JP5265994B2 - Fluorescent polymer and optical device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluorescent material having excellent mechanical properties (high elastic modulus, flexibility and high toughness) and having fluorescence of &ge;500 nm in addition to excellent fluorescent characteristics (strength of fluorescent intensity, long-term stability of fluorescent intensity), high heat resistance (glass transition point of &ge;200&deg;C, and decomposition initiation temperature of &ge;350&deg;C). <P>SOLUTION: The fluorescent polymer has a molecular chain exhibiting fluorescence at wavelength 380-800 nm and a terminal group represented by general formula (I) (wherein R<SP>1</SP>to R<SP>3</SP>is as defined in the specification). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a fluorescent polymer and an optical device using the same. The fluorescent polymer of the present invention has excellent fluorescence characteristics, and exhibits blue-blue-green-green-white fluorescence or red-orange fluorescence with high efficiency when excited by ultraviolet light. It can be used as a device material. In addition, an optical device manufactured using this fluorescent polymer or its precursor has excellent characteristics that have not been achieved in the past, that is, high heat resistance, excellent mechanical strength, excellent electrical characteristics, film formation and microfabrication. Ease, long-term stability, environmental resistance, chemical resistance, etc.

  In recent years, various low-molecular compounds and high-molecular compounds have been developed as organic light-emitting materials used for organic electroluminescence (EL) elements, light-emitting spatial light modulation elements, wavelength conversion elements, and fluorescent surface coating materials. Has been. In the production of light emitting devices, etc., when using low molecular weight compounds, the production process is limited to the vapor deposition method, whereas the polymer compounds can be produced in solution by film formation or ink jet printing, etc. It has the advantage that can be made cheaper. In addition, the polymer compound has excellent characteristics such that fine coating can be performed without fine processing, and the film thickness can be easily adjusted to form a film. Therefore, it is desired to develop a high-molecular light-emitting material that exhibits high-efficiency fluorescence and can easily control the emission wavelength.

  Conventionally known π-conjugated polymers such as polyparaphenylene and polyparaphenylene vinylene are known as polymer light emitting materials. However, such a π-conjugated polymer has not enough heat resistance, environmental resistance, that is, long-term stability of fluorescence intensity and fluorescence spectrum shape, and film formation and microfabrication are not easy. was there. In addition, as a fluorescent coating material, a fluorescent polymer having a dye molecule in the side chain of an acrylate polymer has been reported (for example, see Patent Document 1), but the heat resistance and environmental resistance of the main chain and the dye are described. Is not sufficient, and if the dye is further contained at a high concentration, the dye is precipitated, and therefore the dye concentration cannot be increased. On the other hand, polyimide, which is a typical heat-resistant polymer, has excellent heat resistance and electrical properties, and the precursor polyamic acid has excellent processability such as film formation. Use as a material is expected. For example, a polyimide exhibiting blue fluorescence emission in which a fluorescent furyl group is introduced into a main chain or a side chain has been reported (for example, refer to Non-Patent Document 1), and a polyimide having a light emitting function or a charge transport function has been reported. The used organic EL element has been reported (for example, refer to Patent Documents 2 and 3). However, the reported fluorescence emission of these polyimides is due to the fluorescent functional groups introduced into the main chain or side chain of the polyimide, and the fluorescence intensity is based on the strong interaction between the polyimide molecules. Due to the accompanying concentration quenching, the fluorescence intensity is very low compared to the fluorescence intensity of the low molecular weight compound having the same fluorescent functional group.

  In addition, it has been conventionally known that a wholly aromatic polyimide itself exhibits visible fluorescence by irradiation with ultraviolet rays (see, for example, Non-Patent Document 2). This fluorescence is fluorescence (CT fluorescence) resulting from a charge transfer complex (CTC) formed between a diamine portion (electron donating property) and an acid anhydride portion (electron attracting property) in the molecular structure of polyimide. (For example, refer nonpatent literature 3). However, in the case of wholly aromatic polyimide, the CT interaction is strong and the non-radiation deactivation process is increased, so that the fluorescence intensity becomes weak. A typical wholly aromatic polyimide film, pyromellitic dianhydride and polyimide synthesized from 4,4'-diaminodiphenyl ether (PMDA / ODA) is weak enough to be difficult to observe with a normal fluorescence spectrometer Only fluorescence is observed. In addition, even with wholly aromatic polyimides, it has been reported that polyimides synthesized from biphenyltetracarboxylic dianhydride and paraphenylenediamine (BPDA / PDA) exhibit relatively strong fluorescence (for example, Non-Patent Document 4). reference). However, compared to existing fluorescent polymer compounds, the fluorescence intensity is very weak, and the quantum yield of fluorescence is considered to be as low as 1% or less.

  In addition, charge transfer (CT) can be achieved by using a polyimide having a three-dimensional structure and a structural unit composed of an aromatic dianhydride having fluorine directly bonded to an aromatic ring and a diamine having an alicyclic structure. ) Since the interaction is suppressed, it has excellent fluorescence emission characteristics (intensity of fluorescence intensity, controllability of fluorescence wavelength in the green to red region, long-term stability of fluorescence intensity), heat resistance, chemical stability, It has been reported that monochromatic luminescent fluorescent polyimides excellent in film forming properties can be obtained (see, for example, Patent Document 4). In addition, by using polyimide synthesized from a combination of flexible 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride and alicyclic diamine, it has excellent green fluorescence characteristics, heat resistance It has been reported that a monochromatic luminescent fluorescent polyimide having excellent properties, chemical stability, and film forming properties can be obtained (see, for example, Non-Patent Document 5). In addition, by using polyimide that has a three-dimensional structure and a structural unit consisting of acid dianhydride having a low electron accepting property and a diamine having an alicyclic structure, it has excellent blue fluorescence emission characteristics. However, it has been reported that a monochromatic luminescent fluorescent polyimide excellent in heat resistance, chemical stability and film formation can be obtained (for example, see Patent Document 5). Furthermore, an example in which a light-emitting device by organic electroluminescence (electroluminescence) is produced using these fluorescent polyimide thin films as a light-emitting layer or a hole transport layer has been reported (for example, see Non-Patent Document 6).

According to Patent Documents 4 and 5 and Non-Patent Document 5, it is disclosed that a fluorescent polyimide having excellent fluorescence characteristics can be obtained. The fluorescent polyimides disclosed in Patent Documents 4 and 5 and Non-Patent Document 5 show the controllability of the fluorescence wavelength in the green to red region and the blue fluorescence characteristics, respectively. In general, polyimide is obtained by reacting tetracarboxylic dianhydride (hereinafter referred to as acid dianhydride) and diamine in a polar solvent to obtain polyamic acid, which is subjected to dehydration ring closure (imide) by heat treatment or chemical treatment. ). As a result of studies by the present inventors, it has been clarified that the fluorescence emission wavelength of polyimide strongly depends on the electronic structure and steric structure of acid dianhydride as compared with diamine. That is, polyimide synthesized from non-fluorinated acid dianhydride having a low electron affinity (hereinafter referred to as non-fluorinated anhydride polyimide) has high transparency in the visible region and purple / blue fluorescence. On the other hand, polyimides synthesized from perfluorinated acid dianhydrides having a high electron affinity (hereinafter referred to as fluorinated anhydride dianhydrides) or polyimides synthesized from flexible acid dianhydrides exhibit green and red fluorescence. However, since excitation light suitable for green / red fluorescence emission is visible light, strong green / red fluorescence cannot be obtained by ultraviolet light excitation. Furthermore, polyimide synthesized using a mixture of non-fluorinated acid dianhydride capable of ultraviolet light excitation and several mole percent of perfluorinated acid dianhydride as a raw material has blue fluorescence although it has an orange fluorescence component. Will remain strong and become a composite color of these, so orange to red fluorescence cannot be obtained. In the future, it is expected that ultraviolet light will be used for light sources such as backlights. Therefore, development of light wavelength conversion materials that emit blue to red and white fluorescence by excitation with ultraviolet light is also required as display devices and display materials. It has been.
JP 2006-307129 A Japanese Patent Laid-Open No. 03-274663 Japanese Patent Laid-Open No. 04-093389 JP 2004-307857 A JP 2005-320393 A SM Pyo et al., Polymer, 40, 125-130 (1999) ED Wachsman and CW Frank Polymer, 29, 1191-1197 (1988) M. Hasegawa and K. Horie, Progress in Polymer Science, 26, 259-335 (2001) M. Hasegawa et al., Journal of Polymer Science Part C: Polymer Letters, 27, 263-269 (1998) Jun Wakida, Shinji Ando, Polyimide / Aromatic Polymer Recent Progress 2007, 209-212 (2007) Sho-ichi MATSUDA, Yuichi URANO, Jin-Woo PARK, Chang-Sik HA, Shinji ANDO, J. Photopolym. Sci. Technol., 17 (2), 241-246 (2004).

  Therefore, the object of the present invention is in addition to excellent fluorescence characteristics (fluorescence intensity, long-term stability of fluorescence intensity) and high heat resistance (glass transition point: 200 ° C. or higher, thermal decomposition start temperature: 350 ° C. or higher). A new fluorescent material with excellent mechanical properties (high elastic modulus, excellent flexibility, high toughness), low birefringence, fluorescence emission of 380 to 800 nm by excitation with ultraviolet light, and easy control of fluorescent color It is to provide.

  As a result of repeated studies to achieve the above object, the present inventors have obtained the knowledge that a polymer having a specific acid anhydride structure as a terminal group can achieve the above object, and intensively studied based on that knowledge. As a result of overlapping, the present invention has been completed.

  The present invention has been made based on the above findings, and provides a fluorescent polymer having a molecular chain exhibiting fluorescence emission at a wavelength of 380 to 800 nm and a terminal group represented by the following general formula (I) It is.

In the formula, R ^{1 to} R ³ may be the same or different from each other, and are a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group which may be substituted with a halogen, directly or via a bridging member. The monovalent substituent comprised by the aryl group couple | bonded together or those combination is shown.

  The terminal group represented by the general formula (I) of the present invention is preferably a group represented by the following formulas (1) to (4).

  In the fluorescent polymer of the present invention, the molecular chain exhibiting fluorescence emission at a wavelength of 380 to 800 nm is preferably a polyimide molecular chain obtained by polymerizing at least one acid component and at least one diamine component.

  As the acid component in the polyimide molecular chain, an aromatic or alicyclic tetracarboxylic dianhydride represented by the following general formula (II) or a derivative thereof is preferably used alone.

In the formula, R ⁴ represents a monocyclic or condensed polycyclic aromatic or alicyclic compound, or an aromatic or alicyclic compound which may be the same or different, either directly or via a crosslinking member. 4 represents a tetravalent group of a non-condensed polycyclic aromatic or alicyclic compound connected to each other, wherein the aromatic or alicyclic compound may be substituted.

  Furthermore, as an acid component in the polyimide molecular chain, an aromatic or alicyclic tetracarboxylic dianhydride represented by the general formula (II) or a derivative thereof, and an aromatic tetra represented by the following general formula (II ′) It is also preferred to use in combination with a carboxylic dianhydride or a derivative thereof.

In the formula, R ^{4 ′} represents a monocyclic or condensed polycyclic aromatic compound, or a non-aromatic compound in which the same or different pre-aromatic compounds are connected to each other directly or via a bridging member. 4 represents a tetravalent group of a condensed polycyclic aromatic compound, in which the aromatic compound may be substituted, provided that R ^{4 ′} is not the same as R ⁴ .

  The diamine component in the polyimide molecular chain is preferably an aromatic or alicyclic diamine represented by the following general formula (III).

In the formula, R ⁵ represents an aromatic or alicyclic compound, or a non-condensed polycyclic compound in which the same or different pre-aromatic or alicyclic compounds are connected to each other directly or via a cross-linking member. 2 represents a divalent group of a cyclic aromatic or alicyclic compound, wherein the aromatic or alicyclic compound may be substituted.

  Therefore, as the molecular chain exhibiting fluorescence emission at a wavelength of 380 to 800 nm in the fluorescent polymer of the present invention, a polyimide molecular chain represented by the following general formula (IV) is preferable.

In the formula, R ⁴ , R ⁵ and n are as defined above.

  Furthermore, as the molecular chain that exhibits fluorescence emission at a wavelength of 380 to 800 nm in the fluorescent polymer of the present invention, a polyimide molecular chain represented by the following general formula (IV ′) is preferable.

In the formula, R ⁴ , R ^{4 ′} , R ⁵ and n are as defined above.

  Typically, the fluorescent polymer of the present invention having a molecular chain exhibiting fluorescence emission at a wavelength of 380 to 800 nm and the terminal group represented by the general formula (I) is represented by the following general formula (V). Polyimide.

In the formula, R ^{1 to} R ³ , R ⁴ , R ⁵ and n are as defined above.

  Furthermore, the fluorescent polymer having a molecular chain exhibiting fluorescence emission at a wavelength of 380 to 800 nm and a terminal group represented by the general formula (I) according to the present invention is represented by the following general formula (V ′). Polyimide is preferred.

In the formula, R ^{1 to} R ³ , R ⁴ , R ^{4 ′} , R ⁵ and n ′ are as defined above.

  In addition, this invention can also provide the polyamic acid represented by the following general formula (VI) which is a precursor of the polyimide represented by the said general formula (V) as a precursor of the fluorescent polymer of this invention. it can.

In the formula, R ^{1 to} R ⁵ and n are as defined above.

  Similarly, a polyamic acid represented by the following general formula (VI ′), which is a polyimide precursor represented by the general formula (V ′), may also be provided as a precursor of the fluorescent polymer of the present invention. it can.

In the formula, R ^{1 to} R ⁵ and n ′ are as defined above.

  Moreover, this invention provides the organic light-emitting device manufactured using the said fluorescent polymer or its precursor. Examples of organic light emitting devices include light emitting elements such as organic EL elements and organic lasers, wavelength conversion elements that convert short-wave excitation light (ultraviolet rays) into visible light, and spatial light modulation elements that incorporate them.

  Moreover, this invention provides the organic light wavelength conversion device manufactured using the said fluorescent polymer or its precursor.

  Furthermore, this invention provides the fluorescent surface coating material manufactured using the said fluorescent polymer or its precursor.

  ADVANTAGE OF THE INVENTION According to this invention, the novel fluorescent polymer which has the outstanding fluorescence emission characteristic, and was excellent in heat resistance and a mechanical characteristic is provided. In particular, the fluorescent polymer of the present invention is useful in that, in addition to having a high fluorescence intensity, it is possible to easily control the fluorescence intensity and the fluorescence wavelength by adjusting the ratio of the terminal groups.

The present invention is described in detail below.
The present invention provides a fluorescent polymer having a molecular chain that emits fluorescence at a wavelength of 380 to 800 nm and a terminal group represented by the following general formula (I).

In the general formula (I), R ^{1 to} R ³ may be the same or different from each other, and are a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group that may be substituted with a halogen, It is an aryl group bonded directly or via a bridging member, or a monovalent substituent constituted by a combination thereof.

  Here, unless otherwise stated in this specification, the term halogen atom or halogen means a fluorine, chlorine, bromine or iodine atom.

  Moreover, unless otherwise indicated in this specification, the term alkyl group alone or in combination with other terms means a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, and a hexyl group. The alkyl group which may be substituted with halogen is a concept including an alkyl group substituted with one or more halogens together with the alkyl group. Examples of the latter include a fluoromethyl group, a chloromethyl group, and trifluoro. A methyl group etc. are mentioned.

  Also, unless otherwise stated herein, the term alkoxy group, alone or in combination with other terms, means an alkyl-oxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a hexyloxy group. The alkoxy group which may be substituted with a halogen is a concept including an alkoxy group substituted with one or more halogens together with the alkoxy group. Examples of the latter include a fluoromethoxy group, a chloromethoxy group, and a trifluoro group. A methoxy group etc. are mentioned.

Further, unless stated otherwise herein, alone or in combination with other terms, the term aryl group means a phenyl group or a naphthyl group, and the bridging member is an oxygen atom (—O—), carbonyl Group (—CO—), ester group (—C (O) O— or —OC (O) —), sulfur atom (—S—), sulfinyl group (—SO—), sulfonyl group (—SO ₂ —) , An alkylene group (—CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — etc.) which may be substituted with halogen, or an arylene group. Accordingly, examples of the aryl group bonded through a cross-linking member include a phenoxy group and a benzyl group.

  Unless otherwise specified in the present specification, the term alkylene group alone or in combination with other terms is a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms. means. Examples of the alkylene group include a methylene group, an ethylene group, an isopropylidene group, and a hexamethylene group. The alkylene group which may be substituted with halogen is a concept including an alkylene group substituted with one or more halogens together with the alkylene group, and examples of the latter include a hexafluoroisopropylidene group.

  Furthermore, unless stated otherwise herein, the term arylene group, alone or in combination with other terms, means a phenylene group or a naphthalene group. The arylene group which may be substituted with a halogen is a concept including a phenylene group or a naphthalene group together with a phenylene group or a naphthalene group. Examples of the latter include fluorophenylene and difluorophenylene. Groups and the like.

In R ^{1 to} R ³ of the general formula (I), the monovalent substituent constituted by a combination thereof is a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group optionally substituted with a halogen, or directly Or a monovalent substituent composed of a combination of two or more groups selected from aryl groups bonded via a bridging member, such as an alkyl group or alkoxy group substituted with a hydroxyl group; or a hydroxyl group, halogen Examples thereof include an aryl group substituted with one or more groups selected from an atom or an alkyl group or an alkoxy group optionally substituted with a halogen.

As R < ¹ > -R < ³ > in the terminal group represented by the said general formula (I), what is a hydrogen atom or a hydroxyl group is preferable, for example, what is represented by following formula (1)-(4) is mentioned.

  Examples of the molecular chain that exhibits fluorescence emission at a wavelength of 380 to 800 nm in the fluorescent polymer of the present invention include molecular chains such as polybenzoxazole, polyfluorene, polyimidazole, polyparaphenylene, polyparaphenylene vinylene, and polyimide, Although it does not specifically limit as long as it is the range which does not deviate from the content of this invention, Preferably, the polyimide molecular chain obtained by superposing | polymerizing at least 1 type of acid component and at least 1 type of diamine component is mentioned.

  In the polyimide molecular chain, the at least one acid component includes an aromatic or alicyclic tetracarboxylic dianhydride represented by the following general formula (II) or a derivative thereof. Here, the term “derivative” includes a concept in which a part and / or all of the acid dianhydride is ring-opened and a part and / or all of the carboxyl group resulting from the ring opening are esterified. It is. The esterification alcohol is not particularly limited, and examples thereof include hydrocarbon alcohols such as methanol, ethanol and propanol, and aromatic alcohols such as phenol and cresol. By using an aromatic or alicyclic tetracarboxylic dianhydride represented by the following general formula (II) or a derivative thereof, a polyimide molecular chain exhibiting fluorescence emission at 380 to 800 nm, particularly 380 to 500 nm can be obtained. .

In the general formula (II), R ⁴ represents a monocyclic or condensed polycyclic aromatic or alicyclic compound, or the aromatic or alicyclic compound which may be the same or different, directly or 4 represents a tetravalent group of a non-condensed polycyclic aromatic or alicyclic compound connected to each other via a cross-linking member, wherein the aromatic or alicyclic compound may be substituted. Moreover, you may use these acid dianhydrides individually or in combination as an acid component. It is preferably used in combination with an aromatic tetracarboxylic dianhydride represented by the following general formula (II ′) or a derivative thereof.

R ⁴ in the general formula (II) is preferably a monocyclic or condensed polycyclic aromatic or alicyclic compound having 6 to 36 carbon atoms, or the same or different fragrance A tetravalent group of a non-condensed polycyclic aromatic or alicyclic compound in which an aromatic or alicyclic compound is connected to each other directly or via a cross-linking member. Examples of such monocyclic or condensed polycyclic aromatic compounds include benzene, naphthalene, anthracene, phenanthrene, and the like. Examples of the monocyclic or condensed polycyclic alicyclic compound include cyclobutane, cyclohexane, norbornane, spiro [4.5] decane, and the like.

  These are selected from a monovalent substituent constituted by a halogen atom, an alkyl group optionally substituted with a halogen, an aryl group bonded directly or through a bridging member, or a combination thereof on the ring. It may be substituted with one or more groups.

Examples of R ⁴ in the general formula (II) include those represented by the following formulas (5) to (8).

R ⁷ and R ⁸ in formula (5), and R ^{9 to} R ¹⁴ in formula (6) may be the same or different, and may be a hydrogen atom, a halogen atom, or an alkyl optionally substituted with a halogen. It is either a group or an aryl group bonded directly or via a bridging member, or a monovalent substituent constituted by a combination thereof.

In the formula (7), R ¹⁵ is a single bond, or an oxygen atom, a sulfur atom, a sulfonyl group, or an alkylene group or an arylene group which may be substituted with a halogen, or It is a divalent cross-linking member constituted by a combination.

The divalent bridging member constituted by a combination thereof in R ¹⁵ of the above formula (7) is selected from an oxygen atom, a sulfur atom, a sulfonyl group, or an alkylene group or an arylene group optionally substituted with a halogen Means a divalent cross-linking member constituted by a combination of two or more kinds of groups, for example, -O- (arylene) -O-, -O- (arylene) -O- (arylene) -O-, -O- (arylene)-(alkylene)-(arylene) -O-, -S- (arylene) -S-, -S- (arylene) -S- (arylene) -S-, -S- (arylene) -SO 2 - _(arylene) -S- [wherein, alkylene or arylene may be substituted with one or more halogens], and the like.

In the formula (8), R ¹⁶ and R ¹⁷ may be the same or different, and are a single bond, or an alkylene group which may be substituted with an oxygen atom, a sulfur atom, a sulfonyl group or a halogen. Alternatively, they are either an arylene group or a divalent cross-linking member constituted by a combination thereof.

Examples of R ⁴ in the general formula (II) include those having a structure capable of forming an acid dianhydride, for example, those represented by the following formulas (9) to (34).

  As an acid component used in combination with the aromatic or alicyclic tetracarboxylic dianhydride represented by the general formula (II) or a derivative thereof, the aromatic tetracarboxylic dianhydride represented by the following general formula (II ′) Or a derivative thereof. Here, the derivative is synonymous with that in the general formula (II). By using in combination the aromatic tetracarboxylic dianhydride or derivative thereof represented by the following general formula (II ′), a polyimide molecular chain exhibiting fluorescence emission at 500 to 800 nm can be obtained in addition to 380 to 500 nm. .

In the general formula (II ′), R ^{4 ′} represents a monocyclic or condensed polycyclic aromatic compound, or the same or different aromatic compounds which may be the same or different from each other directly or via a bridging member. Represents a tetravalent group of a non-condensed polycyclic aromatic compound linked to, wherein the aromatic compound may be substituted, provided that R ^{4 ′} is not the same as R ⁴ .

R ^{4 ′} in formula (II ′) is preferably a monocyclic or condensed polycyclic aromatic compound having 6 to 36 carbon atoms, or the same or different aromatic compound Is a tetravalent group of a non-condensed polycyclic aromatic compound linked to each other directly or via a bridging member. Examples of such monocyclic or condensed polycyclic aromatic compounds include benzene, naphthalene, anthracene, phenanthrene, naphthacene, pyrene, triphenylene, chrysene, picene, and perylene.

  These are selected from a monovalent substituent constituted by a halogen atom, an alkyl group optionally substituted with a halogen, an aryl group bonded directly or through a bridging member, or a combination thereof on the ring. It may be substituted with one or more groups.

Examples of R ^{4 ′} in the general formula (II ′) include those represented by the following formulas (10), (25), and (88).

  In the fluorescent polymer of the present invention, when the molecular chain that emits fluorescence at a wavelength of 380 to 800 nm is a polyimide molecular chain, the diamine component is an aromatic or alicyclic diamine represented by the following general formula (III): Can be mentioned.

In the formula, R ⁵ represents an aromatic or alicyclic compound, or a non-condensed polycyclic compound in which the aromatic or alicyclic compounds, which may be the same or different, are connected to each other directly or via a cross-linking member. 2 represents a divalent group of a cyclic aromatic or alicyclic compound, wherein the aromatic or alicyclic compound may be substituted. Moreover, you may use these diamines individually or in combination as a diamine component.

R ⁵ in the general formula (III) is preferably an aromatic or alicyclic compound having a total carbon number of 4 to 36, or the aromatic or alicyclic compound which may be the same or different, directly or It is a divalent group of a non-condensed polycyclic aromatic or alicyclic compound connected to each other via a cross-linking member. Examples of the alicyclic compound include cycloalkane and cycloalkene. Although there is no restriction | limiting in particular in carbon number which comprises an alicyclic compound, Usually, 4-30, Preferably it is 5-20, More preferably, it is 5-15. When the carbon number is within the above range, a fluorescent polymer having excellent heat resistance can be obtained. Examples of the aromatic compound include those containing one or more aromatic rings such as benzene and naphthalene. When R ⁵ is a divalent group of an aromatic compound, the two bonding sites of R ⁵ are preferably directly present on the aromatic ring from the viewpoint of imparting rigidity to the resulting polyimide.

  The aromatic or alicyclic compound is a monovalent group constituted by a halogen atom, an alkyl group optionally substituted with a halogen, an aryl group bonded directly or via a bridging member, or a combination thereof on the ring. It may be substituted with one or more groups selected from these substituents. In particular, in order to suppress the non-radiative deactivation due to the charge transfer interaction, it is preferable to have an electron withdrawing group such as a fluorine atom, a chlorine atom or a trifluoromethyl group on the ring.

Examples of R ⁵ in the general formula (III) include those represented by the following formulas (35) to (38).

In formula (36), R ¹⁸ represents an alkylene group which may be substituted with halogen (particularly fluorine). Examples of the alkylene group include a methylene group, an ethylene group, an isopropylidene group, and a hexamethylene group. In particular, examples of the alkylene group substituted with fluorine include a difluoromethylene group and a hexafluoroisopropylidene group.

In the formula (37), R ¹⁹ is a hydrogen atom, or an alkyl group or an alkoxy group that may be substituted with a halogen (particularly fluorine). Examples of the alkyl group or alkoxy group include a methyl group, a methoxy group, an ethyl group, an ethoxy group, an isopropyl group, and a hexyl group. In particular, examples of the alkyl group or alkoxy group substituted with fluorine include perfluoroalkyl groups such as trifluoromethyl group, trifluoromethoxy group, and pentafluoroethyl group, and perfluoroalkoxy groups.

In formula (38), R ²⁰ represents a hydrogen atom, halogen, or an alkyl group substituted with halogen (particularly fluorine). In particular, examples of the alkyl group substituted with fluorine include perfluoroalkyl groups such as a trifluoromethyl group and a pentafluoroethyl group.

  What should be noted in the fluorescent polymer of the present invention is that the fluorescence intensity and the fluorescence wavelength derived from the polymer chain can be easily controlled by introducing the terminal group represented by the general formula (I). For example, the fluorescent polymer represented by the general formula (V) of the present invention is represented by the blue region centered on the wavelength 400 nm derived from the polyimide molecular chain represented by the general formula (IV) and the general formula (I). Strong fluorescence is emitted in the green region centered on the wavelength 520 to 530 nm derived from the terminal group, and no light absorption in the visible light region is observed. For this reason, the fluorescent color of blue-light blue-white-green can be obtained by adjusting the ratio of the terminal group represented by general formula (I). Similarly, the polyimide molecular chain composed of two types of structural units represented by the general formula (IV ′) of the present invention emits fluorescence in a red-orange region centered at a wavelength of 600 nm in addition to a blue region centered at a wavelength of 400 nm. Indicates. Therefore, the fluorescent polymer represented by the general formula (V ′) of the present invention has the fluorescence emission intensity shown in the red-orange region derived from the polyimide molecular chain represented by the general formula (IV ′). It can be enhanced by introducing a terminal group represented by

  The reason why the end group of the polymer of the present invention absorbs ultraviolet light and emits green fluorescence is as follows. The terminal group represented by the general formula (I) in the ground state is an enol type that does not absorb visible light (an intramolecular hydrogen bond is formed between a phenolic hydroxyl group and an imide carbonyl group), and is temporarily photoexcited. Even in the state, if the enol type is maintained, it is considered to emit blue fluorescence. However, in the photoexcited state caused by ultraviolet light absorption, hydrogen atom transfer (proton transfer) from the phenolic hydroxyl group to the carbonyl group occurs, resulting in the formation of a keto type that has a longer conjugate length than the enol type and a lower transition energy. Therefore, it is considered that green fluorescence is emitted. For this reason, it is essential for the fluorescent polymer of the present invention to have a terminal group having a phenolic hydroxyl group at the 3-position adjacent to the imide ring. These findings are supported by the fact that similar light absorption / fluorescence behavior is observed in a low molecular weight model compound synthesized using 3-hydroxyphthalic anhydride.

  In the fluorescent polymer represented by the general formula (V) of the present invention, since the intensity ratio of blue fluorescence and green fluorescence strongly depends on the ratio of terminal groups in the polymer, it is visible by changing the ratio of terminal groups. Fluorescent polymers having various fluorescent colors that are excellent in light transmittance in the light region can be obtained. For example, when the molar ratio of terminal groups to all imide rings is φ, blue fluorescence is obtained when φ = 0, light blue fluorescence when 0 <φ <0.02, white fluorescence when φ = 0.03, and φ> 0.07. Showed green fluorescence. Thus, by controlling the ratio of the terminal groups, it is possible to control the fluorescence wavelength from blue to light blue to white to green. Conventionally, end groups such as phthalic anhydride have been used to control the molecular weight of polyimide, so the end group fraction is changed without changing the molecular structure of the main chain (that is, the molecular weight is changed). A fluorescent polymer capable of controlling the fluorescent color can be obtained by a simple method.

The reason why the polymer represented by the general formula (V ′) of the present invention absorbs ultraviolet light and emits reddish orange fluorescence is as follows. When the terminal group is not introduced, the absorption wavelength of the R ^{4 ′} unit and the fluorescence wavelength of the R ⁴ unit do not coincide with each other, so that the energy transfer efficiency between both units is lowered. As a result, the intensity ratio becomes a small value and blue fluorescence is strongly observed. On the other hand, in the case of terminal group introduction, the absorption wavelength (near 500 nm) of the R ^{4 ′} unit and the fluorescence wavelength (near 530 nm) of the terminal group are almost the same, so the R ⁴ unit to R ^{4 ′} unit via the terminal group It is considered that energy is efficiently transferred to the fluorescent substance, and as a result, the fluorescence intensity ratio increases.

When the polyimide chain contained in the fluorescent polymer of the present invention has a divalent organic group having an alicyclic structure, a molded product obtained from such a polymer has high heat resistance and exhibits excellent mechanical properties. Furthermore, since the charge transfer interaction within and between the polyimide molecules is suppressed, high fluorescence intensity can be expressed, and therefore, it can be suitably used as a material for a fluorescent optical device. In particular, when R ⁵ in the diamine component represented by the general formula (III) has a perfluoroalkyl group, the light transmittance, fluorescence intensity, and long-term stability of the fluorescence spectrum shape of the fluorescent polymer of the present invention As a result, the water absorption can be reduced.

  Examples of the fluorescent polymer of the present invention include polyimides represented by the following general formula (V).

In the formula, R ^{1 to} R ⁵ and n are as defined above.

  Specific examples of the fluorescent polyimide represented by the general formula (V) of the present invention include polyimides represented by the following formulas (40) to (83).

  Furthermore, as a fluorescent polymer of this invention, the polyimide represented by the following general formula (V ') is mentioned, for example.

In the formula, R ^{1 to} R ⁵ and n ′ are as defined above.

  Specific examples of the fluorescent polyimide represented by the general formula (V ′) of the present invention include polyimides represented by the following formulas (89) to (132).

  The molecular weight (the number of n or n ′) of the fluorescent polymer of the present invention is not particularly limited as long as the fluorescent properties are exhibited. Even if the polymer has a high degree of polymerization, the degree of polymerization is not limited. May be a low (imide) oligomer.

  The end group raw material used in the synthesis of the fluorescent polymer of the present invention may be selected according to the type of the molecular chain. Specifically, based on the reactive group present in the molecular chain or capable of being introduced into the molecular chain, a raw material capable of introducing the terminal group represented by the general formula (I) of the present invention is, for example, What is necessary is just to select suitably from a phthalimide, phthalic anhydride, or those derivatives. When the molecular chain is a polyimide molecular chain, it is preferable to use an acid anhydride as a raw material for the end group. Examples of such acid anhydrides include those represented by the following general formula (VII).

^R 1 to R in the general formula (VII) ³ has the same meaning as ^R 1 to R ³ in the general formula (I).

  Representative examples thereof include 3-hydroxyphthalic anhydride represented by the following formula (84), dihydroxyphthalic anhydride represented by the formula (85), trihydroxyphthalic anhydride represented by the formula (86), a formula ( 87) and the like, and the like.

  In addition, in the fluorescent polymer of this invention, the terminal group represented by general formula (I) may use only 1 type, or may use it in combination of 2 or more type. Therefore, as the raw material of the terminal group used in the synthesis, only one kind of acid anhydride represented by the general formula (VII) may be used, or two or more kinds may be used in combination. Furthermore, a group derived from a known acid anhydride having no hydroxyl group may be introduced as a terminal group as long as it does not interfere with the fluorescence characteristics of the fluorescent polymer of the present invention. Accordingly, for example, phthalic anhydride, benzophenone dicarboxylic acid anhydride, diphenyl ether dicarboxylic acid anhydride, diphenyl dicarboxylic acid anhydride, diphenyl sulfone dicarboxylic acid anhydride, naphthalene dicarboxylic acid anhydride, anthracene dicarboxylic acid anhydride, etc. You may use in combination with the acid anhydride represented by.

  In addition, when a group derived from an aromatic acid anhydride having an intramolecular triple bond is used together with a terminal group represented by the general formula (I) within a range that does not impede its fluorescence properties, the fluorescent polymer of the present invention Can be imparted with thermosetting property in a high temperature region. Examples of the intramolecular triple bond include an ethynyl group and a phenylethynyl group, and examples of the aromatic acid anhydride having such an intramolecular triple bond include a compound represented by the following general formula (VIII). By using both the end-capping agent of the following general formula (VIII) and the acid anhydride represented by the general formula (VII), the resulting polyimide or imide oligomer has a chain extension reaction and aromatic ring formation at a certain temperature or higher. A thermosetting reaction occurs due to the reaction, and mechanical properties such as elongation at break of the film are improved. This is particularly effective when the mechanical strength and film-forming property of an imide oligomer having a low degree of polymerization of the main chain (that is, molecular chain) is low.

Here, in the formula, R ⁶ is a monocyclic or condensed polycyclic aromatic compound having 6 to 30 carbon atoms in total, or the aromatic compound which may be the same or different may be directly or cross-linked. 3 represents a trivalent group of non-condensed polycyclic aromatic groups interconnected via each other, wherein the aromatic compound may be substituted. Examples of the acid anhydride of the general formula (VIII) include 3-hydroxy-4-phenylethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, 3-hydroxy-6-phenylethynyl phthalic anhydride, and 3-phenylethynyl. Phthalic anhydride, phenylethynylnaphthalenedicarboxylic anhydride, phenylethynyldiphenyldicarboxylic anhydride, phenylethynyldiphenyletherdicarboxylic anhydride, phenylethynylbenzophenone dicarboxylic anhydride, phenylethynyldiphenylsulfone dicarboxylic anhydride, phenylethynylanthracene dicarboxylic acid An anhydride etc. can be mentioned. These are selected from a monovalent substituent constituted by a halogen atom, an alkyl group optionally substituted with a halogen, an aryl group bonded directly or through a bridging member, or a combination thereof on the ring. It may be substituted with one or more groups. These may be used alone or in combination of two or more.

  The method for producing the fluorescent polymer of the present invention, particularly the fluorescent polyimide of the present invention is not particularly limited. For example, the acid anhydride represented by the general formula (VII) or the general formula (VIII) and the general formula ( II) an acid dianhydride (optionally combined with the acid dianhydride represented by the above general formula (II ′)) and a diamine compound represented by the above formula (III). The polyamic acid obtained in this manner can be produced by heating and ring closure at a temperature of 200 ° C. or higher. There is no restriction | limiting in particular in the method of carrying out a heat ring closure, A conventionally well-known method is used.

  Below, an example of the manufacturing method of the film using the fluorescent polyimide of this invention is shown.

  First, in a polar organic solvent, a mixture of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3-hydroxyphthalic anhydride in an arbitrary molar ratio is mixed with 4,4′-diaminodicyclohexylmethane. Polycondensation is performed to obtain a polyamic acid solution. At this time, when a silyl esterified product such as N, O-bis (trimethylsilyl) acetamide or N, O-bis (trimethylsilyl) trifluoroacetamide is mixed, insolubilization (gelation) of the raw material aggregate or product is unlikely to occur. Become. Examples of the polar organic solvent to be used include N-methyl-4-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like. The concentration of the raw material compound in the polymerization solution is preferably 5 to 40% by weight, more preferably 10 to 25% by weight. This reaction is shown in Schemes 1 and 2 below.

  The polyamic acid solution obtained as described above is spin-coated on a substrate such as a fused quartz plate, and the temperature is about 70 ° C. to about 300 ° C. in an inert gas (eg, nitrogen) atmosphere. Heating stepwise or continuously to dehydrate ring closure (imidization). This reaction is shown in the following formula. Examples of stepwise heating may be, for example, 70 ° C for 2 hours, 160 ° C for 1 hour, 250 ° C for 30 minutes, 300 ° C for 2 hours, or continuous at 5 ° C per minute. It is also possible to increase the temperature. After imidation, a polyimide film is obtained by peeling from the substrate in air or water. When peeling from the substrate is difficult, the polyimide film is obtained by spin-coating the polyamic acid solution on the aluminum plate, thermal imidization, and then immersing the substrate together with 10% hydrochloric acid to dissolve the aluminum plate. Further, as a substrate material, not only an inorganic material such as fused quartz or single crystal silicon but also an organic polymer such as a polyimide molded body may be used. This reaction is shown in Schemes 3 and 4 below.

  As a method for synthesizing the polyamic acid, in addition to the method of synthesizing using a polar organic solvent as described above, the sublimation property of the acid dianhydride and the diamine compound as raw materials is used to form a polyamic acid on the substrate by vacuum deposition polymerization. The method of synthesizing is mentioned. As a method for synthesizing the polyimide film in this case, specifically, an acid dianhydride monomer, an acid anhydride monomer and a diamine monomer are evaporated by heating respective vapor deposition sources in a vacuum chamber, and a polyamide is formed on the substrate. A polyimide thin film can be obtained by synthesizing an acid, heating it in an inert gas, and dehydrating and ring-closing. Further, if necessary, imidization may be performed by chemical treatment with a combination of a ring-closing catalyst such as pyridine / acetic anhydride and a dehydrating agent.

  Moreover, regarding the thermosetting polyimide and / or imide oligomer which introduce | transduced the group induced | guided | derived from the aromatic acid anhydride which has an intramolecular triple bond with the group represented by general formula (I) of this invention as a terminal group. Can obtain a molded article (cured product) having further excellent mechanical properties by heating to a high temperature region. For example, the acid anhydride monomer was obtained as described above, except that the terminal blocker represented by the general formula (VIII) was used together with the acid anhydride represented by the general formula (VII). The film-like polyimide and / or imide oligomer can be obtained by heat-curing in a high temperature region. A part of these polyimides and / or imide oligomers may be polyamic acid and / or amic acid oligomers. In addition, a thermosetting treatment can be performed simultaneously with the thermal imidization.

  The thermosetting temperature varies depending on the type of polyimide and / or imide oligomer or polyamic acid and / or amic acid oligomer, but is 100 ° C. to 500 ° C., more preferably 250 to 300 ° C. Although the heat treatment time varies depending on the kind of polyimide or polyamic acid and the heat treatment temperature, generally, the time during which the polyimide is not thermally denatured is desirable because the heat-crosslinking reaction of the carbon-carbon triple bond is sufficiently completed. Specifically, it is 1 minute to 1 hour.

  Therefore, the fluorescent polymer of the present invention can be used as the polymer or its precursor itself, or as a varnish containing the polymer or its precursor. In particular, when the molecular chain is a polyimide molecular chain, the fluorescent polymer of the present invention is a varnish containing polyimide, an imide oligomer, or a precursor thereof, polyamic acid, amide acid oligomer itself, or any of them. Can be used. The solvent used for preparing the varnish is not particularly limited as long as it is inert to the polymer or its precursor and can be dissolved. Preferably, the solvent used in the polymerization reaction of the polymer or its precursor is used as it is.

  Next, the organic light emitting device and the organic light wavelength conversion device of the present invention will be described. The organic light-emitting device and the organic light wavelength conversion device of the present invention are manufactured using the above-described fluorescent polymer of the present invention.

  The fluorescent polymer of the present invention can be used as a material for organic light-emitting devices such as organic EL elements, organic lasers, wavelength conversion elements, and spatial light modulation elements, or organic light wavelength conversion devices. For example, the film of the fluorescent polymer of the present invention is used as a light emitting layer / light receiving layer to form an organic EL device by forming a laminate of transparent substrate / transparent electrode / charge transport layer / light emitting layer / light receiving layer / electrode. be able to. Moreover, by using the fluorescent polymer film of the present invention as a sealing material for ultraviolet light LED, the LED wavelength conversion element of a surface emitting device (converts ultraviolet light from blue to light blue to white to green, or red to orange) Can be. Existing LEDs use rare metals such as yttrium, europium, and tantalum as phosphors. However, problems such as rising raw material prices, depletion of resources, and harmfulness to human bodies are considered, and conversion to organic compounds that do not contain these atoms is required. In addition, it can be used for optical waveguides and light sources for communication, optical fiber amplifiers, optical brighteners, paints, inks, fluorescent collectors, scintillators, plant growth films, and the like. Further, by using it as a surface coating material, the presence or absence of coating can be confirmed by irradiation with ultraviolet light, so that product inspection can be greatly simplified.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

Example 1
<Production of Thin Film of Fluorescent Polymer of the Present Invention (Polyimide of Formula (40) above)>
Into an Erlenmeyer flask, 0.4829 g (1.557 mmol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (s-ODPA) and 0.3341 g of 4,4′-diaminodicyclohexylmethane (DCHM) ( 1.588 mmol) was added, and 4.685 g of N, N-dimethylacetamide (DMAc) was added so that the concentration of the raw material in the solution was 14.85% by weight. After stirring the solution in the Erlenmeyer flask in a nitrogen atmosphere at room temperature for 24 hours, 0.0103 g (0.063 mmol) of 3-hydroxyphthalic anhydride (3HPA) was added, and the mixture was stirred in a nitrogen atmosphere at room temperature for 24 hours to form polyamide. A DMAc solution of the acid oligomer was obtained. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 220 ° C. for 1.5 hours, and heated in two steps for imidization. It was. A layer formed by heating imidization was peeled off from the quartz plate to obtain a polyimide thin film. The degree of polymerization (n) of the polyamic acid calculated from the charged amount is 100, and the molar ratio (φ) of terminal groups to all imide rings is 0.0198.

The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm ^-1 and 1719 cm ^-1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm ⁻¹ and 1637 cm ⁻¹ disappeared, and it was confirmed that imidization proceeded completely. It was 2.1 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. Moreover, it was 452 degreeC when the thermal decomposition start temperature (5% weight reduction | decrease temperature) was measured with the thermogravimetric analyzer (TGA). When the fluorescence emission spectrum of the obtained polyimide thin film was measured at an excitation wavelength of 334 nm and a fluorescence observation wavelength of 330 to 800 nm, strong fluorescence was observed at a wavelength of 350 to 700 nm. The results are shown in FIG. FIG. 1 is a graph showing the results of measuring fluorescence emission intensity. In FIG. 1, the wavelength dependence of each fluorescence spectrum in the polyimide of Example 2, 3, 4 mentioned later and the comparative example 1 is shown collectively. In FIG. 1, the vertical axis represents fluorescence intensity (logarithmic display), and the horizontal axis represents wavelength (nm). As shown in FIG. 1, the fluorescent polymer obtained in Example 1 emits blue fluorescence most strongly, but since the fluorescence wavelength is spread over the entire blue to green region, the fluorescent color is light blue. When the absorption edge of this polyimide thin film was measured with a self-recording spectrophotometer, it was an ultraviolet region with a wavelength of 365 nm. Absorption only in the ultraviolet region indicates that this polyimide is colorless and transparent throughout the visible region. The results are shown in Table 1.

Examples 2-4
As in Example 1, except that the ratio of terminal groups was changed as shown in Table 1, polyimide thin films were prepared. The results are also shown in Table 1.

Comparative Examples 1-7
In the same manner as in Example 1, except that the types and proportions of the terminal groups were changed as shown in Table 2, polyimide thin films were prepared. The results are also shown in Table 2.

Example 5
A DMAc solution of a polyamic acid oligomer was prepared from s-ODPA, 3HPA, and DCHM in the same manner as in Example 2 with the concentration of acid dianhydride and diamine (solid content) being 35%. When this solution was applied onto a quartz plate having a thickness of 1 mm and thermally imidized at a maximum temperature of 220 ° C., a film having a thickness of 18 μm was obtained. When the polyamic acid solution coating, drying, and thermal imidization were repeated twice, a polyimide film having a thickness of about 50 μm was obtained. The whole substrate was cut into a size of 5 × 5 mm using a dicing saw, and an ultraviolet sharp cut filter (glass substrate) was attached to the polyimide film side with an acrylic optical adhesive. When an ultraviolet light-emitting diode (emission wavelength: 386 nm, current: 20 mA, light output: 70 mcd) was irradiated from the back surface of the quartz substrate, white bright fluorescent emission extending from 350 to 700 nm from the surface of the polyimide was observed. It has been clarified that the polyimide according to the present invention functions as a wavelength conversion material in an organic light wavelength conversion device of ultraviolet light → visible light.

Example 6
<Manufacture of a thin film of fluorescent polymer (polyimide of the above formula (89))>
To an Erlenmeyer flask, 0.6246 g (2.013 mmol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (s-ODPA), 1,4-difluoropyromellitic dianhydride (P2FDA) 0 0.0568 g (0.2235 mmol), 3-hydroxyphthalic anhydride (3HPA) 0.0300 g (0.1828 mmol) and 4,4′-diaminodicyclohexylmethane (DCHM) 0.4898 g (2.328 mmol) were added to the solution. 4.685 g of N, N-dimethylacetamide (DMAc) was added so that the concentration of the raw material in it was 20% by weight. The solution in the Erlenmeyer flask was stirred for 24 hours at room temperature in a nitrogen atmosphere, and then added at room temperature for 24 hours in a nitrogen atmosphere to obtain a DMAc solution of a polyamic acid oligomer. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 220 ° C. for 1.5 hours, and heated in two steps for imidization. It was. A layer formed by heating imidization was peeled off from the quartz plate to obtain a polyimide thin film. The degree of polymerization (n) of the polyamic acid calculated from the charged amount is 50, the molar ratio of s-ODPA and P2FDA is 9: 1, and the molar ratio (φ) of terminal groups to all imide rings is 0.0392.

The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm ^-1 and 1719 cm ^-1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm ⁻¹ and 1637 cm ⁻¹ disappeared, and it was confirmed that imidization proceeded completely. It was 6.4 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. Moreover, it was 400 degreeC when the thermal decomposition start temperature (5% weight reduction | decrease temperature) was measured with the thermogravimetric analyzer (TGA). When the fluorescence emission spectrum of the obtained polyimide thin film was measured at an excitation wavelength of 331 nm and a fluorescence observation wavelength of 330 to 800 nm, strong fluorescence was observed at a wavelength of 350 to 800 nm. The results are shown in FIG. FIG. 2 is a graph showing the results of measuring the fluorescence emission intensity. In FIG. 2, the wavelength dependence of each fluorescence spectrum in the polyimide of Examples 7-9 mentioned later and Comparative Examples 8 and 11 is shown collectively. In FIG. 2, the vertical axis represents fluorescence intensity, and the horizontal axis represents wavelength (nm). As shown in FIG. 2, the fluorescent polymer obtained in Example 6 emits fluorescence over the entire visible light region by ultraviolet light excitation, but emits orange fluorescence most strongly. When the light absorption spectrum of this polyimide thin film was measured with the self-recording spectrophotometer, since the absorption peak derived from P2FDA exists in wavelength 500nm, the obtained polyimide thin film exhibits light red. The results are shown in Table 3.

Examples 7-9
As in Example 6, except that the ratio of terminal groups and the copolymerization ratio were changed as shown in Table 3, polyimide thin films were prepared. The results are also shown in Table 3.

Comparative Examples 8-6
As in Example 6, except that the end groups were not used as shown in Table 4, polyimide thin films were prepared by changing the copolymerization ratio. The results are also shown in Table 4.

It is a graph which shows the result of having measured the fluorescence intensity of the polyimide obtained in Examples 1-4 and Comparative Example 1. FIG. It is a graph which shows the result of having measured the fluorescence intensity of the polyimide obtained in Examples 6-8, the comparative example 8, and the comparative example 13. FIG.

Claims (14)

A molecular chains exhibiting fluorescence emission in the wavelength 380 to 800 nm, the following formula (1):

A fluorescent material comprising a fluorescent polymer having a terminal group represented by the formula: And at least one acid component, obtained by polymerizing at least one diamine component, and polyimides molecular chains exhibiting fluorescence emission in the wavelength 380 to 800 nm, the following formula (1):

A fluorescent material comprising a fluorescent polymer having a terminal group represented by the formula: The acid component alone is the general formula (II):

(Wherein R ⁴ is a monocyclic or condensed polycyclic aromatic or alicyclic compound, or the aromatic or alicyclic compound which may be the same or different may be directly or cross-linked. Represents a tetravalent group of a non-condensed polycyclic aromatic or alicyclic compound interconnected via each other, wherein the aromatic or alicyclic compound may be substituted) The fluorescent material according to claim 2, which is an aromatic or alicyclic tetracarboxylic dianhydride or a derivative thereof. The acid component is represented by the general formula (II):

(Wherein R ⁴ is as defined in claim 3) and an aromatic or alicyclic tetracarboxylic dianhydride or derivative thereof, and a general formula (II ′):

(Wherein R ^{4 ′} is a monocyclic or condensed polycyclic aromatic compound, or the same or different aromatic compounds may be linked to each other directly or via a bridging member. Represents a tetravalent group of a non-condensed polycyclic aromatic compound, wherein the aromatic compound may be substituted, provided that R ^{4 ′} is not the same as R ⁴ The fluorescent material according to claim 2, which is a combination with a group tetracarboxylic dianhydride or a derivative thereof. The diamine component has the general formula (III):

(Wherein R ⁵ represents an aromatic or alicyclic compound, or a non-condensed product in which the aromatic or alicyclic compounds, which may be the same or different, are connected to each other directly or via a cross-linking member. An aromatic or alicyclic diamine represented by a divalent group of a polycyclic aromatic or alicyclic compound, wherein the aromatic or alicyclic compound may be substituted). The fluorescent material according to any one of claims 2 to 4. A molecular chain exhibiting fluorescence emission at a wavelength of 380 to 800 nm is represented by the general formula (IV):

Wherein R ⁴ is as defined in claim 3, R ⁵ is as defined in claim 5, and n is an arbitrary number. The fluorescent material according to any one of claims 1 to 3 and 5, wherein: A molecular chain exhibiting fluorescence emission at a wavelength of 380 to 800 nm is represented by the general formula (IV ′):

Wherein R ⁴ is as defined in claim 3, R ^{4 '} is as defined in claim 4, R ⁵ is as defined in claim 5, and n' is a polyimide molecular chain represented by any of a number), the fluorescent material according to any one of claims 1, 2, 4 and 5. The polymer has the general formula (V):

Wherein R ^{1 to} R ³ are hydrogen atoms , R ⁴ is as defined in claim 3, R ⁵ is as defined in claim 5, and n is any The fluorescent material according to claim 1, which is a polyimide represented by a formula (1). The polymer has the general formula (V ′):

Wherein R ^{1 to} R ³ are hydrogen atoms , R ⁴ is as defined in claim 3, R ^{4 ′} is as defined in claim 4, and R ⁵ is The fluorescent material according to any one of claims 1, 2, 4, 5, and 7, which is a polyimide represented by the definition defined in item 5 and n 'is an arbitrary number. General formula (VI):

(Wherein, R ¹ to R ⁵ and n being as defined in claim 8) represented by the fluorescent material comprising a precursor of a fluorescent polymer. General formula (VI ′):

(Wherein, R ¹ to R ⁵ and n being as defined in claim 9) represented by a fluorescent material comprising a precursor of a fluorescent polymer. The organic light emitting device manufactured by using the fluorescent material according to any one of claims 1 to 11. Claim 1-11 manufactured organic light wavelength conversion device using the fluorescent material according to any one of. Fluorescent surface coating material manufactured by using a fluorescent material according to any one of claims 1 to 11.

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