TWI220902B - A composition comprising a solid organic support material to which either directly or via a bridging group, the process for preparation thereof and application thereof - Google Patents

Abstract

Composition comprising a solid organic support material to which either directly or via a bridging group, are covalently linked fluorescent host chromophores and fluorescent guest chromophores, wherein the fluorescence emission spectrum of the host chromophore overlaps with the absorption spectrum of the guest chromophore, wherein the host chromophore is selected from the group consisting of benzo[4,5]imidazo[2,1-a]isoindol-11-ones.

Description

1220902 A7 ____B7__ 5. Description of the invention () (Please read the precautions on the back before filling out this page) The present invention relates to a composition containing a solid organic branch-like material directly or via a bridge base and a fluorescent body. The chromophore and the fluorophore chromophore are covalently connected, where the fluorescence emission spectrum of the host chromophore and the chromophore of the accessory! The absorption spectrum of the I group overlaps, and the remainder of the chromophore of the host is selected from the group consisting of benzo 4,5] imidazo [2,11 -a] isoazindene (is 〇ind ο 1)-11 -ones c Even more, the present invention relates to a method for preparing the composition, which has鼷 Used as a fluorescent material and related to the novel functionalized benzo [4,5] oxazo [2, bua] isoazindene-1bucones. In EP-A-0 4 5 6 6 G9, a 1,2,3,4-tetrachlorobenzo [4,5] imidazo [2, bua] isoazindene- i Method of buconone and its derivatives. These compounds are pigments that exhibit solid fluorescence and have improved outdoor durability. It is also mentioned therein that a combination of 95% 1,2,3,4-tetrachlorobenzo [4,5] imidazo [2, bua] isoazepine-1bu and 5% indanthrene blue Produces green fluorescent pigments. This system is a pigment compound, in which a new color is generated only by combining the two component colors. Therefore, the creation of this color is not due to the complex formation, molecular level, and energy transfer process caused by the close interaction between the components of the mixture. F · W · H a I1 ris and his research colleagues in ACSS y hip · Ser. 1 3 2, 3 9 (1 9 8 ΰ) 逑 and 1 3 2, 3, 4 -tetraphenylbenzo [4 , 5] oxazolo [2,1 -a] isoazepin-11-ones as a molding material, which is used to study the potential of phenylated polyoxazolopyrrolone for aviation applications use. However, its fluorescent properties are not mentioned. For example, in the field of electrical cold light, Tang and his research colleagues have demonstrated that this paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1220902

V. Explanation of the invention () Sensitizing cold light to produce extremely bright electric cold light devices (j · appl. Ρ η YS. 65 (9) ^ 3610 (1989)) 〇 Also 'in the field of biological diagnosis' Sensitized cold light is perfectly established to be used as a universal and highly sensitive tool to detect specific target biomolecules, such as nucleic acids or antigens, such as ANAL by Vener and his research colleagues. BIO-t: Η £ Μ. 1 b 8 (1 9 9 1) 3 0 8- 3 1 1 °

Siobodyanik and colleagues (j. LUMINESCENCE 29, 309 (1984)) proposed energy transfer between energy donors and energy receptors covalently connected to the same polymer.

Kamaehi and his research colleagues (Journal of Physical Chemistry (J. PHYS, CHEM. 96 (4), 190 (19 2))) demonstrated and discussed the energy transfer between the two inclined units of the copolymer system.

Brink ley and colleagues in his research revealed the use of sensitized cold-light polymeric materials to detect biomolecules, such as DNA and RNA, and their use in flow cytometry and analytical microscopy (W0 9 3/2 3 4 9 2). However, only the polyazofluorene dye (p0iyazaindaeene) dyes and coumarin materials have been explicitly disclosed as fluorescent materials for the preparation of fluorescent polymer micro-a-'aft 'only useful fluorescent polymerization The possibility that sexual beads are used for biological diagnosis' covalently attaching the fluorescent part to the polymer host 'is mentioned, and even more' it suggests that this method is complicated and unnecessary for such biological applications. Therefore, 'no specific examples of polymer cells containing polymer systems in which the main and auxiliary bodies are covalently linked to the polymer are revealed, and there is no suggestion for useful main / auxiliary materials outside specific biological applications. This paper size applies to China National Standard (CNS) A4 specifications (21〇X 297 public love) (Please read the precautions on the back before filling this page) — · ϋ ϋ ϋ 1 · ί ϋ n) -OJβ nnn ϋ ϋ ϋ ϋ I Λ 1220902 A7 __B7___ V. Description of the invention () (Please read the notes on the back before filling this page) Therefore, the purpose of the present invention is to provide a composition without the above disadvantages, which includes a solid hungry support material directly Or it is covalently connected via a bridge bond based fluorescent host chromophore and a fluorescent accessory chromophore, in which the fluorescence emission spectrum of the primary chromophore overlaps with the absorption spectrum of the secondary chromophore, and the main chromophore in it The group is selected from the group consisting of benzo [4,5] imidazo [2, ll-a] isoazindene-n-ones. In particular, the composition provides a) strong solid fluorescent light, preferably in which the emission wavelength is in the visible region of the electromagnetic spectrum. B) high ratios of main and auxiliary molecules can be incorporated as part of the polymer. Maintain solid-state fluorescence properties (and negligible concentration decrease), c: · Use Li V and wavelengths in the visible region to excite the material 'd :) can achieve excellent light stability, e) via subsidiary molecules The choice (color adjustment) can achieve a wide range of emission wavelengths, f) can achieve high thermal stability, g) can generate soluble and insoluble fluorescent compositions' i) the migration essence of fluorescent host and accessory molecules The above materials are easy to be prepared, and a single bottle reaction is possible. Based on this, a composition was found, which contains a solid organic support material directly or via a bridge bond group with the fluorescent host chromophore and The covalent connection of the side chromophore of the fluorescent accessory body, in which the fluorescence emission spectrum of the main chromophore overlaps with the absorption spectrum of the auxiliary chromophore, and the main chromophore is selected from the group consisting of fluorinated f 4 'D j _Zolo [2, il-a] isoazindene_1B_Class ° -5-Paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 1220902 A7 ________ B7_ V. Description of the invention () «re has also been issued a method for preparing the composition, ® m @ _ 光 材料 · Applications, and novel functionalized benzo [4,5] _sialo U, i-a] isoazindene ~ 11 — _ class stellant Tai Mingzhi. The first ~ specific embodiment relates to a composition, It includes an @ state, an organic support material, or a covalent connection of the fluorescent host chromophore and the fluorescent side chromophore directly or via a bridge bond group, in which the fluorescent II of the host chromophore emits light and the secondary side hair color The absorption spectrum of the group is predominantly heavy, and its main hair color 11 is selected to contain benzo [4,5] B mizolo [2,11_a] isoazindene-1b_. In the scope of the present invention, the host molecule means a fluorescent molecule, preferably selected from the group of solid pretty light organic compounds, such as dyes, pigments and their derivatives. »^ BS HU v and / or the appropriate area of sunlight At the emission wavelength, 'them @ 3 and the energy harvested' This energy system is preferably a M resonance method that transfers the full ... accessory body chromophore almost quantitatively. The host monomer or functionalized host molecule used to prepare the composition of the present invention is preferably sufficiently dissolved in the reaction medium, so that it can simply be ribbed to participate in the fluorescent polymer formation reaction itself. The reaction medium may be a comonomer or a suitable solvent. It is also possible to use a less soluble host monomer II ', however at this time special equipment may be required to continuously dissolve the monomer or functionalized molecule into the reaction medium. The solubility may be influenced by the choice of the core structure ' substituents, functional groups and / or the space or length of the functional groups. In the scope of the present invention, the chromophore of the sub-body means a fluorescent molecule, which has an absorption region that partially overlaps with the emission area of an individual subject in the system-'wherein, these sub-chromophores receive from The energy of the main molecule, and-6-^ The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)

1220902 A7 __ B7__ V. Description of the invention () (Please read the precautions on the back before filling this page). &Amp; The energy of emission transfer becomes radiation and its wavelength is the same as that of the same subsidiary in molecular form dissolved in solvent The emission wavelength of the molecule. A further requirement is that the concentrations of the subsidiary molecules in the composition must not be combined with each other to form a localized subsidiary domain, but in fact exist as separate entities in the polymer as a whole, as if they were dissolved in molecular form. The subsidiary monomer or functionalized subsidiary molecule used for preparing the composition of the present invention is preferably sufficiently dissolved in the reaction medium, so that it can simply be ribbed to participate in the fluorescent polymer formation reaction itself. The reaction medium may be a comonomer or a suitable solvent. A less soluble auxiliary monomer may also be used. However, special equipment may be required at this time to continuously dissolve the monomer or functionalized molecule into the reaction medium. Inside. Solubility may be affected by the choice of core structure, substituents, functional groups and / or space or length of functional groups. According to the above description, a chromophore may have the ability to function as a main or auxiliary compound in a separate system, and M can provide all the requirements. Compared with the solid-state emission intensity of a polymer containing a host unit but lacking a subsidiary unit, or a polymer containing a host unit but lacking a subsidiary unit, the solid fluorescent light emitted by the fluorescent composition of the present invention has greatly enhanced emission intensity. . The "strength factor" as used herein is defined as the comparison of the peak emission intensity of a solid polymer containing the fluorescent part of the main body and the auxiliary body with that of the same polymer that does not contain the fluorescent auxiliary body part. Reduced factors (such as those often shown in the case). As long as the wavelength of the excitatory radiation is the same, this ratio-Ί-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A7 ______B7__ 5. The description of the invention () can be regarded as true. When compared with the same material without auxiliary body composition, the emission wavelength of the carcass / auxiliary material is generated at a longer wavelength (lower energy): the enhancement factor of the present invention is generally positive and preferably should be at least 丨. 3, more preferably at least 2 denier, most preferably at least 2 (). Furthermore, in the context of the present invention, the significance of the overlap of the absorption spectrum of the secondary chromophore and the fluorescence emission spectrum of the host chromophore is clear to those skilled in the art. However, to help others understand, overlap can be defined as "spectral overlap" by the following integral f + 〇〇S = Jo / f (v) / a (v) dv where / F (v) is normalized, so j / 00 / p (v) dv is equal to the fluorescence quantum yield of the host, where v is the wave number, f is the main fluorescence spectrum measured by κ quantum, and / A is the spectral distribution of the Mohr extinction coefficient of the subsidiary. The spectral superposition of light and cold light enhancement is usually greater than 10, preferably greater than 1 ϋ 0, and more preferably greater than 5 0 0. The upper limit does not make any sense because the amount of "overlap" does not have a maximum value (the larger the value, the better). In the context of the present invention, the terms "uniform" and "uniformly" mean to the matrix, that is, the polymer, the components (ie particles) in the matrix are evenly, uniformly or homogeneously distributed or dispersed in the matrix (the polymer matrix ), And in the ideal case, are preferably substantially equal to each other. According to observations, the coexistence of bright and dark fluorescent areas and the emission color areas that are closer to the subject's emission color than those of the subsidiary body is reduced, and a more even or uniform distribution is better fluorescence properties. ft 舛, homogeneous or homogeneous or evenly distributed is preferred, as the usual chance of aggregation is reduced. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----------- installation -------- order --------- ( Please read the precautions on the back before filling this page) 1220902 1 A7 ____ B7 V. Description of the invention () In the context of the present invention, the word "dissolved" means that the molecule exists in the tested environment or the matrix is free and separated. The chick entity 'is preferably in this way that it is detached from any interaction between molecules of the same kind, and also completely encapsulated by the I matrix molecule. Usually the matrix can be a liquid organic solvent, or a solid material such as a polymer or other fluorescent material (host), which has a different chemical composition or particles, in which the polymer is dissolved. The concentration limit of molecules in the dissolved state is usually extremely extreme. The ground depends on the merging nature between the molecules and the matrix medium 'and / or the intrinsic cohesion between the molecules of the accessory body. Based on this, it is not possible to define a general range for the better concentration, and therefore, it is usually necessary to deal with errors based on trials, for example, by some simple experiments. The emission light of the fluorescent polymer of the present invention preferably has a maximum emission range from about 400 to about 80 (1 nanometer, more preferably from about 42G to about 780 nanometers, particularly preferably from about 4 2 (3 to Approximately 750 nanometers. The support material may include, for example, a linear or crosslinked polymer having a main body and a subsidiary body overhang, or a surface-modified polymer structure containing a main body and a subsidiary body structure and depending on the surface. In principle, The composition of the present invention may have two different complete forms, | 卩 (a) consists essentially of a polymer having a host and a subsidiary molecule directly or via a bridging group covalently connected to the polymer main bond, or BB) by The main and auxiliary molecules are essentially composed directly or via bridges based on the covalent connection of the surface of the organic support material. The following description first relates to the complete form (B), compared to the complete form (Α), because the main and auxiliary The body molecules are not located inside the organic particles, which has the further advantage of reducing the consumption of main and auxiliary molecules. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first matter Complete this page)

[子 20902 A7 B7 V. Description of the invention (Complete or permeability, when a good support material is needed, sulfur materials can be equivalent. Synthetic with official vitamins, or chemical compounds are known as polymers.) Acrylic alkene alkyl acrylate or propylene propylene in full form. Thermoplastics are electrically supported on the surface support material (B). The organic support material is preferably a glass machine support material. Cross-linked plastic or selective functional groups are used for plastics. For example, the functional group is preferably alcohol one, carboxyl group, and S03 group is starch or C i-which can be a polymer energy group and vinyl alcohol can be used. Polymer; Folic acid, which is a copolymer of methyl propylene, propylene substituted for acetamide, and the surface modification can also be a carcass. Polyamino C 8 醯 acrylate acid And / or the hydrocarbon is a propylene-based polymer or a synthetic polymer emulsion polymer, a natural polymer of glucose, which can be esterified in a known manner to produce alcohols and copolymers of acrylic acid, poly and / or butyl butadiene; Juhe The co-acid amine of cis-butene or cis-butene dimer, the methyl material can be 0. Suitable glue, the glass is reactively connected to the main body, if it has an official system selected from the group consisting of clathrate or isofluoric acid. And lattice, examples are opaque support, ceramic gas and amine-containing ester groups in the secondary energy group. It is functional by plasma which contains glycans, C 4 alkanes, translucent materials are heat and minerals, etc. Branched molecules. More plastic.-At least one of the hydroxyl organic support treatment, or sex of the carcass, for example, is a fluorenyl part of the ether via C 1. Officially prepared. Substituted or via acrylic acid oxalic acid hydroxyalkane dicarboxylic acid Some examples of polymerized substituted olefins and polycis and unsynyl propenyl alkyl alkyl polyacrylamides or homosynthetic polymers of hydroxy polymers; copolymers are copolymerized monobutenedioic acid and substituted or With acid esters, polyhydroxy esters, and methyl esters with non-fermented amines and polymethylates with unsubstituted: 0 ^ 1 ϋ n I ϋ. ^ 1 n ϋ I · fli nn an nn I ϋ ϋ ϋ III ml I (Please read the notes on the back before filling this page) -10 sheets Zhang scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1220902! A7 ______B7___ 5. Description of the invention () or copolymer of substituted olefin as comonomer; polyamino alkyl acrylate, monomethyl Acrylic acid_ and maleic acid esters and amino alkyl acrylates, monomethacrylates, maleic acid esters or two or three of the above are copolymerized with unsubstituted or substituted olefins Copolymers of monomers; polyhydroxyalkyl! Mono- or polyaminoalkyl vinyl alcohol and hydroxyalkyl vinyl ether, amino alkyl ethylene | _ or both uncoated or substituted olefins are comonomer copolymers Hydroxylated polybutadiene and butadiene, isoprene, chloroprene, or two or three of the above obtained from butadiene, isoprene, or chloroprene with unsubstituted or Copolymers with substituted olefins as comonomers; hydroxy mono- or amine polystyrene, chloroshenyl polystyrene, and polystyrene sulfonic acid and hydroxystyrene, amine styrene, chloromethylstyrene, polybenzene Ethylene sulfonic acid, or two or three of the above, copolymerized with unsubstituted or substituted olefins The body of the copolymer; and polyglycidyl ethers of hydroxyalkyl amine or alkylated polyglycidyl ether; available from polyesters, and hydroxyl-containing monomers, polyamide and the polyurethane. The support material may also be composed of a thermosetting resin, such as epoxy resin, melamine-formaldehyde resin, and phenol resin. Suitable olefin comonomers are, for example, ethylene, propylene, butene, pentene, octene, vinyl chloride, dichloroethylene, styrene and propylene. The support material may also be composed of cross-linked polymers, such as functionalized culverts, optionally non-functionalized olefin monomers, and diene monomers such as butadiene, divinylbenzene, or diol-diacrylate Or a diol-dimethacrylate polymer, the olefin may be selected from the functional groups containing olefins on the top. Further suitable vinyl polymers are polyvinylpyrrolidone, polyvinylpyrrolidone and polyvinylpyridine, and vinylpyrrolidylvinylazole. -11- This paper is in accordance with Chinese national standards (CNS ) A4 size (210 X 297 mm) ------------ install -------- order --------- (Please read the precautions on the back first (Fill in this page) 1220902 A7 _B7_ V. Description of the invention () Copolymer of vinyl sulfide, vinyl pyridine or two or three of the above and unsubstituted or substituted olefin as comonomer. The polymer may be a block polymer, an alternating polymer (alternating pol yiuers), a graft polymer or a random polymer. In a concrete example and a further object of the present invention, the composition of the present invention is composed of an organic material in the form of particles, whereby the main and auxiliary molecules are covalently connected to the surface of such particles directly or via a bridge bond group. . The particles may have an average diameter of from 50 mm to 1000 μm, preferably from 0.1 to 500 μm, more preferably from 1 to 100 μm, and particularly preferably from 5 to 50 μm. The particles may be circular or irregular in shape according to the manufacturing method, and may be dense or porous. The size of the particles is the same as their final application requirements. The organic composition may be, for example, a shaped article obtained from a polymer and the like. The size and shape of the item is arbitrary and depends on the end use. These shaped articles are further preferred embodiments of the present invention. The surface of the supporting material used for the shaped article may be smooth or porous. Such shaped articles include any composite structure. When the weight average molecular weight of the non-crosslinked polymer of the present invention is determined by, for example, M gel permeation color history analysis, using polystyrene as a calibration standard, the usual range is from 103 to 2 X 106, preferably 104 to II) 6, more preferably 2 X 1 ί) 4 to 1 0 6, and most preferably 4 X 1 04 to 5 X 1 0 5 gm ο 1-0 The number of host chromophores on the surface relative to the total composition The material is preferably from 0. 0 0 G 0 I to 10, more preferably 0. 0 0 1 to 5, more preferably 0. 0 1 to 3, and -12. This paper size applies Chinese national standards ( CNS) A4 size (210 X 297 mm) (Please read the notes on the back before filling this page)

Γ n n n ^ ^ 0 ϋ βϋ ϋ n ϋ i ^ i 1220902 A7 __B7__ 5. Description of the invention () The best is 0. 0 ίΠ to 2 weight percent. The number of body chromophores is preferably from 0.0000 1 to 5 weight percent with respect to the total composition, more preferably 0. ϋ 0 0 0 1 to 3, and most preferably 0 · 0 0 0 0 1 to 2 weight percent. The weight ratio of the main body to the auxiliary body ranges from 50:50 to 9 9 9 5: 5, preferably 6: 4 to 9 9 9: 1, and more preferably 70: 3 G to 9 9 9: 1. The main and auxiliary molecules are advantageously covalently linked to the support material via a bridge group. The bridging group may contain 1 to 60 atoms, preferably 1 to 3 G atoms, and particularly preferably 1 to 20 atoms, and is selected from the group consisting of C, 0, S, and N. Particularly preferred bridging groups are hydrocarbon residues which can be inserted through one or more heteroatoms selected from the group consisting of 0, S, N or C (0) and / or one of the fluorene atoms is final, and It preferably contains from 1 to 40 atoms in total, preferably from 2 to 30 atoms and particularly preferably from 3 to 20 atoms. The host and accessory molecules are covalently linked to the support material directly or via a bridge group. The surface can be represented by Formula I and ίa,-X t-(R t) r-(X 2) s-R 3-host (I ), -X!-(R i) x- (X2) y-R3-auxiliary body (la), where X t and X 2 respectively mean direct 鐽, or X ί and X 2 respectively mean -0 one, , -NRz-,-(() 0) +, -0_C (G)-,-0-C (0) -0 ...-SUj: -0-,-0-S 0 2 one,-0-S 0 z -0-,-NR2 -C (0)-, -C (()), z ..., -c (〇) +, 0-C (0)-NR2-, -NR2-c (〇)-, -nr2 -sο2 I, ~ s〇2 -NR2-, -S〇2 A paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling in this Page) -------- Order ---------

1220902 A7 _B7_ V. Description of the invention () 0-,-0-S 0 2 ~ NR 2-or -NR 2-S 0 2 ~ NR 2 _, each R means a divalent bridge bond group, (please Read the notes on the back before filling in this page) The host is a monovalent host molecule, and the accessory is an m-valent accessory molecule, R 2 is Η, C ί a C 1 2 alkyl, C 5 — or C e cycloalkyl ——— Ce cycloalkylmethyl or monoethyl, phenyl, benzyl or 1-phenyl-2-ethyl, R3 is a direct bond, C! —C! 8 alkylene, C5—or C6 cycloalkylene, C 6-C t 〇 arylene or C 7-C i 2 aralkylene

Γ means the number 0 or 1 and S means the number 0 or 1, except that if r is 0, then S is 0, and X means the number 0 or 1 and y means the number 0 or 1, except if X is 0. Except y is 0. In the context of the present invention, the alkyl group of R 2 is preferably from 1 to 6 and particularly preferably] to 4 carbon atoms. Some examples are methyl, ethyl, n- or iso-propyl, butyl, pentyl, hexyl and heptyl. In the present invention, a cycloalkyl group of R 2 is preferably a cyclohexyl group, and a cycloalkylmethyl group, and a cyclohexylφ group is more preferable. In a preferred embodiment, R 2 means fluorene or C .. C 4 alkyl. The divalent bridge bond group is preferably a hydrocarbon residue, which preferably contains 1 to 30, more preferably 2 to 20, most preferably 3 to 20, and particularly preferably 3 to 18 carbon atoms. Substituted or substituted with one or more Ci-C4 alkyl, Ci-C4 alkoxy or = 0. Hydrocarbon residues can also be selected from the package one or more times.-1 4-This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1220902 A7 _B7__ 5. Description of the invention () Contains-(!- The insertion of heteroatoms of -S- and -NR2- makes R 2 is preferably fluorene or C i -C 4 alkyl. The divalent bridge fluorenyl may be linear or branched ci-C 2 0—, preferably C 2-C i 2 alkylene. Some examples are methylene, ethylene, 1, 2- or 1, 3-propylene, 1, 2-, 1, 3- or 1, 4- Butylene, pentylene, hexylene, heptylene, octylene, dodecylidene, tetradecylidene, hexadecylidene, and octadecylidene. The divalent bridging group may have Polyoxyalkylenes having 2 to 12, preferably 2 to 6, and most preferably 2 to 4 alkylene oxide units and having 2 to 4, preferably 2 or 3 carbon atoms in the alkylene moiety Particularly preferred are polyethylene oxide and polypropylene oxide having 2 to 6 alkylene oxide units. The divalent bridging group may be C 5 — C ί 2 —, preferably CS — C 8 and most preferably C 5 —Or Ce cycloalkylene, such as cyclopentylene, cyclohexylene, cyclooctyl, or cyclotenyl The divalent bridging group is preferably CS — C ί 2 —, preferably c S — C 8 — and more preferably c 5 — or C 6 cycloalkyl — C; — C t 2 alkylene and The most preferred is Cς—or c 6 cycloalkyl—ci—C 4 alkylene. In some cases, -f is cyclopentyl—C η Η 2 η — and cyclohexyl—C η Η 2 η-, Where η means the number @ 1 1 4. Particularly preferred is a cyclohexyl-CH2-. The divalent bridging group may be-Ci 2-, preferably C5 -C3-and more preferably C 5-or C β cycloalkane Radicals (C 1 -C i 2 alkylene) z 1 and most preferably 1 -C 4 alkylene) 2. Some examples are a cyclopentyl- (C η Η 2 η-) 2 and a cyclohexyl- (C η Η 2 η-) 2, of which π means -15-. This paper standard applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) ------------ Installation -------- Order --- (Please read the notes on the back before filling this page) 1220902 A7 _B7____ V. Invention Explanation () is the number 1 to 4. Particularly preferred is -CH2 ~ cyclohexyl_CH2-. The divalent bridge fluorenyl may be C, 5—C! 4arylene and preferably C $ ~ Ci. Arylene, for example naphthylene or more preferably is phenylene. The divalent bridge base may be C 7-C 2. Preferably, C 7 -C i 2 aralkylene ° is more preferably arylene-CnHz η-, where arylene means naphthylene and phenylene, and η means the number 1 to 4. Examples are benzyl and phenethyl. The divalent bridging group may be an aromatic hydrocarbon group (CiiHz η-) 2-, wherein the aromatic hydrocarbon group is preferably a naphthylene group and more preferably a phenylene group, and η means a number of 1 to 4. Examples are phenylene dimethyl and phenylene (CH2 CHz) 2-. The alkylene group of R 3 is preferably 1 to 12 and more preferably 1 to 6 carbon atoms. Particularly preferred examples are methylene, ethylene, 1,2- or 1,3-propylene, and 1,2-, 1,3- or 1,4-butylene. When R 3 is an arylene group, it is preferably a phenyl group, and when R 3 is an aralkylene group, a benzyl group is preferable. In a preferred embodiment, the bridge group may be selected from the formula I b -C (0)-0-R, -〇- C (0)-(r,)-(lb) where R ′ is C 2 to C 2 0, preferably C 2 to c! 2., and most preferably c 2 to (: 6 alkylene, phenylene, benzyl, or having preferably 2 to 6, And more preferably an oligoalkylene oxide of 2 to 4 alkylene oxide and / or propylene oxide units, and R '〃 means direct fluorene, ci to C! 2 alkylene fluorene, phenylene or phenylene φ group. Host molecule Preferably, it is selected from those having an absorption wavelength in the range of 300 to 700 nm, and a fluorescence in the wavelength range of 4 G ϋ to 7 8 {) nm. The accessory molecules are preferably selected from those having an absorption wavelength in the range of 380 to 780 millimeters. 16-This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) {Please read the note on the back first? Matters refill this page}

n ϋ n n I n n n n I 1220902 A7 _B7_ 5. Description of the invention () Huanmi and fluorescence in the wavelength range of 400 to 8 ϋϋ nanometers. Preferably, the accessory molecule has a fluorescent quantum yield of 0.1 to 1.0, more preferably (K3 to 1.0, more preferably ΰ. 5 to 1. ΰ, and most preferably, 0.7 to] .. 0. The more preferable is The solubility of the main and auxiliary monomer structures is such that they can be simply ribbed to their own solution polymerization or can be easily dissolved in the copolymerized body of the overall polymerization mixture. The solvents that can be used in solution polymerization are Those skilled in the art are familiar with. The accessory chromophores used in the complete form (B) are preferably monovalent. These secondary chromophores can be selected from a wide range of chromophores as long as they have fluorescent The emission wavelengths of light and emission wavelengths of the main component at least partially overlap. The adjuvant in Formula Ia is preferably a monovalent residue and is selected from the group consisting of quinifridine _, jb, di_ | Slightly, fluorescein, rhodamine, coumarin, glutamate, hydrazone, oxazine, oxazole, cyanine, cyanine, porphyrine, styryl, more preferably, the auxiliary in formula I a Monovalent residues and are selected from the group consisting of 嗤 acridine_, diketone, pyrrolidine, rhodamine, and north. In the best case, the selected accessory may be unsubstituted Or substituted with a halogen such as F, C ί, B r,]:, -CN, -N 0 2, C i to C | 8 alkyl, C 3 to C! Z cycloalkyl, C 6 to C i 8 Aryl, C 5 to C t 7 heteroaryl, C 3 1 C ^ 2 cycloalkyl, C 6 to C i 8 aralkyl, C 5 to C f 7 heteroaralkyl, C 至 to C i 8 Alkoxy, C 3 to Ci 2 cycloalkoxy, 8aryloxy, C5 to Ci 7 heteroaryloxy, c 3 to Ci 2 cycloalkylalkoxy, C 6 to ci 8 aralkyloxy Base-17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) — * i ···· i · — nn ϋ n ov fl ϋ i_s nnnn ϋ I · 1220902 A7 _B7_ V. Description of the invention ()

, C S to Ci 7 aralkyloxy, C! To C, 8 alkylthio, C 3 to C! 2 cycloalkylthio, C 1 to C 1 8 arylthio, C 5 To CI 7 heteroarylthio, C 3 to C 1 2 cycloalkylalkylthio, C 6 to C, 8 aralkyl telluryl, C 5 to C i 7 heteroarylalkylthio, C 1 To Cl 8 alkyl-SO- or -S02, C3 to C! 2 cycloalkyl-SO- or -302, C 6 to C! 8 aryl-S0- or -S02, C 5 to C! 7 Heteroaryl-S0- or -S02, C 3 to C! 2 cycloalkylalkyl_so- or -so 2, C β to C ί 8 arylfluorenyl-s ()-or -S 0 2, C B to C 1 7 heteroaralkyl-S0- or -S02, a secondary amine group having 2 to 30 carbon atoms, and an alkoxyalkyl group having 2 to 2 (i carbon atoms. Cycloaliphatic and Aromatic residues < substituents) may also be substituted, for example, substituted M_ elements such as F, C1 or ΒΓ, -CS, -N02, C! To Ci8 fluorenyl, c3 to ci2 ring Alkyl, C 6 to C 8 aryl, C 3 to C! 2 cycloalkyl, C 6 to 〇 1 8 aralkyl, C? To Ci 7 heteroaralkyl, Ci to C! 8 alkoxy Group, C3 to Ci 2 cycloalkoxy f C 6 to C; A aryloxy. Alkyl substituents may be linear or branched and may be substituted with halogen SOF or C 丨. Examples of substituents are F, Ci, Br, methyl, ethyl, propyl, jyl, ri, methyliso, ethoxy, propoxy, j.oxy, doxy, m Methylfluorenyl, ethylthio, methyl- or ethyl-so-, methyl- or ethyl-S02-, phenyl, benzyl, toluenyl, dimethyl cage, phenylene Phenyl, dimethylbenzyl, chlorophenyl, dichlorophenyl, methoxy3: yl, bisphenyloxyphenyl, methoxybenzyl, dimethoxybenzyl-18-benzyl Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) ϋ ϋ ϋ n a ^ OJ n ϋ ϋ ϋ ϋ ϋ 12-1220902 Α7 Β7 5 , Description of the invention ()

^^ • 09 ^ 010

and

And rhodamine residues, including salts with = N + R〇 ^ t R〇i 2 group, where R 〇6 is a 鐽, and R Cl 7 and 〇8 are or H or Substituents, or one of which is R7 and the other R0s, R. 7 and R 〇3 are each Η or a substituent, or R 〇8 is a 鐽, and the other R 〇7 and R 〇6 are Η or a substituent, respectively. -19 A paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I? 20902 A7 _B7 _ V. Description of the invention () One of B is a fluorene and the other is fluorene or a substituent, R 0 I! Means Ci to C2 alkane Or phenyl or benzyl, which are unsubstituted or substituted with Ci to 0.8 alkyl, R 0 9 SR 0; meaning Η, Ci to C 2 0 alkyl, or phenyl, respectively Or benzyl, which are unsubstituted or substituted with Ci to (: 18 alkyl substituted R. 0.2 is Η or C ^ to CI 8 alkyl, wherein the ring is unsubstituted or MF, C 1 , B r, I, ~ C Ν,-Ν 0 2, C! To C 1 8 alkyl, C 3 to C t 2 cycloalkyl, C s to C! 8 aryl, c 5 to C 1. 7雑 aryl, C 3 to C i 2 cycloalkylalkyl, C 6 to C! 8 aralkyl, C to C 1 7 aralkyl, C i to C! 8 alkoxy, C 3 to C i 2 cycloalkoxy, C 6 to C 1 8 aryloxyfluorene, c5 1C! 7 雑 aryloxy, C3 to Cl 2 cycloalkylalkoxy, to Cl 8 arylalkoxy, C5 to : ^ 7 heteroarylalkoxy, Cl MCt 8 alkylthio, C3 to (: ^ 2 cycloalkylthio, C6 per C! 8 arylthio, C 5 to C i 7 arylthio , C 3 to C! 2 cycloalkylalkylfluorenyl, cl5 to Cl 8 aralkylthio, C5 to Cl 7 heteroaralkylthio, C! To Ci 8 alkyl-so- or -so2, C 3 to ci 2 cycloalkyl-SO- or -S02, C 6 to C 1 8 aryl-S0- or -S02, C 5 to C 1 7 heteroaryl-so- or -S02, C 3 to C 1. 2 cycloalkylalkyl-so- or -S02, Ce to C! 8 aralkyl-so- or -S〇2, to () i 7 heteroaralkyl-SO- or -S〇2, With 2 to 30 -20- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -Install -------- Order --------- · 1220902 丨 A7 _B7_ V. Description of the invention () _ carbon atom of two _ amine group, and alkoxyalkyl group with 2 to 20 carbon atoms 0 cycloaliphatic and aromatic The residue (substituent) may also be substituted, for example, substituted with ", (: 1,131 ', 1,-^ 102, (: jade to (: 18 alkyl, C 3 to C 1 2 cycloalkyl, C 6 to C 1 8 aryl, C 3 to (: ί 2 ring heptyl C 6 is C 1 3 aralkyl, C 5 to C 1 7 heteroaralkyl, C i to C! 8 alkoxy, C 3; to C t 2 cycloalkylalkoxy, C β to ci 8 Aryloxy. The alkyl group may be substituted with a halogen such as F, C 1 or B r. More preferred substituents are F, C1, Br, methyl, ethyl, propyl, butyl, hexyl, methoxy, ethoxy, propoxy, butoxy, hexyloxy, methylsulfide Methyl, ethylthio, methyl- or ethyl-S 0-, methyl- or ethyl-Soz_, phenyl, benzyl, tolyl-methyl, xylyl, methylbenzoyl Group, dimethylbenzyl, chlorophenyl, dichlorophenyl, methoxyphenyl, dimethoxyphenyl, methoxybenzyl, dimethoxybenzyl OR «:» 1 f preferably means linear or branched C 1 to C 1 8 alkyl, or cage or benzyl, which are unsubstituted or substituted with Ci to Ci 2 alkyl, and R 0.9 And R 〇 100 are preferably Η, CI to C; s mirror group, or phenyl or benzyl, respectively, which are unsubstituted or substituted with C ^ to C 1 z alkyl. Examples are methyl, ethyl, and propyl, butyl, pentyl, hexyl, heptyl, octyl, daughter, decyl, undecyl, dodecyl, tridecyl, tetradecane Base, pentadecyl, cetyl, decyl, 10-2 1- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before (Fill in this page) -Install -------- Order ---------

1220902 A7 _B7__ 5. Description of the invention () Isomers of octadecyl, nonadecyl, eicosyl, phenyl, benzyl, methylphenyl, ethylphenyl, propylphenyl, butyl Phenylphenyl, pentylphenyl, hexyl, heptylphenyl, octylphenyl, sylbenzyl, ethylbenzyl, propylbenzyl, butylbenzyl, pentylbenzene Methyl, hexyl benzyl, heptyl benzyl, and octyl benzyl.

Ro ί 2 preferably means Ci to (:! 2 alkyl, more preferably C 1 to C 8 alkyl and most preferably C 1 to C 4 alkyl. Suitable salts may be derived from inorganic or organic acids, For example HC 1, HBr, Hz S04, carboxylic acids such as acetic acid, chloro- or fluoroacetic acid, propionic acid, benzoic acid, chloro- or fluorobenzoic acid, sulfonic acids such as methanesulfonic acid, chloro- or fluoromethylsulfonic acid Acid, phenyl sulfonic acid, toluene sulfonic acid, and chloro- or fluorobenzene sulfonic acid. -22- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the Note for this page, please fill in this page) ---- Order --------- ^ 9— 1220902 A7

This paper size applies Chinese National Standard (CNS) A4 specification (210 χ 297 mm) 1220902 A7 _B7 _ V. Description of the invention () (Please read the notes on the back before filling this page) Used in the complete form (B) The host chromophore is preferably unit price. These host chromophores can be selected from a wide range of chromophores, as long as they emit solid-state fluorescent light, and their emission wavelengths correspond to the absorption range of the corresponding auxiliary bodies in the system! At least partly. The monovalent host residue in Formula I may be unsubstituted or substituted KF, Ci, BI ,, I, -CN, -NO2, C! To Ci8 alkyl, C3 to Cl2 cycloalkane , C6 to Cl8 aryl, Cs to Ci7 heteroaryl, C 3 to C 1 2 cycloalkylalkyl, C 6 to C t 8 aralkyl, C 5 to Cl 7 heteroaralkyl, Ci to ( :! 8 alkoxy, C3 to (: 1 2 cycloalkoxy, C6 to (: 1 8 aryloxy, C5 to (: 1 7 雑 aryloxy, C3 to Ci 2 cycloalkyl alkoxy, To Ci 8 aralkyloxy, C 5 to C t 7 heteroaralkyloxy, C! To C t 8 alkylthio, C 3 MCt 2 cycloalkylthio, C6 to Ci 8 arylthio, C5 to Ci 7 heteroarylthio, C3 to Ci 2 cycloalkylalkylthio, Ce to Cl 8 aralkylthio, C5 to Ci 7 heteroarylalkylthio, Ci to Ci 8 fluorenyl ** s 〇- or -s 0 2, C 3 to C 1 2 cyclohexyl -S 0-or -S〇 2, C e to C! 8 aryl -so- or -S〇 2, C 5 to C t 7 heteroaryl-SO- or -S0 2, C 3 to C 2 cycloalkylalkyl-SO- or -S oz, c 6 to C 1 8 aralkyl-so- or -S 〇2, C 5 to C! 7 aralkyl-S0- or -S02, secondary amine groups having 2 to 3 carbon atoms, and 2 to 20 carbon atoms Alkoxyalkyl. Cycloaliphatic and aromatic residues (substituents) can also be substituted, such as substituted MF, C1, Br, I, -CN, -NO2, C! To C [ 8 -24-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 ____B7____ 5. Description of the invention () Alkyl, C 3 to C t 2 cycloalkyl, C 6 to C i 8 aryl, C 3 to ct 2 cycloalkylalkyl, c 6 to Ci 3 aralkyl, C 5 to Ci 7 aralkyl, Ci to (:; 3 alkoxy, C3 to 〇1 2 cycloalkylalkoxy, CS to ci 8 aryloxy. The alkyl substituent may be linear or branched and may be substituted with halogen such as F or Ci. Examples of substituents are F, C, Br, Methyl, ethyl, propyl, butyl, hexyl, methoxy, ethoxy, propoxy, butoxy, hexyloxy, methylthio, ethylthio, methylmono or ethyl Mono-SO-, methyl- or ethyl-S 0 2-, phenyl, benzyl, tolylmethyl, xylyl, methylbenzyl, dimethylbenzyl, chlorophenyl, di Chlorophenyl, methoxyphenyl, dimethoxyphenyl, pyroxybenzyl Ο number dimethoxybenzyl group substituted by an arbitrary and substantially with respect to the sum of the synthetic possibilities and the desired optical properties of the fluorescence absorption of the set. Particularly preferred monovalent host residues are derived from benzo [4,5] B mizolo [2, bua] isoazepine-1 bu. Benzo [4,5] imidazo [2, bua] isoazindone-1buconones used in the complete form (B) are preferably monovalent residues and may be selected from the formulae E and Ia,

The adjacent carbon atoms of the benzene ring can be condensed by a benzene ring, a heteroaromatic ring or the above. The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 _B7 _ V. Description of the invention () , And ft and other rings are easier to connect with free bonds than the benzene ring system of the nuclear polycyclic structure (please read the precautions on the back before filling this page)

Aromatic rings are substituted or taken MF, C1, Br, I, -CN,-㈣2, Ci to C, 8 alkyl, C3 to (:! 2 cycloalkyl, C6 to C; 8 Aryl, C 5 to C 1 7 heteroaryl, C 3 to C; 2 cycloalkyl, C6 MC, 8 aralkyl, C 5 to C; 7 aralkyl, C; to C i 8 alkane Oxygen, C3 to Cl 2 cycloalkoxy, to 8 aryloxy, C5 to Ci 7 heteroaryloxy, C3 to Ci 2 cycloalkylalkoxy, c S to C! 8 aralkoxy, CS to C 1 7 heteroarylalkoxy, c! To C 1 8 alkylthio, C 3 to C! 2 cycloalkylthio, C 6 to C 8 arylthio, C 5 to C i 7 hetero Arylthio, C 3 to C! 2 cycloalkylalkylthio, C 6 to C i 8 aralkylthio, c S to C — and 7 heteroaralkylthio, C i to C 1 8 alkyl-SO- or -SO2, C3 to 〇1 2 cycloalkyl-SO- or -S02, C6 to Ci 8 aryl-SO- or -S02, C5 to C.! 7 雑 aryl -SO- or -S02, C 3 to C 12 cycloalkylalkyl-so- or -S02, c 6 to C i 8 aralkyl-SO- or -S02, C s to Ci 7heteroaralkyl-SO- or -S02, secondary amine group with 2 1 30 carbon atoms, and alkoxyalkyl group with 2 to 20 carbon atoms. Cycloaliphatic and aromatic Residues can also be substituted, such as substituted MF, CI, Br, I, -CN, -Noz, C! To CI8 alkyl, C3 to C! 2 cyclofluorenyl, C6 To C i 8 aryl, C 3 to C 1 2 cycloalkylalkyl, C 6 to C 1 8 aralkyl, C 5 to C i 7 heteroaralkyl, Ci MCi 8 alkoxy, C3 to Ci Z-Cycloalkylalkoxy, this paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (oxy. Aromatic residues (, C ί or B 3 Health U i 2 alkylalkyl,, c! To c 6 to C 1 8 elements such as F or C are F, C methoxy, ethylethylthio, > phenyl "benzyl benzyl Phenyl, methyl I 8 aromatic and aromatic compounds such as F group, C r® 1 Z oscillating alkyl group, C can be halo group such as hexyl, thio, S02-methyl, dimethoxy C 6 to C Cyclolipid substituted M halo C i 8 alkane C 3 to CC i 7 heteroalkyl alkoxy or branched and substituted, j-based, radical, methyl or ethyl-mono, methylphenylphenyl, substituent) Substituted, for example, via r; or -CN, -N 0 2, C! To cycloalkyl, C 6 to C! 3 aryl, C 6 to CI 8 aryl, C 5 to i S alkoxy, C 3 to C .1.2 cycloaryloxy. Alkyl substituents may be linear i-substituted. I, Br, methyl, ethyl, propyloxy, propoxy, butoxy, hexyloxymethyl- or ethyl-SO-, methyl-methyl, tolylmethyl, xylyl Chlorophenyl, dichlorophenyl, methoxybenzyl, and dimethoxybenzyl are preferred. One or two rings are condensed with adjacent carbon atoms to form a bicyclic or tricyclic system. These may be selected from the group consisting of benzene, furan, pheno, pyrrole, pyridine and pyrimidine. In a preferred embodiment, the monovalent body residues correspond to the formulas Η b and H c, (please read the notes on the back before filling this page)

R03, R04 R05 (Hb),

(He), -27- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention () where R 0 1 R 0 ZR 〇 3 R 0 4 and R 0 5 means fluorene, C 1, C 1 to C ί 8 alkyl, C ί to C 1 8 methoxyphenyl, benzyl C 1 to C 1 2 alkylphenyl, or C 1 to (Γ * 1 2 alkyl benzyl group R 0 5 in the formula IC is preferably Η 〇 R 0 1 R 0 2, R 〇 3 and R 0 4 are particularly preferably Η 9 phenyl $ benzyl t C 1 To C 1 alkylphenyl or C 1 to C 1 2 alkynyl and R 0 5 are preferably 较佳 〇 The portion corresponding to the chromophore of the main m bottle of formula I is a preferred embodiment

C (0) -0-CH2CH2-0-C (0)-

Please read the memorandum on the back to write this page. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1220902

I A7 _ B7 V. Description of the invention () The composition of the complete form B can be prepared according to the conventional fixing method (i 0 biiizati ο η). A further preferred embodiment of the present invention is a method for preparing the complete form B. The method of the composition 'is characterized in that an inorganic or organic supporting material containing a functional group on the surface and a functionalized fluorescent subsidiary chromophore S functionalized fluorescent host chromophore are reacted simultaneously or in a two-step reaction The reaction can be carried out by dissolving the functional main and auxiliary compounds on an inert solvent surface, adding a supporting material and at an appropriate temperature, 'for example 0 to 2 G 0 Ό and preferably 2 Q to i 5)) ΐ]. Appropriate solvents will be described below. Separation is performed by filtration methods known to M, and the materials can be purified by washing and finally dried. The fixing and synthesis of bridge bonds can be performed according to methods known to those skilled in the art and are fully documented in the literature. In principle, it may convert one functional group into another functional group, such as _CH2 0Η- group becomes carboxylic acid through oxidation, carboxylic acid becomes amidine or carboxylic acid becomes halide, amine group becomes isocyanase group, alcohol Or the amine becomes carbonate or urethane S6. It is also possible to react an alcohol or amine with a halogen carboxylic acid (such as monochloroacetic acid or chloromethylbenzoic acid, which may then be attached to a hydroxyl or amine group). It is further possible to use difunctional tests such as epoxides, alginine (Uzirines), glycols, diamines, dicarboxylic acids or mono- and diisocyanates for bond extension. The reaction using a bifunctional reagent depends on the required chain length and can be a single step or multiple steps. The bridge group can be compounded through the functional group or the main body and the auxiliary body of the supporting material. 2 9- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----------- -Install -------- Order --------- (Please read the precautions on the back before filling out this page) 1220902 1 A7 ______ B7 V. Functional Description of the Invention Import. In a preferred embodiment and a further object of the present invention (complete form (A)), the composition of the present invention includes a polymer main material as a support material, and a material directly or via a bridge bond group with a fluorescent host molecule and fluorescent The photon _ chromophore is covalently linked, in which the fluorescence emission wavelength of the subject overlaps with the absorption wavelength of the accessory by at least «Γ. For the main and auxiliary compounds and bridge bonds, the achievements and preferred embodiments mentioned in the full form (B) can also be considered to be applicable to the full form (A). The preparation of polymers and their immobilization are well known in the art. Two steps can be used in principle. In the first direction, it may polymerize monomers with overhanging main and auxiliary molecules. In the second direction, it is possible to use a polymer having a pendant functional group and to react with a functional group-containing main and auxiliary molecule. The main and auxiliary compounds are connected to the structural unit of the main bond through a functional group. Examples of functional groups are -OH, -SH ,, _NHR2,-"= 0 'carboxylic acid, _S03 fluorene, epoxide, vinyl or isocyanate, with fluorene or C! To C4 alkyl being preferred. Polymerization The substance may be selected from natural or synthetic polymers. Examples of natural polymers are glycans, such as cellulose, starch or polyglucosamine, which may be etherified by a C 1 -C 4 alkyl moiety or C! A C 8 alcohol group is partially esterified. Synthetic polymers with functional groups are known and can be made by conventional methods. An example of synthetic polymers is polyvinyl alcohol and vinyl alcohol with unsubstituted or -30- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) —I —Bi I nnn) ^ OJa ϋ ϋ ϋ II ϋ I · 1220902 A7 ____B7____ 5. Description of the invention () Copolymers that replace olefins as comonomers; polymethacrylic acid, polyacrylic acid and polymaleic acid and methacrylic acid, acrylic acid and / or maleic acid Copolymers with unsubstituted or substituted olefins as copolymers; polyhydroxyalkyl acrylates, polyhydroxy Copolymerization of methacrylic acid esters and hydroxyalkyl maleates, and hydroxyalkyl esters of methacrylic acid, acrylic acid, and / or maleic acid with unsubstituted or substituted olefins as comonomers Materials; polypropylene saxamine and polymethacrylamine and allylamine, methacrylamine or copolymers of unsubstituted or substituted olefins as comonomers; polyaminoalkyl acrylates, Monomethacrylate and maleate and aminoalkyl acrylate, monomethacrylate, maleate or two or three of the above with unsubstituted or substituted olefins are Copolymer of comonomers; copolymerized with polyhydroxyalkyl mono or polyaminoalkyl vinyl alcohol and hydroxyalkyl vinyl B, amino alkyl vinyl ether or both and unsubstituted or substituted olefin as comonomer Polybutadiene and butadiene, butadiene, isoprene, chloroprene, or two or three of which are unsubstituted or modified from butadiene, isoprene or chloroprene Copolymers of substituted olefins as comonomers; hydroxy mono or amine polystyrene, chloromethyl polystyrene, Polystyrene sulfonic acid and hydroxystyrene, aminostyrene, chloromethylstyrene, polystyrene sulfonic acid, or a copolymer of two or three of the above and an unsubstituted or substituted olefin as a comonomer; Polyglycidyl ether and hydroxy-alkylated or amine-alkylated polyglycidyl and polyesters derived from hydroxy-containing monomers, polyamines and polyamine esters. The polymer may also consist of a thermosetting resin , Such as epoxy resin, honeycomb string of aldehyde resin and phenolic resin. Examples of suitable olefin comonomers 3 1- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --- --------- # 装 ------ (Please read the precautions on the back before filling this page) tr --------- 1220902 A7 _B7___ V. Description of the invention () Such as For ethylene, propylene, butene, pentene, octene, vinyl chloride, vinyl chloride, styrene ethyl® and propylene. Further suitable vinyl polymers are polyvinyl 1ft pyrrolidine, polyvinyl oxazole and polyvinyl pyridine, and vinylpyrrolidene, vinylimidazole, vinylidazole, vinylpyridine or vinyl The second or third is a copolymer of unsubstituted or substituted olefin as a comonomer. The polymer may also consist of crosslinked polymers, such as functionalized olefins, optionally non-functionalized olefin monomers, and diene monomers such as butadiene, divinylbenzene, or diol-diacrylate Or the polymerization product of diol-dishenyl acrylate. When the weight-average molecular weight of the polymer of the present invention is determined, for example, by gel permeation color history analysis, and polystyrene is used as a calibration standard, the usual range is from] to 2 × 106, preferably from 104 to: [〇6, More preferably 2 X 104 to, and most preferably 4 X 1 X4 to 5 X 105 grool- 1. The weight ratio of the main body to the auxiliary body structural unit ranges from 50:50 to 9 9 9 5: 5, preferably 6: 4 to 9 9 9: ί, and more preferably 7 0: 3 0 to 9 9 9: 1 . (Main structural unit plus auxiliary structural unit): The weight ratio of non-fluorescent structural unit depends on the actual application, so there is no complete definition of a better ratio except for a wide range of 100: 0 to 1: 9 9 9. In the partial application where both color intensity and fluorescence are required, the preferred ratio of chromophore structural unit to non-fluorescent structural unit is 20: 801100: (3, preferably 50: 50 to 100: 0 and better It is 8 0: 2 0 to i 0 0: ϋ. When the fluorescence is required but the color intensity is not required, the better ratio of the chromophore structural unit to the non-fluorescent structural unit is 20: 8ϋ1 1 : 999, preferably 10: 90 to 1: 9 9 9 and -32-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) ---- Order --------- 1220902 A7 ___B7__ V. Description of the invention () More preferably 5: S5 to 1: 9 9 9. A specific example of the polymerizable composition of the present invention and In a further object of the present invention, the polymer may be in the form of particles, which is derived from grinding polymer I or emulsion polymerization. Particles such as I 跎 may have an average diameter from 50 nm to 1000 μm, and more preferably from ·: [To 500 micrometers, more preferably from 0.1 to 200 micrometers, most preferably from 0.1 to 10 micrometers, and particularly preferably from 5 to 50 micrometers. These particles Depending on the manufacturing method, it can be round or irregular, and these particles can be compact or porous. The size of the particles can be the same as those required for their final application. The main and auxiliary molecules connected to the polymer It can be derived from monofunctional or polyfunctional host and subsidiary molecules. It is preferred that these molecules be mono- to tri-functional, and particularly preferably mono- or difunctional. The polymer can be composed of monomer units and host molecules. Monovalent and / or divalent residues are covalently linked, and can be composed of monomeric units and subsidiary molecules with monovalent and / or divalent residues covalently linked, and optionally composed of other comonomer units. Including the host The monomer structure (represented by K k) can exist in a wide range from ϋ. 0 ί] I) 5 to 0.9 9 9 5. In partial applications where both color intensity and fluorescence are required, the preferred ratio of host chromophore structural units to non-fluorescent structural units is β-2 to ϋ · 9 3 S 5. In an environment where fluorescence is required but color intensity is not required, the preferred ratio of the main chromophore structural unit is 0 · (i 5 to 0 · 2. Monomer structure containing subsidiary bodies (K m) From 0, 0,005 to 0.5, more preferably 5. 0 ϋ 1 to 0 · 2, and most preferably 0 · 0 01 to this paper size apply Chinese National Standard (CNS ) A4 size (210 X 297 mm) (Please read the notes on the back before filling out this page) nnnn ^ OJ_ n ϋ n ϋ ϋ ϋ I · ^ 2009092 A7 B7 V. Description of the invention ((j. 0 5. The non-fluorescent monomer structure (indicated by η) is in a wide range of 0 to 0, 999. In the part of the application cycle where both the color intensity and the preparation Λ are required, the non-fluorescent structural unit is preferred. The ratio is () · ㈣ϋ5 to ί) · 2. When the fluorescent charge is required but the color intensity is not required, the preferred ratio of the non-fluorescent structural unit is 0.8 to 0 · 9 9 9 5 ， Among them, k, m and η are generally selected to comply with k + m + π = 1 0. The polymer may be composed of a re-maturation structural unit of formula 丨 11 and a re-maturation structural unit of formula ffi a. _, (Ilia), or may be composed of re-cure crosslinking sites of formula IS b or 111 C 'single or combined with one or both of the structural sites of formula I and ® a' (lllb), 4 (Please read the notes on the back before filling out this page) ——A3—Subsidiary One Order 3—II where A is a trivalent residue, A 1 is a trivalent residue which is the same or different from A group, A 2 is a trivalent organic residue, A 3 is a trivalent residue -34- (lllc) which is the same or different from the A 2 group, and this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A7 _B7___ V. Description of the invention () The non-body is a monovalent or divalent fluorescent host chromophore as defined above or covalently connected directly or via a ffi-bridge bond group, and the sub-body is a trivalent as defined above Or the divalent fluorescent accessory chromophore is covalently connected directly or via a bridge bond group, wherein the fluorescence emission spectrum of the host and the absorption spectrum of the accessory at least partially overlap. The polymer may additionally contain a structural unit of formula md- A 4-(Id), where A 4 means the same or different divalent residues A, A i, A z, A 3 and A. 4 which can be copolymerized with A to A 3 Monomers selected from the group consisting of olefins, polyolefins such as di- or tri-olefins, polyalcohols such as diols and triols, polyamines such as diamines and triamines, polyisocyanates such as di- or triisocyanates, and polyacids Mono- and tri-carboxylic acids, and polyepoxides such as di- and tri-epoxides. The weight ratio of individual structural elements to other structural units of Formula 1 {, or 1b is determined by actual application, so in addition to a wide range of There is no complete definition of better ratios beyond 9995: 5 to 5: 3 9 9 5. For partial application where both color intensity and fluorescence are required, the preferred ratio of Structural Unit® to other structural niches is: 80 to 9 9 9 5: 5, preferably 5 ϋ: 5 G to 9 9 3 5: 5 and more preferably 80: 2 G to 9 9 9 5: 5. In an environment where fluorescence is required but color intensity is not required, the preferred ratio of chromophore structural units to non-fluorescent structural units is 20:80 to 5: 9 3 9 5 and preferably i 0: 9 0 to 5: 9 9 9 5 and more preferably 5: 35 to 5: 9995 ° -3 5-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---- ---------------- Order— (Please read the precautions on the back before filling this page) 1220902 A7 B7 V. Description of the invention (the number of auxiliary bodies depends on the rules, Therefore, there is no better defined ratio. In general, the individual structural elements of Formula ia, or 111 b are present in an amount of 0.05 to 50% by weight, preferably 0.1 to 5% by weight, and more preferably 0. i. 15% by weight, most preferably 0.1 to 3% by weight. In a specific embodiment, the polymer of the present invention contains a re-cure structure unit of formula IV, a re-cure structure mask of formula IV, and an optional formula V re-mature structural unit, r5 r4 r i4 —cc one (IV), (please read the precautions on the back first to write this page) r «install

Re Xr (Ri)-(x2),-R3-ill R. R. I5 I4—c ~ c— (IVa), R6 Xr (R々 (x2) s-R3-auxiliary

8 -10 RIC—R 7 -9 RIC—R \ — / where X i and X 2 respectively mean direct 鐽, or x 1 and x 2 respectively mean -〇-, -S-,-NR 2 _,- (C0) _0_, -〇- * 0 (0)-1 -0-C (0) ~ 〇- j -S Ο 2 -0-,-Ο-S Ο 2-, -〇-S〇2 -〇 -,-NR 2 -C (0)-, -C (ϋ) · ~ NR 2 ~?-NR 2-C (Ο)-Ο-? Ο-C (Ο) ~ NR 2 * J NR 2 -C (Ο)-Ν R2 one,-Ν R2-3 Ο 2-,-S Ο2-Ν R2-, ~ Ν Rz-S Ο 2 * " -36-

This paper size applies the Chinese National Standard (CNS) A4 specification (210 χ 297 H 1220902 A7 _B7 V. Description of the invention () 0- 5 -0 -S〇2-NR2 -or-NRz-S〇2-Mz multiplied by the mother One R 1 is a divalent bridge bond group _ m means a monovalent fluorescent accessory chromophore, and the subject means monovalent fluorescent- 彳: Μ 曲 m > 苴 fluorescence emission wavelength and absorption wavelength of the subsidiary Overlapping at least m parts of R z means Η, I — C l 2 or 9 9 C 5 or C 6 ring 5 C 5 — or CG cycloalkylmethyl or monoethyl% phenyl > benzyl Or phenyl-2 'ethyl' from TΛ K 3 'is directly m 1 —C 1 8 alkylene' C — or C 6 cycloalkylene 9 C 6 —C 1 0 square or C 7 — C 1 ZO aralkylene 5 Γ means number 0 0 or 1 and S means number of 0 or 19 respectively, except that if S is 0 then Γ is 0, and R 4 and R 5 mean Η, C 1 — C β alkane , C < 5 — C 1 0 aryl or 7 — C! 2 arylfluorenyl> R is Η or-(C 0) 0 -R 1 1 radical R 7 is > η I — C β Alkyl C 6 — C 0 0 aryl or C 7 — / ^ I 2 aralkyl> R 8 means Η? FC i 9 N, C 1 -C 6 alkane or C 6 — η 1 〇aryl 5 R 9 Kun 'is Η 1 C 1-6 U base or-(00) 0 -RI 1 base, (Please read the notes on the back before filling this page) · ma— II n ϋ ϋ I TJ · ϋ I ϋ I i_i ϋ ϋ I t

R i 〇 means Η, C ί —C 6 alkyl, C 6 — C! 〇 aryl, C 7 -Ct 2 aralkyl, _azolyl, fluorrolidinyl, F, C ί, CN _ -X1-(R t) r- (Xz) sH-based, and -37- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 _B7 _ V. Description of the invention () R ii Meaning Η, K, Na, C1-C ^ 8 alkyl, C ^ -Ci-8 hydroxyalkyl, cyclohexyl, cyclopentyl, cyclohexylmethyl, phenyl, C i -C 4 alkylbenzene Radical, benzyl or C 1 -C 4 alkyl benzyl. For Xi, X2, R !, R2, R3, r, s, the meaning and preferred embodiments of the subject and subsidiary body, such as those in the complete form (B) above, are also as complete form ( A). The alkyl group of R 4 and R 5 is preferably C; a C 4 alkyl group, examples of which are methyl, ethyl, tert- or iso-propyl, and n-, iso-, or tri-a-Γ groups, which are aromatic When it is a base, naphthyl or phenyl is preferred; and when it is an aralkyl, benzyl is preferred. R 4 is particularly preferably fluorene and R 5 is fluorene or methyl. R 6 preferably means fluorene, -C (0) 0H or-(CO) OC i to C 4 alkyl, and when R 7 means alkyl, preferably C i to C 4 alkyl, examples are methyl, ethyl Radicals, n-mono or iso-propyl, and n-mono, iso- or tertiary mono-butyl; when aryl is preferred, naphthyl or phenyl; and when aralkyl is preferred, benzyl. R 7 is particularly preferably Η.

When Re means alkyl, C i to O 4 alkyl is preferred, examples are methyl, ethyl, n- or iso-propyl, and n-, iso- or tertiary mono-butyl; when it is aryl Phenyl or naphthyl is preferred. R8 is particularly preferably fluorene, C], CN, phenyl, or Ct to C4 alkyl.

When Rg means alkyl, C!-() 4 alkyl is preferred, examples are methyl, ethyl, n- or iso-propyl, and n-, iso- or tertiary mono-butyl. Yu-( C 0) 0-R i, radical, R i! Is preferably Η or CI — C ί 2 m group, more preferably C i -C 6 alkyl, such as methyl, ethyl, propyl, butane- 38- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling in this page) — · · ϋ ϋ ϋ ni · — nn 一 -OJI i_l n ϋ n mmmmt in i 1220902 A7 _B7_ V. Description of the invention (5) pentyl, hexyl, heptyl, octyl, shiki, decyl, undecyl, dodecyl, tetradecyl, hexadecyl And octadecyl. R 9 is particularly preferably fluorene, -C (0) 0H or-(CO) O-Ci -C4 alkyl. When R i 〇 means alkyl, preferably C i -C 4 Alkyl, examples are methyl, ethyl, it:-or iso-propyl, and n-, iso- or secondary-j groups, and when aryl is preferred, phenyl or naphthyl, and aralkyl In the case of benzyl, a benzyl group is preferred. Preferably, it means fluorene, Ci-C4 alkyl, benzyl, pyrrolidino, F C !, CN or -X,-(R!) R- (X2) s-fluorenyl. R1! May be, for example, fluorene, K, Na, Ct-C6 alkyl, Ci-C6 hydroxyl Alkyl, cyclohexyl, cyclopentyl, cyclohexylmethyl, phenyl, methylphenyl, benzyl or methylbenzyl. The weight ratio of the structural element of formula iV to other structural units is based on actual use. Because of this, there is no complete definition of a better ratio except for a wide range of 9995: 5 to 5: 9 9 9 5. When the color intensity and fluorescence are required for some applications, the structural unit W is used for other structural units. The preferred ratio is 20:80 to 9 9 9 5: 5, more preferably 50:50 to 9 9 9 5: 5 and more preferably 80:20 to 9 9 9 5: 5. In an environment where fluorescence is required but color intensity is not required, the preferred ratio of chromophore structural unit to non-fluorescent structural unit is 2 (3: 80 to 5: 9 9 9 5, preferably 1 ΰ: 9 丨] to 5: 9 9 9 5 and more preferably 5: 9 5 to 5: Β 9 Β 5 ° The number of faces is system-dependent, so there is no better defined ratio. In general, The structural element of formula IV a is present in an amount of 0.05 to 50% by weight of the polymer, preferably ΰ. 1 to 5 weight Amount of 96, more preferably 0.1 to 5% by weight -3 9- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Order --------- 1220902 A7 _B7_ 5. Description of the invention (), the best is () · i to 3% by weight ·: 'The weight ratio of the structural element of formula v to the m-position of the fluorescent structure is based on the actual situation Depending on the application, there is no complete definition of a better ratio, except for a wide range of 0: 99 to 9 99: 1. In partial applications where both color intensity and fluorescence are required, the preferred ratio of structural unit V to fluorescent structural unit is 20:80 to 0:] ί) 0, preferably 1 0: 9 ί) to 0: 1 0 and more preferably 5: 9 5 to 0: 1 0 0. When the fluorescence is required but the color intensity is not required, the preferred ratio of the formula V structural unit to the fluorescent structural unit is 20: 8 [1 to 999: 1, preferably 50: 50 to 9 9 9: 1 and more preferably 8 0: 2 0 to 9 9 9: 1. The number of auxiliary bodies depends on the system, so there is no better-defined ratio. In general, the structural element of Formula IV a is present in a quantity of 0.5 to 50% by weight of the polymer, preferably 0.1 to 5% by weight, more preferably Gi to 5% by weight, and most preferably ϋ. 1 to 3% by weight. The polymer having the formula IV, IV a and the optional V structural element may be a combination of a functional η and a multifunctional monomer, for example, 0.0 to 8% by weight relative to i ο {) grams of the polymer; 1) to 6% by weight of these monomers are preferred. Depending on the type of polymer, at least trifunctional acetic acid, isocyanate, alcohol, amine, vinyl or epoxide can be used. Progressive residues containing at least two olefins (olefinic) non-conical and radicals can also be used. The ethylenically unsaturated cross-linking agent may be selected from the group consisting of divinylbenzene, bis (dimethyl cis butene diimide), an alkylene group such as bis (dimethyl cis butene diimide), and methylene Amine or monoethylene, propionate mono- or methacrylate or one of the polyhydric alcohols, preferably diols to tetraols, more preferably diamines to tetraamines. -4 0-

ίThe paper size is applicable to China National Standard (CNS) A4 (210 X 297 H ----------- installation -------- order --------- (please first Read the notes on the back and fill out this page) 1220902 ί Α7 Β7

I. Explanation of the invention () i — i The preferred ethylenically unsaturated cross-linking agent may be selected from acrylic acid containing aliphatic, cycloaliphatic and cycloaliphatic monoaliphatic diol to tetraol and diamine to tetraamine. Methacrylic alcohols preferably contain 2 to U, more preferably 2 to 8 carbon atoms. Some examples of these glycol alkylene glycols are ethylene glycol, 1,2- or 1,3-propyldiol, 1,2-, 1,3-, and 1,4-butyldidiol Alcohol, pentyl glycol, hexyl glycol, octyl glycol, decyl glycol, dodecyl glycol, cyclohexyl glycol, bis (hydroxyfluorenyl) -cyclohexane, preferably from C 2 — C 6 alkylene glycol and preferably 2 to 1 QG alkylene glycol units, more preferably 2 to 50 alkylene glycol units, and most preferably 2 to 20 alkylene glycols Polyoxyalkylene glycols of diols, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polyethylene / polypropylene glycol, further 1, 1, 2 Trihydroxymethylethane or monopropane, pentaerythritol and dipentaerythritol. Some examples of polyamines are ethylenediamine, 1,2- and 1,3-propyldiamine, U2-, 1,3- and 1,4-butyldiamine, 1,6-hexyldiamine Amine, diethylenetriamine, triethylenetetramine, cyclohexanediamine, (aminomethyl) cyclohexylamine, isopyridine-diamine and bis (aminomethyl) cyclohexane. In a specific embodiment of the present invention, the polymer contains structural elements of formula VI and VI a, H R12 II 12 —c—c— A main body Λ / 丨, H R12 I 丨 12 —0 a —- auxiliary paper The dimensions are applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

12 丨 20902 A7 B7 V. Description of the invention (where R i 2 is fluorene or methyl, and X,, X 2, R 〖, r 2, R 3, subsidiary, main body, r and s have the same as above The meaning of 且 and includes preferred embodiments; and the optional structural unit of formula V. -X i-(R ^) I '-(X £) s _ g 3 _ The radical preferably means-((: 0 ·) -0-,-(C0) -0-C2 -c6 alkylene ~ 0- (c〇)-,-(C () _)-0-(C 2-C 6 alkylene-〇) U-(C 0) _ and U is a number from 2 to 1 ′ '~ 0 ~ * C (0) -C6 Hs ~ CH2-, Ης-or + c (0 )-c, the polymer with formula can be combined with the structural element of the dimorphic structure, where R: ί 2 in the above group through the existence of poly functional groups exist. With the formula main C 1 2 The arsonylene group 0 IV ′ iV a or V [, VI a, and at least a difunctional monomer of a selective V structural element are additionally crosslinked. IV, IV a or Vi, VI a structural element, and a selective formula v In the polymer, $ contains additional identical or different formulas: H R12 II 12—cc— IIH R3-iX2> s-iRl) fX1-H (VII), X 1 X 2, β 〖, R 3, r s has the same meaning and includes preferred embodiments. When the pendant functional groups on the host and the auxiliary compound and the reactions between the host and the auxiliary molecules are respectively led to the polymer, these structural elements are particularly IV , [V a or VI, Vi a structural elements, and optional v -42 This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back first ^ copy (Page) Equipment-line "flat 0902 A7 B7 V. Description of the invention () The comparison of the elementary element and the elementary element is better than the elementary element.

2 | 3 R1.ICIR1 I HICIH

(Wherein R ^ 2 means fluorene or methyl, and R! 3 means fluorene, Ct-C4alkyl, Ci-C4alkoxy, -CN ^ C1, phenyl, pyrrole Alkanone, pyridinyl, oxazolyl, -C (0) 0 R i 4 or -C (0)-NR i 5 R 1 6, R i 4 means 1 " {or〇] 1 — Ci 8 —And preferably Ci—Cl 2 alkyl, and R is and R! S respectively represent Η or C! —C i 2 — and preferably C 1 -C s alkyl. It has the formula IV, iV a Or VI, VI a structural elements, and optionally polymers having the same or different structural elements of formula V or formula Vi », which may additionally contain structural elements of formula IX or X as preferred crosslinker units,

HICIH VI / (Please read the notes on the back before filling this page)

2 R1IC—— I HICIH c () c 0) 3 · (-Χ 7qf

HICIH 121 RICI 3 4 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention () where R 1 2 means hydrazone or methyl,

Xs means _〇_, 1Η- or-N (C t —C4 alkyl)-, and R 7 means C 2 —C i 2 — and preferably C i -C s alkylene, ring Hexyl, cyclohexyldimethylene, phenylene, or X 3 means -0 _ and R 1 7 means C 2 -C 6 alkylene- (C 2 -C salkylene-0) 2 _ 2 0-C 2 -C salkylene. The polymerized product and the preferred polymerized product of the above may contain additional identical or different ionic structural elements, such as formula X I,

V one? -? One (XI), latch 18 latch 19 where R 1 2 means fluorene or methyl, R 1 8 means Η and R Jt 9 means -C (0) 0R2 〇, -S03 R2 0, -Ce H4 -COORz 〇, -c6 H4 -S〇3 Rz 〇, -Ce H4 -R2 1 or -C (0)-) U -C2 -C6 alkylene-R2 2, X 4 means -0 or n, R i 8 and R n 9 mean -C ((.)) 0 R 2 〇 or -C (0)-X 4-C 2 -C6 alkylene-R2 2, R z 〇 means alkali metal, preferably Is L, Na or K, R 2 i means ammonium or ammonium methyl, and R 2 2 means mirror. The ammonium in ammonium or ammonium methyl can be derived from primary, secondary or tertiary amines. -44- This paper size applies to China National Standard (CNS) A4 (210x 297 mm). Please read it first

Order «

1220902 A7 B7 V. Description of the invention (

A quaternary ammonium group is preferred. Ammonium in ammonium or ammonium methyl may correspond to formula X I

-N Rz 3 R2 4 Rz 5 (X] [[), where r '\ K 2 3, R 2 4 and R 2 5 are Η CX-CI 8 — preferably C t-C 1 Z — and more Preferred is C 1 —C sm group, C 5 — or C β cycloalkyl group, phenylbenzyl, 1-phenyl-2 -ethyl, or R Zn 3 and RZ 4 tetramethylenepentamethylene Or -ch2 ch2-0-CHz CH 2; R ζ β 1 ic has the same meaning as described above. Appropriate anti-anions can be derived from inorganic or organic acids, such as osmic acid, sulfonic acid and hydrohalic acid. Preferred counter anions are chlorides and bromides. The poly (8) products and preferred polymerization products may contain additional Acidic structural elements, such as -C (0) 0 Η or-S 0 3 Η f, especially when it comes to emulsion polymerization products, 0 acidic structural elements may correspond to the formula XI > H R12 I 丨 12 —Cc— II (please read the note on the back to write this page) (XIII), Taiwan 27 Lu 26 where R i 2 means Η or methyl, R 2 7 means Η and R 2 s means -〇. (0) 011, -30311,-(: 6114 -C00H ^ -Ce H4 -SO3 H, or R 2 6 and R 2 7 means -C (0) ϋ H. Polymers with amine or acid groups Good to dissolve in water or can be made with milk-4 5-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1220902

I A7 _______B7___ j 'V. Description of the invention () j Disperse and / or dissolve in monomer by liquid polymerization to prepare c (Please read the precautions on the back before filling this page) In another preferred embodiment The polymers of the present invention can be crosslinked with difunctional host and / or accessory molecules. These polymers may contain re-mature structural elements of the formula X] V, X IV a or both, and the elements of the structure of the formula jy, 丨 V a or both alone or together, V > Η 一? 一? —一 | —〒- H Xr (R1) r- (X2) s-R3-ili-R3MX2) sMRl) r ^ Η (XIV), "一? 3 二 卜] 1 丨? ? -c—c —

: H Xr (RA- (x2) s-fV Subbody A (XlVa), where R 1 'R 3 9 R iz 5 X 1, X 2, r, s, -subject • and -subbody-, have the same In the meaning given above and including the preferred embodiment 0, the weight ratio of the structural elements of Formula X IV to other structural units depends on the actual application, so in addition to a wide range of 9995: 5 to 5: 9995 and There is no complete definition of a better ratio. When the color intensity and the part of the fluorescent fluorescein are required to be applied, the better ratio of the 'structural unit X IV to other structural units is 20: 80 to 9 9 9 5: 5, preferably 5 0: 50 to 9 9 9 5: 5 and more preferably 8 0: 2 0 to 9 9 9 5: 5. When the fluorescence is required but the color intensity is not required, the chromophore is The preferred ratio of structural unit to non-fluorescent structural unit is 2 0 -46- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1 ^ 20902 A7 B7 V. Description of the invention (: 8 ϋ To 5: 9; 9 9 5, preferably 10: 9 0 to 5: 9 9 9 5 and more preferably 5: 9 5 to 5: 9 9 9 5. The number of auxiliary bodies depends on the system , So there is no better-defined ratio. In general, formula XI V a structural element is present in an amount of 0.05 to 50% by weight of the polymer, preferably 0.1 to 5% by weight, more preferably 0.1 to 5% by weight, and most preferably 0.1 to 5%. 3% by weight. The crosslinked polymer having one or two ditching elements of the formula X IV and X IV a in the upper part may contain formula IV, IV a, V, 11, IX, X, XI, X Ιί and X 11 or a combination of at least two structural elements of the above, or a structural element which may contain preferred residues of formulas V, IX and boron, and further containing formulae IX, X, XI, X II and X M alone or combined At least two of the above structural elements. A good example of a part of the structural unit of formula X IV a is (please read the precautions on the back before filling this page) ·: installation • cr-line. Η • c- -CH0

Η -CH0

H -47- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (（

ch2 -h2c, c 〇 Η

The preferred divalent residue of the host chromophore corresponds to the formula X V (Please read the precautions on the back before filling this page)

(XV), where the adjacent carbon atoms of the benzene ring can be condensed by a benzene ring, a heteroaromatic ring, or a fluorene ring, and the ft ring is easier to connect with free fluorene than the benzene ring system with a polycyclic core structure, The group ring is unsubstituted or substituted by halogen such as F, C1 or Br, -CN ,, C! To Ci8 alkyl, C3 to Ci2 cycloalkyl, Cs1C! 8 aryl, (: 5 to 01 7 heteroaryl, C3 to C! Z cycloalkylalkyl, C (5 to C i 3 aralkyl, C 5 to C i 7 heteroaralkyl, C 1 to C 1 8 alkane Oxygen, C 3 to C i 2 cycloalkoxy, CS to C i 8 aryloxy, C 5 to C i 7 heteroaryloxy, C 3 to ct 2-48- This paper applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) 1220902 A7 _B7___ 5. Description of the invention () Cycloalkylalkoxy, C 6 to C 1 8 aralkyloxy, C 5 to C 1 7 aralkyloxy, ; To C, 8 alkylthio, C 3 to C i 2 cycloalkyl (please read the notes on the back before filling this page) thio, c 6 1 C, 8 arylthio, C 5 to C 7 heteroarylthio, C 3 to Ci 2 cycloalkylalkylthio, C 6 to Ci 8 aralkylfluorenyl, c 5 to C ^ 7 heteroarylalkylthio, C! To C i 8 -So- or -S02, C3 to C! 2 cycloalkyl-SO- or -S02, C6 to Ci8, aryl-S ()-or -S02, Cs to C1 7 fluorenyl-S 0-or -S 0 2, C 3 to C 1 2 cycloalkylalkyl-SO- or -S02, C 6 to C! 8 aralkyl-SO- or -S〇2, c S to C! 7 aralkyl-so- or -S〇2, secondary amine group having 2 to 3) carbon atoms, and alkoxyalkyl group having 2 to 20 carbon atoms, cycloaliphatic Groups and aromatic residues (substituents) can also be substituted, for example, by removing M halogen such as F, C1 or Br, -CN, -NO2, Ci to Ci, C3 to C3 to C 1 2 cyclofluorenyl, c (3 to Ci 8 aryl, C3 1 Ci 2 cycloalkylalkyl, c6 to Ci 8 aralkyl, to C,. 7 heteroaralkyl, Ci MCt 8 alkoxy , C3 to c; 2 cycloalkylalkoxy, C β MC ί. 8 aryloxy, and A d A 7 means direct fluorene or a divalent organic group. Examples of substituents are F, C1, Br, Methyl, ethyl, propyl, butyl, hexyl, methoxy, ethoxy, propoxy, oxy, hexyloxy, methylthio, ethylthio, methylmono or ethyl -S0-, methyl- or ethyl-S02-, phenyl, benzyl, toluene Cyl, xylyl, methylbenzyl, diphenylbenzyl, chlorophenyl, dichlorophenyl, methoxyphenyl, dimethoxycyl, dimethoxybenzyl, di Methoxybenzyl-49- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1220902 j

I Α7 Β7 I-V. Description of the invention () I: Λ Preferably, 1 or 2 rings are condensed with adjacent carbon atoms to form a bicyclic I or tricyclic system. They can be selected from the group consisting of benzene, sulfan, benzene, pyrrole, pyrimidine | and pyrimidine. j In a preferred concrete example, A and A. 7 correspond to the formula! X Vi,! -Xi-(Rt) r- (X2) s -R3 ** (X VI), where X 1, X 2, R 1, R 3, r and s have the same meanings as above and include preferred embodiments. In a better concrete example, the bivalent body residues correspond to the formula X W R X VI a ^ (Please read the note on the back-β installation sound j matters write this page)

Where R 0 t R 0 Z > R 0 3, R 0 4 and R 0 5 are Η, CI > C 1 to C \ 8 alkynyl C ί. .Zti C 1 8 alkoxy 'phenyl , Benzyl > C 1 to C ί azynylphenyl or C. ~ Fr. 1 Z alkylbenzyl OR 0 is more preferred, i is Η 9 and A 6 and A 7 phases iOLL m. Univalent residues 0 -50 in formula X Vi-This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1220902: A7 _B7_ j 5. Description of the invention () For example, A 6 and A 7 can be selected from the following formulas -C (0)-0-R?-0-C (0)-(R ") u-and -C (ϋ)-NH m C ( 0)-(R ,,) ii-, wherein R / is C 2 to C 2 0, preferably C 2 to C ′ 2, and most preferably C 2 ii ClS alkylene, phenylene, benzyl, Or an oligo-oxygenate having preferably 2 1 6 and more preferably 2 to 4 ethylene oxide and / or propylene oxide units, R 〃 means C! To Ci 2 alkylene, phenylene or phenylene Methyl, and u mean 0 or 1. A preferred example of the portion corresponding to the host chromophore residue of formula XIV is

-5 The size of this paper applies the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

1220902 A7 _B7 V. Description of the invention ()

C (0) -0CH2CH20- (0) CC (CH3) -CH- In a preferred embodiment of the present invention, the polymer of the present invention may contain a functional host monomer, which itself has two or three The functional group is covalently linked to one ring of the host core structure via a bridging group. Therefore, the polymer has a re-maturation structural unit of the formulas i, ilf a, I b, and mc. In this case, all units may additionally contain HI b, which may be represented by the formulas M e, ffi f, or both. Replacement by curing cross-linking unit, the main one is 3-1 (me),

I host is a — 1 —, where A 8 means a trivalent or tetravalent organic residue, which can be copolymerized with A to A 4 groups, and the host is a monovalent fluorescent host chromophore as defined above. -52- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Please read the note on the back and write this page 1220902 A7 B7 V. Description of the invention (Best price for the main chromophore) And trivalent residues can also correspond to the formula XXV and XXV a,

〇 (XXV),

The adjacent carbon atom of the benzene ring may be benzene ring, heteroaromatic ring or upper ring, and the aromatic ring is unsubstituted or MH halogen such as F, Ci-CN, 1 ϋ2, C !. to CI 8 Alkyl, c 3 to ct Ce 8 aryl, C5 to Cl 7 aryl, C cycloalkylalkyl, Ce to C, .8 aralkyl, to C, C t to C, 8 alkoxy , C 3 to C! 2 cycloalkane to Ci 3 aryloxy, Cs to 〇7 heteroaryloxy, C cycloalkylalkoxy, C 6 to C ί 8 aralkyloxy, C 5 aralkoxy Group, Ci to Ci 8 alkylthio, c 3 to C thio, Cs to Ci 8 arylthio, c5 to (: 17, C 3 to C 2 cycloalkylalkylthio, C to C t group, c 5 to c [7heteroaralkylthio, C 1 to C i or -S 0 2, C 3 to C ί 2 cycloalkyl group ~ 3 0- or -S 0 2, -5 3 -(XXVa), the two are condensed or B r, z cycloalkyl, 3 to C i 2 ί 7 aralkyloxy, C β 3 to C 1 2 to C i 7 heteroi 2 cycloalkyl heteroaryl Basic thio group 8 aralkyl sulfide 8 alkyl group ~ S 0-C β SC 1 8 (Please read first! —S write this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 _B7____ 5. Description of the invention () Aryl-S)) or -S 0 2, C 5 to C i 7 heteroaryl -s 0-or -S 0 2 'C 3 to C i 2 cycloalkylalkyl-S0- or-S〇 2, C 6 to C! 8 aralkyl-SO- or -SO 2, C 5 to C! 7 heteroaralkyl-SO- or-S 2, secondary with 2 to 3 carbon atoms Amine groups, and alkoxyalkyl groups having 2 to 2 1) carbon atoms, cycloaliphatic and aromatic residues (substituents) can also be substituted, for example substituted M halogen such as F, C 1 or B r , -CN, -NOz, Ct to Ci8 alkyl, C3 to (: 2 cycloalkyl, C6 to Ci 8aryl, C3 to C! 2 cycloalkylalkyl, c6 to C ί 8 aralkyl, cS to Cl7 heteroaralkyl, C! To Cl 8 alkoxy, c3 to Ci2 cycloalkylalkoxy, C 6 to Ci 8 aryloxy, and A 8 means trivalent Or a tetravalent organic group. Examples of substituents are F, C1, Br, methyl, ethyl, propyl, butyl, hexyl, methoxy, ethoxy, propoxy, butoxy, hexyl Oxy, fluorenylthio, ethylthio, methyl- or ethyl-S0-, methyl- or ethyl-S02-, phenyl, benzyl, tolylmethyl, xylyl , Benzyl benzyl, dimethyl benzyl, chlorine Phenyl, dichlorophenyl, methoxyphenyl, dimethoxyphenyl, methoxybenzyl, dimethoxybenzyl Γί Preferably, 1 ring is condensed with an adjacent carbon atom M To form a bicyclic ring system, they can be selected from benzene, furan, benzophene, pyrrole, Oftidine and pyrimidine. In a better concrete example, A8 corresponds to the formula XX VI or XX Vi a, _ 5 4-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----- -------- Installation -------- Order --- (Please read the precautions on the back before filling this page) 1220902 A7 _B7 _ V. Description of the invention () -R3r (X4) a -R3r (X5) b (XXVI), / R3l—X7 —r3—x6n, r31 —x '(XXVIa), where (a) R 3 i is direct hydrazone, C i to C i 2. Phenyl or cresyl; X 4 is N, 0, S, C (0) 0 or C (0) N; R 3 2 is C 2 to C! 2 alkyl when a is 1 and b is 2 Triyl (t ny 1), phenyltriyl or benzyltriyl, or C 2 to C 1 2 alkyl tetrayl (tetr ay 1) when a is 1 and b is 3, phenyl tetrayl Or benzyl tetrayl; OC (O) —ch-ch2—

X 5 means 0, S, N Η, C (0) 0, C (0) NH, I f; or 0C (0) —C (CH3) —CH2 — HNC (0) CH-CH2 HNC (0) -C (CH3) -CH2— t $ (b) R 3 z is a direct bond, a is 0 and b is 2 or 3, X 5 has the meaning of 逑, and R 3 1 is when b is 2 C 2 to Ci 2 alkyltriyl, phenyltriyl or benzyltriyl, or C2 to C2alkyltetrayl, phenyltetrayl or benzyltetrayl when 3; c) R 3 i is a direct bond, (: 1 to (: 12 alkylene, phenylene, or tolylylene; X 6 is N or C (0) N; R 3 3 is C 2 to C 1 2 Alkyl;-55- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Please read the note on the back first

Order

1220902 A7 _B7 _ 5. Description of the invention ()! X 7 is 0, S, C (0) 0 or C (0) N Η, OC (0) —CH-CH- 〇C (0)-C (CH, ) A CH2 — HNC (0) -CH-CH, —- HNC (O) 'C (CHJ —CH? — 丨, 丨, 1, 丨 or ch-ch2- 〇R 3 ί and R 3 3 are The meaning of an alkylene group preferably contains 2 to 8 and more preferably 2 to 4 carbon atoms. R3 2 preferably contains 2 to 8 fakes, more preferably 2 to 6 in the meaning of fluorenyltriyl. , And most preferably 2 to 4 carbon atoms. In a preferred embodiment, the divalent host residues correspond to the formulae XW and XW a,

R〇2 Feet 03 N

(Please read the notes on the back before filling this page) (XXVII), where R ο I »R 〇 z, R 0 3, R 0 4 and R 0 5 respectively mean Η,

Cl, () 1 to (: 18 alkyl, C t to Cl 8 alkoxy, phenyl, benzyl, ct to Ci 2 alkylphenyl, or c 1 to Ci 2 alkyl benzyl, and A 8 corresponds to the formula XX VI or XX VI a. R 〇5 preferably means Η. -56- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm> 1220902 A7 B7 V. Invention Explanation (In a preferred embodiment, the A 8 group may select C —N [CH-CH ——CH2] 2— • C_ II 〇CH; • ch2—〇-c- II 〇.〇-CH;- C — 0-CH; II 〇Γ3 -ο- Ι -c- II 〇CH; I -c-

〇 II

〇II -c- II 〇 · 0 —CH; -CH- CH, 0 -C-CH -CH, II II 0 1 1 -c-〇- II 〇 · CH; -CH-CH.O — (I / CH, 0 -C — C — -II I 〇CH,? H3 • c — CHn CH, CH,

0 II CH, ch2o—c—ch-ch2 C — 0 — CH, — C- II I 〇CH2〇-C-CH — CH. -C- II 〇-o —CHr 〇CH. I ii I 31 • ch2o —C—c—ch2 II 〇CH, 〇-C —C — 2 II I 0 CH, • CH, 〇2 H cl H2 .c- H .c 0 CH, II I less ch2o—c—c—ch2— 0 ch7 II I 3 -C-O-CH-- II 〇c-ch2o-c-ch-ch2 CH, 〇-C-CH — CH, II 1 I 0 1 1 -c- II 〇CHr -CH, 0 One C — C one CH, CH, 〇-C- ~ C ~ 2 II I 〇CH, -CH, -57-This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

1220902 A7 B7 V. Description of the invention (Some of the preferred examples are residues selected from the following groups (Ph means phenyl)

Ph

C (0) N (CH2CH20-)

Ph

Ph

Ph c (o) och2ch (ch2ch2o-):

SC6H4 (C〇2-) 2

N (Please read the notes on the back before filling this page)

Ph

Ph

N〇Wco2-):

Ph

Ph C (0) 0CH2C (CH2CH20-) 3

-C6H4 (NH-) 2

Ph

Ph

〇C6H4 (C〇2-) 2

Ph

csh4 (〇-):

Ph Ph Ph

C6H4 (NHCH2CH2〇-) Ph-58-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (

Ph

(CH2〇 — C (O) —CH — CH2) 3

‘I -If-C (O) OCH, —CH— (CH2〇- -C (O) —CH-CH2) 2 (Please read the precautions on the back first to write this page)»:

Ph

• C (0) 0CH2—C (CH3)-(CH20-C (0) —ch-ch2) 2-line · The polymer of the present invention can be random, block, graft or milk fatigue polymer * (Lattice). The preparation of polymers and their fixing methods are well known to those skilled in the art 1 #. One of the methods is to polymerize monomers with overhanging main and auxiliary molecules ' > One is to use a polymer with overhanging functional groups and react it with main and auxiliary molecules that also have an official gs. A further preferred embodiment of the present invention is a method for preparing the compound of the present invention, which involves compounds of the formula xw 5 X IX, XX, XX and XX VIB in any subject / subsidiary combination alone or together. Co-monomer reaction, A 't-subsidiary body (X VI), -59- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (2-body S- Host-A, 3 4 Subsidiary-A '4 (X IX), (XX), (XXI), (XX V1B), Host-(A) c where A' 1 is a fluorene functional or polymerizable group, A '2 is a monofunctional or polymerizable group co-reacted with A, A' 3 is a monofunctional or polymerizable group co-reacted with A 5! And A 5 2, A 4 is a mono-functional or polymerizable group with A ' ί, A '2 and A' 3 co-react, A '5 is a monofunctional or polymerizable group co-f ipte with A' ^, A '2, A' 3, and A 4 懕-anti- 懕, and c is 2 or 3, and the auxiliary body and the main body have the meaning as above, and A,, A, z, A '3 and A4 are directly or through the bridge base connected to the main body and the auxiliary body core structure. A further preferred embodiment of the present invention example A method for preparing the full form (A) polymer of the present invention, which involves a polymer system having re-cured structural elements, each containing a functional or polymerizable group covalently linked directly or via a bridging group, to any host / side Compounds of the formula X 婣, X ίχ, XX, and XXI react individually or collectively in a combination of monomers, A '1-the auxiliary (X «), A ^-the main body (X IX), A' 3- Main body_ λ, 3 A%-Sub-body-A% (XX), (XXI) (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Centi) 1220902 A7 _B7___ 5. Description of the invention () Main body-(A '5) c (XXIX), where A, is fluorene functional or polymerizable group, A' 2 is fluorene functional or polymerizable group and polymer The functional or polymerizable group is co-reacted, A ′ 3 is a fluorene functional or polymerizable group co-reacts with the functional or polymerizable group on the polymer, and A ′ 4 is a monofunctional or polymerizable group with the polymer. Co-reaction of functional or polymerizable groups, A 'is a monofunctional or polymerizable group and polymer The functional or polymerizable group is co-reacted, and c is 2 or 3, and the subsidiary and the main body have the meanings as above, and A,, A2, A'3, A4, and AS are directly or via a bridge bond group and the main body. And auxiliary somatic core structure connection. The polymers of the present invention can be prepared according to methods known in polymer chemistry, such as the steps of growth, anionic, cationic and free radical polymerization. Polymerization methods are, for example, solution, monolith, emulsion, photo- and boundary glucose polymerization. The general range of the reaction temperature is from 0 to 2 5 0 υ. The use of appropriate and fully known catalysts and photoinitiators is not detailed here. An effective free radical catalyst known in the thermal polymerization of azobisisobutylene-based unsaturated compounds. Polymerization can be performed by co-mixing monomers, catalysts and selectively dissolving surfaces, and heating, irradiation, or both heating and irradiation. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------ Installation -------- Order --- (Please read the Note for this page, please fill in this page) 1220902 A7 _B7_ V. Description of the invention () The separation of these polymers can be achieved by precipitation to non-solvent or removal of solvent. If necessary, further purification can be performed by repeating precipitation and drying. Carcasses are partly new and partly known, or they can be prepared by self-knowledge or similar methods. C Functional accessory chromophores are known or can be synthesized by self-knowledge or similar methods. Their synthesis can be A selectively protected functional intermediate is used. The accessory chromophore can be obtained from a chromophore precursor containing an NΗ group, which is reacted by a haloalkane which additionally contains a functional group such as a carboxyl group or a vinyl group. Polyfunctional auxiliary compounds can be prepared in a similar manner as described in the literature EP 0 3 3 7 9 5 1 The main monomer can be prepared according to the method EP 0 4 5 6 6 0 9 Dicarboxylic anhydride reacts with 1,2, -diaminobenzenes, so that the anhydride, diaminobenzenes, or both contain selectively protected functional groups. The bifunctional benzo [4,5] imidazo [2,1 -a] isonitro 15-U-ketones are novel, and a further preferred embodiment of the invention in a range is the formula XXI [ Compound,-Host A, '! (XX II), where A "s is a valence functional group (also means a polymerizable group), which can be directly or via a bridging group connected to the main body, and the main body is a divalent benzo [4,5] imidazo [2,1-a] Isoindene-1 1-Tone, the carbon atoms of the non-benzene ring can be replaced by benzene ring, heteroaromatic ring or upper ring -62- This paper applies Chinese national standard ( CNS) A4 specification (210 X 297 mm) (please read the precautions on the back before filling this page) ϋ 一 n-OJI 1 ^ 1 I— 1 n ϋ ϋ 12-1220902 A7 _B7___ 5. Description of the invention () Zhonghe, and these rings are more easily connected to functional groups than the benzene ring system of the main core structure, and the aromatic rings are unsubstituted or substituted MF, C 丨, Br, -CN, -N〇2:, Cl to Cl 8 _ group, C3 to Cl! 2: Ring heald,

To C! 8 aryl, C 3 1 C 杂 7 heteroaryl, C 3 to C 1 2 cycloalkylalkyl, C 6 to 0.8 aralkyl, 0 to C; 7 heteroaralkyl, Cl to Ci 8 alkoxy, C3 to C; 2 cycloalkoxy, c6 to C 1 8 aryloxy, C5 to Cl 7 heteroaryloxy, C3 to Ci2 cycloalkylalkoxy, Cs to (^ 8 aromatic Alkoxy, Cs to (^ 7 heteroarylalkoxy, CilC! 8 alkylfluorenyl, c3 to (: 12 cycloalkylthio, Ce to Cl 8 arylthio, C5 to C! 7 hetero Arylthio, c 3 to Cl 2 cycloalkylalkylthio, C6 to Ci 8 aralkylthio, C5 to Cl 7 aralkylthio, Ci to (: 18 alkyl-SO- or -S 0 z, C 3 to C i 2 ring mesogenic -s 0-or _ S 0 z, C 6 to C 1 8 aryl-so- or -S () 2, C 3 to ct 7 雑 aryl -so- or -S〇2, C3 to Ci Z cycloalkylalkyl-so-or-S〇2, C6 to C! 8 aralkyl-SO- or -S () 2, C5 to C i 7 heteroaralkyl-so- or -so2, a secondary amine group having 2 M of 80 carbon atoms, and an alkoxyalkyl group having 2 to 20 carbon atoms, except when two are separated- The N Η 2 group is directly bonded to a different benzene ring, and at least one of the additional substituents is connected to the benzene ; And two 0Η groups are directly bonded to a benzene ring. Cycloaliphatic and aromatic residues can also be substituted, such as substituted MF, -6 3- This paper applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) -------------------- Order --------- (Please read the precautions on the back before filling in this Page) 1220902 A7 _B7_ V. Description of the invention () C 1 or B r,-CN,-㈣ 2, C 1 to C i 8 alkyl, C 3 to (Please read the notes on the back before filling this page) C i 2 cycloalkyl, C 6 to C 1 8 aryl, C 3 to C! 2 cycloalkyl alkyl * C 6 1C, 8 aralkyl, C 5 to 〇 7 heteroaralkyl, CCl to ci 8 alkane Oxy, C3 to 纟] ^ cycloalkylalkoxy, c6 to C 8 aryloxy. Examples of substituents are F, C ί, ΒΓ, methyl, ethyl, propyl, Γ group , Hexyl, syloxy, ethoxy, propoxy, butoxy, hexyloxy, methylthio, ethylthio, methyl- or ethyl-SO-, methyl- or ethyl- S 〇2-, phenyl, benzyl, tolylmethyl, xylyl, methylbenzyl, disylbenzyl, chlorophenyl, dichloro Group, methoxyphenyl, dimethoxyphenyl, methoxybenzyl, dimethoxybenzyl, 0, preferably, 1 or 2 rings are condensed with adjacent carbon atoms to form a bicyclic or tricyclic Ring system. These can be selected from the group consisting of benzene, furan, benzophene, pyrrole, Oftidine and pyrimidine.

In a preferred embodiment, the bridge bond corresponds to the formula XXI -Xt-(Ri) r- (xz) S-R3-(XX®), where X i, X 2, R i, R 3 , R and s have the same meanings as above and include preferred embodiments. The functional group A ″ may be selected from the group consisting of an alkyl-bonded halogen such as C 1 and B r; -N 3, epoxide, -OH, -S Η, -C Ν, -NHR j 〇〇, -64 -This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A7 _B7_ V. Description of the invention () = C = NR | 〇〇, = C 0 »-CH-0, -NC 0 >-CH = C Η z, -c (C Η 3) = CH2, -C (()) GH, -S〇3 H, -S〇z Cl, -S〇z Br,-S 0 2 B r ,-C (0)-C i,-C (0)-B r,-0 C (0)-0 R i 〇 ;, -0 C (0)-NR, 〇z R · i 〇3,- C (0)-0 R.! 〇4 '-3 0 z ~ 〇K t 〇4 5 ~ C (0)-NR ι 〇2 K i 〇3 J Ά ~ S 0 2-N R't 〇z R ι 〇3, where

Ri 〇〇 means H, Ci — Cl 8 alkyl, phenyl, or benzyl 'R! 〇 I means C »— Ci 8 alkyl, phenyl, or benzyl, R 1 〇 2 and R i 〇3 means fluorene, Ci-C! 8 alkyl, phenyl, or phenyl φ group, and 〇4 means Cl-C! 8 alkyl, phenyl, or benzyl. RI 〇〇 'R.! 〇JL 9 R 1. 〇 2, R i 〇 3 and R 1 0 4 when the alkyl group preferably contains 1 to 12, more preferably 1 to 8 and most preferably 1 To 4 carbon atoms. More preferably, the functional group A ″ may be selected from the group consisting of C 1 and B r including an alkyl bond; an epoxide, —OH, —SH ′ −〇, —CH = CH2, and —C (CH3) = CH2. , -NCO, -C (0) 0H, -C (0) -U, -C (0) -Br, -C (0)-0 R 1 〇4, -C (0)-Μ 1 〇2 R 1 〇3, where R ι. 〇 means Η, C ι — C i 2 alkyl, R t 〇 2 and R 1 〇 3 means H or C 1 -C 4 alkyl, and R 1. 〇 4 It means C t-C 8 alkyl. -65- This paper size is applicable to China National Standard (CNS) A4 specification (210 χ 297 mm) (Please read the precautions on the back before filling this page) ---- Order -------- 1220902

I A7; _B7 V. Description of the invention () In a preferred embodiment, the compound corresponds to the formula X X IV and X X IV a,

Where R ·) [, R 0z, R 0 3, R 0 4 and R 0s respectively represent Η, C i, €: ^ to (: 18 alkyl, Ci to Cl8 alkoxy, phenyl, benzene Fluorenyl, C i to C t 2 alkylphenyl or C! To C i 2 alkylbenzyl, A 6 and A 7 are divalent residues of formula XX M, and A ”3 may be selected from the group consisting of C i and B r in an alkyl group; epoxide, -OH, -SH, -NHRI 〇〇, -CH = CH2, (CH3) = CHz, -NC0 »-C (0) 0 H, -C (0) -Ci, -C (0) -Br, -Cm-OR! 〇4, ~ C (0) -NR i 〇2 R i 〇3 J where P: i ο 〇® is H, CI-C 1 2 alkyl, R i 〇2 and R i 〇3 means H or C 1 -C 4 alkyl, respectively, and R! 〇 4 means C,.-C 8 alkyl. R 〇 5 preferably means H. In a particularly preferred embodiment, the divalent radicals A 6 and A 7 may be selected from the following formulae -C (0) -0-R, -0-C (0)-(R ") i [ -And one 66-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (-C (0)-N Η-R,-N Η-C (0 )-(R ,,) u-, where R 'is C 2 to C 2 0, preferably C 2 to CI 2, and most preferably Cs to C 6 alkylene, phenylene, benzyl, or having preferably 2 to 6, and more preferably 2 to 4 ethylene oxide and / or propylene oxide units Oligooxyalkylene, R〃 means Ci to Ci 2 alkylene, phenylene or benzyl, and u means 0 or 1, and -CH = C H2 or -C (C H3) = C Hz Attached to a C (0)-group. Particularly preferred compounds correspond to the formula XX Di,

(Please read the note on the back to write this page first) (XXIX), where A 6 is C κ: H4 and A 7 are direct bonds or C! To C s alkylene, phenylene, or benzylidene, and A ”3 means -C00H,, -C (0) -C1,-C (())-β ϊ ',-C (0)-0 R ί 〇4,-C (〇)-NR 1 〇2 RI 〇 3 '-C (0) 〇- C 2 to C! 2 alkylene-() Η,-C (0) 0-C 2 to ci 2 alkylene-0-Cu) CH = C H2, or _C (0) 0-C2 to ci2: alkylene 0-C (0) -C (CH3) = cti2. Except for monofunctional benzene substituted with amine, carboxyl and fluorenylphenyl Benzo [4,5] imidazo [2,1-a] isoazindene-1 ketones, and benzo [4,5] pyrazolo [2, bua] iso with one multifunctional substituent The indene-i-b_ class is also novel, and a further preferred embodiment of the present invention in a range -67-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A7 _B7___ V. Description of the invention () Examples are compounds of formulas XXX and XXX a, host-A "4 (XXX), host-A" 5 (XXX a), where A "4 is a monovalent functional group (also Is a polymerizable group), which can be connected to the main body directly or via a bridging group, and A 'is a di- or trifunctional group (also means a polymerizable group), which can be connected to the main body directly or via a bridging group. And the main body is a valence benzo [4,5] oxazo [2, bua] isoazindene-11-one, the adjacent carbon atoms of the main moss ring can be replaced by a benzene ring, a heteroaromatic fluorene ring or a fluorene ring. These are condensed, and these rings are more easily connected to functional groups than the benzene ring system of the main core structure. The aromatic ring is unsubstituted or MF, C1, Br, -CS, -㈣2, ct to Ci 8 Hexyl, c 3 to C 2 cycloalkyl, c 6 SCi 8 aryl, C5 to C! 7 aryl, C3 to Ci 2 cycloalkyl, C6 to C! 8 aralkyl, Cs to 〇; 7 heteroaralkyl, Ca ICi 8 alkoxy, c3 to Ci 2 cycloalkoxy, Ce to Ct 8 aryloxy, C5 to (: 1 7 heteroaryloxy, C3 to Ci 2 cycloalkyl Alkoxy, to C.i 8 aralkoxy, to C! 7 heteroaryl complex, C 1 to C! 8 alkylthio, C 3 to c 1 2 cycloalkylthio, C 6 to C! 8 arylthio, C 5 to C 7 heteroarylthio, C3 to Ci 2 cycloalkylalkylthio, C6 to Ci 8 aralkylthio , C 5 to C i 7 aralkylthio, ci to C i 8 alkyl-s 0-or _ δ 8-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ( (Please read the notes on the back before filling out this page)

Γ. Ί I tmt n ^ ^ I i Hi H ϋ I 11 I 1220902 A7 _B7_ V. Description of the invention () -SOz, C 3 to C 1 2 cycloalkyl-so- or -S02, C 6 to c I 8 Aryl-SO- or -S02, C5 to Ci7 Heteroaryl-SO-or-S02, C3 to C ί 2cyclofluorenylalkyl-SO- or -S02, C6 to Ci8 Aralkyl-30-or-S〇2, Cs to ci7 heteroaralkyl-so- or -S02, a secondary amine group having 2 to 3 carbon atoms, and a secondary amine group having 2 to 20 carbon atoms Alkoxyalkyl, except when (aUOH is directly bonded to a benzene ring, or U2) -NH2 is bonded directly or via a phenylene bridge, or U3) when COO is bonded via a phenylene bridge The phenyl ring is bonded to the benzo [4,5] Benzene [2,1-a] isoazepine-11-_ nucleus of the nucleus structure, and then at least one of the substituents in the compound of the formula XXX is fused To the benzene ring. Cycloaliphatic and aromatic residues (substituents) can also be substituted, such as substituted MF, C ί or B r, -CN, -N02, CI to Ci 8 alkyl, C 3 to C Ϊ 2 ring Fluorenyl, C 6 to C t 8 aryl, C 3 to C; Z cycloalkylalkyl, C 6 to C ί. 8 aralkyl, C 5 to C; 7 fluorenyl aralkyl, Ci gCt 8 alkane Oxygen, c3 to C! Z cycloalkylalkoxy, C6 to CI8aryloxy. Examples of substituents are F, C, Br, methyl, ethyl, propyl, hexyl, hexyl, syloxy, ethoxy, propoxy, butoxy, hexyloxy, methylsulfide Methyl, ethylthio, methyl- or ethyl-so-, methyl- or ethyl-S02-, caged, phenylmethyl, methylbenzyl, xylyl 7 , Dimethylbenzyl, chlorophenyl, dichlorophenyl, methoxyphenyl, dimethoxyphenyl, methoxybenzyl, dimethoxybenzyl-6 9-Ben Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --------------------- Order ---------. (Please read the precautions on the back before filling this page) 1220902 A7 _B7_______ V. Description of the invention () Poorer * 1 or 2 er rings are condensed with adjacent carbon atoms to form a bicyclic or tricyclic m system. These can be selected from the group consisting of benzene, furan, atphen, atrole, pyridine, and _. In a preferred embodiment, the bridging group of the compound of formula XXX corresponds to formula XXI, -X t-(R 1) r- (Xz) s-R3-(XXI), where X1, X2, R.I, R3, r and S have the same meanings as above and include preferred embodiments. The functional group A "4 and A% may be selected from the group consisting of alkyl-halogenated halogens such as C1 and Br; -N3, epoxide, -0H, -SH, -CN, -NHR! 〇〇, = C = NR i 〇〇, = C0, -CH = 0, -NCO, -CH = CHZ, -C (ί: H 3) = CH z, -C (0) 0 H, -S 0 3 H, ~ S 0 2 C i,-S 0 2 CI, -S () 2 Br, -C (0) -C1, -C (0) -Br, i, -0C (0) -rjRi 〇2 Ri 〇3?- C (0)-0 R i 〇4, -S 0 2-0 R i 〇4,-C (0)-NR! 〇 2 R! 〇3, and -S 0 z-NR! 〇z K i 〇 3, where R! 〇〇 means H, C!-C; 8 alkyl, phenyl, or benzyl, R 1 〇 1 means C i-C i 8 alkyl, phenyl, or benzyl , R t 〇2 and R 1 〇3 means Η, C! -C i 8 alkyl, phenyl, or benzyl, and -7 0-This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) (Please read the precautions on the back before filling out this page) ---- Order --------- 0 1220902 A7 B7 Five Invention Instructions (κ ί 〇04 grace is C ί 1 C 1 8 alkyl, phenyl, or methyl. R 〇〇, R-I 〇1, R 1 0 2 · R t 0 3 and R When -〇4 is an alkyl group, it preferably contains 1 to 12, more preferably 1 to 8, and most preferably 1 to 4 carbon atoms.

More preferably, the functional group A ″ 4 and may be selected from the group consisting of C i and B r including alkyl groups; epoxide, -OH, -SH, -NHR i 〇〇, -CH = CH2, -C ( CH3) = CH2, -NC0, -C (0) 0H, -C (0) -C1, -C (0) -Br, -C (0) -0Ri 〇4 ^ -C (0) -NRi 〇z Ri 〇3 J where

Ric〇〇 means H, Ci-alkyl, R i. 2 and R! 03 means H or C i -C 4 alkyl, and R 1 O 4 means C t -C S alkyl, respectively. In a preferred embodiment, the compounds of formula X X X correspond to formulas X X X I and X X X I a. Please read the notes on the back page first.

Among them, R 〇 1, R 〇 2,: R. 3, R 0 4 and R 0 5 respectively represent Η, C 丨, Ci to Ci! 8 alkyl, C! To C! 8 alkoxy, phenyl, benzyl, C! To C * 2 alkane Phenyl or ci to Ci 2 alkyl benzyl-7 1-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 _B7_ V. Description of the invention () The base, A 9 is A direct bond or a divalent residue corresponding to the formula XXXI, and A ″ 4 may be selected from the group consisting of C 丨 and B r through an alkyl bond; epoxide, (Please read the precautions on the back before filling this page ) -ϋΗ, -SH, -NHR »〇〇, -CH = CHz, -C (CΗ3) = CH2, -NCO, -C (0) i) H, -C (0) -C1, -C (0) -Br,-{: (0) -〇 {^ 〇4, -C (0)-NR i 〇2 R i 〇3, where R I. 〇 means H, CI-C i 2 alkane Groups, R i 〇2 and R i 〇3 mean H or C 1 -C 4 alkyl, respectively, and R ο 4 means C 1 -C 8 alkyl. R 5 preferably means H. In one In a particularly preferred embodiment, A9 is direct fluorene, Ci to Ci £ alkylene, phenylene, benzyl, Ci to CI 2 alkylene oxide, oxyphenylene, oxymethylene, Ct To (: 1 2 Thioalkylene, thiobenzylidene or thiobenzylidene, or a divalent group may be selected from the formula -C (0)-() -R, -0-C (0)-(R ,,) u- and -C (0) -NH-R? -NH-C (0)-(R ") u- ^ where R 'is C 2 to C 2 0, preferably C 2 to C! ζ, and most preferably C 2 to C 6 alkylene, phenylene, benzyl, or having preferably 2 to 6 pseudo, and more preferably 2 to 4 ethylene oxide and / or propylene oxide units Oligoalkylene oxide, R〃 means C 1 to C! 2 S alkyl, phenylene or benzyl, and u means 0 or 1, and-CH = CH2 or-C (CH3) = CH2 1 c (ο) -based. Particularly good compounds correspond to formula XXXI,-72- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A7 B7 Five invention descriptions (

(XXXII), where A 9 is a direct bond or C! To (: 6 alkylene, phenylene, or benzyl, and A "4 means -C 0 0 Η ,,-C (ϋ)-C i,-C (0)-B r, -C (0)-0 R1 〇4, -C (0) -N8i 〇2 R j 〇3, -C (0) 0 -C 2 SC! 2 ® alkane -OH, -C (0) 0-C2 MCi 2 alkylene -0-C (0) -Cfi = (: H2, or -C (0) 0-C2 to Ci 2 alkylene-0- C (0)-C (CH3) = CH2. An example of a compound of formula XXX is (Ph means phenyl):

Please read the note on the back first and write this page where R 3 4 is c 1, 〇 Η, 0 R! ·: · 4 or R! 〇4 means ct-C 8 alkyl, S 1 2 R 1 〇3 and R ^ 〇2 and R i 3 respectively represent Η, C—C 4 alkyl or C 2 to C 4 hydroxyalkyl, -C (0) 0 _ C 2 to C 1 2 alkylene H (()) -CH = CH2, -C (0) 0-Cz to C! 2 alkylene- (Bu (:( 0) 1 (() 113) 4) 12, -〇 (0) 0! ^-〇2 to (: 12 alkylene H (0) -CH = CH2, or -C (()) NH-C2 to C! 2 alkylene-73- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 Mm) 1220902 A7 B7

Ph

V. Description of the invention (0-C (u) -C (CH3 l ^ CHz;

among them

R 3 5 is a direct bond, methylene, ethylene, 2,2-propylene, 0, S, NH, N (Ci to C4 alkyl), C (0) or C (()) SH, And R3 4 has the meaning as above; R35-C6Hr0-R36 where r3 5 has the meaning as above and R3s means H, C2 to C4 hydroxyalkyl, glycidyl or ORs 6 means NH-glycidyl or NHCz to C4 hydroxyalkyl; and (Please read the notes on the back first to write this page)

Ph

Ph

nX) ~ NH-C (0) -C (CH3) = CH2 74- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (Ph

Ph

-C (O) -c (ch3) = ch2

Ph

Ph nh-ch2-ch = ch2

Preferred compounds of formula XXX correspond to formulas xxx I and XXX I a.

(XXXIII), (Please read the notes on the back before filling this page)

(XXXIIIa), where adjacent carbon atoms of the benzene ring can be condensed by a benzene ring, a heteroaromatic ring, or a sulfonium ring, and the aromatic heterocyclic ring is an unsubstituted or substituted M halogen such as F, C 丨 or Br,- CN ,, C t to C 1 8 alkyl, C 3 to C 1 2 cycloalkyl, C 6 to CI 8 aryl, C 5 to C! 7 heteroaryl, C 3 to ci 2 cycloalkylalkyl , Cl to 8 aralkyl, C3 to Cl 7 aralkyl, Ci to Ci 8 alkoxy, c3 to Ci 2 cycloalkoxy, c6 to C 18 aryloxy, C 5 to C 1 7 heteroaryloxy Group, C 3 to c L 2 cycloalkylalkoxy group, C 6 to C! 3 aralkyloxy group, C 5 to C i 7 hetero-75- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A7 _B7_ V. Description of the invention () Aralkyloxy, C 1 to C! 8 alkylthio, C 3 to C i 2 cycloalkylthio, C 6 to C i 8 aryl Thio, C 5 to C i 7 heteroarylthio, C 3 to C 1 2 cyclofluorenylthio, C 6 to C; 8 aryl i thio, to Cl 7 heteroaralkyl thio Group, Cl to 0) ^ alkyl-SO- or -S02, C3 to C12 cycloalkyl-SO- or -S02, C6 to Ci8 aryl-SO- or -S. 2, Cs to Cl 7 heteroaryl_S0- or-S〇2, c3 All C i 2 ring t-endyl-S 0-or -S 0 2, C 6 to C 1 8 aralkyl-SO- or-S02, C 5 to C 1 7 heteroaralkyl-so- or- S02, a secondary amine group having 2 to 31) carbon atoms, and an alkoxyalkyl group having 2 to 2G fluorene carbon atoms, cycloaliphatic and aromatic residues (substituents) can also be substituted, such as by Substituted K halogens such as F, C 1 or B r, -CN, -N 0 2, Ci to C 8 8 i end, C 3 to Ci 2 cycloalkyl, CS to C j. 8 aryl, C 3 all C! 2 cyclo'alkyl_yl, C 6 to C 1 8 aralkyl, C s to C! 7 heteroaralkyl, Ci to Ci 8 alkoxy, C3 to C! 2 cycloalkylalkane Oxygen, C6 to c, Saryloxy, and A, 0 means a trivalent organic group and A means a tetravalent organic group. Examples of substituents are F, C1, Br, methyl, ethyl, propyl, butyl, hexyl, methoxy, ethoxy, propoxy, butoxy, hexyloxy, methylsulfide Methyl, ethylthio, methyl- or ethyl-so-, methyl- or ethyl-S02-, phenyl, benzyl, tolylmethyl, xylyl, sylbenzyl , Dimethylbenzyl, chlorophenyl, dichlorophenyl, methoxycyl, dimethoxyphenyl, methoxybenzyl, dimethoxyfluorenylmethyl 0-76- This paper Standards are applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

n n ϋ I-β · ϋ ϋ · ϋ ^ 1 ϋ ^ 1 ϋ I 1220902 A7 B7 V. Description of the invention () Preferably, a ring without a functional group is condensed with an adjacent carbon atom to form a bicyclic system. They can be selected from the group consisting of benzene, furan, warm phen,% role, pyridine, and ug. In a preferred embodiment, A ^ 0 corresponds to the formula XXXIV and A!! Corresponds to the formula XX XIV a,- R3r (X4) a * R32 '(Xs) b (XXXIV), please read the notes on the back first • R3T < R33 · χιο (XXXIVa),

Wherein (a) R 3 i is direct fluorene, C! To 0] 2 alkylene, phenylene or tolylylene; X 4 is N, 0, S, C (0) 0 or C (0) N R3 2 is C2 to Ci 2 when a is 1 and b is 2 alkynyl triyl, phenyltriyl or benzyltriyl, or C 2 to C t when a is 1 and b is 3 2 alkyltetrayl, phenyltetrayl or benzyltetrayl; X8 means (] H, SH, SHz, C (0) 0H, C (0) [Niii2, 0C (0) -CH =, 〇 (; (〇)-C (C (i3) = CH2, HNC (())-CH = CH2, HNC (ϋ) -C (CH3) = CH2, or (b) R 3 2 is a direct bond, a is 0 and b are 2 or: 3, X 8 has the meaning of 逑, and R 3; when b is 2, meaning C 2 to C i 2 alkyltriyl, phenyltriyl or benzyltriyl , Or C 2 to -77 when it is 3- This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) Order «

1220902 A7 B7 5 Description of the invention (please read the notes on the back first)

Ci 2 alkyl tetrayl, phenyl tetrayl or benzyl tetrayl; ί C) R 3 i is a direct bond, Ct to Ctz alkylene, phenylene or tolylyl; X 9 is N or C ( 0) N; R 3 3 is C 2 to C! 2 alkylene; XL ·: · means 0 Η, S Η, N, C (0) 0 Η, C (0) N Η 2, 0C (0) -CH = CH2, 0C (0) -C (CH3) = CHz, HNC (O) -CH = CH2, HNC (Ci) -C (CH3) = CH2, or -CH = CH2. In the sense that R 3! And R 3 3 are alkylene, it preferably contains 2 to 8 carbon atoms, and more preferably 2 to 4 carbon atoms. R 3 2 preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and most preferably 2 to 4 carbon atoms. In a preferred embodiment, the polyfunctional compound corresponds to the formula X X X V and X X X V a.

Wherein R 〇ί, R 〇z ^ R 〇3, R 〇4 and R. 〇5 respectively means Η, C ί, C to C t 3 alkyl, Ci to C! 8 alkoxy, phenyl, Benzyl, C ί to C t 2 alkylphenyl or C t to C ί alkylbenzene-78- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (Base, A! 〇 corresponds to the formula XXX [V and A. R 〇5 preferably means Η.

Corresponds to the formula XXXIV -------------------- Order --------- (Please read the precautions on the back before filling this page) 7 9 -This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 B7 V. Description of the invention (

In a better specific example, A

And the A group may be selected from the following groups: -ο- ΙΙΟ: ch2] 2-C -N-CCHr-II 〇-ο- ΙΙ〇-ο-CH; -CH-CH, ch2oh * C-0-CH, — Ο- ΙΙ 2 I 〇Cl · ° C — 0 —CH; II 〇 • C—〇—CHr II 2 〇0 II—CH CH2〇—C — CH = CH2 ch2o-c—ch = ch2 0 CH, II I 3 -c- II 〇 • O — CH; -C = CH, i, 0-c ——C = CH, 2 II I 2 0 CH, -------------- install —— (Please read the notes on the back first \ ^ Write this page) -ο- ΙΙ 〇Ό —CHr Γ3 -c—

〇II CH, ch2o-c—ch = ch2 〇-c—0 — CH; II 〇0 CH ^ II I 3 -ch2o—c—c = ch2 CH, 0 — C —C = 2 II I 0 CH,: CH,

〇 II

〇 II CH, ch2o—c—c = ch2 --line ·

0 II • c — o —CH, — C- II 2 I 〇ch2o-c—ch = ch2 ch2o—c—ch = ch2 C —o —CH; II 2 〇 • ch2o—c—c = ch2 II 〇- ο- Ι CH, 〇-C — C = 2 II I 0 CH, 80- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7B7 V. Description of the invention (Formula XXXI and XXX SI Part of the preferred example of a is the compound street (Ph means phenyl) with the following formula:

Ph Ph Ph

C (0) N (CH2CH20H) 2 Ph 〇

Ph Ph Ph

Ph

Ph Ph

Ph Ph

Ph Ph Ph

Ph

Ph Ph Ph

^^-c6h4 (nh2) 2 Ph

N Please read the notes on the back first

Order

Ph Ph Ph

Nt > CH2C6H4 (C〇2H) 2 Ph

N

Ph Ph Ph

0C6H4 (C02H) 2 Ph This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1220902 A7

This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 1220902 A7 B7 V. Description of the invention (In the example of the main compound of the palace energy base, the following compounds can be extracted.

(〇 〇 一

It can be dried because of a step of dissolving ethyl methyl. For example, the residual tritium is removed, the phase is chlorine, and the heat is the best K phase counterpart. For example, propylene is dissolved by dissolving the acid, such as by the hydroxyl group. _ It is better to complete the nitrogen stream corresponding to the two radicals such as anhydrous esters, completely reverse HC 1 > Vacuum evaporate ethyl methyl chloride with solvents such as, for example, removal. The acid chlorinated chloridin is the pyridine, and its preferred mixture is M to form a gas. The crude acrylic acid is then poured into a better synthesis of anhydrous benzene to reflux temperature. For example, it is better to dissolve in the phase and slowly precipitate. The precipitate is preferably an ester. The pure large excess is the corresponding reaction. The degree. If the solvent is poured into ice by adding a large amount of the same solvent, the precipitate can be further refined or it can be burned by itself. The diacid reaction is mixed with an excess of ADB in this amount of hydroxyl groups. Passivate the reactant by filtration and dry purification. M-reprecipitated crops and sulfites can be synthesized by adding sulfur chloride. For example, diphenyl-3,4,3'-83- This paper size applies Chinese national standards ( CNS) A4 size (210 X 297 mm) (Please read the notes on the back before filling this page)

1220902 A7 _B7_ V. Description of the invention () The starting of tricarboxylic acid can be obtained from the method described in Zhi. Org. Khifli 2 (7), 1288 (19δ6). -Diaminobenzoic acid, preferably reacted in a solvent such as acetic anhydride. The resulting benzo [4,5] oxazolo [2, Ιέ] isoazindene-1 benzonecarboxylic acid can be filtered and washed with water such as commonly used water and methanol, and further purification can be performed using a column The chromatographic analysis method preferably uses M chloroform as the elution solvent. (I) Ph Ph The synthesis can be started by the corresponding tetraphenyl-benzo [4,5] imidazo [2,1-a] isoazindene-U-fluorene phosphonium chloride (available freely In a similar manner to diazepyl chloride), by reacting with diallylamine, preferably in a solution such as anhydrous pyridine. The purification step can be performed by slowly pouring the reaction mixture into cold water, and the resulting crude reaction product M is washed with water and dried. Further purification can be performed by column chromatography using e.g. chloroform as the eluent. As an example of a trifunctional host compound, the following compounds can be manufactured: OOCH = CH2 ch2 COOH2C-C-CH2P〇CH = CH2 OOCH = CH2 The preparation of this compound can be carried out by the corresponding tetraphenyl-benzo [ 4, 5] -84-

This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) .---------------- (Please read the notes on the back first to write this page) Order: • Line 1220902 A7 _B7_ V. Description of the invention () Flavor beer and 〖2, 1-a] Isoindene-il-fluorene trifunctional 0H-derivative starting, brewing with propylene chlorine is better than solvent such as dichlorostring Alkanes. The purification step can be performed by pouring the reaction mixture into a large excess of water, and then filtering the resulting precipitate. If necessary, the crude product can be further washed, such as water and methanol, and then dried, for example, in a reduced pressure atmosphere. The corresponding trifunctional 0Η-derivative is preferably synthesized by pentaerythritol (a large excess) and tetraphenyl-pyrido [4,5] _azolo [2,: 11] isoazepine-11 __carboxyl. Acid chlorides (available from the reaction of the corresponding osmic acid with tellurium chloride) are preferred over solvents such as anhydrous pyridine. Purification steps can be carried out in the usual and above-mentioned manner. The methods for preparing the materials and compounds of the present invention are generally carried out in an inert solvent. Inert means that there are no unwanted side reactions between the ingredients and the solution. Solutions can also be used when using the materials of the invention. Suitable inert solvents are, for example, protic and aprotic solvents, which can be used alone or as a mixture of at least two soluble surfaces. Examples are: water, alcohols, alcohols, ethanol, propanol, butanol), ethylene glycol monomethyl mono or monoethyl ether, mystery (dibutyl B, tetrahydrofuran, dioxane, ethylene glycol di Methyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), hydrogenated hydrocarbons (methylene dichloride, chloroform, 1,2-dichloroethane, 1 , 1,3-trichloroethane, 1,1,2,2-tetrachloroethane), carboxylic acid esters and lactones (ethyl acetate, methyl propionate, ethyl crotanoate, 2-methyl Oxyethyl acetate, 7-] 'acid lactone, δ-cis valprolactone, pivalolactone), gallic acid _ saddle and lactam; Ν, Ν-dimethylmethanine Amine, Ν, Ν-Diethylformamide, Ν, -85- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) π binding --------- 1220902 A7 _B7_ V. Description of the invention () N-dimethyl ethyl amine, tetramethyl intestine, hexamethyl phosphite tri amine, 7-butyrolactam , Ε-caprolactam, N-methylpyrrolidine, 1ethyl-pyrrolidone, N-methylhexanone Endoamines: Yaji (Dishenylamine), Sm (Dimethyl, Diethyl, Trishenyl », Tetramethyl), San Luojun (N -methylpyridine, N-methylmorpholine), aliphatic and aromatic hydrocarbons such as petroleum, pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted benzene (chlorobenzene, 0-dichlorobenzene, ί, 2,4-trichlorocage, nitrobenzene, xylene, xylene) and nitriles (acetic acid, propionitrile, benzonitrile, phenylacetonitrile), ketones (propanyl, isopropyl-isobutyl-methyl) 1,2,3,4-tetraphenyl-benzyl [4, 5] imidazo [2, bua] isoazin-11-one and its derivatives which are used as preferred groups of the host compound of the present invention have At a maximum warm harvest of about 3 7 fi nanometers, it is located in the UV region. However, the emission wavelength is stretched by about 350 nanometers of U V to 450 milliohms in the visible region of the electrical cooling light spectrum. In contrast, the use of such compounds as the host / body type material of the carcass is because they are easy to burst themselves under both UV and sunlight radiation sources and can be extended to a wide range of applications. Therefore, materials such as ft can be useful as coloring agents, such as road markings and traffic signs used at night or white B, because they show extremely bright sunlight and can also be used by car halogens. The lamp is excited by the UV light, which can provide intensity and bright colors during the day and night. Other applications include their use as pigments, colorants, scintillator materials, solar collector materials, light-emitting electrical chillers, and fluorescent image materials. And R, the choice of the host compound can be obtained with many kinds of elasticity _ System Institute-8-This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) ---------- ---------- Order --------- (Please read the notes on the back before filling out this page) 1220902 A7 _B7 _ V. Description of the invention () The required length of the propellant, of which The ability to adjust the color and adjust the core system by adjusting the length of the saccharine liquid to reduce the core system to a specific color application. It is also possible to generate fluorescent images (highly embossed structures) by the conventional light SB Sf technology. The composition of the present invention is also used in coatings, lacquers and printing inks. The composition of the present invention can be used in various forms depending on the end use purpose. Complete form ί A) Polymerization_ can be produced in the form of grinding or M particles 进一步 A further preferred embodiment of the present invention is the complete form (A) polymer in the form of particles, especially particles with microfacets separated. The average diameter or particle size corresponds to the particles of the complete form (B). The polymer of the present invention may be mixed with other polymers, that is, a further preferred embodiment of the present invention is a composition comprising (a.) Non-fluorescent Aggregation of polymer matrix and (b) full form (A) polymer. The amount of the component (b) with respect to the g composition may be, for example, from 0.1 to 99.9 psychic percentages, preferably from 1. 1 to 50% by weight. The amount used is essentially based on the amount of main and auxiliary structural units in the full form polymer, as well as on compatibility with the polymer matrix. The polymers can be selected from the group consisting of thermoplastic polymer blends, thermosetting pillars, and cross-linked polymers. The full form thermoplastic and thermoset blend is a polymeric ft alloy. These polymers can be homopolymers, copolymers, block copolymers, graft polymers, or random polymers. These polymers can be opaque, translucent or transparent, preferably transparent -87- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling (This page)

1220902 A7 _B7 _ 5. Explanation of the invention (). The polymer may be selected from, for example, thermoplastic polymers such as polyesters, polyamines, poly saddles, polyamines, polyamines, polyacetic acid, polyheterocycles, polyhydrocarbons; derived from substituted olefins Polymers such as vinyl ether, vinyl office, vinyl alcohol, vinyl chloride, dichloroethylene, propylene, propylene, acrylic acid and acrylic acid esters and acrylic acid esters and amines, styrene, chloroacetophenone , Shenyl styrene, styrene sulfonic acid and its esters and amines, vinyl, vinylpyridine, ethynylpyrrolidine; polymaleic acid and esters and amines derived therefrom; polyethers Polyurethane, Polyurethane, Polyphenyl Sulfide, and Polyaldehyde; and Cellulose and Polyphenols, and Starch or Starch Derivatives. Examples of thermosetting resins and structural crosslinked resins are polyepoxides, unsaturated polyesters, light crosslinked resins such as those obtained from acrylic and / or methacrylic esters and / or amines and / or polymers derived from polyhydric alcohols. Fermented amines, melamine / formaldehyde resins, and phenol / formaldehyde resins; polymers obtained from butadiene, isoprene and / or chloroprene, and copolymers with feminine, which may be crosslinked and Rubber-like properties; and, for example, silicates from the conventional sol / gel process. The thermoplastic composition is, for example, obtainable by dissolving and removing solvent blue by conventional mixing methods such as mixing polymers, injection molding and extrusion molding. The thermosetting and structural cross-linking composition can be obtained by dissolving the polymer in the full form (A), which is preferably a low molecular weight, by a conventional method such as a compression molding method. It is also a further scope of the present invention that the complete form (A) polymer can be mixed with non-fluorescent cross-linking units, such as a polyfunctional monomer or prepolymer, and the cross-linker to form a semi-permeable valerate structure. -8 8-The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------------- φ (please read the precautions on the back before filling this page) ) Order ---------. 1220902 A7 _B7_ V. Description of the invention () (Please read the notes on the back before filling out this page) In a further range, complete form (B) or complete form (A ) Or both polymer particles can be used as fillers for thermoplastics, thermosetting and structurally polymerizable plums. A further preferred embodiment of the present invention is a composition comprising (a) a polymer matrix, and (b) full form (B) particles, full form (A) polymer polymer particles, or both of which are uniform Distributed among them. The amount of the particles with respect to the total composition may be, for example, from 0.01 to 90% by weight, preferably from 0.1 to 90% by weight, and most preferably from 1 to 50% by weight. The polymer matrix may include those described above. The composition can be easily prepared by a conventional mixing method as described above, whereby the particles are dispersed before polymerization of the precursor composition. The polymerizable composition of the present invention may contain further components M to enhance some properties, such as electrical, physical, and mechanical properties, and / or processing capabilities, such as dispersants used to achieve uniform particle distribution, slip agents, and plasticized surfaces. , Antistatic agents, solvents, forming surfaces, antioxidants, light stabilizers, fillers and reinforced filling surfaces such as glass beads and glass fibers, quartz powder, silicates (e.g. S master, white clay, wollastonite), metals and Semiconductor gold hafnium oxide, metal carbonate, gold hafnium salt, metal and semiconductor metal, powdered carbon black, or carbon dimension, whisker, metal and semiconductor metal carbide, metal and semiconductor metal nitride, dye , Pigments and others. The composition of the present invention can be used in the form of shaped articles, including the complete form of B) to modify the composition. -8 9- __ This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 _B7_ V. Description of the invention () * A further preferred embodiment of the invention is therefore a shaped article, which A composition of Θ (a) complete form (A) polymer, or (b)-the composition comprises (b 1) a polymer matrix that contains (b 2) complete form (A) polymer or (b3) complete The polymer particles of the form (A), the complete form (B), or both, are separately or collectively distributed with the complete shape (A) polymerized uniformly in the polymerized Juma matrix. In another area, polymers and full form (A) particles or full form (B) particles can be used as a coating composition as a coating layer on a carrier material. Another object of the present invention is a composition comprising (a)-a support material, and (b) at least one surface is coated with M: (1) a full form (A) polymer, (2) a polymer matrix Which contains uniformly distributed particles of complete form (A), complete form (B) or both, or (3) a polymer mixture comprising a matrix polymer and a uniformly distributed complete form (A) soluble polymer mixture Particles of M complete form (A), complete form (B) or both. Dada's carrier material can be selected from the group consisting of organic or inorganic materials such as glass, ceramics, minerals, plastics, paper, wood, semiconductors, metals, metal oxides and semiconductor metal oxides, and metal or semiconductor metal nitrides or—carbonized_ ° The thickness of the coating layer depends on the application and is usually from 0.1 to 100, preferably from 0.5 to 500 microns, and particularly preferably from 1 to 100 microns- 9 0-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -H ϋ n ϋ nn ϋ ftn n ϋ i ^ i · ϋ n ϋ nnnn I nnn n ϋ I (Please read the back first Please note this page and fill in this page again) 1220902 A7 _B7_ V. Description of the invention () r. The coating can be protected by a transparent coating. Such coatings are commonly known, and usually photocrosslinked coatings are used primarily for this purpose. What's more, materials which are surface modified and belong to the complete form (A) can also be protected by coatings. Coated materials are generally available from conventional methods, such as direct application, or application using a dispersion of a polymerizable composition, casting or spin coating. It is also possible to make a polymerizable composition comprising a polymer formed from a monomer, particularly a crosslinkable olefin unsaturated monomer. The polymerization can be induced thermally, or by actinic radiation or both. These coating compositions are further specific examples of the novelty of this invention. A further specific embodiment of the invention is therefore a liquid and a solvent containing a composition comprising (1 ') a full form (A) polymer, and a selective non-fluorescent polymer (2) polymer matrix, which Contains uniformly dispersed complete form (A), (B), or both particles, alone or in a mixed complete form (A) soluble polymer content. These constituents may contain a solvent, such as those mentioned herein, and optional surface active and dispersing surfaces. The viscosity range of the composition depends on the application required for the coating, and the required viscosity can be achieved by selecting the amount of solvent and polymer. To further achieve the required viscosity, thickeners can be used in addition. Appropriate lysates have been mentioned above. -9 1- The size of this paper applies to China National Standard (CNS) A4 (210 X 297 mm) ------------ installation -------- order ----- ---- (Please read the notes on the back before filling this page) 1220902 A7 _B7 _ V. Description of the invention () The preparation of the composition can be achieved by simply co-mixing the ingredients using appropriate mixing equipment. Dispersion is usually stable depending on viscosity. If the particles are aggregated, they can be redispersed by stirring. In an excellent embodiment, a polymerizable composition can be used in the preparation of the coating, in which at least one surface of the support material is coated, and then polymerized by heat. Photopolymerizable mixtures can also be used to produce fluorescent images by conventional photoresist technology. A further preferred embodiment of the present invention is a polymerizable composition comprising a) a polymerizable carcass or a prepolymer mixed with M complete form (A), (B) or both particles, and optionally completely Form (A) polymer is dissolved therein; b) polymerizable carcass or prepolymer and complete form (A) polymer are dissolved therein; or c) polymerizable main system contains at least one polymerizable group or at least two functions Group or its prepolymer, the polymerizable auxiliary chromophore contains at least one polymerizable group or at least two functional groups or its prepolymerizable group that can be copolymerized with the host, and optionally can be simultaneously Non-fluorescent® body or prepolymer copolymerized with host compound and auxiliary chromophore. Compositions which can be used to form the full form (A) polymer are those previously described. The composition preferably contains a solvent when a coating film or an image is generated. The specific implementation examples described above and the preferred embodiments are also used. The composition tree is 0 -92-This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --- ----------------- Order --------- (Please read the precautions on the back before filling this page) 1220902 A7 _B7 _ V. Description of the invention () In a preferred embodiment, the composition of the polymerizable monomer and / or the prepolymerized polymer contains a functional group selected from olefin unsaturated groups, preferably obtained from -CH = CHz and -C (CH3) = CH2, which can be thermally polymerized or photopolymerized. Photopolymerizable monomers and prepolymers are known to those skilled in the art and are trapped in, for example, EP-A-0 6 5 4 7 1 1. Preferred photopolymerizable monomers and prepolymers are esters or amines, polyols, polyamines, and polyamines based on propionic acid or methacrylic acid and alcohols. The first polymerizable composition is particularly suitable for generating coatings and images. A further preferred embodiment of the present invention is a composition comprising (a)-a carrier material, at least one surface of which is (b)-a highly embossed image of a polymerized optical gambling material, comprising (b 1) Uniformly distributed particles of complete form (A), (B) or both, and selective complete form (A) polymers dissolved therein; (b2) complete form (B) polymers uniformly distributed therebetween; or ( b 3) — a polymer obtained from a photopolymerizable main system containing at least one polymerizable group or at least a difunctional functional photoactivatable group or a prepolymer thereof, and the secondary hair coloring system containing Compounds copolymerized with at least one polymerizable group or at least two photo-activatable functional groups or its prepolymers, and monomers or monomers that can be copolymerized with the host compound and the subsidiary chromophore upon irradiation Prepolymer. A further preferred embodiment of the present invention is a method for preparing a fluorescent high-relief image on a carrier h, which involves irradiating under a photomask or coating the light on the carrier by laser writing. Aggregate composition (it has been dried-93- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ------------- installed (please read the note on the back first) (Fill in this page again)

Order --------- Line I 1220902 A7 _B7 _ V. Description of the invention () ti M remove solvent _), develop the radiated composition, and finally remove the non-radiated radiation to remove the non-radiated part This is most often performed using a dissolving surface treatment. : All materials above are highly fluorescent materials that can be widely used in the optical and electrical cold light devices currently observed. A further preferred embodiment of the present invention is a method for manufacturing fluorescent radiation, which requires M electricity or excitation of the fluorescent composition of the present invention by UV or visible light radiation or both. Another preferred embodiment of the present invention is the use of the composition of the present invention as a fluorescent material. The following examples are provided to demonstrate the invention. A) Fung §§-Preparation of egg bodies / polymer intermediates. Endeavor Example A 1: 1,2,3,4-tetraphenylbenzo [4,5] oxazolo [2,1 -a] isoazindene-i 1-one-?-Carboxylic acid (A 1 , Including 8-isomers) To the reaction vessel equipped with a condenser, a small amount of nitrogen exhauster and a magnetic stirrer, add 10 grams (0.02 2 moles) of tetraphenylphthalic anhydride and 3. 35 grams (0.22 moles) of 3,4-bisanthylbenzoic acid and 100 ml of glacial acetic acid. Grey reaction mixing_ After being heated to the late flow temperature D for several hours, the reaction started to turn dark yellow. The reaction mixture was then placed at a temperature slightly below the late flow temperature for 7 2 hours (1G 5 t: :). The pale yellow precipitate was filtered and washed with water and methanol. The yellow product is then dried in a water aspirator before the final overnight vacuum drying (6 ϋ υ) -94- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---- ---------------- Order --------- line (Please read the precautions on the back before filling this page) 1220902 A7 _B7_ V. Description of the invention (). The yield obtained was 8 i%. Fen Ting example A 2: (Please read the precautions on the back before filling this page) 1,2,3,4-tetraphenyl cage [4,5] _azolo [2, ia] isoazepine-1 Ketone-7 (or 8) carboxylic acid chlorides (A 2 including 8-isomers) Add 5 grams of moles to a reaction vessel equipped with a condenser, a small amount of nitrogen exhaust, and a magnetic stirrer) Compound A 1 and 3G ml of anhydrous benzene. Keeping at room temperature, a molar excess of thionyl chloride was added to the reaction mixture, and then stirred for 3 (3 minutes. The reaction mixture as a yellow suspension was then heated to reflux temperature for about 2 hours K to produce a clear golden color Solution. Solvent and excess sulphur-containing chlorine were removed using a nitrogen stream to form a yellow acid chloride derivative. The yield was 94. B) The functional group 彳 h was prepared. Example R 1: 1,2,354-tetraphenylbenzo [4,5] _azolo [2, bua] isoazepine-II-face-7-carboxyethylmethylpropionate (B1 , Including 8-isomers) 4 grams of A 2 was dissolved in 30 ml of anhydrous pyridine at room temperature for about 30 minutes, slowly added to contain 5 grams (a large excess) of hydroxyethyl acrylic acid brewed in 1 () Stirring solution of milletane anhydrous fft. The reaction mixture was allowed to stand at room temperature. The reaction mixture was further reacted at a rate of 2 / j, and then the reaction mixture was completely stirred and then slowly added to a beaker containing 1 μg of ice and 100 mL of 1 M H C 1. A yellow wart lake was obtained and left to stand before filtration (porous glass G3) to produce a crude product. The crude precipitate was further purified to remove residual hydroxyethyl methacrylate, which was dissolved in chlorine-9 5-this paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902

I ί A7 i _____SI_______ ί --------- V. Description of the invention () j Re-precipitation after pouring to a large excess of hexane (yield δ6%). (Please read the precautions on the reverse side before filling out this page) ΩΛ-JkJLM fh by-product 彳 h compound: storage 〇I sedative example c 1: I carboxyethyl methacrylate derivative of rhodamine B (C 1) In a reaction vessel equipped with a condenser tube's small amount of nitrogen exhauster and magnetic stirrer, 3.5 grams (0.07 mol) of rhodamine B was added to about 30 milliliters of anhydrous dichloromethane. (A idrich premium). Keeping at room temperature, 54 grams (0.09 mol, 1.3 times excess) of carbonyl dipropiazole was added to the vigorously stirred rhodamine during about 10 minutes. The reaction was left to stir at room temperature for a further 4 hours to obtain the desired acid oxazole. Three equivalents of 2-hydroxyethylfluorenyl acrylate (2.89 g, 0.02 mole) were then added to the reaction mixture and stirred for another 72 hours under room temperature. The solvent was removed from the crude reaction mixture and the product was purified by column chromatography. 90 CHCU / 10 MeOH was used as the stripping solvent. Example C 2: Preparation of a polyfunctional dipyrrolopyrrole K similar to the following formula C 2 is achieved by a method of EP () 3 3 7 9 5 1 or more explicitly similar to EP -A? 87 7 31 (especially Example 12): (C 2)

This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 public love) 1220902 A7 _B7_ V. Description of the invention () mm ιΨ \ L · ^ -N, factory-divinylbenzylquinacridine_ of Preparation (Please read the notes on the back before filling this page) Under nitrogen atmosphere, 1.6 g of potassium tertiary butoxide is added to 200 ml of dimethylformamide ("DMF") in about 40 minutes. :) and 4 g of finely divided sulfonium acridine mixture, and the entire reaction mixture was stirred for a further 20 minutes. A large excess of vinyl benzyl chloride (4 g) was slowly added to K over about 30 minutes to obtain a dark green solution, which was left at room temperature overnight. Then, the reaction mixture was poured into vigorously stirred water to obtain a pale orange precipitate. After drying, the orange precipitate was purified by column chromatography, using dichloromethane as the eluent. D) Preparation of fluorescent party. Fen Ting down ί) 1: Yu! A 0 ml reaction bottle (cleaned with chromic acid) was charged with 0.01 4 2 g of the monomer (C 2) and dissolved in 5 ml of chloroform. Then, 1 g of the main monomer (B 1) and another 2.0 ml of chloroform, and 0.5 g of recrystallized azobisisobutyronitrile (ΑΙΒΝ) were added as starting agents. The reaction solution The dissolved oxygen was then removed by bubbling nitrogen gas for 30 minutes. The reaction mixture was then polymerized in a water bath in turt and terminated when the viscosity of the reaction mixture was increased to a sufficient () hours. The polymer was passed through a series of toluene (or Chloroform) to reprecipitation and purification of S alcohol. Yield: 40% 〇Mw = 2 X 105 g / M · ° Fendi Example D 2: Place in if) ml reaction bottle (cleaned with chromic acid) 0.6 3 6 6 grams of -9 7- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1220902 A7 _B7 _ V. Description of the invention () B 1, 0. 3 9 7 Methylpropionate and 0.0 i 4 2 g of C 2. The monomer mixture was dissolved in 3 ml of chloroform, and 0.0052 g of the recrystallized AIBN was used as a starting agent. The reaction feed mixture was degassed by passing in anhydrous nitrogen to dissolve 3 β · min. The reaction was mixed in a water bath of δ 0 " C, and the polymerization was terminated when the viscosity of the solution was increased enough (2 hours). The polymer was separated by string S_ 中 中 定 _ and purified through a series of re-sinking c. Yield: 25%. M W = 2 · 5 X 11) 5 g./mole. Fen Ting Ling ί) 3: 0. 74 grams of B 1, 0. 01 grams of C 2, 0. 71 grams of ethylene glycol dimethacrylate and ϋ. Ϋ 23 grams of AI ΒΝ was dissolved in 1. 8 grams of chloroform comonomer solution was added to a vigorously stirred 60 υ aqueous solution. After 8 hours, highly fluorescent, highly cross-linked insoluble particles were generated. Yield 80%. Fusu_ D 4: 5.5 g of purified polymer (mole% composition is about 70 methyl methylpropionate / 3 (ihydroxyethyl methyl propionate) is dissolved in 1 5 ( ! M 弁 弁 anhydrous pyridine and maintained at room temperature in a nitrogen atmosphere. In this stirred polymerization solution, dissolved in 5ϋmL anhydrous 0¾ pyridine of 0.01 mole (5.86 g) B1 and 0. () () 0 0 4 mol (G. 0 22 7 g :) carboxylic acid chloride derivative of damormin B _ mixed _ was added over 1 hour. After stirring for 4 hours in a chamber, the reaction mixture was heated to reach A further 12 hours. Upon cooling, the reaction mixture was precipitated to a large excess of Shen alcohol three times. Before the final drying, the polymer was washed with water and methanol. ¾ Water and methanol were completely removed to remove unreacted rhodamine. -98- —_ ______-____________-— ...... _____ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page) ---- Order --------- · I? 20902 A7 _____B7______ V. Description of the invention () Examination example D 5: Put it in a reaction bottle (cleaned by chromic acid) of) ml. · 9 7 3 5 g of host monomer B 1 and dissolved in 1 5 ml of chloroform. Then add Q · ϋ 0 2 5 g of guest monomer C 3 and another 2.0 ml of chloroform, and 0 · ϋ "g after recrystallization Azobisisobutyronitrile (ΑΙΒΝ) was used as the eluent. The reaction solution was then removed by passing nitrogen gas through for 2 hrs. The dissolved oxygen was removed. The reaction mixture was then polymerized in a 60 ν water bath, and when the reaction When the viscosity of the mixture is increased enough (3 3 minutes), the polymerization is purified by reprecipitation through a series of methylbenzyl (or chloroform) to methanol. Yield: 3 = X ΙΡ 克 / moleF :) Light path command block material: > system ^^ __ It may be possible to prepare a thin film device containing the non-commissioning composition of the present invention by dissolving a suitable solvent of the material, wherein the amount of beauty is one volume (w / v). The required thinness 1 and thickness depend on the final application, but are usually in the range of Q · 001 to 3 ϋ W / V%. The solution can then be applied by any technique known to those skilled in the art. Matrix) F) Example: F1 Example: Photoluminescence and excitation spectra of all fluorescent polymer samples For standard reflections 式 11 ach 1 F-4 5 ϋ 0 Fluorescence spectrophotometer record, and with the help of a commercial solid-state sample holder with a transparent stone window. All polymer samples use standard laboratory research The bowl and Xu are ground into a powder, and are evenly packed into the sample holder. The length of the monochromatic excitation solution is 3 65 μm and the scanning rate is 2 40 nanometers 9 9 1 This paper size is applicable to Chinese national standards ( CNS) A4 size (210 X 297 public love) (Please read the phonetic on the back? Please fill in this page for more details) ---- Order ----- 1220902 A7 B7 V. Description of the invention (Table S_ clock. The emission wavelengths measured by various polymerizable systems are detailed in the polymer ratio U t% ) Example of the maximum emission intensity (ηπι) of the main body and the auxiliary body in the embodiment. Please read the notes on the back before filling out this page) D3 D4 (61 wt X) (I wt%) (38 wt%) Bl C2 EGDM i 557 (4 9 wt%) (iwt%) (50 wt%) A 2 Rhodamine B — 583 (52 wt%) (0.2 wt%) 2240 192 2390 218 * EGDM: ethylene glycol dimethyl propionate; 8i ffl a: methyl methacrylate-100- this paper Standards apply to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

1220902 098892 ABCD VI. Patent application scope A 5 2 is 蜇 functional or polymerizable group co-reacts with A '1 (Please read the precautions on the back before writing this page) A' 3 is 蜇 functional or polymerizable Co-reacts with A 'Λ and A' 2, A% is m-functional or polymerizable group co-reacts with AS, A, 2 and A, 3, A ^ is fluorene-functional or polymerizable group with A '! , A '2, A' 3 and a '4 co-react, and c is 2 or 3, and the subsidiary body and the subject have the meaning shown in item 1 of the scope of the patent application, and A', A,, A '3 And A'4 is directly or through the bridge base connected to the main and auxiliary structures. 3. A method for preparing a composition according to item 1 of the scope of the patent application, which comprises a polymer having a recuring structural element and each containing a functional or polymerizable group covalently linked directly or via a bridging group with any In the host / auxiliary combination, there are comonomers of formula XW, XK, XX, and XX]: and XX VIB compounds, A'-auxiliary (X Vffl), A '2-host (X ίχ ), A '3-non-body-A' 3 (XX), A, 4-auxiliary body-A '4 (XXI), main body-(A' 5) c (XX) IX, where A 'i is Qin Functional or polymerizable group, A '2 is the co-reaction of the functional or polymerizable group with the functional or polymerizable group on the polymer. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 1220902 A8 B8 C8 D8 6. Scope of patent application (please read the precautions on the back before writing this page) A. It is for the functional or polymerizable group to react with the functional or polymerizable group on the polymer, A , Is a monofunctional or polymerizable group co-reacts with a functional or polymerizable group on the polymer, A, Is a monofunctional or polymerizable group co-reacted with a functional or polymerizable group on the polymer, and c is 2 or 3, and the subsidiary and the main body have the meanings as above, and A,, A, z, A ' 3, A'4 and A'5 are connected directly or via the bridge base to the main and auxiliary structures. 4. A composition, which represents (a) a blend of a non-fluorescent polymer matrix and (b) the substance of the main and auxiliary molecules covalently connected by the polymer to the polymer's main bond directly or via a bridging group The ground composition is based on the polymer in complete form (A). 5, a composition comprising a solid organic support material covalently linked to a fluorescent host chromophore and a subsidiary chromophore directly or via a bridging group, which contains (a) a polymer matrix, and (b) a host A complete form (B) particle consisting essentially of a covalent connection of a pendant support material directly or via a bridge, based on a surface of a pendulum support material, or a polymer by a polymer and directly or via a bridge bond with a polymer The polymer particles or the polymer particles of the polymer according to the complete form (A) are substantially uniformly distributed in the body of the monomer and accessory molecules. 6 ♦ A composition containing a solid organic support material directly or via a bridge bond group covalently linked to the Leiguang corporal chromophore and the accessory chromophore, which contains the Chinese paper standard (CNS) A4 Specifications (210 X 297 mm) 1220902 A8 B8 C8 D8 Patent application scope Main 2 {. Connection: M-valence polymerization: it (Coated 鐽) Surface Master A Surface ί A combination of all together and less Base end to 鐽 之} bridge into b by group it-iu rM r: tt and or equal, followed by real materials and points | according to the object ,: ¾u.1I »y -i ΛΒ0 together and, table} of Α Material (wood type support machine is complete on the cloth base. The tillering bridges are composed of warp-containing or connected, straight proton-based sub-objects are aggregated or aggregated 2 t.:r J, B / ϊ \ · The complete set of geological formations and successive layers are in total or complete. The complete distribution, points} uniform A are ί. And the shape of the whole shape: ¾ quality M base and mixed bag The zygote, the solution of the polygranular solution, the mixed solution can be rained} or combined A} 聚 ί 'Β 式 ί' 3 full form The shape of the base and the bridge group is supported by the direct combination of materials that can be connected or connected. The branch machine has a hair body, a solid pair, and a color package. The main package contains 7 light-packed fluorescents. 'The bridge is formed by the group bond through the ground bridge or by the solid through the straight son or directly with the tapping object, and the split body t person · j 5..4riy. ± coupled or mixed body Even the main price is based on the pre-order, or key.}. The main owner A single _ {合 · # 式 聚 m »: can be combined with all) The material that completes the a key is supported by two or the machine has B nine '/ / .Poor, complete and complete shape of the assembly} A into the group of topographical quality is completely complete and connected to the fi price of a total of S _ 'table (Please read the precautions on the back before writing this page ) And its monomers are aggregated and dissolved in solution A / .. Formula M 有 含 系 si Principal # gt¾ -y¾. Its C polymerization may or may not be official. The paper dimensions are applicable to Chinese national standards ( CNS) A4 specification (210 X 297 mm) 1220902 A8 B8 C8 D8 6. Scope of patent application (please read the precautions on the back before writing this page) Group or its oligomer, polymerizable chromophore contains at least one polymerizable group or at least two functional groups or its prepolymer copolymerizable with the host compound, and the selectivity can be simultaneously with the host Non-fluorescent monomers or prepolymers copolymerized with compounds and auxiliary chromophores. 8. A composition comprising a solid organic support material covalently connected to a fluorescent host chromophore and a secondary chromophore directly or via a bridging group, comprising (a) a carrier material whose at least one surface is ( b) —Highly embossed image of polymerized photoaceae, including (bl) a uniform distribution consisting of a polymer and a host and a subsidiary molecule that are covalently connected directly or via a bridging group to the polymer host The complete form (A), consisting of particles of the complete form (B) or both, directly or via a bridge, based on the covalent access of the surface of the organic support material, and the particles dissolved therein (A) polymer; (b 2) complete form (B) polymer uniformly distributed therebetween; or (b 3) —polymer obtained from a photopolymerizable host system containing at least one polymerizable group or At least two functional photo-activatable groups or its prepolymer, and the subsidiary chromophore contains at least one polymerizable group or 1 less two photo-activatable functional groups or its pre-polymerization Material, and optionally A monomer or prepolymer that is copolymerized with the host compound and the subsidiary chromophore during injection. 9 ♦ A polymerizable composition according to item 8 of the scope of patent application, which is used to prepare a fluorescent high relief image on a carrier. ] 〇 ♦ According to the composition of item [] in the scope of patent application, the paper size of the main body applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1220902 A8 B8 C8 D8 Derived from the formula XX]]: 的 合 合 _, (Please read the notes on the back before writing this page) A ”-Body-A”】 (XX)), where A ”Α is an S-valent functional group (also (Meaning polymerizable group), which can be connected directly or via a ® bridge group to the host core structure, and the host is a divalent benzo [4,5] oxazolo [2,1-a] isonitrogen methane, The adjacent carbon atoms of the main benzene ring can be condensed by a benzene ring, an aromatic ring or an upper ring, and a free fluorene can be connected to these rings instead of being connected to the benzene ring of the main core structure. The aromatic ring is not Substituted or substituted M halogen, —CN, —NO2, Ci to Ci 8 alkyl, C. 3 to Ci 2 cycloalkyl, c 6 to Ci 8 aryl, to Ci 7 aryl, C3: lCi 2 cycloalkylalkyl, c6 to C 18 aralkyl, C5 to Ci 7 aralkyl, Ci to Ci8 alkoxy, c3 to Ci 2 cycloalkoxy, C6 to Cj 8 aryloxy, C 3 to ci 7 , C 3 to C t 2 cycloalkylalkoxy, C 3 to c 8 aralkoxy, C5 to Ci 7 aralkoxy, Ci to C, 8 alkylthio, C 3 to C 1 2 cycloalkylthio, cs to C! 8 arylthio, C5 to C! 7 arylaryl, C3 to C; 2 cycloalkylthio, Ce to Ci 8 aralkylthio , C5 to Cl 7 aralkylthio, C, to Ct 8 alkyl-so- or -so2, c3 to C 1 2 cycloalkyl-SO- or -S02, C 6 to C ^ 8 aryl -so- or-so 2, C 5 to C 1 7 aryl-SO- or -S02, C 3 to C; 2 cycloalkylalkyl-SO- or-S02, C6 to (: 1 8 Aralkyl-so-or-so2 -6-This paper size applies to Chinese National Standard (CNS) A4 (210 x 297 mm) 1220902 358 8 99 ABCD 々, patent application scope, c; to C i 7 雑Burning group -S 0-or -S 02, with 2 to 30 carbon atoms (please read the precautions on the back before filling this page), secondary amine groups, and alkanes with 2 to 20 carbon atoms Oxyalkyl, except that when two separated -N fi2 groups are directly bonded to different benzene rings, at least one of the additional substituents is connected to the benzene ring; and two 涸 0 Η groups are Direct key 5 —one ring. 11 * The composition according to item 1 of the scope of patent application, wherein the main chromophore residue is derived from the compounds of formula XXX and XXX a, main _A ”4 (XXX), main -A” s (XXX a), where A "4 is a trivalent functional group (also means a polymerizable group), which can be directly or via a bridge bond group connected to the main core structure, and A" 5 is a di- or tri-functional group (also means Is a polymerizable group), which can be connected to the host core structure directly or via a bridging group, and the host is an m-valent cage and [4,5] _azolo [2, la] isoazepine-1b_ Adjacent carbon atoms of the ring can be condensed by a benzene ring, a heteroaromatic ring or an epicyclic ring, and these rings are more easily connected to functional groups than the benzene ring system of the main core structure. The aromatic ring is unsubstituted or Substituted KF, C1, Br, -CN,-^ ϋ 2, C 5i MC ί 8 alkyl, C 3 to C 2 2 cycloalkyl, C 6 to C 8 aryl, C 5 to C! 7 雑 aryl , C 3 to C i 2 cycloalkylalkyl, Ce to C; 8 aralkyl, C 5 ic, 7 heteroaralkyl, ί. 8 彳, Yuan oxygen race 'C 3 MU j 2 soil comprehensive oxygen, U 6 C. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1220902 098899 ABCD VI. Application for patent scope 1 8 Aryloxy, 7 雑 aryloxy, C3 to Ci 2 cycloalkane (Please read the notes on the back before filling this page) Alkoxy, C 6 to C ί 8 Aralkoxy, c 5 to Ci 7 aralkyloxy, c 1 to C {8 alkylthio, C3 to Ci 2 cycloalkylthio, C 6 to C 8 arylsulfenyl, c 5 to c ί 7 heteroarylthio , C 3 health C! 2 ring fe-based burned base is thin! , C 6 to C! 8 aryl-sulfanyl, C 5 to ci 7 aralkylalkyl, C! To C 1 8 alkyl-so- or -S02, C3 SCi 2 cyclofluorenyl- so-or -S02, c6 to Ci 3 aryl -S 0-or S 0 2:, c 5 to ci 7 heteroaryl -S 0-or -S 0 2, c 3 rong Li i 2 iw fet group * S 0-or -S 0 2, C 6 to C i 8 aryl heptyl -so- or -S02, c5 to C; 7 heteroaralkyl-SO- or -S〇2, with 2 1 30 carbons Atomic secondary amine groups, and alkoxyalkyl groups having 2 to 2i) carbon atoms, except that when UUO fluorenyl groups are directly bonded to a benzene ring, or U2) -NΗ2 groups are directly or via a phenylene bridge Radical bonding, or U3) When the COO fluorenyl group is bound to the benzo [4,5] _azolo [2, la] isoazindene core structure via a phenylene bridge, it is compounded in formula XXX Juzhong additionally has at least one of its substituents bonded to a benzene ring. -8- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm). Application date ,,, --- --- 11 V 4 ... .......... 1 Case No. Category __ (the above are filled out by this Bureau) '— Special, A4 C4 1220902 Description Invention Type New Name Invention Creator Applicant Chinese English Name Nationality Residence, Home Name (Name) Nationality Residence, Residence (Office) Name of Representative A composition containing a solid organic support material directly or via a bridge key®, covalently linked with a fluorescent chromophore and a fluorescent chromophore, Method and Application_ A composition comprising a solid organic support material to which either directly or via a bridging group, the process for preparation thereof and application thereof ⑴ 比昂 · 格拉德 David Lin⑵ 淳 谷 谷 二 二Hiroshi Abu Kobe, Hyogo Prefecture 5-1-1201, Shinoharadai, Shitan-ku, Japan ⑶ Japan 569-11 4-9-3, Akutagawa, Takahata City, Osaka Prefecture ⑷ 1732 Akosir, Switzerland 202, 202 Switzerland 1784 Keltin, Lager 籣 Defen Bart Chemicals Holding, Switzerland 4f: i57 Basel City, 141 Kleiber Street (1) Ernst Athaler Hans-Petter ♦ Wetling -1- This paper applies China National Standard (CNS) 8 4 specifications (21 × 297 mm) binding line 1220902 A8 B8 C8 r- Scope of patent application The base and the bridge are formed by the group or the direct valence materials. The body supports the hair coloring. The body has a pair of first-fixing and fluorescent-coloring hairs. The main light is the light absorption spectrum. Group, 5 colors [4 hairs with benzene side-by-side spectroscopy and self-selection %% hairs with light color and fluorescent body »main color in the hair body and main body, superimposed azobisisoindene as the body ff The main model has a ratio of supporting materials supporting the material body to the main body, and the S type M Ηϋ 畐 and the body main body have a transitive or sexual line structured suspension The auxiliary and hanging if. A-shaped co-full bond completes the main one and contains the base and the base. The support machine and the body are made by the main system of the} B group, and the valence group of geological sub-substances is divided into geological material materials to support the perimeter to the Fan Jie Lilian. One connection. Straight 2 sub-fractal method is full. Fang Wan and Nian 1 The body surface contains the main ingredients of the package or its material items, or supports 1, the branch X of the same type or the combination of the anti-single unitary single object / combined main II Ho X Ren X In S Contains I Package X Its XXX IX X Reverse Monopoly Common Ground (Please read the precautions on the back before writing this page) Shoulder Body Body Deputy Leader MΪ X IX XXXXX Body Leader In VI XX, the base aggregate or performance official sheet is based on the Chinese paper standard (CNS) A4 (210 X 297 mm).