a hydrogen atom, a halogen atom, and a carbon number of 1 to 4. Alkyl or alkoxy having 1 to 4 carbon atoms. L1 represents an oxygen atom, a sulfur atom or _(〇R3)n〇_, L3 represents an oxygen atom, a sulfur atom, -C(0)0- or -N(R6)-, and L4 represents a single bond, an oxygen atom, a sulfur atom. , thiol or alkyl. Further, η represents a number from 1 to 4, R3 represents an alkylene group, and R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, the carbon number of the alkylene group is preferably from 1 to 6, more preferably from 1 to 4, particularly preferably from 1 to 3, and may be exemplified by the compound represented by the formula (2): 9,9-double (Meth)acrylic acid adduct of (4-hydroxyphenyl)indole diglycidyl ether, 9,9-bis(4-hydroxy-3-methylphenyl)indole diglycidyl ether (methyl An acrylic acid adduct, a (meth)acrylic acid addition product of 9,9-bis(4-(2-hydroxyethoxy)phenyl)indole diglycidyl ether, and the like. The compound represented by the formula (3) may, for example, be a vinyl benzoic acid addition of 9,9-bis(4-phenylphenyl) diglycidyl ether, -20-201106104, the same vinyl Vinyl benzoic acid addition of phenol adduct, same vinyl thiophenol, same vinyl aniline adduct, 9,9-bis(4-hydroxy-3-methylphenyl) fluorene glyceryl ether , the same vinyl phenol adduct, the same vinyl thiophenol adduct, the same vinyl aniline adduct, 9,9-bis(4-(2-hydroxyethoxy)phenyl) condensed water A vinyl benzoic acid adduct of glyceryl ether, the same vinyl phenol adduct, the same vinyl thiophenol adduct, the same vinyl aniline adduct, and the like. The compound represented by the chemical formula (4) may, for example, be a (meth)acrylic acid addition product of a bisphenol A type epoxy resin or a (meth)acrylic acid addition product of a bisphenol F type epoxy resin. The compound represented by the chemical formula (5) may, for example, be a vinyl benzoic acid adduct of a bisphenol A type epoxy resin, a vinyl phenol adduct, a vinyl thiophenol adduct, or the like. Vinyl aniline adduct, vinyl benzoic acid adduct of the same bisphenol F type epoxy resin, same vinyl benzoquinone adduct, same vinyl thiophenol adduct, same vinyl aniline adduct, etc. . The compounds represented by the above formula (1) or (2) to (5) may be used singly or in combination of two or more. [Radical Polymerizable Monomer] The photosensitive material of the present invention can be used as an optical product in which a refractive index modulation structure is formed in a material, and is particularly suitable as an hologram recording medium. In the above optical article, in general, it is preferred that the refractive index modulation is high. For this reason, if the refractive index difference between the polymer substrate and the radical polymerizable monomer or the polymer of the polymer is changed as much as possible, More favorable. For example, by combining a lower refractive index polymer substrate with a higher refractive index radical polymerizable monomer, the refractive index difference can be increased. The radically polymerizable monomer to be formulated in the photosensitive material of the present invention or a precursor thereof is not particularly limited as long as it is well known to those skilled in the art, but it is preferred to employ a high refractive index having an aromatic ring in the molecule. The rate of free radical polymerizable monomer. The radically polymerizable monomer having a high refractive index of an aromatic ring in such a molecule may, for example, be styrene, chlorostyrene, bromostyrene, α-methylstyrene, divinylbenzene or vinyl. Naphthalene, divinylnaphthalene, vinylbiphenyl, divinylbiphenyl, vinyltriphenyl, vinyl anthracene, indene, acenaphthylene, dibenzofulvene, benzene (vinyl phenyl) sulfide, benzyl (vinyl) sulphate, N- ethane ruthenium (vinylcarbazole), phenyl (meth) acrylate, benzyl (meth) acrylate, benzene Oxyethyl (meth) acrylate, naphthyloxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, oxidized alkene Modified di(meth)acrylate of bisphenol A, 9,9-bis(4-hydroxyphenyl)Jiang di(meth)acrylate, 9,9-bis(4-hydroxy-3-methyl Di(meth) acrylate of phenyl) phenanthrene, di(meth) acrylate of 9,9-bis(4-(2-hydroxyethoxy)phenyl) fluorene, bis (4-methyl) Propan-acyl-thiophenyl) sulfide, bis (4-vinyl-thiophenyl) sulfide and the like. These radically polymerizable monomers may be used alone or in combination of two or more. The amount of the radical polymerizable monomer to be added is preferably from 1 to 3 % by weight, more preferably from 2 to 25% by weight, based on the total amount of the photosensitive material or the precursor of the photosensitive material of -22 to 201106104. 3 to 20% by weight. [iight-induced radical polymerization starter] The photoinitiated radical polymerization initiator formulated in the photosensitive material of the present invention or a precursor thereof can be used by a peer Various photoinitiating radical polymerization initiators are known, and can be appropriately selected according to the wavelength of light used. A preferred photoinitiated polymerization initiator can be exemplified by bis(5_2,4-cyclopentadiene- 1-yl)bis(2,6-difluoro-3-(1^1-pyrrol-1-yl)phenyl)titanium, bis(2,4,6-trimethylphenylhydrazino)phenyl oxide Phosphine, 2,4,6-trimethyldecyldiphenylphosphine oxide, 2-benzyl-2-(dimethylamino)-1-[4-morpholin-4-yl)phenyl]butane 1-ketone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-[4-(morpholin-4-yl)phenyl]butan-1-one, 2 _Methyl-1-[4-(methylthio)phenyl]-2-(morpholin-4-yl)propan-1-one, 2,2-dimethoxy-1,2-diphenyl Alken-1-one, (1-hydroxycyclohexyl) phenyl ketone, and the like. The amount of the photoinitiated radical polymerization initiator to be used is determined by the type of the radical polymerization initiator which is used for the light to be used, and the amount of the radical polymerizable monomer varies, and it cannot be determined. Preferably, the photosensitive material or the photosensitive material precursor is preferably in the range of 5 to 20% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.2 to 5% by weight in terms of 〇·〇. range. Further, in the photosensitive material and photosensitive material precursor of the present invention, yttrium may contain a plasticity, a compatibilizing agent, a chain transfer agent, a polymerization accelerator, a polymerization inhibitor, and a surface when required by -23 to 201106104. Additives such as active agents, defoamers, strippers, stabilizers, antioxidants, and flame retardants. [Production of Photosensitive Material] A method for producing the photosensitive material of the present invention will be described. First, the photosensitive material precursor of the present invention, that is, a polymer base material forming component, a radical polymerizable monomer, and a photoinitiated radical polymerization initiator are prepared, and are contained as the polymer base material forming component. A photosensitive material precursor of a cyclic oligosaccharide derivative. Next, a component is formed on the polymer substrate to cause polymerization of a reaction other than photoinitiating radical polymerization to form a polymer substrate. In this case, the polymer base material is formed by polymerizing a polymer base material forming component in the coexistence of a radical polymerizable monomer and a photoinitiated polymerization initiator. Preferably, the polymer substrate is preferably formed in a process of producing a photosensitive material (in-situ). In this case, the photosensitive material precursor is applied to glass or poly. A transparent substrate such as a carbonate, a polymethyl methacrylate or a cycloolefin polymer is injected between the substrates, and then a polymerization reaction is carried out by a reaction other than photoinitiated radical polymerization to form a polymer base. Thus, a photosensitive material comprising a radical polymerizable monomer and a photoinitiated radical polymerization initiator in a polymer substrate containing a cyclic oligosaccharide derivative, which is a constituent unit, can be obtained. A protective layer is provided between the substrate and the photosensitive material for the purpose of blocking oxygen-24-201106104 gas or moisture. For the protective layer, for example, the same as the substrate may be used, or polyolefin. Films such as polyvinyl chloride, polydivinylidene chloride, polyvinyl alcohol, polyethylene terephthalate or polyethylene 2,6·naphthalenedicarboxylate, etc. [Application of photosensitive materials] The photosensitive material of the present invention It is suitable to use a volume phase type hologram record medium or a filter for recording a light and dark interference pattern generated by interference of coherent light as a refractive index modulation structure. Beam splitter, head mounted display-like holographic optical element (HOE), photonic crystallographic optics made by three-dimensional lithography, or direct-write photolithography [Embodiment] [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. 1) [Preparation of Photosensitive Material Precursor] Methylated cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.), a hydroxyl equivalent of 367_4g/, is formulated as a cyclic oligosaccharide derivative among the polymer substrate forming components. Eq. (equivalent)) 10.0 parts by weight (to the total amount of the polymer base material forming component & -25-201106104 is 12.3% by weight) 'As the radical polymerizable compound represented by the chemical formula (1), the 9,9-double is formulated. (4- Acrylic acid adduct of phenyl hydrazine diglycidyl ether (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400) (refractive index nD = 1.616) 4.0 parts by weight, hexamethylene diisocyanate (Tokyo Chemical Industry Co., Ltd.) 22.4 parts by weight, polyether triol (manufactured by Sanyo Chemical Industries Co., Ltd., GP-600, average molecular weight 597) 44.9 parts by weight), which is used as a polymer substrate to form a catalyst to prepare dibutyltin Sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) 〇. 5 parts by weight, phenyl (4-vinylphenyl) sulfide as a radical polymerizable monomer (Nippon Chemical Co., Ltd.) (refractive index nD=1.648) 1 5.0 parts by weight, as a photoinitiated polymerization initiator, bis(7? 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro) Generation-3-(1^pyrrol-1-yl)phenyl)titanium (Chiba•Special Chemicals, Ilgayia 784) 1.2 parts by weight, formulated as a chain transfer agent 2,4-diphenyl- 2.5 parts by weight of 4-methyl-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.) to prepare a photosensitive material precursor. [Production of hologram recording medium containing photosensitive material] Next, the photosensitive material precursor prepared as described above is introduced through a silicone film spacer (thickness: 0.2 mm). A gap of two glass substrates (30 mm x 30 mm, thickness: 1.2 mm) was combined and heat-treated under a nitrogen atmosphere at 60 ° C for 5 hours to form a polymer substrate to obtain a penetrating hologram containing a photosensitive material. Permeation type hologram record medium ° [Evaluation of hologram recording medium containing photosensitive material] -26- 201106104 Then 'Two-beam interference type plane wave tester (pulse technology) The interference type plane wave tester) SHOT-5 00G was evaluated as a Permeati〇n type hologram record medium obtained as described above. For recording/reproduction of the hologram, continuous oscillating (CW) total solid laser (wavelength: 532 nm) is used. » Recording light is recorded on the recording medium. The optical strength (the total of the two beams) is set to 7 mW (milliwatts)/cm2, and the angle multiplex recording is performed in such a manner that the total exposure amount can be 5000 mJ (millijoules)/cm 2 ( 49 multiplex). The diffraction efficiency of the recorded hologram is the intensity of the diffraction light and the transmitted light when read and reproduced by an optical power meter. The following formula is calculated. Diffraction efficiency (%) = [diffractive light intensity / (transmitted light intensity + diffracted light intensity)] xl00 This diffraction efficiency is used as an index of the hologram recording medium, and M/# is calculated according to the following formula (M number) ). The M/# of the hologram recording medium in this embodiment is 2.3. Μ/# = Σ / (diffraction efficiency) and 'shrinkage as the recording occurs, the angle from the hologram recording and the peak angle of the diffraction peak at the time of reproduction (peak top angle) The difference (detuning angie) is calculated as the apparent shrinkage ratio -27 - 201106104 (apparent shrinkage). The shrinkage ratio of the hologram recording medium in the present embodiment is 0.2%. Further, in this embodiment The hologram recording medium is transparent before and after recording. (Example 2) Methylated-α-cyclodextrin (Cycl〇Ub.Ltd.) was used in addition to being a cyclic oligosaccharide derivative (Cycl〇Ub.Ltd. Test Institute (manufactured by the company), hydroxyl group equivalent: 273.4 g / eq.) 10.0 parts by weight (to 12.13% by weight of the entire polymer substrate forming component), and hexamethylene diisocyanate (Tokyo Chemical Industry Co., Ltd.) In the same manner as in Example 1, except that 22.9 parts by weight of polyether triol (GP-600 manufactured by Sanyo Chemical Industries Co., Ltd., average molecular weight 597) was prepared to be 44.3 parts by weight, the photosensitive material was prepared in the same manner as in Example 1. Penetrating hologram recording media and evaluation. The M/# of the image recording medium is 3.1, and the shrinkage rate is 2.2%. Furthermore, the hologram recording medium in this embodiment is transparent before and after recording. (Comparative Example 1) Except that no ring is used An oligosaccharide derivative, and hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was made into 23.7 parts by weight, and polyether triol (Sanyo Chemical Industry Co., Ltd., GP-600, average) A photosensitive material precursor was prepared in the same manner as in Example 1 except that the molecular weight of 597) was changed to 5 3 · 5 parts by weight. A penetrating hologram was produced in the same manner as in Example 1 using the obtained photosensitive material precursor. The recording medium was recorded and evaluated. The M/# of the obtained hologram recording medium was 2.0, and the shrinkage rate was 0.3%. Furthermore, -28-201106104 the hologram recording medium in this comparative example was transparent before recording. However, there was a slight turbidity after the recording. (Example 3) Methylated cyclodextrin was formulated as a cyclic oligosaccharide derivative among the polymer substrate-forming components (Tokyo Chemical Industry Co., Ltd.) , hydroxyl equivalent 3 67_4g / eq.) l5.0 parts by weight (on the poly Acrylic acid in which 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether was blended as a radical polymerizable compound represented by the formula (丨) as a whole of the material base forming component was 17.7% by weight. Adduct (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400) (refractive index nD = 1.66) 4.0 parts by weight, hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.1 parts by weight 45.7 parts by weight of a polyether triol (manufactured by AdeKA Co., Ltd., G-700, average molecular weight 740), and a dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) was prepared as a catalyst for forming a polymer substrate. 〇. 〇 3 parts by weight 'as a radical polymerizable monomer, phenyl (4-vinylphenyl) sulfide (manufactured by Nippon Steel Chemical Co., Ltd.) (refractive index nD = 1.648) l2.0 weight 'As a photoinitiated radical polymerization initiator to formulate bis(7? 5-2, 4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1^pyrrole- 1-yl)-phenyl) titanium (manufactured by Chiba Special Chemicals, Ilga 784) 1.2 parts by weight, 2,4-diphenyl-4-methyl-1-pentene as a bond transfer agent (Tokyo Chemical Industry ( ) Ltd.) 2.0 parts by weight, to modulate the photosensitive material precursor. Using the obtained photosensitive material precursor, a penetrating all-image recording medium was produced and evaluated in the same manner as in Example 。. The obtained hologram recording medium had M/# of 3.1 and a shrinkage of 0.2%. Furthermore, the hologram record -29 - 201106104 media in this embodiment is transparent before and after recording. (Example 4) The methylated-y3-cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group equivalent: 367.4 g/eq.) was made into 20.0 parts by weight (the total amount of the polymer substrate forming component was 23-6 wt%). And hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was made into 19.7 parts by weight, and polyether triol (made by Adeka Co., Ltd., G-700 'average molecular weight 740) was made into 41.1 parts by weight. The rest was prepared in the same manner as in Example 3 to prepare a photosensitive material precursor. Using the obtained photosensitive material precursor, a penetrating hologram recording medium was produced in the same manner as in Example 1 and evaluated. The obtained hologram recording medium had M/# of 3.0 and a shrinkage of 0.2%. Furthermore, the hologram recording medium in this embodiment is transparent before and after recording. (Example 5) The methylated cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent: 367.4 g/eq.) was formulated as a cyclic oligosaccharide derivative in the polymer substrate-forming component. (94.1% by weight of the entire polymer substrate-forming component), and 9,9-hydroxy(4-hydroxyphenyl)fluorene diglycidyl ether was formulated as a radically polymerizable compound represented by the chemical formula (1). Acetic acid adduct (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400) (refractive index nD = 1.616) 4.0 parts by weight, hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 19.2 parts by weight, polyether 39.7 parts by weight of a triol (made by ADEKA Co., Ltd., G-700, average molecular weight 740), and a dibutyltin laurate (Tokyo Chemical Industry Co., Ltd.) was prepared as a polymer substrate to form a -30-201106104 catalyst. 0.04 parts by weight, as a radical polymerizable monomer, phenyl (4-vinylphenyl) sulfide (manufactured by Nippon Steel Chemical Co., Ltd.) (refractive index nD = 1.648) was added in an amount of 4.0 parts by weight. Photoinitiated free radical polymerization initiator to formulate bis(7; 5-2,4-cyclopentadien-1-yl)-bis (2,6 -Difluoro-3-(111-pyrrol-1-yl)-phenyl)titanium (made from Chiba Specialty Chemicals, Ilgayia 784) 1.2 parts by weight, formulated as a chain transfer agent 2,4-di Phenyl-4-methyl-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.) in an amount of 1 part by weight, and 10.8 parts by weight of propylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared as a plasticizer to prepare a photosensitive film. Material precursors. Using the obtained photosensitive material precursor, a transmission type hologram recording medium was produced in the same manner as in Example 1 and evaluated. The resulting hologram recording medium had a Μ/# of 1.7 and a shrinkage of 0.1%. Furthermore, the hologram recording medium in this embodiment is transparent before and after recording. (Example 6) The same procedure as in Example 5 was carried out, except that 2-vinylnaphthalene (manufactured by Nippon Steel Chemical Co., Ltd.) (refractive index nD = 1.655) was used as the radical polymer. The holographic image is recorded and evaluated. The obtained hologram recording medium had M/# of 1.7 and a shrinkage ratio of 0.09%. Furthermore, the hologram recording medium in this embodiment is transparent before and after recording. (Example 7) Except that the terpene naphthalene (manufactured by Xinyi Iron Chemical Co., Ltd.) (refractive index nD = 1 · 67 8) was used as the radical polymerizable monomer, the same as in Example 5, e - 31 - 201106104 Way to make a penetrating hologram recording media and evaluate it. The obtained all-image chart recording medium had M/# of 1_8 and a shrinkage ratio of 0.07%. Furthermore, the hologram recording medium in this embodiment is transparent before and after recording. (Comparative Example 2) A polyether triol (ADEKA) was prepared by using hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in an amount of 20.9 parts by weight. The photosensitive material precursor was prepared in the same manner as in Example 5 except that the amount of G-700 and the average molecular weight of 740 was 58.1 parts by weight. A transmission type hologram recording medium was produced and evaluated in the same manner as in Example 1 using the obtained photosensitive material precursor. The obtained hologram recording medium had M/# of 1.0 and a shrinkage of 0.2%. Further, the hologram recording medium in this comparative example, although transparent before recording, produced slight turbidity after 3 days of recording. It is understood from the examples and the comparative examples that the photosensitive material obtained according to the examples of the present invention is a photosensitive material which is different from the present invention and does not contain a cyclic oligosaccharide derivative, and has a small volume shrinkage ratio. It is also confirmed that the transparency before and after the record is also different. Further, it is confirmed that the M/# of the all-image recording medium is relatively high. The above is a detailed description of the present invention based on the specific examples described above, but the present invention is not limited to the specific examples described above, and various modifications may be made without departing from the scope of the invention. Deformation -32-