TWI261153B

TWI261153B - Recording material for a holographic volume storage medium, holographic volume storage medium, the dyes used therein and process for the preparation thereof

Info

Publication number: TWI261153B
Application number: TW089103298A
Authority: TW
Inventors: Thomas Bieringer; Horst Berneth; Johannes Eickmans; Rainer Hagen; Serguei Kostromine
Original assignee: Bayer Ag
Priority date: 1999-03-08
Filing date: 2000-02-25
Publication date: 2006-09-01
Also published as: WO2000054112A1; DE19910247A1; AU3159900A; KR20020002401A; JP2002539476A; EP1166187A1; CA2366846A1

Abstract

Novel recording material for a holographic volume storage medium, holographic volume storage media, the dyes used therein and process for the preparation thereof are described.

Description

1261153 A7 B7 五、發明説明（1 ) 本發明係有關一種雷射攝影術體積儲存媒體用之記錄用材料，其製備及其供記錄體積全像圖之用途。雷射攝影術是一種利用兩相干光束（信號波及對照波）之間的干涉，使物體可在適當儲存材料上成像，且該等影像可利用光（讀出光束）再被讀出的方法（D Gabor,自然151，454(1948)，N.H.Farath，雷射攝影術之進展，第3 冊，Marcel Decker(1977)，Η· M· Smith，雷射攝影術用記錄用材料，Spdnger(1977))。藉由一方面改變信號波及對照波之間的角度，另一方面改變雷射攝影術用儲存材料，可將各種全像圖以同一樣品位置寫入材料，最後亦可個別地再被讀出。所用之干涉光源通常是雷射光。許多種類之材料被描述作為儲存材料，例如無機晶體（如UNb03)、有機聚合物（例如 M. Eich，J. H. Wendorff，Makromol. Chem.，Rapid Commim· 8, 467(1987)，J.H· Wendorff，M Eich，Cryst. Liq. Cryst 169, 133(1989))或光聚合物（Uh-SockRhee et al·，Applied Optics， 34(5), 846(1995)) 〇然而，此等材料尚無法符合構成雷射攝影術儲存材料的所有要求。尤其，記錄後之全像圖不具有適當之安定性。重覆記錄的可能性通常很有限，因為當記錄一種新的全像圖時，巳記錄的全像圖會被重寫且因此被抹除。特別是對於無機晶體而言也是如此，其接受複雜的熱處理，為的就是要補償該等安定性的問題。另一方面，光聚合物具有收縮的問題且對雷射攝影術之成像特性有不利的影饗。具有高度安定性之記錄全像圖之材料亦為已知，例如可本紙張尺度適用中國國家榡準（CNS ) a4規格（210X29?公釐） (請先閱讀背面之注意事項寫本頁)1261153 A7 B7 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) The present invention relates to a recording material for a laser photographic volume storage medium, the preparation thereof and the use thereof for recording a volume hologram. Laser photography is a method in which an object can be imaged on a suitable storage material using interference between two coherent beams (signal waves and contrast waves), and the images can be read out using light (readout beam). D Gabor, Nature 151, 454 (1948), NHFarath, Progress in Laser Photography, Volume 3, Marcel Decker (1977), Η·M· Smith, Materials for Laser Photography, Spdnger (1977) ). By changing the angle between the signal wave and the control wave on the one hand, and changing the storage material for laser photography on the other hand, various holograms can be written to the material at the same sample position, and finally can be read separately. The interference source used is typically laser light. Many types of materials are described as storage materials, such as inorganic crystals (such as UNb03), organic polymers (eg, M. Eich, JH Wendorff, Makromol. Chem., Rapid Commim 8, 8, 1987), JH Wendorff, M. Eich, Cryst. Liq. Cryst 169, 133 (1989)) or photopolymer (Uh-SockRhee et al., Applied Optics, 34(5), 846 (1995)) However, these materials are not yet compatible with the composition of All requirements for photographic storage materials. In particular, the recorded hologram does not have proper stability. The possibility of repeating records is usually very limited, because when a new hologram is recorded, the hologram of the 巳 record is overwritten and thus erased. This is especially true for inorganic crystals, which accept complex heat treatments in order to compensate for these stability problems. On the other hand, photopolymers have problems with shrinkage and have an adverse effect on the imaging characteristics of laser photography. The material of the recorded hologram with high stability is also known. For example, the paper size can be applied to the Chinese National Standard (CNS) a4 specification (210X29?mm). (Please read the note on the back first to write this page)

T _I--- 經濟部智慧財產局員工消費合作社印製 1261153 Α7 Β7 五、發明説明（2 ) ^- 由EP 0 704 513 (LeA 30 655)及德國專利申請案De_ai9 703 132 ( LeA 31 821)(其尚未被公開）中獲知。然而，該等材料之高光學密度不容許製備供各種全像圖儲存在儲存材料上所需要之雷射攝影術體積儲存媒體。因此，亟需一種材料，其可適合製備充分厚度之雷射攝影術體積儲存媒體，且其可容許各種全像圖以一種使彼等具有長期安定性的方式被儲存在記錄用材料之同_樣口位置上。就迄今所知的材料而言，各種全像圖一個接著:個的被儲存在同一位置上，會導致以雷射攝影術儲存之訊息逐漸被抹除：後來記錄的全像圖會編址與建構先前記全像圖所使用者相同的分子，致使較早之全像圖的訊息僅在些微進一步的記錄過程之後即喪失。“ 因此本發明提供一種雷射攝影術體積镩存媒想用之記錄用材料’其包含至少一種染料，當全像圓被記錄時，會改變它的空間排列，及選棵之至少一種形狀·各向異性基群，其特徵在於其容許記錄兩或多個全像囷在一個樣品位置上。理想中，其實施係在於有至少一種染料，以一種其不再被電磁輻射激發的方式來改變其空間排列或改變其吸收行為，特別是降低它對光化光的敏感度，較佳為降低10%至 100 %，尤佳為由50%至最隹為由90%至100%，於各情況中係基於記錄第一個全像圖之前的敏感度而言。然而，染料亦可降低其吸收行為，特別是它對光化光的敏感度，因為它會移動進入垂直於光化光的偏極方向，且本紙張尺度適用中國國家榡準（CNS ) A4規格（21〇Χ297公釐） (請先閱讀背面之注意事項寫本頁) .裝· ;訂經濟部智慧財產局員工消費合作社印製 1261153 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（3 ) 其分子、縱袖會位在先化光之偏極方向10。至90。，較佳為 50。至90。，尤佳為75。至90。，最佳為85。至90。的角度上。以該方式，可成功地實現記錄數種全像圖在一個樣品位置上，也就是說之前的全像圖的訊息不會完全地被抹除。當全像圖被記錄時，其在關於電磁輻射之激光性能上的變化可藉由染料改變其在聚合性或低聚性有機的無定形材料中的空間排列予以達成。該種材料，當全像圖被記錄時，能避免先前已被記錄在該材料上之全像圖無法接受地被縮小、完全地受損或甚至完全地被重寫。由測量技術的觀點，無法接受地減小意表剩餘的訊息關於背景雜訊(noise)不再被解析而言。訊息以雷射攝影被儲存。為該目的，使兩種偏極化的干涉光束在樣品上產生干涉。因為曝露於光化光，所以染料會改變其在聚合物或低聚物層上之空間位置。若光的偏極化位在垂直於入射面者，則染料（當曝露時會使其分子縱轴轉向被兩個記錄光束所旋轉之平面（入射面）上）即不會再被光所激發。在記錄過程期間被記錄在該等染料上之訊息（全像圖）係受到保護，而不會在記錄下一個全像圖期間有所變化。非位在完全垂直於光之偏極方向，但形成就該偏極方向而言為不同於90。之一角度€)的染料進一步在下一個全像圖曝露期間被編址（address)。然而，該等染料被重新定向位的可能性及特別是染料的光敏感度降低的愈多，分子縱轴的角度愈 _—5— ____ 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐）T _I--- Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1261153 Α7 Β7 V. Invention Description (2) ^- From EP 0 704 513 (LeA 30 655) and German Patent Application De_ai9 703 132 (LeA 31 821) (It has not been published) is known. However, the high optical density of such materials does not allow for the preparation of laser photo volume storage media required for storage of various holograms on stored materials. Therefore, there is a need for a material that is suitable for preparing a full thickness laser imaging volume storage medium, and which allows various holograms to be stored in a recording material in a manner that allows them to have long-term stability. The position of the sample. As far as the materials known to date are concerned, the holograms are stored one after the other, and the information stored in the laser photography is gradually erased: the holograms recorded later will be addressed and Constructing the same numerator as the user of the previous hologram, causing the message of the earlier hologram to be lost only after a slight further recording process. "The present invention therefore provides a recording material for use in a laser photography volume storage medium which contains at least one dye which changes its spatial arrangement and at least one shape of the selected tree when the hologram circle is recorded. An anisotropic group characterized in that it permits the recording of two or more holograms at a sample position. Ideally, it is practiced by having at least one dye that is altered in such a way that it is no longer excited by electromagnetic radiation. Its spatial arrangement or change of its absorption behavior, especially its sensitivity to actinic light, is preferably reduced by 10% to 100%, particularly preferably from 50% to 90% to 100%. The situation is based on the sensitivity before recording the first hologram. However, the dye can also reduce its absorption behavior, especially its sensitivity to actinic light, as it moves into perpendicular to actinic light. Polarity direction, and the paper size is applicable to China National Standard (CNS) A4 specification (21〇Χ297 mm) (please read the note on the back to write this page). Install · Customs Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Printing 12 61153 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (3) The molecular and longitudinal sleeves will be in the direction of the polarization of the first light to 10 to 90., preferably 50 to 90. Especially preferably from 75 to 90., preferably from 85 to 90. In this way, it is possible to successfully record several holograms at one sample position, that is, the previous hologram The message will not be completely erased. When the hologram is recorded, its change in laser performance with respect to electromagnetic radiation can be changed by the dye in a spatial arrangement of polymerizable or oligomeric organic amorphous materials. This material, when the hologram is recorded, prevents the hologram that has been previously recorded on the material from being unacceptably reduced, completely damaged, or even completely rewritten. The view, unacceptably reducing the remaining message of the meaning table, the background noise is no longer resolved. The message is stored in laser photography. For this purpose, two kinds of polarized interference beams are placed on the sample. Interference occurs because it is exposed to light Light, so the dye changes its spatial position on the polymer or oligomer layer. If the polarization of the light is perpendicular to the plane of incidence, the dye (when exposed will cause its molecular longitudinal axis to be turned by two The plane (incident surface) on which the recording beam is rotated is no longer excited by light. The message (hologram) recorded on the dye during the recording process is protected and not recorded. The hologram changes during the period. The non-position is completely perpendicular to the polarization direction of the light, but forms a dye different from 90 in terms of the polarization direction. One of the angles of the dye is further exposed during the next hologram exposure. Addressing. However, the possibility that the dyes are redirected and, in particular, the more the light sensitivity of the dye is reduced, the more the angle of the longitudinal axis of the molecule is _—5 — ____ The paper scale applies to the Chinese national standard (CNS) ) A4 size (210x297 mm)

(請先閱讀背面之注意事項V ¾-- Μ寫本頁) 、1Τ if - - -I - --IV» - - - -I _ 1261153 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（4 ) 接近90°的位置。分子縱軸可藉由分子模擬（如CERIUS2)的分子式予以測〇染料在曝露於光化光的重新定向係由對偏極化吸收光嘈的研究而得：在-UV/VIS光度計（如CARY4G uv/a Vis光度計）中之兩個偏極鏡之間，在染料之吸收光譜範圍内，研究-先行曝露於光化光之樣品。當樣品在樣:法線周圍旋轉，且偏極鏡在一適當位置（例如在橫向狀況）時，染料的重新定向係來自消光強度的變動作為樣品角度的函數，結果可清楚地被測定。就記錄數個全像圖而言，有各種多工方法，如角度多工：波長多工、相多工、轉移多工、周邊旋律(peristrophic)多工等0 一種對光化光敏感度的測量為雷射攝影敏感度。其計算係來自例如雷射攝影發生曲線，亦即繞射效率的產生°(= 基於讀數雷射之入射強度所繞射的強度）作為被記錄光束所蓄積之能量的函數。此種敏感度被定義為根據蓄積能量之繞射效率平方根的斜率，而以儲存媒趙的厚度為標準規格0 本發明係提供-種雷射攝影術體積儲存媒艘用之記錄用材料，其在記錄雷射的波長下具有光學密度較佳A 尤佳切.3。於該方式下，能確保光化光導致整個储存媒體之均句透射，及產生一厚的全像圖。光學密度可用 uv/VIS 光度計（如 cary、4g、uv/vis_ = ------^ 定本紙張尺度適财關諸 (請先閱讀背面之注意事項本頁) 裝、11 1261153 A7 B7 五、發明説明（5) 來測量根據本發明之記錄用材料較佳為一種具有a丨毫米，尤佳2〇·5毫米，更佳毫米，最佳不大於5公分之被照射厚度的材料。與電磁輻射互相作用的基群為一種染料。因此根據本發明的材料包含至少一種染料。電磁輻射較佳為雷射光，尤佳在390至800毫微米之波長範圍，較佳在4⑼至毫微米之範圍，最佳在510至570毫微米之範圍。為了讀出，記錄用材料不能如同記錄的情況一樣曝露於兩種干涉光之下，而是僅能用一種光束，即讀出光束。讀出光束的波長較佳為比信號波及干涉波的波長要長，例如長70至500毫微米。然而，以記錄雷射的波長來讀出亦是可能的，且特別可應用在雷射攝影術用體積儲存媒體的商業用途上。惟就該目的而言，讀出光束的能量在讀出過程中會因曝露強度或曝露時間的減少，或因曝露強度及曝露時間的減少而減低。根據本發明之記錄用材料的光學密度係藉由下列兩種參數予以調整：經濟部智慧財產局員工消費合作社印製 a) 藉由其中至少一種染料之莫耳消光係數及/或 b) 藉由其中至少一種染料之在聚合性或低聚性有機材料中的濃度。，具有低消光係數之染料為例如，具有非極性及/或具僅稍微可極化結構之染料。此種染料可來自蒽醌、蕙、気蒽、偶氮或曱川（methine)染料。偶氮染料較佳。由佳者為具有 --- —7~ 本紙張尺度適财_家辟(CNS ) A4規格公釐) 1261153 A7 B7 五、發明説明（6 ) π π*鍵最大吸收度低於或等於4〇〇毫微米，尤佳低於4〇〇毫微米者。偶氮染料，例如具有下式（I)之結構：(Please read the note on the back first V 3⁄4-- Write this page), 1Τ if - - -I - --IV» - - - -I _ 1261153 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5 DESCRIPTION OF THE INVENTION (4) A position close to 90°. The longitudinal axis of the molecule can be determined by the molecular formula (such as CERIUS2). The dye is exposed to the redirected light in the actinic light by the study of the polarized absorption pupil: in the -UV/VIS photometer (eg Between the two polarizers in the CARY4G uv/a Vis photometer, in the absorption spectrum of the dye, the study was first exposed to actinic light. When the sample is rotated around the sample: normal and the polarizer is in a suitable position (e.g., in a lateral condition), the reorientation of the dye is derived from the change in extinction intensity as a function of the angle of the sample, and the results are clearly determined. For recording multiple holograms, there are various multiplex methods, such as angle multiplexing: wavelength multiplexing, phase multiplexing, transfer multiplex, peristrophic multiplex, etc. 0 Measurement of sensitivity to actinic light Sensitivity to laser photography. The calculation is derived, for example, from a laser shot generation curve, i.e., the generation of diffraction efficiency (= intensity based on the incident intensity of the reading laser) as a function of the energy accumulated by the recorded beam. This sensitivity is defined as the slope of the square root of the diffraction efficiency of the accumulated energy, and the thickness of the storage medium Zhao is the standard specification. The present invention provides a recording material for a laser imaging volume storage medium. It has a better optical density at the wavelength at which the laser is recorded. In this manner, it is ensured that the actinic light causes the uniform transmission of the entire storage medium and produces a thick hologram. The optical density can be obtained by uv/VIS luminometer (such as cary, 4g, uv/vis_ = ------^). This paper size is suitable for the money (please read the back note on this page first), 11 1261153 A7 B7 DESCRIPTION OF THE INVENTION (5) The recording material according to the present invention is preferably a material having an irradiated thickness of a 丨 mm, particularly preferably 2 〇 5 mm, more preferably mm, and most preferably not more than 5 cm. The group in which the electromagnetic radiation interacts is a dye. The material according to the invention therefore comprises at least one dye. The electromagnetic radiation is preferably laser light, particularly preferably in the wavelength range from 390 to 800 nm, preferably from 4 (9) to nanometer. The range is preferably in the range of 510 to 570 nm. For reading, the recording material cannot be exposed to the two kinds of interference light as in the case of recording, but only one type of beam, that is, the reading beam can be used. The wavelength of the beam is preferably longer than the wavelength of the signal wave and the interference wave, for example, 70 to 500 nm. However, it is also possible to read the wavelength of the laser, and is particularly applicable to laser photography. Volume storage medium For commercial purposes, the energy of the read beam may be reduced during the reading process due to a decrease in exposure or exposure time, or a decrease in exposure strength and exposure time. The optical density of the material is adjusted by the following two parameters: Printed by the Ministry of Economic Intelligence's Intellectual Property Office, the Consumer Cooperative, a) by the Moore extinction coefficient of at least one of the dyes and/or b) by at least one of the dyes Concentration in polymeric or oligomeric organic materials. Dyes having a low extinction coefficient are, for example, dyes having a non-polar and/or having a slightly polarizable structure. Such dyes may be derived from hydrazine, hydrazine, hydrazine, azo or methine dyes. Azo dyes are preferred. The best is the quality of the paper----7~ This paper scale is suitable for the wealth of the paper (CNS) A4 specification mm) 1261153 A7 B7 V. Invention description (6) π π* bond maximum absorption is lower than or equal to 4〇〇 Nano, especially better than 4 〇〇 nm. An azo dye, for example, having the structure of the following formula (I):

其中 R及R各自互相獨立地代表氫或一非離子性取代基，及 Rl另外可代表-XCr3 ; m及η各自互相獨立地代表一由〇至4，較佳由〇至2的整數； X1及X2各別代表-Xr-R3及-X2’_r4 ; X1 及 X2 代表一直接鍵，-〇-、、-(N_R5)·、-C(R6R7)-、 -(〇0)-、-(CO-0)-、-(CO-NR5)-、-(S02)-、-(S02-0)·、 -(S02-NR5)-、-(C=NR8)-或·(CNRLNR5)-; R3、R4、R5及R8各自互相獨立地代表氫、Ci•至C2G-烷基、 C3-至C1(r環烷基、C2-至C2(r烯基、C6-至C1(r芳基、 Cr至 C20-烷基-(〇0)_、C3-至 Cio-環烷基-(C=0)-、C2-至 C20-稀基、Cr至 Ci〇-芳基、Ci·至 c20-烷基·(S02)_、<：3-至 C1(r 環烷基-(S〇2)-、c2_ 至 c20-烯基-(S02)-或芳基·β〇2)_，或及-X2’-R4各自代表氫、鹵素、氰基、硝基、CF3或 CC13; ___—8—______ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項寫本頁) •裝· 訂經濟部智慧財產局員工消費合作社印製 1261153 A7 _—_ _ B7 五、發明説明（7 ) R6及R7各自互相獨立地代表氫、鹵素、Ci-至c2(r烷基、 Cl-至C2(T烧氧基、C3·至CiG-環烧基、C〗-至C2(T稀基或C6i c1(r芳基。非離子性取代基應瞭解係為函素、氰基、硝基、Cr至 C2(r烷基、Ci-至 C2(r烷氧基、苯氧基、0：3-至C1G-環烷基、 C”至C20-稀基或C6-至Cur芳基、Ci-至C20-烧基-(〇0)-、 c6-至 C1(r芳基-(〇0)-、C!-至 C20•烷基-(S〇2：l·、CV至 C20-烷基_(00)_0·、Ci-至 C2(r烷基-(O0)_NH-、（：6_至 c1(r芳基-(OO)-NH-、C!_至 C20_烷基-0_(00)-、CV至 C20-烷基 -NH-(OO)-或 C6-至 C1(r芳基-NH-(OO)-。烷基、環烷基、烯基及芳基基團可依次被至多達三個選自鹵素、氰基、硝基、Ci-至 C20-烷基、Ci-至 C20-烷氧基、 <：3_至c1(r環烷基、c2-至C2(r烯基或（：6-至c1(r芳基所取代，且燒基及稀基可為直鏈或支鏈。鹵素應瞭解為氟、氣、溴及碘，特別是氟及氣。根據本發明之記錄用材料較佳為聚合性或低聚性的有機無定形材料，尤其是一種側鏈聚合物，亦特別是一種嵌段共聚物及/或接枝聚合物。側鏈聚合物的主鏈源自下列基本結構··聚丙烯酸酯、聚甲基丙烯酸酯、聚矽氧烷、聚脲、聚胺基甲酸酯、聚酯或纖維素。聚丙烯酸酯及聚甲基丙烯酸酯較佳。嵌段共聚物包括多數嵌段物，其中至少一種類型包含上述共聚物系統。其他嵌段物包括非官能化聚合物結構，用來稀釋功能性阻斷（functional block)，以調節所需要的光學本紙張尺度適用中國國家標準（CNS ) μ規格（210X297公釐） (請先閱讀背面之注意事項本頁) 裝·Wherein R and R each independently represent hydrogen or a nonionic substituent, and R1 may additionally represent -XCr3; m and η each independently represent an integer from 〇 to 4, preferably from 〇 to 2; X1 And X2 respectively represent -Xr-R3 and -X2'_r4; X1 and X2 represent a direct bond, -〇-, -(N_R5)·, -C(R6R7)-, -(〇0)-, -( CO-0)-, -(CO-NR5)-, -(S02)-, -(S02-0)·, -(S02-NR5)-, -(C=NR8)- or (CNRLNR5)-; R3, R4, R5 and R8 each independently represent hydrogen, Ci• to C2G-alkyl, C3- to C1 (r cycloalkyl, C2- to C2 (r-alkenyl, C6- to C1 (r-aryl), Cr to C20-alkyl-(〇0)_, C3- to Cio-cycloalkyl-(C=0)-, C2- to C20-dilute, Cr to Ci〇-aryl, Ci· to c20- Alkyl·(S02)_, <:3- to C1(r cycloalkyl-(S〇2)-, c2_ to c20-alkenyl-(S02)- or aryl·β〇2)_, or And -X2'-R4 each represent hydrogen, halogen, cyano, nitro, CF3 or CC13; ___-8-______ This paper scale applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the back first) Precautions for writing this page) • Installed and subscribed to the Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperation Co., Ltd. 1261153 A7 _-_ _ B7 V. Inventive Note (7) R6 and R7 each independently represent hydrogen, halogen, Ci- to c2 (r alkyl, Cl- to C2 (T alkoxy, C3·) To CiG-cycloalkyl, C- to C2 (T-dense or C6i c1 (r-aryl). Non-ionic substituents should be known as cyclin, cyano, nitro, Cr to C2 (r-alkyl, Ci- to C2 (r alkoxy, phenoxy, 0:3- to C1G-cycloalkyl, C" to C20-saturated or C6- to Cur aryl, Ci- to C20-alkyl-(〇 0)-, c6- to C1 (r-aryl-(〇0)-, C!- to C20•alkyl-(S〇2:l·, CV to C20-alkyl_(00)_0·, Ci - to C2(r-alkyl-(O0)_NH-, (:6_ to c1(r-aryl-(OO)-NH-, C!_ to C20_alkyl-0_(00)-, CV to C20 -alkyl-NH-(OO)- or C6- to C1(raryl-NH-(OO)-. The alkyl, cycloalkyl, alkenyl and aryl groups may in turn be up to three selected from halogen , cyano, nitro, Ci- to C20-alkyl, Ci- to C20-alkoxy, <:3_ to c1 (r cycloalkyl, c2- to C2 (r alkenyl or (:6-) To c1 (r-aryl group substituted, and the alkyl group and the dilute group may be linear or branched. Halogen is understood to be fluorine, gas, bromine and iodine, especially fluorine and gas. The recording material according to the present invention is preferably a polymerizable or oligomeric organic amorphous material, especially a side chain polymer, and particularly a block copolymer and/or a graft polymer. The backbone of the side chain polymer is derived from the following basic structures: polyacrylate, polymethacrylate, polyoxyalkylene, polyurea, polyurethane, polyester or cellulose. Polyacrylates and polymethacrylates are preferred. The block copolymer comprises a plurality of blocks, at least one of which comprises the above copolymer system. Other blocks include non-functionalized polymer structures used to dilute functional blocks to adjust the required optical paper size to the Chinese National Standard (CNS) μ specification (210X297 mm) (please Read the notes on the back page)

V1T 經濟部智慧財產局員工消費合作社印製 1261153 A7 五、發明説明（8) 密度。功能性阻斷的程度低於光的波長，較佳在低於2〇() 毫微米，尤佳低於100毫微米的範圍。嵌段共聚物之聚合例如可藉由自由基或陰離子性聚合或藉由其他適當之聚合方法，視情況接著聚合物·類似性反應，或藉此等方法之組合來實施。系統之均勻度為低於2.0, 較佳低於1·5之範圍。藉自由基聚合法所獲得之嵌段共聚物的分子量達到50,000的數值；大於ι〇〇,〇〇〇的數值可藉陰離子性聚合法予以調節。染料（特別是式（I)之偶氮染料）共價地被鍵結至該等聚合物結構上，通常係藉由一間隔物。例如X1 (或X2)即代表此種間隔物，特別是在之定義中，其中 X1-為如上述所定義； Q1 代表·0·、-S-、-(N-R5)·、-C(R6R7 )-、-(〇0)-、-(COO).、 _(CO_NR5)-、-(S02)·、-(S02_0)_、-(S〇2_NR5)-、 -(ONR8)-、-(CNR8-NR5)-、-(CH2)p-、對-或間-C6H4-或下式之二價基團 , (請先閱讀背面之注意事項本頁)V1T Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1261153 A7 V. Description of invention (8) Density. The degree of functional blockage is less than the wavelength of light, preferably less than 2 Å () nanometers, and more preferably less than 100 nanometers. The polymerization of the block copolymer can be carried out, for example, by radical or anionic polymerization or by other suitable polymerization methods, optionally with a polymer/similar reaction, or a combination of such methods. The uniformity of the system is below 2.0, preferably below the range of 1.5. The molecular weight of the block copolymer obtained by the radical polymerization method reaches a value of 50,000; if it is larger than ι, the value of ruthenium can be adjusted by an anionic polymerization method. The dye (especially the azo dye of formula (I)) is covalently bonded to the polymer structure, usually by a spacer. For example, X1 (or X2) represents such a spacer, especially in the definition, where X1- is as defined above; Q1 represents ·0·, -S-, -(N-R5)·, -C( R6R7 )-, -(〇0)-, -(COO)., _(CO_NR5)-, -(S02)·, -(S02_0)_, -(S〇2_NR5)-, -(ONR8)-,- (CNR8-NR5)-, -(CH2)p-, p- or m-C6H4- or a divalent group of the following formula, (please read the back note on this page first)

、1T 經濟部智慧財產局員工消費合作社印製, 1T Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

或or

广NT i代表一由0至4之整數，其中當i>l時，個別基團Qi 可具有不同的意義； T1代表-(CH2)P-，其中該鏈可鍵結-0-、-NR9-或-OSiR'O-; S1代表一直接鍵、-Ο-、-S·或_NR9-; -10— 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇Χ297公釐） 1261153The broad NT i represents an integer from 0 to 4, wherein when i > 1, the individual groups Qi may have different meanings; T1 represents -(CH2)P-, wherein the chain may bond -0-, -NR9 -or-OSiR'O-; S1 stands for a direct key, -Ο-, -S· or _NR9-; -10— This paper scale applies to the Chinese National Standard (CNS) Α4 specification (21〇Χ297 mm) 1261153

RR

X2 A7 B7 五、發明説明（9 ) p代表一由2至12,較佳由2至8,尤佳由2至4之整數； R9代表氩、甲基、乙基或丙基； R1G代表甲基或乙基，及 R5至R8為如上述所定義。較佳聚丙烯酸酯或聚曱基丙烯酸酯用之染料單體具有式 (Π), 〇 (II) 〜本-- (請先閲讀背面之注意事項\^^馬本頁) 其中 R代表氫或甲基，及其他基團為如上述所定義。特別適合者為下式（Ila)之染料單體：〇X2 A7 B7 V. Description of the invention (9) p represents an integer from 2 to 12, preferably from 2 to 8, particularly preferably from 2 to 4; R9 represents argon, methyl, ethyl or propyl; R1G represents a The base or ethyl group, and R5 to R8 are as defined above. Preferably, the dye monomer for polyacrylate or poly(methacrylate) has the formula (Π), 〇(II)~本-- (please read the back note on the back of the page), where R represents hydrogen or Methyl, and other groups are as defined above. Particularly suitable for the dye monomer of the following formula (Ila): 〇

RR

X3 (Ila)X3 (Ila)

、1T 經濟部智慧財產局員工消費合作社印製其中 X3代表氫、鹵素或-至C4·烷基，較佳為氫，及基團R S1、T1、Q1、X1’、R1及R2及i、m及η為如上述所定義特佳式（Ila)之單體為例如： -11- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 1261153 A7 B7 五、發明説明（10 ) 〇1T Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed in which X3 represents hydrogen, halogen or - to C4 alkyl, preferably hydrogen, and groups R S1, T1, Q1, X1', R1 and R2 and i, m and η are the monomers of the preferred formula (Ila) as defined above, for example: -11- This paper scale applies to the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm) 1261153 A7 B7 V. Description of invention (10 ) 〇

Ο CH,Ο CH,

N"l〇N"l〇

(請先閲讀背面之注意事項(Please read the notes on the back first)

『本頁) 訂經濟部智慧財產局員工消費合作社印製『This page】 Ordered by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives

X" 亦適合者為式（lib)之染料單體，當彼等被包含在聚合物中時，用量S10莫耳％，較佳S5莫耳％，尤佳莫耳％，〇 (Ilb)， —12 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1261153 A7 B7 五、發明説明（11 ) 其中 X4代表氰基或硝基，及基團R、s1、T1、Q1、X1’、R1及 R2及i、m及η為如上述所定義。特佳式（lib)之單體為例如：X" Also suitable for the dye monomers of formula (lib), when they are included in the polymer, the amount of S10 mol%, preferably S5 mol%, especially the molar %, 〇 (Ilb), —12 — The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1261153 A7 B7 V. Inventive Note (11) where X4 represents a cyano group or a nitro group, and the groups R, s1, T1, Q1 X1', R1 and R2 and i, m and η are as defined above. The monomer of the lib is for example:

本紙張尺度適用中國國家標準（CNS) A4規格（210X 297公釐） 1261153 A7 B7This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1261153 A7 B7

五、發明説明（12V. Description of the invention (12

uCN 根據本發明之聚合性或低聚性有機無定形材料除了例如式⑴之染料外，可帶有形狀·各向異性基群。此等基群一般也是藉由一間隔物共價地被鍵結至聚合物結構上。形狀·各向異性基群具有例如式（Ιπ)之結構： (III) (請先閱讀背面之注意事項uCN The polymerizable or oligomeric organic amorphous material according to the present invention may have a shape-anisotropic group in addition to the dye of the formula (1). These groups are also typically covalently bonded to the polymer structure by a spacer. The shape/anisotropic group has a structure of, for example, the formula (Ιπ): (III) (Please read the back note first)

其中 Ζ代表下式基團 .X4Where Ζ represents the group below. X4

(r12)「 (Ilia)或 (R15), (mb) 訂經濟部智慧財產局員工消費合作社印製其中 A代表Ο、S或N-Ci•至C4-烷基； X3 代表-X3’-(Q2)j-T2-S2-; X4-代表 X、R13 ; X -及X4各自互相獨立地代表一直接鍵、-〇-、-S-、 •(N-R5)-、-C(R6R7)·、·(〇0)·、·(<：0-0)-、·(CO-NR5)-_(S02)_、-(S02_0)-、-(S〇2-NR5)_、-(ONR8)-或 -(CNR8-NR5)-; R5、R8及R13各自互相獨立地代表氫、•至C2(r烷基、一 14— 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1261153 A7 B7 五、發明説明（13 ) C3-至C1(r環烧基、C2-至C2〇·烯基、。6-至C1(r芳基、 CV至 C20-烷基-(〇0)-、（：3-至 C1(r環烷基至 C2(r烯基_(〇〇)_、<：6_至 C1(r芳基-(〇〇)-、C!-至 c20-:^基-(S02)_、C3-至 C10-環烧基-(S〇2)-、Cr至 c20-烯基-(S02)_或芳基_(S〇2)-，或 X4 -R13可代表氫、鹵素、氣基、石肖基、CF3或CCI3 ; R6及R7各自互相獨立地代表氫、鹵素、Ci-至C2G·烧基、 Cl-至C2Q-烧氧基、C3-至CiG-環烧基、C2-至C2G-稀基或C6-至ClQ-芳基； Y 代表一單鍵、-COO-、0C0-、-C0NH-、-NHC0-、 -C0N(CH3)-、·Ν((：Η3)(：0-、-0-、-NH-或-N(CH3)-; 經濟部智慧財產局員工消費合作社印製 R11、R12、R15各自互相獨立地代表氫、氰基、硝基、Cr 至C2(r烷基、CV至C2G_烷氧基、苯氧基、0：3-至C1(r 環烷基、C2-至C2〇·烯基或（：6-至C1(r芳基、Q-至C20-烷基-(〇〇)-、（：6-至 C1(r芳基-(〇〇)-、Ci-至 C2〇-烷基 • _(S〇2)-、Ci-至 C20-烧基_(C=0)-0-、Ci-至 C20,烧基 •(ΟΟ)-ΝΗ-、0：6-至 C1(r 芳基-(C=0)-NH-、CV至 C20-烷基-〇-(〇〇)-、Ci-至 C2(r烷基-NH-(C=0)-或 C6-至 C1(r芳基-ΝΗ·(Ο0)-; q、r及s各自互相獨立地代表一由〇至4，較佳由0至2 之整數； Q2 代表-0-、、-(N-R5)-、-C(R6R7)·、-(〇0)-、-(CO-O)-、 _(C0-NR5)·、_(S02)_、_(S02-0)-、_(S02-NR5)_、 -(ONR8)-、-(CNR8-NR5)·、-(CH2)p-、對-或間·ί：6Η4· _________ —15-— 本紙張尺度適用中國國家標準（CNS ) A4規格（21 Ox 297公釐） 1261153 A7 Β7 五、發明説明（K) 或下式之二價基困(r12) "(Ilia) or (R15), (mb) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives, where A represents Ο, S or N-Ci• to C4-alkyl; X3 stands for -X3'-( Q2) j-T2-S2-; X4- represents X, R13; X- and X4 each independently represent a direct bond, -〇-, -S-, •(N-R5)-, -C(R6R7) ·,·(〇0)·,·(<:0-0)-,·(CO-NR5)-_(S02)_, -(S02_0)-, -(S〇2-NR5)_,- (ONR8)- or -(CNR8-NR5)-; R5, R8 and R13 each independently represent hydrogen, • to C2 (r-alkyl, one 14 - this paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 PCT 1261153 A7 B7 V. INSTRUCTION DESCRIPTION (13) C3- to C1 (r cycloalkyl, C2- to C2 〇 alkenyl, 6- to C1 (r aryl, CV to C20-alkyl-( 〇0)-, (: 3- to C1 (r cycloalkyl to C2 (r alkenyl), <:6_ to C1 (raryl-(〇〇)-, C!- To c20-:^-(S02)_, C3- to C10-cycloalkyl-(S〇2)-, Cr to c20-alkenyl-(S02)- or aryl_(S〇2)-, Or X4 - R13 may represent hydrogen, halogen, gas group, schlossyl, CF3 or CCI3; R6 and R7 each independently represent hydrogen, halogen, Ci- to C2G·alkyl, Cl- C2Q-alkoxy, C3- to CiG-cycloalkyl, C2- to C2G-dilute or C6- to ClQ-aryl; Y represents a single bond, -COO-, 0C0-, -C0NH-, -NHC0 -, -C0N(CH3)-, ·Ν((:Η3)(:0-,-0-,-NH- or -N(CH3)-; R11, R12, printed by the Consumers’ Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs R15 each independently represents hydrogen, cyano, nitro, Cr to C2 (r alkyl, CV to C2G-alkoxy, phenoxy, 0:3- to C1 (r cycloalkyl, C2- to C2) 〇·Alkenyl or (:6- to C1(r aryl, Q- to C20-alkyl-(〇〇)-, (:6- to C1(r aryl-(〇〇)-, Ci- to C2〇-alkyl• _(S〇2)-, Ci- to C20-alkyl group _(C=0)-0-, Ci- to C20, alkyl group • (ΟΟ)-ΝΗ-, 0:6- To C1(r aryl-(C=0)-NH-, CV to C20-alkyl-〇-(〇〇)-, Ci- to C2 (r-alkyl-NH-(C=0)- or C6 - to C1(r aryl-ΝΗ·(Ο0)-; q, r and s each independently represent an integer from 〇 to 4, preferably from 0 to 2; Q2 represents -0-, -(N -R5)-, -C(R6R7)·, -(〇0)-, -(CO-O)-, _(C0-NR5)·, _(S02)_, _(S02-0)-, _ (S02-NR5)_, -(ONR8)-, -(CNR8-NR5)·, -(CH2)p-, 对-或间·ί:6Η4· _________ —15 - This paper scale applies to China National Standard (CNS) A4 specification (21 Ox 297 mm) 1261153 A7 Β7 V. Invention description (K) or the second-price base of the following formula

或or

广NT j代表一由0至4之整數，其中當扮1時，個別基團Ql 可具有不同的意義； T2 代表-(CH2)p-，其中該鏈可鍵結-NR9j-〇siRi〇2(> S代表"直接鍵、-0-、-S -或-NR9-; P代表一由2至12,較佳由2至8,尤佳由2至4之整數 R9代表氫、甲基、乙基或丙基，及 R1()代表甲基或乙基。較佳具有供聚丙烯酸酯或聚曱基丙烯酸酯之此種形狀-各向異性基群之單體具有式（IV):Wide NT j represents an integer from 0 to 4, wherein when group 1, the individual groups Q1 may have different meanings; T2 represents -(CH2)p-, wherein the chain may be bonded-NR9j-〇siRi〇2 (> S stands for "direct key, -0-, -S- or -NR9-; P represents a number from 2 to 12, preferably from 2 to 8, especially preferably from 2 to 4, the integer R9 represents hydrogen, A a group, an ethyl group or a propyl group, and R1() represents a methyl group or an ethyl group. Preferably, the monomer having such a shape-anisotropic group for a polyacrylate or a polydecyl acrylate has the formula (IV) :

〇^Y^s2/r、(c^) R〇^Y^s2/r, (c^) R

(IV) (請先閱讀背面之注意事項再本頁) 、τ Y〆經濟部智慧財產局員工消費合作社印製〇(IV) (Please read the precautions on the back page for this page), τ Y〆 Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs 〇

其中 R代表氫或甲基，及其他基團為如上述所定義。特佳之式（IV)之形狀-各向異性基群單體為例如Wherein R represents hydrogen or methyl, and the other groups are as defined above. A particularly preferred shape of the formula (IV) - an anisotropic group monomer is, for example

—15-~~ 本紙張尺度適用中國國家標準（CNs ) μ規格（210X297公釐） 1261153 A7 B7 五、發明説明（15 ) 〇—15-~~ This paper scale is applicable to China National Standard (CNs) μ specification (210X297 mm) 1261153 A7 B7 V. Invention description (15 ) 〇

〇〆〇〆

〇〇

經濟部智慧財產局員工消費合作社印製 (V)Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing (V)

〇 I R 烷基、環烷基、烯基及芳基基團可依次被至多達三個選自鹵素、氰基、硝基、CV至C2(r烷基、Ci•至c20-烷氧基、 <:3-至c1(r環烷基、c2·至c2(r烯基或<:6-至c1(r芳基所取代，且烷基及烯基可為直鏈或支鏈。鹵素應瞭解為氟、氣、溴及碘，特別是氟及氣。除了該等官能單元，根據本發明之低聚物或聚合物亦可包含主要用來降低官能單元（尤其是染料單元）百分比含量之單元，除了該功能外，彼等亦與其他低聚物或聚合物的特性有關，例如玻璃態轉移溫度、液體結晶性、成膜特性等。就聚丙烯酸酯或聚甲基丙烯酸酯而言，此種單體為式（V) 之丙烯酸或甲基丙烯酸之酯類：〇丄〇 14 其中 -17 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1261153 A7 B7 五、發明説明（16 ) R代表氫或甲基，及 R14代表選擇之分支Ci•至C2(r烷基或一含有至少一個其他丙烯基單元之基團。根據本發明之聚丙烯酸酯或聚甲基丙烯酸酯包含較佳為式（VI)，尤為式（VI)與（VII)，或式（VI)與（VIII)，或式（VI)、 (VII)與(VIII)者作為重覆單元：The 〇IR alkyl, cycloalkyl, alkenyl and aryl groups may in turn be up to three selected from the group consisting of halogen, cyano, nitro, CV to C2 (r alkyl, Ci• to c20-alkoxy, <;: 3- to c1 (r cycloalkyl, c2· to c2 (r alkenyl or <: 6- to c1 (r-aryl), and the alkyl and alkenyl groups may be straight or branched. It should be understood that it is fluorine, gas, bromine and iodine, especially fluorine and gas. In addition to these functional units, the oligomer or polymer according to the invention may also comprise mainly used to reduce the percentage of functional units (especially dye units). Units, in addition to this function, are also related to the properties of other oligomers or polymers, such as glass transition temperature, liquid crystallinity, film forming properties, etc. In the case of polyacrylates or polymethacrylates This monomer is an ester of acrylic acid or methacrylic acid of formula (V): 〇丄〇14 where -17 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1261153 A7 B7 V. DESCRIPTION OF THE INVENTION (16) R represents hydrogen or methyl, and R14 represents a selected branch Ci• to C2 (r alkyl or one contains at least one a group of other propylene-based units. The polyacrylate or polymethacrylate according to the invention preferably comprises formula (VI), especially formulas (VI) and (VII), or formulas (VI) and (VIII) , or the formula (VI), (VII) and (VIII) as the repeating unit:

HXHX

R HXR HX

〇、R14 (請先閱讀背面之注意事項\^^舄本頁)〇, R14 (please read the notes on the back first\^^舄this page)

τ2 (R)n (Q2)j X1' > 和 % y Y、z V x2 (VI) (VII) 及或取代式（VI)，為式（Via)或（VIb)之重覆單元 (VIII) 訂經濟部智慧財產局員工消費合作社印製Τ2 (R)n (Q2)j X1' > and % y Y, z V x2 (VI) (VII) and or substituted formula (VI), which is a repeating unit of formula (Via) or (VIb) ) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

(R1)n x° (Via)(R1)n x° (Via)

(R)n -線- -18— 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1261153 A7 B7 五、發明説明（17 ) 其中基團為如上述所定義。其中亦可存在數個式（VI)、（(via) 或（VIb))之重覆單元，及/或式（VII)及/或（VIII)之重覆單元0 VI、（via，b)、VII及VIII之相對比例為如所期望的。視VI、（Via，b)之吸收係數而定之VI、（Via，b)之濃度較佳為由0J至100% (基於所述之混合物為準）。VI、（Via， b)對VII之比例為由1〇〇 : 0至1 : 99，較佳由100 : 〇至 30 : 70，尤佳由 1〇〇 : 〇至 50 : 50。式（I)之染料及式（II)之染料單體在短波範圍具有一主要吸收帶（7Γ-7Γ*帶），在一較長波範圍有第二吸收帶(Π-7Γ* 帶）。η-7Γ*帶之莫耳消光係數ε為在400至5000*103平方公分/莫耳之範圍。在假定染料莫耳質量400克/莫耳下，在〇·1毫米輻射厚度下之低聚物及聚合物，如果它們包含由$1.6% ( ε=5000)至$20% ( ε=400)之此種染料，貝ij 具有$2之光學密度。經濟部智慧財產局員工消費合作社印製根據本發明之聚合物及低聚物較佳具有至少40°C之玻璃態轉移溫度Tg。玻璃態轉移溫度例如可根據B. Vollmer， Grundrip der Markromolekularen Chemie, p.406-410, Springer-Verlag，Heidelberg 1962 來測定。根據本發明之聚合物及低聚物，藉凝膠滲透層析法測董，其以重量平均決定之分子量為由5000至2,000,000,較佳由8000至1500 000 (以聚苯乙烯校準）。接枝聚合物係藉式（II)或（Ila)或（lib)之染料單體，選擇之其他式（IV)之形狀_各向異性單體，及/或，選擇之其他式 ------_ —19—_ 本紙張尺度適用中關家榡準（CNS )八4規格（2丨Qx297公釐） 1261153 Α7 Β7 五、發明説明（18 ) (V)之單體之自由基鍵結至低聚性或聚合性基質系統予以製備者。此種基質系統可為極不同種類之聚合物，例如聚苯乙稀、聚（甲基）丙稀酸酯，澱粉、織維素、胜肽。自由基鍵結可藉光之輻射或藉由使用產生自由基之試劑，例如第三-丁基氫過氧化物、二苄醯過氡化物、偶氮二異丁醯腈、過氧化氫/鐵(II)鹽。由於聚合物及低聚物的結構，式（VI)、（Via，b)彼此，或式（VI)、（Via, b)及（VII)彼此之結構元素之中間分子的交互作用係經調整，使液晶次序狀態之形成受到抑制，而可製得光學各向同性的、透明的非散射性薄膜、箔、板或立方體。另一方面，中間分子的交互作用仍夠強，使得在光之輻射下，引起光致變色及非光致變色側基之光化學誘導性、協力的、直接重新定向的過程。在式（VI)、（Via，b)或式（VI)、（Via，b)及（VII)之重覆單元側基之間較佳為產生一交互作用力，其足使式（VI)、 (Via，b)之侧基的構形產生光誘導性的變化，而使引起其他侧基（(VI)、（Via, b)及/或（VII))之同向（所謂協力的）重新定向。在光學各向同性之無定形光色聚合物中，可引起極高數值之光學各向異性（An至0.4)。由於光化光的影響，在聚合物或低聚物中之次序狀態被形成及改變，而光學特性也因而受到調整。所用的光為偏極光，其波長在式（VI)之重覆單元之吸收帶的範圍内，較佳在長波η·7Γ*帶的範園内6 —20— 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閱讀背面之注意事項本頁)(R)n - Line - -18 - This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1261153 A7 B7 V. Description of invention (17) where the group is as defined above. There may also be several repeating units of formula (VI), ((via) or (VIb)), and/or repeating units of formula (VII) and/or (VIII) 0 VI, (via, b) The relative proportions of VII and VIII are as expected. The concentration of VI, (Via, b) depending on the absorption coefficient of VI, (Via, b) is preferably from 0 J to 100% (based on the mixture). The ratio of VI, (Via, b) to VII is from 1 〇〇 : 0 to 1: 99, preferably from 100 : 〇 to 30 : 70, particularly preferably from 1 〇〇 : 〇 to 50 : 50. The dye of the formula (I) and the dye monomer of the formula (II) have a main absorption band (7Γ-7Γ* band) in the short-wavelength range and a second absorption band (Π-7Γ* band) in the longer wavelength range. The molar extinction coefficient ε of the η-7Γ* band is in the range of 400 to 5000*103 square centimeters/mole. Oligomers and polymers at a 〇·1 mm radiant thickness, assuming a dye molar mass of 400 g/mole, if they contain from $1.6% (ε=5000) to $20% (ε=400) A dye, Beij has an optical density of $2. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, the polymers and oligomers according to the present invention preferably have a glass transition temperature Tg of at least 40 °C. The glass transition temperature can be determined, for example, according to B. Vollmer, Grundrip der Markromolekularen Chemie, p. 406-410, Springer-Verlag, Heidelberg 1962. The polymers and oligomers according to the present invention are measured by gel permeation chromatography and have a weight average molecular weight of from 5,000 to 2,000,000, preferably from 8,000 to 1,500,000 (calibrated with polystyrene). The graft polymer is a dye monomer of the formula (II) or (Ila) or (lib), and the shape of the other formula (IV) is selected as an anisotropic monomer, and/or other formula is selected-- ---_ —19—_ This paper size is applicable to Zhongguan Jiaxun (CNS) 8 4 specifications (2丨Qx297 mm) 1261153 Α7 Β7 5, invention description (18) (V) monomer free radical bond The preparation is carried out to an oligomeric or polymeric matrix system. Such matrix systems can be very different types of polymers, such as polystyrene, poly(methyl) acrylate, starch, oryzanol, peptides. Free radical bonding can be by radiation of light or by the use of reagents that generate free radicals, such as tri-butyl hydroperoxide, dibenzyl hydrazine, azobisisobutyl carbonitrile, hydrogen peroxide / iron (II) Salt. Due to the structure of the polymer and the oligomer, the interaction of the intermediate molecules of the formula (VI), (Via, b) with each other, or the structural elements of the formulas (VI), (Via, b) and (VII) is adjusted. The formation of the liquid crystal sequential state is suppressed, and an optically isotropic, transparent non-scattering film, foil, plate or cube can be produced. On the other hand, the interaction of the intermediate molecules is still strong enough to cause photochemically induced, synergistic, direct reorientation of photochromic and non-photochromic pendant groups under irradiation of light. Preferably, an interaction force is generated between the side units of the repeating unit of the formula (VI), (Via, b) or (VI), (Via, b) and (VII), which is sufficient to make the formula (VI) The configuration of the side groups of (Via, b) produces a light-induced change that causes the other side groups ((VI), (Via, b) and/or (VII)) to be in the same direction (so-called synergistic) Reorientation. In the optically isotropic amorphous photochromic polymer, extremely high numerical anisotropy (An to 0.4) can be caused. Due to the influence of actinic light, the order state in the polymer or oligomer is formed and changed, and the optical characteristics are thus adjusted. The light used is polarized light, the wavelength of which is within the absorption band of the repeating unit of formula (VI), preferably within the range of the long-wave η·7Γ* band. 6-20—the paper scale applies to the Chinese national standard (CNS) ) Α 4 size (210X 297 mm) (Please read the note on the back first)

經濟部智慧財產局員工消費合作社印製 1261153 A7 B7 五、發明説明（19 ) 聚合物及低聚物可藉文獻上習知的方法來製備，例如根據 DD 276 297、DE-A 3 808 430、Makromolekulare Chemie 187, 1327-1334(1984)、SU 887 574、Europ. Polym. 18, 561 (1982)及 Liq. Cryst.2, 195(1987)。薄膜、箔、板及立方體的製備無需利用外場及/或表面效應之複雜的定位法。彼等可藉旋塗、浸潰、洗注或其他由技術觀點為易於控制之塗覆方法將其施至基材上，可藉壓製或流動法將其置於兩透明板之間，或簡單地藉澆注或擠壓被製成自持材料。此種薄膜、箔、板及立方體亦可由包含所述結構元素之液晶聚合物或低聚物，藉驟冷（亦即冷卻速率>100K/分），或藉快速移除溶劑予以製備。較佳者為一種在至多達300°C，較佳至多達220°C，尤佳 180°C的範圍内製備雷射攝影術用體積儲存媒體的方法，其中包含一個根據傳統射出成形方法的步驟。層厚20·1毫米，較佳20.5毫米，尤佳21毫米◊尤佳製備毫米範圍之層的方法為射出成形法。在該方法中，熔融的聚合物被驅使通過一喷嘴進入一有形容器中，在其冷卻後將其由該容器中取出。經濟部智慧財產局員工消費合作社印製製備根據本發明之記錄用材料或聚合物之較佳方法包含一種製法，其中至少一種單體在無其他溶劑下被聚合，聚合反應較佳為自由基聚合，且特別是藉自由基引發劑及/ 或UV光及/或熱予以引發者。此方法係在由20°C至200°C，較佳由40°C至150°C，尤佳由50。(：至i00°C，且最佳約60°C之溫度下來實施。 — ______ —21— 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） 1261153 A7 B7 五、發明説明（20 ) 於一特殊具體例中，AIBN被用作自由基引發劑。經常發現到伴隨使用另一種較佳為液體之單體是有利的此種單體應瞭解為在反應溫度下為液體之單體，該單體較佳為烯屬不飽和單體，尤佳為以丙烯酸及甲基丙烯酸為基礎者，最佳為甲基丙烯酸甲酯。在共聚物中之式（II)單體的含量較佳由0.1至99.9重量 %，尤佳由0.1至50重量％，更佳由0.1至5重量％，最佳由0.5至2重量％。雷射攝影數據儲存的方法被描述於例如LASERFOCUS WORLD，1996 年 12 月，81 頁起。經濟部智慧財產局員工消費合作社印製在記錄全像圖時，上述之聚合物薄膜被兩束具可引起所需要之光誘導重新定向之波長的相干雷射光束所輻射。一光束（物體光束）包含將被儲存之光學訊息，例如由光束通過兩度空間、棋盤狀圖素結構（數據頁）所引起的強度變化。但是原則上，為任何兩度或三度空間物體所繞射、散射或反射之光可被用作物體光束。在儲存媒體上，物體光束被引至具有第二雷射光束（參考光束，其通常為一平面或圓形波）之干涉中。形成之干涉圖型隨著光學常數（折射率及/或吸收係數）的調變而被印記在儲存媒體中。該調變擴及整個輻射區，尤其是儲存媒體的厚度。若物體光束被阻斷，且媒體單獨被曝露於參考光束中，則經調變的儲存媒體即充作一種參考光束之繞射光栅。由繞射而來之強度分布對應於由被儲存之物體而來之強度分布，以致其不再能區別是否光係來自物體本身，抑或是否其係因參考 —22— 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1261153 A7 B7 五、發明説明（21 ) 經濟部智慧財產局員工消費合作社印製光束之繞射而起者。為在-樣印位置切存不同之全像圖，使用各種多工方法.波長夕工轉移多卫、相多卫、周邊旋律多工及/或角度多工等。在角度多工的情況中，儲存媒體（其中全像圖已在有關角度下_存）之間的角度及參光束被改變。由某種角度變化，原先的全像圓消失（Bmggmismatehw 射參考光束不再為料媒體賴射，_建此物體。由其發生之角度視儲存媒體的厚度而定（及視媒體中所產生之光學常數的㈣而定）：_愈厚，#考光束必須被改變的角度愈小。另-全«可被記錄在該新的角度構形卜該全像圖的讀出，在儲存媒體與其所記錄之參考光束之間㈣度構形中再次精碟地發生。藉逐漸地改變媒體與記錄光束之間的角度，因此其能在儲存媒艘上之相同位置上記錄多個全像圖。本專利所述之聚合物系統具有很大的優點，當記錄下一個全像圖時，健存在相對於前-個全像圖之儲存媒體中的訊息不會被抹除，且超過二個全像圖，較佳多於5〇個，尤佳多於i卯個更佳多於500個，最佳多於1〇〇〇個全像圖可被記錄在儲存媒體上之同一位置。被儲存之物體為藉液晶顯示器的傳送所產生之數據頁。該等數據頁具有256χ256圖素，較隹為 512x512的圖素，尤佳為1024x1024的數據圖素。本發明亦提供一種雷射攝影術體積儲存媒體用之記錄用材料，係由聚合性或低聚性有機無定形材料所組成，其含 —23— 本紙張尺度適用中關家標準（CNS ) Μ規格（2ωχ297公釐） (請先閲讀背面之注意事項再一^本頁) 、ν" -811 I Ti -Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1261153 A7 B7 V. INSTRUCTIONS (19) Polymers and oligomers can be prepared by methods known in the literature, for example, according to DD 276 297, DE-A 3 808 430, Makromolekulare Chemie 187, 1327-1334 (1984), SU 887 574, Europ. Polym. 18, 561 (1982) and Liq. Cryst. 2, 195 (1987). The preparation of films, foils, sheets and cubes eliminates the need for complex positioning methods that utilize external and/or surface effects. They may be applied to the substrate by spin coating, dipping, laundering or other technically easy-to-control coating methods, either by pressing or flowing it between two transparent plates, or simply The ground is made of self-sustaining material by pouring or extrusion. Such films, foils, sheets and cubes may also be prepared from liquid crystal polymers or oligomers comprising the structural elements by quenching (i.e., cooling rate > 100 K/min) or by rapid removal of solvent. Preferably, the method of preparing a volume storage medium for laser photography in a range up to 300 ° C, preferably up to 220 ° C, and particularly preferably 180 ° C, comprising a step according to a conventional injection molding method . The layer thickness of 20·1 mm, preferably 20.5 mm, and particularly preferably 21 mm, is preferably a method of preparing a layer of the millimeter range by injection molding. In this method, the molten polymer is driven through a nozzle into a tangible container which is removed from the container after it has cooled. The preferred method for preparing a recording material or polymer according to the present invention comprises a method in which at least one monomer is polymerized in the absence of other solvent, and the polymerization is preferably a radical polymerization. And especially by the use of free radical initiators and / or UV light and / or heat to initiate. The method is from 20 ° C to 200 ° C, preferably from 40 ° C to 150 ° C, particularly preferably from 50. (: to i00 ° C, and the best temperature is about 60 ° C. - ______ - 21 - This paper scale applies to China National Standard (CNS) Λ 4 specifications (210X 297 mm) 1261153 A7 B7 V. Description of invention ( 20) In a special embodiment, AIBN is used as a free radical initiator. It is often found that the use of another preferably liquid monomer is advantageous. Such a monomer should be understood as a liquid at the reaction temperature. The monomer is preferably an ethylenically unsaturated monomer, more preferably based on acrylic acid and methacrylic acid, and most preferably methyl methacrylate. The content of the monomer of the formula (II) in the copolymer. It is preferably from 0.1 to 99.9% by weight, particularly preferably from 0.1 to 50% by weight, more preferably from 0.1 to 5% by weight, most preferably from 0.5 to 2% by weight. The method of laser photographic data storage is described, for example, in LASERFOCUS WORLD, December 1996, starting from page 81. The Ministry of Economic Affairs' Intellectual Property Office employee consumption cooperative printed on the full-image map, the polymer film was subjected to two coherent lasers with wavelengths that caused the required light-induced reorientation. a beam of light The beam) contains the optical information to be stored, such as the intensity change caused by the beam passing through the two-dimensional space, the checkerboard structure (data page), but in principle, it is diffracted for any two- or three-degree space object, The scattered or reflected light can be used as an object beam. On the storage medium, the object beam is directed into the interference with the second laser beam (the reference beam, which is typically a plane or a circular wave). The pattern is imprinted in the storage medium as the optical constant (refractive index and/or absorption coefficient) is modulated. This modulation spreads over the entire radiation area, especially the thickness of the storage medium. If the object beam is blocked, and the medium When exposed separately to the reference beam, the modulated storage medium acts as a diffractive grating of the reference beam. The intensity distribution from the diffraction corresponds to the intensity distribution from the object being stored, so that it does not It is no longer possible to distinguish whether the light system is from the object itself or whether it is a reference.—22—This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1261153 A7 B7 V. Description of invention (21) The diffraction of the printed beam of the employee's consumer cooperative of the Intellectual Property Office of the Ministry of Economic Affairs. In order to store different holograms at the position of the sample, various multiplex methods are used. Wei, Xiang Duowei, peripheral melody multiplex and/or angle multiplex, etc. In the case of angle multiplex, the angle between the storage medium (where the hologram is already under the relevant angle) and the reference beam are changed From a certain angle of change, the original holographic circle disappears (Bmggmismatehw the reference beam is no longer the media medium, _ build this object. The angle of its occurrence depends on the thickness of the storage medium (and depending on the media) The optical constant (four) depends on: _ the thicker, the smaller the angle at which the test beam must be changed. The other - full « can be recorded in the new angle configuration. The reading of the hologram occurs again in the (four) degree configuration between the storage medium and the reference beam it records. By gradually changing the angle between the media and the recording beam, it is possible to record multiple holograms at the same location on the storage media. The polymer system described in this patent has great advantages. When the next hologram is recorded, the information stored in the storage medium relative to the previous hologram is not erased, and more than two Preferably, the image is more than 5, preferably more than i, more preferably more than 500, and preferably more than one hologram can be recorded at the same location on the storage medium. The object to be stored is a page of data generated by the transfer of the liquid crystal display. These data pages have 256 χ 256 pixels, which is a 512 x 512 pixel, and particularly preferably a 1024 x 1024 data pixel. The invention also provides a recording material for a laser photo storage medium, which is composed of a polymerizable or oligomeric organic amorphous material, which comprises - 23 - the paper scale applies to the Zhongguan standard (CNS) Μ Specifications (2ωχ297 mm) (Please read the notes on the back and then ^this page), ν" -811 I Ti -

-.......-I - -I - 1 * 1261153 A7 B7 五、發明説明（22 ) (請先閲讀背面之注意事項再本頁) 有至少一種與電磁輻射交互反應之基群，及選擇之至少一種形狀_各向異性的基群；其特徵在於它具有，較佳尤佳$0·3之光學密度。記錄用材料可被用作儲存資料在無撐膜的形式，或較佳在多層結構上。多層結構例如為一種二明治，其中真正的記錄媒體被至少一種基材所圍繞。基材可為具有高度光學性質之透明媒體，例如玻璃板、石英板或聚碳酸酯板。高度光學性質應瞭解意表散射效率（亦即在該三明治所散射之光與入射光之間的商數）不低於 ⑺4，較佳不低於1〇·5，尤佳不低於10·6。為決定該商數，可將樣品曝露於HeNe雷射光束中。偵測係藉著一種ccd 攝影機來完成。贵施何實施例1 單體的製備-..-I - -I - 1 * 1261153 A7 B7 V. INSTRUCTIONS (22) (Please read the notes on the back and then on this page) There are at least one group that interacts with electromagnetic radiation. And at least one shape- anisotropic group selected; characterized in that it has an optical density of preferably, preferably, greater than 0.03. The recording material can be used as a storage material in the form of a film without film, or preferably on a multilayer structure. The multilayer structure is, for example, a dimethoate in which a true recording medium is surrounded by at least one substrate. The substrate can be a transparent medium having a high degree of optical properties such as a glass plate, a quartz plate or a polycarbonate plate. The high optical properties should be understood that the efficiency of the intentional scattering (that is, the quotient between the light scattered by the sandwich and the incident light) is not less than (7) 4, preferably not less than 1 〇 5, and particularly preferably not less than 10.6. . To determine the quotient, the sample can be exposed to a HeNe laser beam. Detection is done by a ccd camera.贵施何 Example 1 Preparation of monomer

經濟部智慧財產局員工消費合作社印製 a) 4-(2-羥乙基氧基）笨曱酸將138克之對-羥基苯甲酸和〇 5克KI,於攪拌中置入 350毫升的乙醇中。逐滴添加15〇克koh於150毫升水所成之溶液中。在3〇_60°C下於30分鐘内逐滴添加88.6 ---— —24— 尽氏張尺度適财關家標準（CNS ) M規格（训幻97公餐） 1261153 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（23) 克的2_氣乙醇。在迴流下攪拌反應混合物15小時。然後將溶劑先在常壓、後在真空下予以完全地蒸餾。將殘餘物溶解在1公升的水中並用HC1酸化。以抽吸過遽沉澱物並由1.8公升的水予以再結晶〇乾燥產物及再結晶兩次，產量為46克（理論產量的25y V 乙醇。卜 ^)。線點179.5 b) 4-(2-甲基丙烯醯基氧基乙基氧基）苯甲酸將45克之4_(2_羥乙基氧基）苯甲酸、18〇毫升酸、1〇克對-甲苯磺酸和10克氫醌，於15〇甲基丙烯 ‘隨挽拌地予以迴流加熱。於一水分離器中氣仿中間所形成的水分離。以150毫升的氣仿稀释反將反應期每次用100毫升水洗滌數次並以Na2S〇4乾燥晃σ物，燥劑，在迴轉蒸發器中將氣仿蒸餾至三分之二過遽掉乾過濾產物沉澱物並由異丙酵中再結晶兩次，以抽及克（理論產量的45% )。熔點146°C。為28 c) 氣化4-(2-甲基丙烯醯基氧基乙基氧基）笨甲_ 在室溫下，將25克4-(2-甲基丙烯醯基氣基己苯甲酸、80毫升亞磺醯氯化物及〇·5毫井氣基） DMF . 分鐘。然後將過量之亞磺醯氯化物先在中等壓力^评30 高真空下予以蒸餾。以實質定量產率所形成之、後在隨後在室溫下被緩慢地結晶出來。氣化元素分析：C13H13Cl〇4(26&7) 計算值：C 58.11; H4.88; Cl 13.19; 實際值：C 58.00; Η 4·90; Cl 13.20; 物讀背面之注意事項再本頁；> 衣. 本，、=口Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, a) 4-(2-Hydroxyethyloxy) alumic acid, 138 g of p-hydroxybenzoic acid and 5 g of KI, placed in 350 ml of ethanol with stirring. . A solution of 15 g of koh in 150 ml of water was added dropwise. 88.6 --- - 24 - Dian's Zhang scale suitable for wealth control standard (CNS) M specification (training 97 meals) at 3〇_60°C in 30 minutes 1261153 A7 B7 Ministry of Economics wisdom The property bureau employee consumption cooperative printed five, invention description (23) grams of 2_ gas ethanol. The reaction mixture was stirred under reflux for 15 hours. The solvent is then completely distilled at normal pressure and then under vacuum. The residue was dissolved in 1 liter of water and acidified with HCl. The product was dried by suction and recrystallized from 1.8 liters of water, and recrystallized twice to yield 46 g (25 y V ethanol in theory. Bu). Line 179.5 b) 4-(2-Methylacryloyloxyethyloxy)benzoic acid 45 g of 4_(2-hydroxyethyloxy)benzoic acid, 18 ml of acid, 1 g of p- Toluenesulfonic acid and 10 g of hydroquinone were heated under reflux with 15 〇 of methyl propylene. The water formed by the gas phase in the water separator is separated. Dilute with 150 ml of gas and then wash the reaction several times with 100 ml of water each time and dry with Na2S〇4 to smash the sigma, desiccant, and distill the gas to two-thirds in a rotary evaporator. The product precipitate was filtered dry and recrystallized twice from isopropyl acetate to extract gram (45% of theory). The temperature of 146 ° C. Is 28 c) gasification of 4-(2-methylpropenyl methoxyethyloxy) carbamide _ at room temperature, 25 g of 4-(2-methylpropenyl decyl hexyl benzoic acid, 80 ml of sulfinium chloride and 〇·5 wells of gas base) DMF. Min. The excess sulfinium chloride is then first distilled under moderate pressure. It is formed in a substantial quantitative yield and then slowly crystallized at room temperature. Analysis of gasification elements: C13H13Cl〇4 (26 & 7) Calculated value: C 58.11; H4.88; Cl 13.19; Actual value: C 58.00; Η 4·90; Cl 13.20; Note on the back of the object read this page; > Clothing. Ben, = mouth

-25— 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X 297公釐） 1261153 A7 B7 五、發明説明（24 ) d) 4_三甲基乙唯醯基(pivalinoyl)胺基·4，-胺基偶氮苯將36克4,4’_二胺基偶氮苯及62克三乙基胺置於4〇〇毫升THF中。逐滴緩慢地添加23.2克氣化三甲基乙酸於 100毫升THF所成之溶液中。於室溫下攪拌2小時後，將水加至反應混合物中。過濾沉澱物並予以乾燥。獲得 42克產物。藉層析法進行進一步的純化（碎勝；甲苯/ 乙酸乙酿1 : 1)。產量為8克。熔點230。(：。 e) 4-三曱基乙唯醯基胺基對气孓甲基丙烯醯基氧基乙基氧基）本曱醜胺基]偶氣苯將1克4·三甲基乙咁醯基胺基_4，_胺基偶氮苯置入5〇〇c 之10毫升N-甲基-2-吡咯啶酮（NMP)中並添加到5(rCi 1克4-(2-甲基丙稀醯基氧基乙基氧基）苯甲酸於丨毫升 NMP所成之溶液中。在室溫下攪拌反應混合物丨小時並予以冷卻，並添加200毫升的水。過濾沉澱物及在室溫下於30毫升甲醇中攪拌；濾除母液並在真空中進行乾燥。產量為 1_2 克。熔點 194。(：。Amax= 378 nm(DMF); ε = 37000升/(莫耳*公分）。實施例2 a) 在3-5°C下，將32克]^•苯甲醯基_對_伸苯基二胺置於由 210毫升冰醋酸、75毫升丙酸及31毫升濃縮氫氣酸所成之混合物中。在該溫度下，於1小時的期間内，逐滴添加50克亞硝基硫酸（約40%)。 b) 將16克間-甲苯胺溶解於13〇毫升之冰醋酸中。在〇_5 本紙張尺度通用T圏囤豕榡準（CNS ) a4規格（21〇><297公釐） (請先閱讀背面之注意事項再本頁) 本訂經濟部智慧財產局員工消費合作社印製 1261153 A7 五、發明説明（2S) C下，於2小時的期間内逐滴加入由a)而來之重氤化物。在室/孤下授掉展合物過夜。以抽吸過濾形成的染料並懸〆麥在550毫升的水中。利用蘇打提高pH S 8·4。再次以抽吸過濾形成的染料，以異丙醇水洗及乾燥。獲得α 克（理論產量之54·4%)下式之染料··-25- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1261153 A7 B7 V. Description of invention (24) d) 4_Trimethyl acetyl pylinoyl amine group 4 ,-Aminoazobenzene 36 g of 4,4'-diaminoazobenzene and 62 g of triethylamine were placed in 4 mL of THF. A solution of 23.2 g of vaporized trimethylacetic acid in 100 ml of THF was slowly added dropwise. After stirring at room temperature for 2 hours, water was added to the reaction mixture. The precipitate was filtered and dried. 42 g of product were obtained. Further purification by chromatography (crude; toluene / acetic acid ethyl 1: 1). The yield is 8 grams. Melting point 230. (:. e) 4-trimethylphenylethyl decylamino-p-methyl methacryloyloxyethyloxy) 曱曱胺 ] 偶偶苯 1 1 gram 4 · trimethyl ethane Mercaptoamine _4,-aminoazobenzene was placed in 5 ml of N-methyl-2-pyrrolidone (NMP) at 5 〇〇c and added to 5 (rCi 1 g 4-(2-A) The acrylonitrile ethoxyethyloxy)benzoic acid was added to a solution of 丨 ml of NMP. The reaction mixture was stirred at room temperature for a few hours and cooled, and 200 ml of water was added. The precipitate was filtered and placed in the chamber. The mixture was stirred in 30 ml of methanol at room temperature; the mother liquor was filtered off and dried in vacuo. Yield 1 2 g. Melting point 194. (: Amax = 378 nm (DMF); ε = 37000 liters / (mole * cm). Example 2 a) At 3-5 ° C, 32 g of benzylidene phenyl p-phenylenediamine was placed in 210 ml of glacial acetic acid, 75 ml of propionic acid and 31 ml of concentrated hydrogen acid. In the mixture, 50 g of nitrosylsulfuric acid (about 40%) was added dropwise at this temperature over a period of 1 hour. b) 16 g of m-toluidine was dissolved in 13 ml of glacial acetic acid. . In 〇_5 This paper size is universal T圏囤豕榡 (CNS) a4 specification (21〇><297 mm) (please read the note on the back page again) This is the Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed 1261153 A7 V. Inventive Note (2S) C, the heavy telluride from a) was added dropwise over a period of 2 hours. The exhibit was given overnight in the chamber/lone. The dye formed by suction filtration was suspended and the buckwheat was suspended in 550 ml of water. Increase the pH S 8·4 with soda. The dye formed by suction filtration was again washed with water and dried with isopropyl alcohol. Obtain α g (54. 4% of theoretical yield) of the following formula··

〇 Ί〇. 於二甲基甲酿胺中之uv/vis: u16nme C)在赃下’將由b)而來之染料5克溶解於2G毫升之N 甲基吼㈣㈣。添加3·5克之下式之酸氣化物： r\〇 Ί〇. uv/vis in dimethyl ketoamine: u16nme C) 5 grams of dye from b) is dissolved in 2 g of N-methyl oxime (4) (4). Add 3·5 g of the acid hydride below: r\

〇 (請先閲讀背面之注意事項再本頁) 訂經濟部智慧財產局員工消費合作社印製在5〇CT_混合物15小時。最後，添加2〇毫升的水，以抽吸過濾形成的染料。以5()毫升的異以抽吸過渡並乾燥。獲得6.2克（理論產量之乃4^’ 之下式的染料單體：〇 ^〇 (Please read the notes on the back and then on this page) Ordered by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed in 5〇CT_mixture for 15 hours. Finally, 2 ml of water was added to filter the dye formed by suction. Transfer with a suction of 5 () ml and dry. Obtained 6.2 g (the theoretical yield is 4^' below the dye monomer: 〇 ^

〇〇

JxxJxx

〇 ~~27~ 本紙張尺度適用中國國家標準（CNS ) A4規格（ 1261153 A7 B7 五、發明説明（26 ) 於二甲基甲醯胺中之UV/VIS: ；lmax= 386 nm 以類似方法製備下表中之染料單體。〇~~27~ This paper scale applies to Chinese National Standard (CNS) A4 specification (1261153 A7 B7 5. Invention description (26) UV/VIS in dimethylformamide: ;lmax= 386 nm Prepared in a similar manner The dye monomers in the table below.

NN

R53, 丫、N 〇 R52 R56R53, 丫, N 〇 R52 R56

〇〇

〜〇丫、51 Ο 請閱讀背面冬事項經濟部智慧財產局員工消費合作社印製實施例 R51 R52 R53 R54 R55 R56 ^max 2 ch3 H H H H 3 ch3 ch3 H H 0 H 374 nm 4 Η H ch3 H H 386 nm 5 ch3 ch3 H H C2H5 371 nm 6 ch3 H ch3 H H 395 nm 7 ch3 H ch3 JyO 0 ch3 H 373 nm -28- 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐） 1261153 A7 B7 五、發明説明（27) 接枋聚合物的實施例在86°〇下將8.7克澱粉？以^(^11^1八4692(86.3%)(來自 Avebe，Foxhol，NL)溶解於60毫升水中。將1·5克1重量 %FeS〇4水溶液和6.1克3重量％出〇2水溶液之混合物添加於其中。在86艽下進行攪拌15分鐘。然後在該溫度丁於90分鐘期間内，同時逐滴地添加由1.4克下式之染料單體·~〇丫, 51 Ο Please read the back of the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Cooperatives, Printed Example R51 R52 R53 R54 R55 R56 ^max 2 ch3 HHHH 3 ch3 ch3 HH 0 H 374 nm 4 Η H ch3 HH 386 nm 5 Ch3 ch3 HH C2H5 371 nm 6 ch3 H ch3 HH 395 nm 7 ch3 H ch3 JyO 0 ch3 H 373 nm -28- This paper scale applies to Chinese National Standard (CNS) A4 specification (21 OX 297 mm) 1261153 A7 B7 V. DESCRIPTION OF THE INVENTION (27) Example of an indole polymer 8.7 g of starch at 86 ° C? Dissolve in 60 ml of water with ^(^11^1 八 4692 (86.3%) (from Avebe, Foxhol, NL). 1.5 g of 1 wt% FeS〇4 aqueous solution and 6.1 g of 3% by weight of 〇2 aqueous solution The mixture was added thereto. Stirring was carried out for 15 minutes at 86 ° C. Then, at this temperature for a period of 90 minutes, a dye monomer of 1.4 g of the following formula was added dropwise at the same time.

N ^Λ〇^Η3 於12.5克曱基丙烯酸甲酯中的溶液及4·1克3重量％之 Η2〇2水溶液。在該溫度下再經15分鐘後，添加〇 1〇5克第三-丁基氩過氧化物及在86°C下進行攪拌1小時。通過 100微米聚醯胺濾布過濾微細黃色分散液。經濟部智慧財產局員工消費合作社印製以水稀釋分散液1:1〇，將其塗至一玻璃板上並予以乾燥。.在玻璃板上之透明淡黃色薄膜以偏極光（來自Sch〇u 之KL 500冷光燈）照射（斑點直徑6毫升）。在橫向偏極器之間，經照射之斑點可在暗的環境中明顯地被看見。實綠：M_3 :藉嵌段聚合法製備雷射攝影術用材料在一小破璃瓶中，將由0.314克4-(2-甲基丙缔酿基氧基乙基氧基)偶氮苯（1莫耳％ )A solution of N ^ Λ〇 ^ Η 3 in 12.5 g of methyl methacrylate and 4. 1 g of a 3% by weight aqueous solution of Η 2 〇 2 . After 15 minutes at this temperature, 〇1〇5 g of tri-butyl argon peroxide was added and stirred at 86 ° C for 1 hour. The fine yellow dispersion was filtered through a 100 micron polyamine filter cloth. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. Dilute the dispersion with water 1:1 〇, apply it to a glass plate and dry it. The clear pale yellow film on the glass plate was irradiated with a polarized light (KL 500 cold light from Sch〇u) (spot diameter 6 ml). Between the lateral polarizers, the illuminated spots can be clearly seen in a dark environment. Real green: M_3: The material for laser photography prepared by block polymerization is in a small glass bottle, which will be composed of 0.314 g of 4-(2-methylpropanyloxyethyloxy)azobenzene ( 1 mole %)

-*29— 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） 1261153 A7 B7 五、發明説明（28 ) 及0.052克2,2’-偶氮異丁腈於1〇克曱基丙烯酸甲酯中所成之溶液，以乾燥氬氣洗滌30分鐘。以橡膠塞密封小玻璃舨並在60°C下調和7天。獲得一種透明聚合物圓柱體。此聚合物圓柱體可藉打破玻璃瓶及去除破裂的玻璃瓶予以分離。在60°C下進一步儲存2週，用來移除甲基丙烯酸曱酯殘餘物並釋出聚合物嵌段物内之壓力。由此所得之PAP圓柱體在一精確的技術工場被切成具有 17毫升直徑及1.9毫升厚度的平板，然後予以拋光。此平板在重要的波長下具有下列的光學密度：〇D(514nm) = 2.502; OD(532nm) = 0.755; OD(568nm) = 0·052。以一類似的方法，製備具有偶氮染料含量10莫耳％之共聚物。以一類似的方法，製備具有1莫耳％下述單體含量 (請先閱讀背面之注意事項再ΙΡτ本頁)-*29— This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1261153 A7 B7 V. Invention description (28) and 0.052 g 2,2'-azoisobutyronitrile in 1 gram The solution formed in methyl acrylate was washed with dry argon for 30 minutes. The small glass crucible was sealed with a rubber stopper and conditioned at 60 ° C for 7 days. A transparent polymer cylinder is obtained. This polymer cylinder can be separated by breaking the glass bottle and removing the broken glass bottle. Further storage at 60 ° C for 2 weeks was used to remove the decyl methacrylate residue and release the pressure within the polymer block. The PAP cylinder thus obtained was cut into a plate having a diameter of 17 ml and a thickness of 1.9 ml in a precise technical workshop and then polished. This plate has the following optical densities at important wavelengths: 〇D (514 nm) = 2.502; OD (532 nm) = 0.755; OD (568 nm) = 0·052. In a similar manner, a copolymer having an azo dye content of 10 mol% was prepared. In a similar manner, the following monomer content was prepared with 1 mol% (please read the notes on the back and then ΙΡ 本页本页)

-訂-- order -

經濟部智慧財產局員工消費合作社印製及99莫耳％甲基丙烯酸甲酯含量之共聚物。實施例4 將由實施例3而來之聚合物藉由自溶液之旋轉塗隳塗裏一具有150微米厚度之玻璃基材上。位在基材中心之剩量點的層厚為600毫微米。聚合物層之反射係數η係藉辕巍結合法測量三個空間方向X、y (平面層）及2；(法線廣為該目的，稜鏡的底部係緊密地與聚合物層接觸。在姨偏極化之雷射光會合進入該層及以波導方式通過的角虞<提本紙度適用中國國( CNS ) A4規格（210x 297公釐)~ 1261153 A7 B7 五、發明説明（29) 供有關其在光波長下之反射係數的訊息。每次會合進入，在反射偵測器上都變成明顯的信號下降。當雷射的偏極化被選擇垂直於入射平面（s-偏極化）時，可測定在偏極方向的折射係數。根據基材的位向，可測定〜及ny的數值。具有較低折射係數之基材的係數、稜鏡的係數及雷射波長（；l=：633nm)可納入計算。在入射平面中偏極化（p-偏極化）的情況，可測定nz值。為該目的，兩空間方向X或y之一必須與入射平面一致。此外，所選擇方向之折射係數的數值（〜或ny)可納入計算。折射係數nx、ny及nz係在數次曝露及抹除的過程之前、期間及之後，於樣品上測定的。曝露係藉以波長輻射 514nm,垂直入射的雷射光照射聚合物層而起。光強度為 200Mw/cm2。光在X方向被直線地偏極化。在xy平面所引起之位向各向異性的抹除係當y方向之偏極化時發生◊ (請先閱讀背面之注意事項再衣-- 本頁) 、-!! 經濟部智慧財產局員工消費合作社印製樣品在λ-633ηιη下之拼射係私 ηχ _ % ηζ 未處理 1.692 1.692 1.657 在200秒之曝露之後 1.657 1.721 1.682 在500秒之曝露之後 1.626 1.732 1.700 在5000秒之曝露之後 1.596 1.746 1.716 在第1次抹除之後 1.672 1.675 1.723 在第2次曝露之後(5000秒） 1.588 1.721 1.730 在第2次抹除之後 1.650 1.651 ' 1.735Co-products of the Intellectual Property Office of the Ministry of Economic Affairs printed by the Consumer Cooperative and a copolymer of 99 mol% methyl methacrylate. Example 4 The polymer from Example 3 was coated on a glass substrate having a thickness of 150 μm by spin coating from a solution. The layer thickness at the center of the substrate is 600 nm. The reflection coefficient η of the polymer layer is measured by the 辕巍-bonding method to measure three spatial directions X, y (planar layer) and 2; (the normal is widely used for this purpose, and the bottom of the crucible is in close contact with the polymer layer.姨Polarized polarized light will enter the layer and pass through the corners of the waveguide.<Ten is applicable to China (CNS) A4 specification (210x 297 mm)~ 1261153 A7 B7 V. Invention description (29) The message about its reflection coefficient at the wavelength of light. Each time it meets, it becomes a significant signal drop on the reflection detector. When the polarization of the laser is selected perpendicular to the plane of incidence (s-polarization) The refractive index in the direction of the polarization can be measured. Depending on the orientation of the substrate, the values of ~ and ny can be measured. The coefficient of the substrate with a lower refractive index, the coefficient of 稜鏡 and the wavelength of the laser (; l = : 633 nm) can be included in the calculation. In the case of polarization (p-polarization) in the incident plane, the nz value can be determined. For this purpose, one of the two spatial directions X or y must coincide with the plane of incidence. The value of the refractive index of the selected direction (~ or ny) can be included in the calculation The refractive indices nx, ny, and nz are measured on the sample before, during, and after the process of several exposures and erasures. The exposure is obtained by irradiating the polymer layer with laser radiation at a wavelength of 514 nm and perpendicular incidence. The intensity is 200 Mw/cm 2. The light is linearly polarized in the X direction. The anisotropic erasing caused by the xy plane occurs when the y direction is polarized (please read the back note first) Re-clothing--this page),-!! Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed samples under λ-633ηιη spelling system private ηχ _ % ηζ untreated 1.692 1.692 1.657 after 200 seconds exposure 1.657 1.721 1.682 After 500 seconds of exposure 1.626 1.732 1.700 after 5000 seconds exposure 1.596 1.746 1.716 after the first erasure 1.672 1.675 1.723 after the second exposure (5000 seconds) 1.588 1.721 1.730 After the second erasure 1.650 1.651 ' 1.735

>3ν 每個空間方向之折射係數的高低為位在該方向之色團的一一31一____ 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇><297公釐） 1261153 Μ 五、發明説明（30 ) 平均數的測量’因為其與科的偏極化有關且主要係由高分：可偏極化物沿著每個分子輪所構成。由於…本來疋相㈣’ mu在^平面有巨觀的各向同性的分佈。〜的較小值表示平_分子位向係由製備過程而來的。第一次曝露逐漸導致—位向分佈，帶有減少數目之位在X方向的色團m向的消減就統計的方法而言，係平均地發生’使其他_空間方向由逐漸增加之％及„2 的數值中被讀出。在薄膜平面上之雙折射ηχ·%可幾乎完全>3ν The refractive index of each spatial direction is the one of the chromophores in this direction. The paper size applies to the Chinese National Standard (CNS) A4 specification (2丨〇><297 mm 1261153 Μ V. INSTRUCTIONS (30) The measurement of the mean is because it is related to the polarization of the family and is mainly composed of high scores: the polarizables are formed along each molecular wheel. Because...the original ( phase (4)' mu has a giant isotropic distribution in the ^ plane. The smaller value of ~ indicates that the _ molecular orientation is derived from the preparation process. The first exposure gradually leads to the orientation distribution, and the reduction of the chromophore m direction with the reduced number in the X direction is statistically the average occurrence of 'the other _ spatial direction is gradually increased by % and The value of „2 is read out. The birefringence ηχ·% on the plane of the film can be almost completely

地再次被抹除。然而 4ir A 7 +上 M ，位在Z方向之色團的數目會隨著每次進一步的曝露或抹除過程而增加。實施例5 來自實施例3之聚合物係明粒的形式存在。其被施至玻璃基材並被加熱至18〇°c。在該溫度下，聚合物熔化。在玻璃基材上，設有例如聚乙烯對苯二酸(mylar)薄膜或玻璃纖維的間隔物及另一復蓋玻璃。利用玻璃-聚合物_玻璃三明治，製得20至1〇〇〇微米範圍之層。實施例6 藉實施例5的方法所製備之5〇〇微米厚聚合物薄膜，研究其在雷射攝影中之結構。一 SHG Nd: YAG雷射（532nm) 被用作記錄光源。在物體光束之光束路徑中，有一空間調變元件（Spatial Light Modulator),其產生 1024x1024 圖素之數據遮罩。參考光束對物體光束的強度比為7:1,落在 —32— 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再本頁)The ground was erased again. However, on 4ir A 7 + on M , the number of chromophores in the Z direction increases with each further exposure or erasing process. Example 5 The form of the polymer-based granules from Example 3 was present. It was applied to a glass substrate and heated to 18 ° C. At this temperature, the polymer melts. On the glass substrate, a spacer such as a polyethylene terephthalate film or a glass fiber and another cover glass are provided. A layer of 20 to 1 Å micron is produced using a glass-polymer _ glass sandwich. Example 6 A 5 Å thick polymer film prepared by the method of Example 5 was examined for its structure in laser photography. A SHG Nd: YAG laser (532 nm) was used as the recording source. In the beam path of the object beam, there is a Spatial Light Modulator that produces a data mask of 1024 x 1024 pixels. The intensity ratio of the reference beam to the object beam is 7:1, which falls on —32— This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the back note before this page)

、1T —線— % 經濟部智慧財產局員工消費合作社印製 1261153 A7 B7 五、發明説明（31) 樣品上之總電力密度為200mW/cm2。藉重合參考光束及物體光束記錄全像圖，其中兩光束係被偏極化而垂直於入射平面且以彼此相對40。的角度落在樣品上並曝露樣品30 秒；接著藉單獨曝露於參考光束（曝露時間10毫秒）予以讀出全像圖。藉改變參考光束0.25。，Bragg條件消失，而原先的全像圖不復見。在該新的角度構形下記錄新的全像圖。重覆此過程100次。在每次記錄過程之後，除了剛剛所記錄之全像圖之外，亦藉調整對應之參考角度，記錄所有先前記錄之全像圖。即使在100次記錄過程完成之後，在所有全像圖上的訊息仍被保留下來。 (請先閱讀背面之注意事項再本頁), 1T — Line — % Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1261153 A7 B7 V. Invention Description (31) The total power density on the sample is 200mW/cm2. The hologram is recorded by the coincident reference beam and the object beam, wherein the two beams are polarized perpendicular to the plane of incidence and opposite each other 40. The angle is placed on the sample and exposed to the sample for 30 seconds; the full image is then read by exposure to the reference beam alone (exposed time 10 ms). By changing the reference beam 0.25. The Bragg condition disappears, and the original hologram is not seen. A new hologram is recorded under this new angular configuration. Repeat this process 100 times. After each recording process, in addition to the hologram that has just been recorded, the hologram of all previous records is recorded by adjusting the corresponding reference angle. Even after 100 recordings are completed, the messages on all holograms are retained. (Please read the notes on the back and then on this page)

、1T 經濟部智慧財產局員工消費合作社印製 —33— 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）1T Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed —33— This paper scale applies to China National Standard (CNS) Α4 specification (210X297 mm)

Claims

經濟部智慧財產局員工消費合作社印製六、申請專利範圍專利申請案第89103298號 ROC Patent Appln. No. 89103298 修正後無劃線之申請專利範圍中文本-附件(一） Amended Claims in Chinese - Enel. (Ί) (民國94年1月彳|日送呈） (Submitted on January ^ (, 2005) 1. 一種雷射攝影術體積儲存媒體用之記錄用材料，其包含至少一種染料，當全像圖被記錄時，會改變它的空 10 間排列，及選擇之至少一種形狀-各向異性基群，其特徵在於其容許記錄超過50個全像圖在一個樣品位置上，其中該記錄用材料為聚合性或低聚合性的有機無定形材料，且該染料為選自式(I)之化合物： 15 20 25Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. VI. Patent Application No. 89103298. ROC Patent Appln. No. 89103298 The text of the patent application without amendments after the amendment - Annex (I) Amended Claims in Chinese - Enel (Ί) (January 1994, 彳日 | 日送) (Submitted on January ^ (, 2005) 1. A recording material for laser imaging volume storage media, containing at least one dye, when the hologram When recorded, it changes its spatial arrangement and selects at least one shape-anisotropic group, which is characterized in that it allows recording of more than 50 holograms at a sample position, wherein the recording material is a polymerizable or oligomerizable organic amorphous material, and the dye is a compound selected from the group consisting of formula (I): 15 20 25

X2 (I) 其中 R1代表氫、CrC6-烷基或X2 (I) wherein R1 represents hydrogen, CrC6-alkyl or

R2代表氫、Ci-C6-烧基、破基或， m及η各自互相獨立地代表0或1之整數； X1及X2各別代表-X^R3及-X2’R4 ; X1’及 X2’代表-Ο-或-(N-R5)-; R3及R4各自互相獨立地代表氫、CrC6-烷基、CrC6·烷基-(〇0)-、或苯基-(OOKVCV烧基，其中苯基環 -34 -R2 represents hydrogen, Ci-C6-alkyl, or a radical, and m and η each independently represent an integer of 0 or 1; X1 and X2 each represent -X^R3 and -X2'R4; X1' and X2' Representing -Ο- or -(N-R5)-; R3 and R4 each independently represent hydrogen, CrC6-alkyl, CrC6.alkyl-(〇0)-, or phenyl-(OOKVCV alkyl, wherein benzene Base ring -34 -

本紙張尺度適用中國國家標準(CNS)A4規格（210x297公釐） 89060B-接 1This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 89060B-connect 1

經濟部智慧財產局員工消費合作社印製可經Cl-CV^ CrCV_基氧基Ci々餘基，或 x R4代表氳或Crc0-烷基，及 R5代表氫或CrC6-烧基；該記錄用材料為-侧鍵聚合物，其中主鍵為聚丙稀酸 5 S旨或聚甲基丙稀酸s旨且其中式(I)染料係藉由一間隔物鍵結至該主鏈上讀_單體具有細）；該㈣具有一鍵最大吸收度低於或等於彻毫微米；該染料允許至少三個全像圖在-個樣品位置上被記錄，避免已被記錄在該記錄材料上之全像圖無法接受地被縮小、完 10 全地受損或完全被重寫；且該記錄材料具有1.0毫米至 5公分之被照射厚度。 2·根據申請專利範圍帛1項之記錄用材料，其特徵在於有至少一種染料，以一種改變其吸收行為的方式來改變其空間排列，特別是降低它對光化光的敏感度，較 15 佳為降低10%至100〇/〇，尤佳為由50%至100%，最佳為由90%至1〇〇%，於各情況中係基於記錄第一個全像圖之前的敏感度而言。 3·根據申請專利範圍第丨項之記錄用材料，其特徵在於有至少一種染料，以一種改變其吸收行為的方式來改 20 變其空間排列，特別是降低它對光化光的敏感度；尤其在於它會移動進入垂直於光化光的偏極方向，且其分子縱軸會位在光化光之偏極方向1〇〇至9〇〇，較佳為 50〇至90〇，尤佳為750至90〇，最佳為850至90〇的角度上。 -3 5 - 祕:x 2971\复)-—--The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, may print via Cl-CV^CrCV_yloxy Ci, or x R4 for hydrazine or Crc0-alkyl, and R5 for hydrogen or CrC6-alkyl; The material is a side bond polymer, wherein the primary bond is a polyacrylic acid 5 S or a polymethyl acrylate acid and wherein the dye of the formula (I) is bonded to the main chain by a spacer. Has a fineness; the (four) has a maximum absorption of one bond less than or equal to a nanometer; the dye allows at least three holograms to be recorded at a sample position, avoiding the hologram that has been recorded on the recording material The figure is unacceptably reduced, completely damaged or completely rewritten; and the recording material has an irradiated thickness of 1.0 mm to 5 cm. 2. A recording material according to the scope of the patent application, characterized in that at least one dye is used to change its spatial arrangement in a manner that changes its absorption behavior, in particular to reduce its sensitivity to actinic light. Better than 10% to 100〇/〇, especially from 50% to 100%, optimally from 90% to 1%, in each case based on the sensitivity before recording the first hologram In terms of. 3. A recording material according to the scope of the patent application, characterized in that at least one dye is modified in a manner that changes its absorption behavior, in particular to reduce its sensitivity to actinic light; In particular, it moves into a direction perpendicular to the polarization of the actinic light, and its molecular longitudinal axis is in the direction of the polarization of the actinic light from 1 〇〇 to 9 〇〇, preferably from 50 〇 to 90 〇, preferably It is 750 to 90 inches, preferably at an angle of 850 to 90 inches. -3 5 - Secret: x 2971\复)----

10 15 經濟部智慧財產局員工消費合作社印製 20 4. 根據申請專利範圍第！至3項中任—項之記錄用材料，其特徵在於其在39〇至800毫微米，較佳在_ 至65〇毫微米，尤佳在51〇至別毫微米，及最佳在 520至570毫微米之波長範圍中，具有光學密度^ 2，較佳低於或等於1，尤其是低於或等於〇 3。 5. 根據申請專利範圍第丨至3項中任—項之記錄用材料，其特徵在於具有> (U毫米，尤佳>〇 5毫米，更佳 > 1毫米，最佳不大於5公分之被照射厚度。 6·根據巾請專利範圍第丨至3項任巾_項之記錄用材料，其特徵在於其主要包含聚合性或低聚料。 7. 根據中請專利範圍第1至3項中彳壬―項之記錄用材料，其特徵在於記錄用材料之較佳係藉由光學密度係經調整’其中至少—種之染料的濃度予以調整。 8. 根射料利任—奴記錄用材枓，其特徵在於光學密度係藉由其中至少_種莫耳消光係數予以調整。 9. 根據f請專利範圍第丨至3項巾任—項之記錄用材料，其特徵在於其為-種側鏈聚合物及/或嵌段物及/或接枝聚合物。、 10. 根據申請專·圍第丨至3項巾任_項之記錄用材料，其特徵在於電磁輻射是在雷射波長範圍之光，較佳由390至800nm，尤佳由4〇〇至65〇nm，更佳由至570nm，最佳由520至57〇nm。 36 - 本紙張尺度適用中國國家標準(CNS)A4規格（210x297公复） X 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 六、申請專利範圍 11·根據申請專利範圍第1至3項中任一項之記錄用材料，其係供記錄（特別是角度相關的記錄）多於100 個，更佳多於500個，最佳多於1000個全像圖在儲存媒體上之同一位置上。 5 12.根據申請專利範圍第1至3項中任一項之記錄用材料’其係供言買出（特別是角度相關的讀出）全像圖。 13.—種雷射攝影術體積儲存媒體，其特徵在於包含根據申請專利範圍第1至10項之記錄用材料。 14·根據申請專利範圍第13項之雷射攝影術體積儲存媒 10 體，其特徵在於記錄用材料包含一或多種任何形式之無撐物體，較佳為無撐二度空間結構，尤佳為無撐薄膜，彼等被包含在一多層構造，較佳為至少一種基材層中。 15. —種製備根據申請專利範圍第13或14項之至少一項 15 之雷射攝影術體積儲存媒體的方法，其特徵在於其包含一步驟，其中操作係在根據傳統之射出成形法，於至多達30CTC，較佳至多達22(TC，尤佳至多達180°C 之範圍下實施。 16. —種具有式(I)之化學結合性染料之聚合物： 2010 15 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 20 4. According to the scope of patent application! The recording material of any one of the three items, characterized in that it is between 39 Å and 800 nm, preferably _ to 65 〇 nm, particularly preferably 51 〇 to other nanometers, and most preferably 520 至In the wavelength range of 570 nm, it has an optical density of 2, preferably less than or equal to 1, especially less than or equal to 〇3. 5. The recording material according to any one of the claims of the third to third aspects of the patent application is characterized by > (U mm, especially good > 〇 5 mm, more preferably > 1 mm, and most preferably not more than 5) The thickness of the centimeters is irradiated. 6. The material for recording according to the scope of the patents of the third to third items of the towel is characterized in that it mainly contains a polymerizable or oligomeric material. The material for recording of the three items is characterized in that the material for recording is preferably adjusted by adjusting the concentration of the dye of at least one of the optical density systems. Recording material 枓, characterized in that the optical density is adjusted by at least one of the moir extinction coefficients. 9. According to the patent scope of the third to third item, the recording material is characterized in that it is - A side chain polymer and/or a block and/or a graft polymer. 10. A recording material according to the application of the first to third item, characterized in that the electromagnetic radiation is in the laser. Light in the wavelength range, preferably from 390 to 800 nm, particularly preferably from 4 〇 to 65 〇 nm More preferably from 570nm, best from 520 to 57〇nm. 36 - This paper scale applies to China National Standard (CNS) A4 specification (210x297). X Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A8 B8 C8 D8 Sixth, the scope of application for patents 11. According to the application of any of the scope of the patent range of items 1 to 3, which is for recording (especially angle-related records) more than 100, more preferably more than 500, the most Preferably, more than 1000 holograms are in the same position on the storage medium. 5 12. The recording material according to any one of claims 1 to 3 of the patent application 'is purchased for the purpose (especially angle-related) Readout) hologram. 13. A laser imaging volume storage medium characterized by containing recording materials according to items 1 to 10 of the patent application scope. 14. Laser photography according to claim 13 The volume storage medium 10 is characterized in that the recording material comprises one or more unsupported objects of any form, preferably a non-supported space structure, particularly preferably an unsupported film, which is contained in a multilayer structure. , preferably at least 15. A method of preparing a laser photographic volume storage medium according to at least one of clauses 13 or 14 of the patent application, characterized in that it comprises a step in which the operation is based on a conventional The injection molding method is carried out up to 30 CTC, preferably up to 22 (TC, particularly preferably up to 180 ° C. 16. Polymer of a chemically bound dye having the formula (I): 20

本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐）This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

經濟部智慧財產局員工消費合作社印製六、申請專利範圍其中 R1代表氳、CrC6-烷基、氰基或 yO ]ϊ° ； 5 R2代表氫、CrC6-烷基、氰基、硝基或 / m及η各自互相獨立地代表0或1之整數； X1及X2各別代表-Χ1’：^3及-X2’R4 ; X1’及 X2’代表_0-或-(N_R5)-; R3及R各自互相獨立地代表氣、Ci_C6-烧基、C1-C6-烧 10 基-(C=0)-、或苯基-Ci_C6_烧基’其中苯基環可經Ci_ c6-烷基crc6-烯醯基氧基crc6-烷氧基，或 x2’r4代表氫、曱基、氰基或硝基，及 R5代表氫或Crc6-烷基。 17.根據申請專利範圍第16項之聚合物，其特徵在於其包 15 含至少一種式(II)之單體： RPrinted by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives. VI. The scope of application for patents, where R1 stands for 氲, CrC6-alkyl, cyano or yO]ϊ; 5 R2 stands for hydrogen, CrC6-alkyl, cyano, nitro or / m and η each independently represent an integer of 0 or 1; X1 and X2 each represent -Χ1':^3 and -X2'R4; X1' and X2' represent _0- or -(N_R5)-; R3 and R each independently represents a gas, a Ci_C6-alkyl group, a C1-C6-alkyl group 10-(C=0)-, or a phenyl-Ci_C6_alkyl group, wherein the phenyl ring may be via a Ci_c6-alkyl crc6- An ethenyloxy crc6-alkoxy group, or x2'r4 represents hydrogen, a fluorenyl group, a cyano group or a nitro group, and R5 represents hydrogen or a Crc6-alkyl group. 17. Polymer according to item 16 of the patent application, characterized in that it comprises at least one monomer of the formula (II): R

X2 (II) 20 其中 R代表氫或甲基，及其他基團為如上述所定義。 18.根據申請專利範圍第16或17項之聚合物，其特徵在 -38 -X2 (II) 20 wherein R represents hydrogen or methyl, and the other groups are as defined above. 18. A polymer according to claim 16 or 17, which is characterized by -38 -

本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐）六、申請專利範圍於其包含至少一種式(Ila)及/或(lib)之單體。 19. 一種製備根據申請專利範圍第1至10項中任一項的記錄用材料的方法，其特徵在於其中至少一種單體係在無其他溶劑下被聚合，聚合反應較佳為自由基聚合， 5 且尤佳係藉自由基引發劑及/或UV光及/或熱予以引發者。 20. —種製備根據申請專利範圍第16至18項中任一項之聚合物的方法，其特徵在於其中至少一種單體係在無其他溶劑下被聚合，聚合反應較佳為自由基聚合，且 10 尤佳係藉自由基引發劑及/或UV光及/或熱予以引發者0 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準(CNS)A4規格（210x297公釐）This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). VI. The patent application scope includes at least one monomer of the formula (Ila) and/or (lib). A method for producing a recording material according to any one of claims 1 to 10, wherein at least one of the single systems is polymerized in the absence of another solvent, and the polymerization is preferably a radical polymerization. 5 and especially preferred by the use of free radical initiators and / or UV light and / or heat. A method for producing a polymer according to any one of claims 16 to 18, wherein at least one of the single systems is polymerized in the absence of other solvent, and the polymerization is preferably a radical polymerization. And 10 is better to use the free radical initiator and / or UV light and / or heat to trigger the 0 Ministry of Economic Affairs Intellectual Property Bureau employees consumer cooperatives printed this paper scale applies China National Standard (CNS) A4 specifications (210x297 mm)