WO2020071326A1 - Fluorescent polymer and method for manufacturing fluorescent polymer, and fluorescent polymer particles, liquid dispersion, composite, and fluorescent polymer coating method - Google Patents

Abstract

Provided is a novel fluorescent polymer that can be in the form of fluorescent fine particles or the like. A fluorescent polymer having structural units derived from a first monomer and structural units derived from a crosslinking agent, wherein the first monomer is a polycyclic fluorescent compound having two or more hydroxy groups, and is one or more species selected from the group consisting of anthracene derivatives, fluorene derivatives, pyrene derivatives, anthraquinone derivatives, porphyrin derivatives, binaphthalene derivatives, bipyridine derivatives, biphenyl derivatives, bisphenol derivatives, xanthene derivatives, dibenzofuran derivatives, and naphthalene derivatives, and the first monomer constitutes at least a portion of the structural units of the main chain of the fluorescent polymer and is crosslinked by a crosslinking agent.

Description

Fluorescent polymer, method for producing fluorescent polymer, and method for coating fluorescent polymer particles, dispersion, composite, and fluorescent polymer

The present invention relates to a fluorescent polymer and a method for producing a fluorescent polymer. In addition, the present invention relates to a fluorescent polymer particle, a dispersion liquid, and a composite related to the fluorescent polymer. The present invention also relates to a method for coating a fluorescent polymer.

微粒子 Microparticles with fluorescent properties are used in various fields including various sensing materials. Most of the fluorescent fine particles so far have been inorganic nanoparticles having a rare metal or the like as a constituent component, or fluorescent organic molecules introduced into the nanoparticles by a chemical reaction or a doping method.

Patent Document 1 discloses a composition for forming a wavelength conversion film for photoelectric conversion containing a polymer or oligomer having a fluorescent site and a solvent. Here, it is described that examples of the polymer or oligomer include an acrylic resin, a methacrylic resin, a novolak resin, an aminoplast polymer, a polyamide, a polyimide, and a polyester. It is described that the introduction of a fluorescent site (fluorescent site) into a polymer or oligomer side chain can be performed, for example, by graft polymerization.

WO2010 / 050466

Until now, most of the fluorescent fine particles were inorganic nanoparticles containing rare metals or other components, or fluorescent organic molecules introduced into the nanoparticles by chemical reaction or doping. Also, toxicity due to elution of fluorescent organic molecules has been a major issue. In addition, Patent Document 1 also introduces a side chain, so that there are cases where the number of fluorescent sites is small or dropout from the side chain becomes a problem.
Under such circumstances, an object of the present invention is to provide a new fluorescent polymer and a method for producing the same.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the following inventions meet the above-mentioned objects, and have accomplished the present invention. That is, the present invention relates to the following inventions.

<1> A fluorescent polymer having a structural unit derived from a first monomer and a structural unit derived from a crosslinking agent,
The first monomer is a polycyclic fluorescent compound having two or more hydroxy groups, an anthracene derivative, a fluorene derivative, a pyrene derivative, an anthraquinone derivative, a porphyrin derivative, a binaphthalene derivative, a bipyridine derivative, At least one selected from the group consisting of biphenyl derivatives, bisphenol derivatives, xanthene derivatives, dibenzofuran derivatives, and naphthalene derivatives;
A fluorescent polymer in which the first monomer is at least a part of a structural unit of a main chain of the fluorescent polymer and is crosslinked by a crosslinking agent.
<2> The fluorescent polymer according to <1>, wherein the crosslinking agent is a triazinan derivative and / or hexamethylenetetramine.
<3> Fluorescent polymer particles containing the fluorescent polymer according to <1> or <2> and having a diameter of 3 to 500 nm.
<4> A dispersion containing the fluorescent polymer according to <1> or <2>, wherein water and / or an organic solvent is used as a dispersion medium.
<5> A composite of a fluorescent polymer having a site containing the fluorescent polymer according to <1> or <2> on a carrier and / or a substrate.

<6> A method for producing a fluorescent polymer in which the first monomer is crosslinked with a crosslinking agent,
The first monomer is a polycyclic fluorescent compound having two or more hydroxy groups, an anthracene derivative, a fluorene derivative, a pyrene derivative, an anthraquinone derivative, a porphyrin derivative, a binaphthalene derivative, a bipyridine derivative, At least one selected from the group consisting of biphenyl derivatives, bisphenol derivatives, xanthene derivatives, dibenzofuran derivatives, and naphthalene derivatives;
A method for producing a fluorescent polymer, wherein the first monomer is cross-linked by a cross-linking agent so that the first monomer is at least a part of a structural unit of a main chain of the fluorescent polymer.
<7> a mixing step of mixing the first monomer, the crosslinking agent, and the polymerization solvent to prepare a monomer mixture;
In the monomer mixture, a reaction step of polymerizing the first monomer and the crosslinking agent to form a polymer solution containing a fluorescent polymer,
The method for producing a fluorescent polymer according to <6>, further comprising a recovery step of recovering the fluorescent polymer from the polymer solution.
<8> The method for producing a fluorescent polymer according to <7>, wherein the reaction step is a step of copolymerizing by microwave heating.
<9> The fluorescent polymer according to the above <1> or <2> is brought into contact with a carrier and / or a substrate to provide a portion containing the fluorescent polymer on the carrier and / or the substrate. A method for coating a fluorescent polymer.

According to the present invention, there is provided a polymer which is easy to control the production process and exhibits fluorescence. This polymer can also be formed into particles. Further, this polymer has excellent dispersibility, and various liquids such as an aqueous solution and an organic solvent can be used as a solvent.

5 is an image obtained by TEM observation of the polymer (1) of Example 1. 4 is a graph showing the measurement results of zeta potential when the pH of a liquid containing the polymer (1) of Example 1 was changed. FIG. 3 is a diagram showing a change in color of a liquid containing the polymer (1) of Example 1 when the pH is changed. 3 is a graph showing UV-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) of a liquid containing the polymer (1) of Example 1. 5 is a graph showing UV-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) when the pH of a liquid containing the polymer (1) of Example 1 is adjusted to 9; It is a figure which shows the external appearance of the solution which disperse | distributed the polymer (1) of Example 1 in various solvents, (a) It is the observation result excited by normal light and (b) 364 nm. 3 is a graph showing ultraviolet-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) of a solution in which the polymer (1) of Example 1 is dispersed in various solvents. FIG. 2 is a diagram showing a structural formula estimated as a polymer (1) of Example 1 and C, H, and N ratios in the estimated structural formula. 4 is a graph showing UV-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) of a liquid containing the polymer (2-1) of Example 2. FIG. 9 is a view showing an observation result when a liquid containing the polymer (2-1) of Example 2 was irradiated with laser light. FIG. 8 is a view showing an observation result when a liquid containing the polymer (2-1) of Example 2 is irradiated with illumination having a wavelength of 364 nm. 5 is a graph showing UV-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) when the pH of a liquid containing the polymer (2-2) of Example 2 is changed. 9 is a histogram of a particle size distribution of a polymer (3) of Example 3. 5 is a fluorescence spectrum measured by exciting a solution containing the polymer (3) at 500 nm. 9 is an image obtained by TEM observation of a production example of the polymer particles of Example 4. 9 is a histogram of a particle size distribution of Examples 4-1 and 4-7. FIG. 9 is a view showing the results of observation of a dispersion solution of the fluorescent polymer-coated silica particles of Example 5 under normal light (a) and under excitation light (b). 9 is an SEM observation image of a production example of the polymer particles of Example 6. 9 is a graph showing ultraviolet-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) of a solution in which the polymer (6) of Example 6 is dispersed in a solvent. 9 is an SEM observation image of a production example of the polymer particles of Example 7. 9 is a graph showing ultraviolet-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) of a solution in which the polymer (7) of Example 7 is dispersed in a solvent. 9 is a graph showing ultraviolet-visible light absorption characteristics (a) and excitation light-fluorescence characteristics (b) of a solution in which the polymer (8) of Example 8 is dispersed in a solvent.

Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is described below unless the gist is changed. It is not limited to the content of. In this specification, the expression “to” is used to include the numerical values before and after the expression.

[Fluorescent polymer of the present invention]
The fluorescent polymer of the present invention is a fluorescent polymer having a structural unit derived from a first monomer and a structural unit derived from a crosslinking agent, wherein the first monomer is a polymer having two or more hydroxy groups. Cyclic fluorescent compound, anthracene derivative, fluorene derivative, pyrene derivative, anthraquinone derivative, porphyrin derivative, binaphthalene derivative, bipyridine derivative, biphenyl derivative, bisphenol derivative, xanthene derivative, dibenzofuran derivative A derivative, and at least one selected from the group consisting of naphthalene-based derivatives, wherein the first monomer is at least a part of a structural unit of a main chain of the fluorescent polymer and is cross-linked by a cross-linking agent. .

[Production method of fluorescent polymer of the present invention]
The method for producing a fluorescent polymer of the present invention is a method for producing a fluorescent polymer in which a first monomer is cross-linked by a cross-linking agent, wherein the first monomer has two or more hydroxy groups. Anthracene derivative, fluorene derivative, pyrene derivative, anthraquinone derivative, porphyrin derivative, binaphthalene derivative, bipyridine derivative, biphenyl derivative, bisphenol derivative, xanthene derivative, dibenzofuran derivative, and At least one selected from the group consisting of naphthalene derivatives, wherein the first monomer is cross-linked by a cross-linking agent so that the first monomer is at least part of a structural unit of the main chain of the fluorescent polymer. Is what you do.
The method for producing a fluorescent polymer of the present invention is a preferred method for producing the fluorescent polymer of the present invention, and the corresponding configurations in the present application can be used mutually.

蛍 光 The fluorescent polymer of the present invention shows fluorescence. That is, it is a polymer that emits fluorescence when irradiated with excitation light. This fluorescent polymer has a cross-linked structure, is non-degradable, and does not elute a fluorescent site, and has high stability. Further, it can be dispersed in an aqueous solution having a pH of 0 to 14 without adding a dispersant. Further, the composition can be dispersed in an organic solvent without adding a dispersant.

The present inventors use a predetermined polycyclic fluorescent compound as a polymerizable monomer having a fluorescent moiety, and are capable of immobilizing the fluorescent moiety by a covalent bond or a cross-linking reaction in a polymer main chain. The reactive polymer and its production method were studied. As a result of this study, a polymer obtained by using a predetermined polycyclic fluorescent compound and further copolymerizing with a crosslinking agent such as a triazinan derivative becomes a fluorescent polymer having fluorescence to visible light. I found that.
Further, the polymer particles using the fluorescent polymer of the present invention are spherical and exhibit high monodispersity, are excellent in solvent resistance and weather resistance, etc., and have high stability in the fluorescent polymer particles in which the fluorescent portion is hardly eluted. It can also be. Such a fluorescent polymer can also be used as a bioanalytical marker in addition to a conventional fluorescent filler and an analytical marker which are used for a fluorescent substance and the like.

[First monomer]
The first monomer used in the fluorescent polymer of the present invention is a polycyclic fluorescent compound having two or more hydroxy groups. The polycyclic fluorescent compounds include anthracene derivatives, fluorene derivatives, pyrene derivatives, anthraquinone derivatives, porphyrin derivatives, binaphthalene derivatives, bipyridine derivatives, biphenyl derivatives, bisphenol derivatives, xanthene derivatives, and dibenzofuran. And at least one selected from the group consisting of a derivative based on a naphthalene derivative. This first monomer becomes at least a part of the structural unit of the main chain of the fluorescent polymer. As the first monomer, any one compound may be used, or two or more compounds may be used in combination.

[Polycyclic fluorescent compound]
The first monomer is a polycyclic fluorescent compound having two or more hydroxy groups. The polycyclic fluorescent compound is a cyclic compound having fluorescence and having a plurality of closed rings made of carbon or the like. Further, the polycyclic fluorescent compound as the first monomer of the present invention has two or more hydroxy groups (OH groups). When there are two or more hydroxy groups, the polymer is crosslinked by a crosslinking agent to form a polymer having a crosslinked structure or the like. At least one of these hydroxy groups is bonded to the ring structure of a cyclic compound like a phenolic hydroxyl group. These hydroxy groups are preferably those bonded to the ring of a cyclic compound, such as at least two phenolic hydroxyl groups. Further, it is preferable that one or more hydroxy groups are bonded to a plurality of different ring structures.

重合 The polymerization reaction of the fluorescent polymer of the present invention can be based on various polymerization reactions that occur depending on the combination of the first monomer and the crosslinking agent, and is not limited. A typical polymerization reaction presumed is, for example, a phenolic hydroxyl group (a phenolic hydroxy group), which reacts with a crosslinking agent by using both a hydroxy group bonded to an aromatic ring and a carbon atom adjacent thereto. It is considered that the polymerization reaction proceeds while the reaction proceeds. Further, a second phenolic hydroxyl group for accelerating the crosslinking reaction is required in order for the polymer to be formed into particles or the like which can be easily collected as a solid. That is, it is considered that the polymerization reaction and the cross-linking reaction can proceed simultaneously by having two or more phenolic hydroxyl groups, and as a result, spherical particles and the like can be obtained.

The polycyclic fluorescent compound includes an anthracene derivative (skeleton of formula (A)), a fluorene derivative (skeleton of formula (B)), a pyrene derivative (skeleton of formula (C)), and an anthraquinone derivative (formula (C)). (D), a porphyrin derivative (skeleton of formula (E)), a binaphthalene derivative (skeleton of formula (F)), a bipyridine derivative (skeleton of formula (G), etc.), a biphenyl derivative (formula (G)). H), a bisphenol derivative (skeleton of formula (I)), a xanthene derivative (skeleton of formula (J)), a dibenzofuran derivative (skeleton of formula (K)), and a naphthalene derivative (formula (L) ) Is at least one selected from the group consisting of: Any one of the polycyclic fluorescent compounds consisting of these groups may be used alone, or two or more kinds may be used in combination. Further, these polycyclic fluorescent compounds may have another substituent in addition to the hydroxy group. Other substituents are not particularly limited as long as the polycyclic fluorescent compound shows fluorescence and a fluorescent polymer can be obtained, but in addition to the structure serving as a skeleton, the number of other substituents of the hydroxy group is not limited. It may be 5 or less or 3 or less.

These polycyclic fluorescent compounds, when used as the fluorescent polymer of the present invention, become a part of the main chain of the polymer, and further exhibit a fluorescent property at a wavelength of about visible light (370 to 800 nm). It will be shown. This fluorescent characteristic has a strong fluorescent intensity that can be easily confirmed visually. Further, it is considered that a polymer having a crosslinked structure or the like is likely to be formed as a monomer forming the polymer, and the polymer has high stability. These polycyclic fluorescent compounds tend to exhibit fluorescence in the visible region from ultraviolet light to the compounds themselves, and by using the fluorescent polymer of the present invention, the electronic state is changed or the fused ring structure is enlarged. It is considered that the polymer has a structure in which the fluorescence characteristics easily shift or show fluorescence on the long wavelength side, and a polymer showing fluorescence in the visible light region is easily obtained.

The polycyclic fluorescent compound includes an anthracene derivative (skeleton of formula (A)), a fluorene derivative (skeleton of formula (B)), a biphenyl derivative (skeleton of formula (H)), and a bisphenol derivative (skeleton of formula (H)). It is preferably selected from the group consisting of: (skeleton of formula (I)). These derivatives are easy to use in the production of a polymer because the polymerization proceeds easily and the structure of the monomer is easy to adjust, and they are excellent in production efficiency because they are easily available. Among them, it is more preferable to be selected from the group consisting of an anthracene derivative (skeleton of formula (A)) and a fluorene derivative (skeleton of formula (B)). These derivatives are easy to exhibit fluorescence intensity in visible light. In addition, the degree of polymerization can be easily controlled based on the C / N ratio and the like, and it is easy to produce a particulate polymer or a polymer covering a carrier or the like.

Hereinafter, each polycyclic fluorescent compound will be described more specifically. In the following, each derivative includes those having the structure of each skeleton and having fluorescent properties. In addition, those containing optical isomers, including compounds specifically exemplified, include any optical isomers exhibiting fluorescent properties.

[Anthracene derivatives]
In the present application, the anthracene derivative has an anthracene (formula (A)) structure and has two or more hydroxy groups. For example, anthracene derivatives represented by the following formulas (a-1) to (a-5) can be used.

[Fluorene derivatives]
In the present application, the fluorene derivative has a structure of fluorene (formula (B)) and has two or more hydroxy groups. For example, fluorene derivatives represented by the following formulas (b-1) to (b-5) can be used.

[Pyrene derivative]
In the present application, the pyrene-based derivative has a structure of pyrene (formula (C)) and has two or more hydroxy groups. For example, pyrene derivatives represented by the following formulas (c-1) to (c-3) can be used.

[Anthraquinone derivatives]
In the present application, an anthraquinone derivative is one having an anthraquinone skeleton (formula (D)) and having two or more hydroxy groups. For example, anthraquinone derivatives represented by the following formulas (d-1) to (d-2) can be used.

[Porphyrin derivative]
In the present application, the porphyrin-based derivative has a structure of porphyrin (formula (E)) and has two or more hydroxy groups. For example, porphyrin derivatives represented by the following formulas (e-1) to (e-2) can be used.

[Binaphthalene derivative]
In the present application, the binaphthalene derivative has a structure of binaphthalene (chemical formula (F)) and has two or more hydroxy groups. For example, binaphthalene derivatives represented by the following formulas (f-1) to (f-2) can be used.

[Bipyridine derivative]
In the present application, a bipyridine derivative refers to a structure of bipyridine (chemical formula (G)) (more specifically, a chemical formula (G-1) (2,2′-bipyridine) or a chemical formula (G-2) (4, 4′-bipyridine)) and has two or more hydroxy groups. For example, bipyridines of the following formulas (g-1) to (g-2) can be used.

[Biphenyl derivative]
In the present application, a biphenyl-based derivative has a structure of biphenyl (chemical formula (H)) and has two or more hydroxy groups. For example, biphenyl derivatives represented by the following formulas (h-1) to (h-2) can be used.

[Bisphenol derivatives]
In the present application, the bisphenol derivative is a bisphenol having the structure of the chemical formula (I) and having two or more hydroxy groups. Bisphenol is a compound having two or more hydroxyphenyl groups, and X in the chemical formula (I) is a portion having a structure to which the two or more hydroxyphenyl groups are bonded. Examples of the structure to be bonded include a structure derived from any one selected from the group consisting of acetone, acetophenone, hexafluoroacetone, butanone, benzophenone, dichloroketone, acetaldehyde, formaldehyde, sulfur trioxide, trimethylcyclohexanone, and cyclohexanone. Can be For example, bisphenol of the following formula (i-1) can be used.

[Xanthene derivatives, dibenzofuran derivatives,]
In the present application, the xanthene derivative has a structure of xanthene (formula (J)) and has two or more hydroxy groups. In addition, the dibenzofuran-based derivative has a structure of dibenzofuran (formula (K)) and has two or more hydroxy groups. As the xanthene derivative, for example, a xanthene derivative represented by the following formulas (j-1) to (j-2) can be used. The dibenzofuran-based derivatives also have a similar structure according to these, and those in which any one of the 1- to 9-positions (particularly, one or more of 1-4 and one or more of 6--9) is substituted with an OH group. Can be used.

[Naphthalene derivative]
In the present application, the naphthalene-based derivative has a structure of naphthalene (formula (L)) and has two or more hydroxy groups. For example, a naphthalene derivative represented by the following formula (1-1) can be used. Since 1,5-dihydroxynaphthalene tends to have a low fluorescence intensity of visible light when used as a single compound and the polymer of the present invention, a compound exceeding the fluorescence intensity of 1,5-dihydroxynaphthalene is preferably used. . For example, as the naphthalene derivative, a compound (2,6-dihydroxynaphthalene) represented by (1-1) is preferable.

[Crosslinking agent]
The present invention uses a crosslinking agent. The crosslinking agent used in the present invention reacts with the first monomer having a hydroxy group to form a fluorescent polymer. As the crosslinking agent, for example, a two-component crosslinking agent using a mixture of formaldehyde and an aliphatic amine can be used. Further, a triazinan derivative can be used as a crosslinking agent as the second monomer. Hexamethylenetetramine can also be used as a crosslinking agent as the second monomer.
It is considered that formaldehyde and aliphatic amine react at a molar ratio of 1: 1 to form a structure like a triazinan derivative described below, particularly 1,3,5-trimethylhexahydro-1,3,5-triazinan. The structure of the triazinane derivative is considered to react so as to undergo addition condensation with the hydroxy group bonded to the ring of the cyclic compound of the first monomer, and by continuing this, the fluorescent polymer according to the present invention and can do. Further, by using hexamethylenetetramine, the polymer according to the present invention can be obtained by a reaction according to a triazinan derivative.

[Triazine derivative]
In the present invention, a triazinan derivative may be used as the second monomer used as a crosslinking agent. The triazinane derivative is a kind of heterocyclic compound and has a skeleton of a six-membered ring structure containing three nitrogen atoms (formula (X)). It is preferable that the triazinan derivative has two or more substituents. For example, triazinan derivatives of the formulas (x-1) to (x-4) can be used. In particular, 1,3,5-trimethylhexahydro-1,3,5-triazinan of the formula (x-1) is preferably used. Such a triazinan derivative is particularly suitable for producing the fluorescent copolymer of the present invention by reacting with the first monomer. The molar ratio of the raw materials in the production process of the fluorescent copolymer of the present invention can be easily adjusted with the triazinan derivative. In addition, the reaction can be performed without using a polymerization initiator, a metal catalyst, or the like.

[Formaldehyde and aliphatic amine]
As the crosslinking agent of the present invention, a two-component type in which formaldehyde and an aliphatic amine are mixed may be used. At this time, the molar ratio of formaldehyde to the aliphatic amine is adjusted in the range of about 1: 3 to 3: 1, preferably about 1: 2 to 2: 1, and it is most preferable to use it at about 1: 1. As formaldehyde, formalin or the like may be used. The aliphatic amine is represented by the general formula R—NH _2, where R is preferably an alkyl group having 5 or less carbon atoms. Examples of the alkyl group having 5 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. , Cyclopropylmethyl, n-pentyl, cyclopentyl, cyclopropylethyl, and cyclobutylmethyl groups. When used as this cross-linking agent, it is preferable that the molecular weight be smaller, so that R is preferably a methyl group, an ethyl group, or a propyl group. Specific examples of such compounds include methylamine, ethylamine, and propylamine. Particularly, methylamine is preferably used.

[Hexamethylenetetramine]
Hexamethylenetetramine can also be used as the crosslinking agent of the present invention. Hexamethylenetetramine is also called hexamine or 1,3,5,7-tetraazaadamantane. Formula (Y) shows the structure of hexamethylenetetramine.

[Polymer]
The fluorescent polymer of the present invention is a fluorescent polymer having a structural unit derived from a first monomer and a structural unit derived from a crosslinking agent. The fluorescent polymer of the present invention is preferably a fluorescent polymer which is a polymer having a structural unit derived from a first monomer and a structural unit derived from a second monomer. Having a structure derived from each monomer enables the structure to be ascertained from, for example, the result of analyzing the IR spectrum of the polymer. The structural unit derived from the first monomer and the structural unit derived from the second monomer form a three-dimensional crosslinkable polymer.
The structural unit derived from the first monomer forms a structure in which a plurality of hydroxy groups are generated by a reaction such as polymerization with each other or with a substituent or the like of a crosslinking agent. Due to this structure, the structural unit derived from the first monomer is a component constituting the main chain of the polymer. Further, a structural unit derived from a crosslinking agent may be polymerized as a component constituting the main chain.

蛍 光 The fluorescent polymer of the present invention may be a single first monomer or a polymer obtained by polymerizing two or more first monomers. Further, in addition to the first monomer, the crosslinking agent and the second monomer, another monomer may be further polymerized. The other monomer is not particularly limited as long as it is polymerizable, and examples thereof include a compound having one phenolic hydroxy group. The other monomer may not have a structure showing fluorescence as the monomer. Such other monomers include, for example, phenol, 1-naphthol, and the like.

構造 The structure derived from each monomer in the fluorescent polymer of the present invention is preferably at least 10 mol%, more preferably at least 20 mol%, as a percentage of the structure derived from the first monomer. The upper limit of the ratio occupied by the structure derived from the first monomer can be determined within a range in which polymerization is possible. Since crosslinking is carried out by a crosslinking agent for polymerization, the ratio occupied by the structure derived from the first monomer may be set to an upper limit of 90 mol% or less, 80 mol% or less, or 70 mol% or less. The proportion occupied by the structure derived from the cross-linking agent, the second monomer, and the other monomer described above is appropriately set as the balance of the proportion occupied by the structure derived from the first monomer. The proportion occupied by the structure derived from another monomer may have an upper limit of 50 mol% or less, 30 mol% or less, 10 mol% or less.

Since the fluorescent polymer of the present invention can have a cross-linkable structure, the degree of polymerization can be evaluated by the C / N ratio, which is a quantitative ratio of elements, and the charged amount of the monomer as a raw material can be evaluated. Or the degree of polymerization can be evaluated in comparison with the C / N ratio based on the When the fluorescent polymer of the present invention is crosslinked and polymerized, the C / N ratio of the obtained polymer is changed from the C / N ratio of one raw material or the C / N ratio as the total amount of the raw materials. It will be. For example, when polymerization is performed using a first monomer that does not contain N, the C / N ratio as a polymer is calculated by polymerization including N derived from a crosslinking agent. On the other hand, as the polymerization proceeds, the structure of the second monomer that is developed and does not constitute the polymer is eliminated. Therefore, N in the polymer tends to be lower than the C / N ratio based on the charged amount, and the C / N ratio becomes higher. Although depending on the type of the monomer, for example, a C / N ratio of about 3 to 50, about 5 to 30, or about 8 to 20 may be used as an index of the polymer. In particular, when there is no N derived from the first monomer, this numerical range may be an effective index.

For example, a case where an anthracene-based derivative (the above-described chemical formula (a-1)) and a triazinan-based derivative (the above-mentioned chemical formula (x-1)) are charged and synthesized at an equivalent ratio will be described. The C / N ratio of all the monomers based on these charging ratios is about 5.7, and N is not contained in the anthracene-based derivative. Even so, the C / N ratio becomes a very high value. On the other hand, as a polymer, the C / N ratio of the charge ratio is larger than 7 and 8 or more. Although the upper limit of the C / N ratio varies depending on the degree of polymerization, for example, the upper limit can be controlled to 30 or less or 20 or less. The structure presumed to be the main structure at the time of polymerization has a C / N ratio of about 13.7 or 8.1, and it is considered that these are mixed. Therefore, the C / N ratio as a polymer can be in a preferred range of about 9.0 to 13.0 or 9.5 to 12.5.

The fluorescent polymer of the present invention may be used as a substance made of a polymer, or may be used after being complexed with another substance. For example, it can be a particle or pellet substantially composed of a polymer, a dispersion, a solution or a slurry dispersed in a dispersion medium or the like, or a composite with a carrier or a substrate. The fluorescent polymer of the present invention, and a composition, a composite, and the like containing the same can exhibit fluorescence and have a low rare metal content. Here, the content of the rare metal is low, which means that the content of the rare metal is substantially equal to or less than the amount contained as a substantial impurity. Rare metal content of 1.0 × 10 ⁻² mass% or less, 1.0 × 10 ⁻³ mass% or less, 1.0 × 10 ⁻⁴ mass% in purified polymer, composition, composite, etc. An upper limit as described below may be provided or managed, or may not be substantially included as in the detection lower limit or less. This rare metal is a rare metal as a compound having a known fluorescent property.

[Fluorescence]
The fluorescent polymer of the present invention has fluorescence. This fluorescent light includes short-lived fluorescent light, which emits light as soon as the electromagnetic wave for excitation is stopped, and phosphorescent light, which has a long light-emitting life, and is irradiated with short-wavelength light (electromagnetic wave) having high energy. The resulting light emission. In the present application, the generation of this fluorescence is referred to as fluorescence, and the polymer exhibiting this fluorescence is referred to as a fluorescent polymer. In addition, this light emission can generate visible light (wavelength 370 to 800 nm). The emission of this visible light can be strong enough for humans to visually confirm in darkness or the like.

[Polymer particles]
The fluorescent polymer of the present invention can be a fluorescent polymer particle having a diameter of 3 to 500 nm. The fluorescent polymer particles can consist essentially of the fluorescent polymer of the present invention. These fluorescent polymer particles can be produced in a granular form together with the polymerization by adjusting the polymerization time, the polymerization temperature, and the monomer amount ratio in the polymerization step of the fluorescent polymer of the present invention. By making the nanoparticles extremely small, having a diameter of 3 to 500 nm, a dispersion or the like containing the particles can be excellent in light transmission and fluorescence. The lower limit of the diameter of the fluorescent polymer particles may be 5 nm or more, 10 nm or more, or 20 nm or more in consideration of ease of handling and ease of production control. The upper limit may be set to 400 nm or less or 300 nm or less so that the transparency and the dispersibility are further improved. In addition, these diameters may be the average particle diameter of the primary particles of the polymer particles.

[Particle size / monodispersibility]
These particles can be produced and collected as nano-scale particles of about 3 to 500 nm. The particles can have excellent monodispersity in particle size. The monodispersity can be determined using the coefficient of variation (CV value) of the particle size as an index. When the CV value is 20% or less, particles having more excellent handleability and fluorescent properties can be obtained. This CV value is a numerical value calculated as “standard deviation of particle size (nm) / average particle size (nm) × 100”. The smaller the CV value, the smaller the variation in particle size. The average particle size and the standard deviation of the particle size can be measured by analyzing electron micrographs of the particles taken by FE-TEM or FE-SEM using an image analyzer. These calculations are preferably made from 50 or more randomly selected particles.

[Spherical particles]
The particles can be recovered as spherical particles. This spherical shape may be evaluated by average sphericity, and the average sphericity can be 80% or more. The average sphericity can be 90% or more, or 95% or more. The average sphericity can be measured by analyzing the electron micrographs of the particles taken by FE-TEM or FE-SSEM using an image analyzer with the sphericity as the minor axis / major axis. The average sphericity is preferably the average value of the sphericity of 50 or more randomly selected particles.

[Polymer dispersion]
It is a dispersion containing the fluorescent polymer of the present invention using the fluorescent polymer of the present invention, and can be a dispersion using water or an organic solvent as a dispersion medium. Here, the term “dispersion” includes a state including any state in which the fluorescent polymer is dispersed or dissolved, and is referred to as a dispersion. The dispersion medium also includes a solvent, and the dispersion includes a solution.

蛍 光 The fluorescent polymer of the present invention can be an amphiphilic polymer showing hydrophilicity and hydrophobicity. When prepared as an aqueous dispersion or an aqueous solution, it can be dispersed in a wide range of pH from 0 to 14. From these characteristics, the fluorescent polymer of the present invention can be dispersed in various solvents. As the solvent, water, an organic solvent, a mixed solvent thereof or the like can be used. The color of the dispersion can also be adjusted by adjusting the type of solvent, pH, and the like.

濃度 The polymer concentration when forming a dispersion can be appropriately set in consideration of the use of the dispersion, the structure and the degree of polymerization of the polymer, and the like. For example, the lower limit of the concentration of the dispersion can be 1 mg / L or more, 5 mg / L or more, and 10 mg / L or more. The upper limit of the concentration of the dispersion can be 1 g / L or less, 500 mg / L or less, or 300 mg / L or less. In such a range of 1 mg / L to 1 g / L or less which is appropriately adjusted, sufficient fluorescence is exhibited in the state of the dispersion liquid. The dispersion may be handled at a higher concentration than these ranges for storage or distribution. In addition, by solidifying this dispersion, a solid exhibiting fluorescence can be obtained, or this dispersion may be contained in a translucent container and used as having a fluorescent content. .

[Composite with polymer]
In the present invention, a complex of a fluorescent polymer having a site containing the fluorescent polymer of the present invention on a carrier and / or a substrate can be provided. The fluorescent polymer of the present invention is used in a method of coating a fluorescent polymer, in which the fluorescent polymer is brought into contact with a carrier or a substrate to provide a site containing the fluorescent polymer on the carrier or the substrate. be able to.
The fluorescent polymer of the present invention can be coated on a carrier or a base material to have a site containing the fluorescent polymer in the pores of the support or the base material or on the surface layer. In the present application, the fine particles of the fluorescent polymer and the thin film of the fluorescent polymer are widely distributed throughout the carrier and the base material. The coating includes a portion having a polymer and a portion having a layer containing a fluorescent copolymer in a surface layer of a substrate or the like. In this coating, the polymer formed in the reaction step is applied to the carrier or the base by performing the reaction step as described below in a state where the carrier or the base material is immersed in the solution in which the reaction step is performed. The material may be brought into contact with the material to be coated. Further, the reaction step may be completed, and the fluorescent polymer solution in which the fluorescent polymer is dispersed and dissolved may be coated by bringing it into contact with a carrier or a base material. In addition, the collected fluorescent polymer is brought into contact with the collected fluorescent polymer by performing a collecting process described below, or coated, or the collected fluorescent polymer is dissolved and dispersed in a solvent or a dispersion medium, and is brought into contact with a carrier or a base material. Then, drying and the like may be performed as appropriate to coat.

[Carrier / substrate]
As the carrier, porous particles or the like can be used. The polymer dispersed in the solvent penetrates into the pores of the porous particles, or forms a polymer in the pores of the porous particles, thereby providing a polymer layer up to the pores of the porous particles. be able to. Since the polymer can be in the form of small fine particles or a thin film, blockage of the pores of the porous particles can be prevented.
The base material can be various molded articles. The fluorescent polymer of the present invention has excellent dispersibility in various solvents such as a hydrophilic solvent and a hydrophobic solvent, and therefore, a polymer that easily adheres to various substrates as a substrate. can do. By immersing the molded body in a polymer solution (dispersion liquid) or coating the polymer solution by various coating methods, a polymer layer can be provided on the molded body to obtain a molded body exhibiting fluorescence. Can be.

[Production method of fluorescent polymer of the present invention]
As described above, the present application relates to a method for producing the fluorescent polymer of the present invention. In the present application, the method for producing the fluorescent polymer of the present invention is a preferable method for producing the fluorescent polymer of the present invention, and the configurations corresponding to each part can be mutually used as described above. .

[Process for producing fluorescent polymer]
The method for producing the fluorescent polymer of the present invention can be carried out by various methods for copolymerizing the first monomer used in the present invention and a crosslinking agent (preferably the second monomer used in the present invention).
The method for producing a fluorescent polymer of the present invention comprises a first monomer used in the present invention, a crosslinking agent, and a mixing step of preparing a monomer mixture by mixing with a solvent for polymerization, and reacting the monomer mixture. The method preferably includes a reaction step of polymerizing the first monomer and the crosslinking agent to form a polymer solution containing a fluorescent polymer, and a recovery step of recovering the fluorescent polymer from the polymer solution.

[Mixing process]
The method for producing a fluorescent polymer of the present invention can include a mixing step of mixing the first monomer used in the present invention, a crosslinking agent, and a solvent for polymerization to prepare a monomer mixture. Based on the mixing ratio and the like in this mixing step, the component ratio and the like of the produced fluorescent polymer can be adjusted.

[Monomer, etc.]
As the first monomer and the cross-linking agent used in the present invention, the first monomer, the cross-linking agent, and the like that are derived from the structural unit of the fluorescent polymer of the present invention described above can be used. These can be used in accordance with the state of the substance such as each monomer, depending on the temperature and the atmosphere under the mixing conditions and the like. From the viewpoint of operability, it is preferable to use a liquid or solid material at room temperature or about room temperature (eg, about 20 to 30 ° C.). Further, in consideration of volatility and the like, a container or the like used for mixing may be used in a closed state, or may be mixed in an open state.

[Polymerization solvent]
The mixing step according to the present invention uses a polymerization solvent. As the solvent for polymerization, a solvent capable of dispersing or dissolving the first monomer and the crosslinking agent can be appropriately used. The first monomer and the crosslinking agent used in the present invention include those which are solid at room temperature, but by mixing using a polymerization solvent, the first monomer or the crosslinking agent is highly uniform in the mixed solution. The reaction can be carried out as a dispersion in nature.

The polymerization solvent used in the mixing step is, for example, a group consisting of alcohols (preferably lower alcohols having 1 to 5 carbon atoms), tetrahydrofuran, water, ethylene glycol, acetonitrile, ethyl acetate, dimethylformamide, benzene, toluene, and chloroform. One containing one or more solvents selected from the following can be used. The polymerization solvent can be appropriately selected according to the physical properties such as the solubility of the monomer and the particle size of the fluorescent copolymer to be produced. As the solvent, a single solvent may be used, or a mixed solvent of a plurality of solvents may be used. The solvent as described above does not inhibit the dispersibility of the first monomer and the second monomer and polymerization as a place where they react, and can be an excellent dispersion medium. Further, in the present invention, it is possible to have a step of recovering the fluorescent polymer, but also in this recovery, separation from centrifugation and the like, from the viewpoint of volatility during drying, these viewpoints Solvents are preferably used. When the reaction proceeds in a solvent, it is considered that the more the hydroxy group (OH) of the monomer is dissociated, the more the reaction proceeds. For this reason, it is preferable to use a protic polar solvent or an aprotic polar solvent.

[Solution adjustment]
Adjustment conditions such as the concentration of each of the first monomer, the second monomer, and the solvent for polymerization in the mixing step, the order of mixing, and the like, the type of each monomer and solvent, and the particle size and molecular weight of the fluorescent polymer to be produced It can be appropriately set in consideration of the physical properties such as the above, the use, and the like.

For example, the mixing ratio of the first monomer and the second monomer is 10: 1 to 1:10 or 8: 2 in a molar ratio (the molar amount of the first monomer: the molar amount of the second monomer). ２2: 8, 6: 4 ～ 4: 6, etc. As the concentration in the solution, the total molar amount of the first monomer and the second monomer is represented by the mass ratio to the whole solution (“the total molar amount (mol) of the first monomer and the second monomer / mol of the solution). The total amount (L) ") can be about 1 mmol / L to 1 mol / L. Since a monomer having a relatively large molecular weight is used, the upper limit may be reduced to 0.3 mol / L or less, 0.1 mol / L or less, or 50 mmol / L or less. In addition, the lower limit may be set to make the reaction easier, or may be set to 3 mmol / L or more, 5 mmol / L or more, and 10 mmol / L or more depending on the shape (size or the like) of the target polymer.

The mixing of the first monomer, the crosslinking agent, and the polymerization solvent can be appropriately set according to the state of the monomer and the like (liquid or solid, etc.). The monomers may be mixed and then the weighed crosslinking agent or the like may be mixed, or the order may be changed as appropriate to mix. Further, the mixture may be mixed little by little while dripping, or may be agitated to make the mixture more uniform.

[Reaction step]
The reaction step according to the method for producing a fluorescent polymer of the present invention is a step of reacting a monomer mixture to polymerize a first monomer and a crosslinking agent to obtain a polymer solution containing a fluorescent polymer.

[polymerization]
In the reaction step, the reaction conditions can be appropriately set in consideration of the respective substances of the first monomer and the crosslinking agent, the reactivity, the physical properties of the polymer to be obtained, and the like. Main reaction conditions to be set are a reaction temperature and a reaction time. The polymer formed by the reaction is dissolved and dispersed in the polymerization solvent to form a polymer solution. In addition, depending on the type and degree of polymerization of the polymer and the affinity with the solvent, the polymer may be dissolved in the solvent, dispersed in the form of particles, or may be in a state of being easily precipitated. In the present application, the state of dissolution, dispersion, and the like of the compound is referred to as a polymer solution.

反 応 The reaction temperature in the reaction step is preferably in the range of 0 ° C to 300 ° C. The higher the reaction temperature, the more the reaction can be promoted. If the reaction temperature is too high, the solvent or monomer may evaporate, making it difficult to adjust the reaction conditions. If the reaction temperature is too low, the polymerization may not proceed or a long time may be required. The reaction step is preferably performed at a temperature higher than room temperature, and the lower limit of the reaction temperature is preferably 20 ° C. or higher, 40 ° C. or higher, 60 ° C. or higher, 80 ° C. or higher. The upper limit of the reaction temperature is preferably 250 ° C. or lower, 200 ° C. or lower, or 180 ° C. or lower so that the volatilization of the solvent and the like can be prevented and the reaction can be easily controlled.

反 応 The reaction time of the reaction step is preferably one in which the reaction is performed for 1 minute to 48 hours. The reaction time is the time from setting the temperature set as the reaction temperature to stopping the reaction in the polymerization system. The reaction can be stopped when the reaction temperature is lowered from the set temperature or when a recovery step described later is started. If the reaction time is too short, it may not be possible to obtain a polymer having a sufficient degree of fluorescence, stability, shape and the like. Even if the reaction time is too long, the degree of copolymerization such as the degree of polymerization is saturated, and there is a possibility that deterioration or the like may occur due to heating or the like. The lower limit of the reaction time can be set in consideration of the degree of polymerization of the polymer to be obtained, such as 2 minutes or more, 5 minutes or more, and 10 minutes or more, and the particle size at the time of forming particles. The upper limit of the reaction time may be 20 hours or less, 10 hours or less, 1 hour or less, or 30 minutes or less since the fluorescent polymer according to the present invention can be obtained even if the reaction time is short.

反 応 The reaction process according to the method for producing a fluorescent polymer of the present invention may be carried out while appropriately stirring, applying microwaves, or the like. By performing the stirring and the application of the microwave, the heating conditions can be moderated so that the reaction conditions can be easily controlled or the uniformity can be improved. In particular, it is preferable to conduct the polymerization by reacting by microwave heating in which heating is performed while applying a microwave. In the method for producing a fluorescent polymer of the present invention, sufficient polymerization can be performed even under atmospheric pressure, and the production conditions can be easily controlled. For example, a polymerization reaction that takes about 6 hours at 70 ° C. in an oil bath or a water bath can be converted into a polymerization reaction of about several minutes by heating to 150 ° C. by applying a microwave.

[Recovery process]
The recovery step according to the method for producing a fluorescent polymer of the present invention is a step of recovering a polymer from a polymer solution. The fluorescent polymer polymerized in the reaction step can form particles. In some cases, the particles are in a state of being easily dispersed or precipitated in the polymerization solvent. In order to recover these fluorescent polymers, it is preferable to perform centrifugation, filtration, and drying to evaporate the solvent, and to recover the polymers. For example, the precipitate after centrifugation and removal of the supernatant can be used as a polymer concentrate.

(4) In recovering the fluorescent polymer, drying may be performed. This drying may be performed on the polymer solution after the reaction or on the polymer concentrate after centrifugation. The drying temperature may be appropriately set in consideration of the boiling point and volatility of the liquid used as the solvent, the stability of the polymer, and the like, and may be, for example, about 50 to 300 ° C., preferably about 80 to 150 ° C. Alternatively, drying under reduced pressure may be appropriately performed in combination with drying by heating or the like.

方法 The method for producing a fluorescent polymer of the present invention enables so-called one-pot synthesis in which mixing and reaction are performed in a single reaction vessel to obtain a predetermined fluorescent polymer. For this reason, the introduction load of the manufacturing equipment is low, and it is easy to perform various types of production from small-quantity multi-product production to mass production.

[Features of the present invention]
The present invention is a three-dimensionally crosslinked fluorescent polymer composed of a completely organic polymer and having a fluorescent site incorporated in the polymer main chain. This relates to a fluorescent particle or a luminescent material whose diameter can be made to be a nano size, a method for producing the same, and the like. The fluorescent polymer of the present invention is hardly decomposed and has a structure exhibiting fluorescence in the main chain of the polymer, so that the fluorescent site is hardly eluted and has high stability. In addition, it has high thermal stability and solvent resistance, and its use range is wide. For example, it is expected to be applied as a fluorescent filler or a marker for analysis, or as a marker for biological analysis.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless the gist is changed.

[Evaluation item]
<UV-visible spectrum>
-Measuring device: UV-visible spectrophotometer (JASCO Corporation model number: V-560)
-Measurement conditions: The measurement was performed by setting the absorbance measurement mode, the bandwidth to 1.0 nm, and the scanning speed to 200 nm / min. An optical cell having an optical path length of 10 mm was used for the measurement.

<Excitation light-Fluorescence spectrum>
-Measuring device: spectrofluorometer (JASCO Corporation model number: FP-6500)
Measurement conditions: Measurement was performed in an emission mode, with an excitation bandwidth of 3 nm, a fluorescence bandwidth of 3 nm, and a scanning speed of 200 nm / min. An optical cell having an optical path length of 10 mm was used for the measurement.

<Observation of particle size>
-Measuring device: TEM (JEOL Ltd. model number: JEM1400-plus)
Measurement conditions: Observation was performed under an acceleration voltage condition of 80 kV. The observation sample used was a TEM grid that had been subjected to a surface hydrophilization treatment at 5.5 mA for 90 seconds using a plasma ion bombarder (Vacuum Device Inc., model number: PIB-10). The sample was cast on a TEM grit and then stained using a 0.1% uranyl acetate aqueous solution.

<Zeta potential>
-Measuring device: Zeta potential measuring device (MALVERN company model number: Zetasizer Nano ZS)
Measurement conditions: Disposable folded capillary cells (MALVERN model number: DTS 1070) were used as measurement cells. The measurement was performed at 25 ° C., and Smoluchowski approximation was used for the F (ka) value.

[Polymerization method]

[Reagents, etc.]
<First monomer>
・ DHA: 2,6-Dihydroxyanthracenen (Tokyo Chemical Industry, purity:> 95%)

・ BHPF: 9,9'-Bis (4-hydroxyphenyl) fluorene (Tokyo Chemical Industry, purity:> 96%)

・ 2,6-DHN: 2,6-Dihydroxynaphthalene (Tokyo Chemical Industry, purity:> 95%)

・ 2,2'-DHBP: 2,2'-Dihydroxybiphenyl (Fujifilm Wako Pure Chemical, purity:> 97%)

・ 4,4'-DHBP: 4,4'-Dihydroxybiphenyl (Fujifilm Wako Pure Chemical, purity:> 97%)

・ 2,2'-BHPP: 2,2'-Bis (4-hydroxyphenyl) propane (Tokyo Chemical Industry, purity:> 99%)
(Also known as: 4,4 '-(propane-2,2-diyl) diphenol)

<Second monomer>
・ TA: 1,3,5-Trimethylhexahydro-1,3,5-triazinane (Tokyo Chemical Industry, purity:> 98%)

<Second monomer>
・ HMT: Hexamethylenetetramine (Katayama Chemical Industry, special grade)

<Solvent etc.>
· EtOH: Ethanol-THF: Tetrahydrofuran-DMF: dimethylformamide, DMSO: dimethyl sulfoxide-CHCl _3: trichloromethane, EtOAc: ethyl acetate - Acetone: acetone water: Pure water

[Example 1] (DHA-TA)
A fluorescent polymer was produced using DHA as the first monomer and TA as the second monomer. Using a mixed solvent of THF: water (volume ratio 8: 2), the concentration of DHA is 10 mmol / L (“mmol / L” may be abbreviated as “mM”), and the concentration of TA is 10 mmol / L. A certain monomer mixture (1) was prepared. This monomer mixture (1) was heated at 150 ° C. for 3 minutes while stirring at 300 rpm using a microwave synthesizer (Anton Paar model: Mono wave 300), and the monomer was copolymerized to obtain a polymer solution (1). Obtained.
The polymer solution (1) was diluted with ethanol, centrifuged at 20,000 rpm for 45 minutes, the supernatant was removed, and the dispersion on the precipitate side was collected. This dispersion contains a polymer (1) of DHA and TA.
This dispersion was further dried under reduced pressure at room temperature to obtain a polymer (1). The physical properties of the polymer (1) were evaluated.

FIG. 1 is a TEM observation image of the obtained polymer (1). As shown in FIG. 1, spherical particles having a diameter of about 30 nm were obtained.
FIG. 2 is a graph showing the pH dependence of the charge state at the particle interface of the obtained polymer (1). Under acidic conditions, the lower the pH, the more positive the zeta potential (Zeta Potential). Therefore, it is considered that the polymer (1) has a structure having N. Under basic conditions, the higher the pH, the more negative the zeta potential becomes. Therefore, it is considered that the polymer (1) has a structure having OH. The two electrolytic properties indicate that an anionic dihydroxy compound and a cationic triazinan unit are present at the particle interface.

(Observation of polymer solution)
FIG. 3 is a photograph showing a dispersion solution containing water as a dispersion medium containing the polymer (1) at a concentration of about 5 mg / mL. PH was adjusted from 0.1N hydrochloric acid or 0.1N sodium hydroxide aqueous solution to acidic to basic from left to right in FIG. pH 2.5, pH 3.0, pH 3.5, pH 4.0, pH 7.0, and pH 12.0. It was yellow in the acidic state on the left side and red in the basic state on the right side, and it was confirmed that the dispersion medium whose color changes with pH can be adjusted.

(Optical properties of polymer solution (1))
FIG. 4 confirms the ultraviolet-visible light absorption characteristics (FIG. 4 (a)) and the excitation light-fluorescence characteristics (FIG. 4 (b)) of the polymer (1). 4 shows an ultraviolet-visible spectrum and a fluorescence spectrum when the obtained polymer particles are dispersed in a mixed solution of ethanol and water (volume ratio: 9: 1). The broken line in the graph is a mixture of the monomer (DHA) as it is, and the solid line is the dispersion medium containing the polymer (1).
In the polymer particle dispersion medium, an absorption band not observed in the monomer dispersion medium appears around 500 to 550 nm. Further, when excited at 345 nm, light emission not found in the monomer was observed at 550 to 700 nm in the polymer particle dispersion.

(Optical properties of polymer solution (2))
FIG. 5 shows the results obtained by changing the pH of the solution of the polymer (1) and confirming the ultraviolet-visible light absorption characteristics (FIG. 5A) and the excitation light-fluorescence characteristics (FIG. 5B). 4 shows an ultraviolet-visible spectrum and a fluorescence spectrum when the obtained polymer particles are dispersed in a mixed solution of ethanol: water (volume ratio: 9: 1) adjusted to pH9. A normal broken line is a mixture of the monomer (DHA) as it is, and a solid line is a dispersion medium of pH 9 containing the polymer (1).
By adjusting to the basic condition, in the ultraviolet-visible spectrum of the dispersion medium of the polymer particles, the absorption intensity around 500 nm was reduced and changed to a spectrum having a specific absorption maximum at 564 nm. When excited at 346 nm, a fluorescence spectrum not observed with the raw material was observed at 500 to 800 nm.

FIG. 6 shows observation results of a solution in which the polymer (1) is dispersed in various solvents, (a) excited under normal light and (b) excited at 364 nm. In addition, FIG. 7 shows the results of measuring the ultraviolet-visible and fluorescence spectra of a typical solution in FIG. It was confirmed that the optical characteristics, particularly the fluorescence characteristics, changed significantly depending on the dispersion medium.

Thus, the DHA solution of the monomer has a fluorescence intensity around 420-440 nm and shows bluish fluorescence. By using the polymer (1) according to the present invention, a broad and strong fluorescence intensity around 540-600 nm was exhibited, and a strong yellow fluorescence was exhibited.

(Structural formula of polymer (1) and C / N ratio)
The chemical structure of the polymer (1) is presumed to be that of Structure 1 or Structure 2 shown in FIG. These C / N ratios are 13.71 and 8.14, respectively. Since the actually measured C / N ratio of the polymer (1) is 12.05, the polymer (1) is a crosslinkable polymer in which Structure 1 and Structure 2 are mixed.

(Stability of polymer (1))
The stability of the polymer (1) to acids and alkalis was evaluated by an ultraviolet-visible spectrum and an excitation light-fluorescence spectrum. A 5 mg / mL aqueous solution of the polymer (1) at pH 2 and pH 13 was prepared, allowed to stand in a dark place at 25 ° C., and the spectrum was measured after a lapse of 7 days. There was no significant change in spectrum before and after the passage of time, and the stability was high.

[Example 2]
[Production of polymer (2-1) (BHPF-TA)]
A fluorescent polymer was produced using BHPF as the first monomer and TA as the second monomer. Ethanol: water (volume ratio 9: 1) was mixed, and mixed with a mixed solvent (2-1) adjusted to pH 12 with a 0.1N NaOH aqueous solution so that BHPF 20 mmol / L and TA 20 mmol / L. A monomer mixture (2-1) was prepared.
The monomer mixture (2-1) was heated at 150 ° C. for 30 minutes while stirring at 300 rpm using a microwave synthesizer, and the monomers were copolymerized to obtain a polymer solution (2-1).
Ethanol was added to the polymer solution (2-1) in an amount equal to that of the polymer solution (2-1), and the dispersion was evaluated as a two-fold diluted liquid (2-1). This dispersion liquid (2-1) contains a polymer (2-1) of a fluorene-based monomer and TA.

9 to 11 show the evaluation results of the dispersion liquid (2-1) containing the polymer. FIG. 9 confirms the ultraviolet-visible light absorption characteristics (FIG. 9A) and the excitation light-fluorescence characteristics (FIG. 9B). The excitation light in FIG. 9B has a wavelength of 407 nm at which strong absorption of the polymer (2-1) is confirmed. The broken line in the graph is a mixture of the monomer (BHPF) as it is, and the solid line is the dispersion medium containing the polymer (2-1).
FIG. 10 shows the observation results when the polymer solution was irradiated with laser light. FIG. 11 shows an observation result obtained when irradiation with light having a wavelength of 364 nm is performed. In FIG. 11, (a) shows the evaluation result of the liquid before polymerization in which the monomer was dispersed in ethanol at the same concentration as the dispersion liquid (2-1). (B) shows the evaluation result of the dispersion liquid (2-1) containing the polymer.
The dispersion liquid (2-1) containing the polymer was colored yellow. In addition, it was confirmed that the dispersion liquid (2-1) exhibited strong fluorescence by excitation at a wavelength of 364 nm or 407 nm (FIGS. 9 and 11). Irradiation of the dispersion liquid (2) with laser light causes light scattering, so that it was confirmed that a very small granular polymer was dispersed (FIG. 10).

[Production of polymer (2-2) (DHA-TA)]
Similarly to Example 1, a monomer mixture (2-2) having a DHA concentration of 10 mmol / L and a TA concentration of 10 mmol / L was prepared using a mixed solvent of THF: water (volume ratio: 8: 2). did. The monomer mixture (2-2) was heated at 150 ° C. for 3 minutes while stirring at 300 rpm using a microwave synthesizer (Anton Paar model number: Mono wave 300) to copolymerize the monomer and polymer solution (2). -2) was obtained. The polymer solution (2-2) was diluted with acetonitrile, centrifuged at 20,000 rpm for 45 minutes, the supernatant was removed, and the dispersion on the precipitate side was collected. This dispersion contains a polymer (2-2) of DHA and TA.

This dispersion was further dried at room temperature under reduced pressure to obtain a polymer (2-2). FIG. 12 shows an ultraviolet-visible spectrum and a fluorescence spectrum when the polymer (2-2) is dispersed in a mixed solution of ethanol and water (volume ratio 9: 1) adjusted to pH 13 and pH 2. Under both acidic and alkaline conditions, as compared with Example 1, the ultraviolet-visible spectrum shifts toward the longer wavelength side by about 50 nm. In addition, under acidic conditions, a characteristic fluorescence emission is confirmed when excited at 495 nm.

Example 3 (2,6DHN-HMT)
A monomer mixture (3) was prepared so that the concentration of 2,6-DHN was 30 mmol / L and the concentration of HMT was 30 mmol / L in ethanol. The monomer mixture (3) was heated at 200 ° C. for 10 minutes while stirring at 300 rpm using a microwave synthesizer, and the monomers were copolymerized to obtain a polymer solution (3). The polymer solution (3) was diluted with ethanol, centrifuged at 20,000 rpm for 30 minutes, and the supernatant was removed to obtain a polymer (3).

FIG. 13 is a histogram of the particle size distribution of the polymer (3). Particles having an average particle size of 39 nm and a CV value of 17.5% were observed. FIG. 14 shows the UV spectrum of the ethanol solution (3) and the polymer solution (3) of 2,6-DHN and the result of fluorescence spectrum measurement excited at 500 nm. Polymer solution (3) has an absorption band at 400-500 nm that is not found in 2,6-DHN. Further, when each solution was excited at 500 nm and the fluorescence spectrum was measured, light emission not observed in the ethanol solution of 2,6-DHN was observed.

[Example 4]
Table 1 shows the production conditions of the polymers produced according to Example 1 and Example 2. From Example 4-1 it was confirmed that a fluorescent polymer could be obtained under any of the production conditions of Example 4-8. The average particle size shown in Table 1 is a value obtained by randomly measuring the particle size of 50 or more particles from an image obtained by TEM observation, and dividing the sum of the measured values by the number of measured values.
FIG. 15 shows a TEM observation image of the obtained fluorescent polymer. As shown in FIG. 15, it was confirmed that particles having a particle size of about 26 nm to 215 nm can be obtained under these manufacturing conditions. In each case, particles having high monodispersity were obtained, and typically, in Example 4-1 and Example 4-7, CV values of 17.5% and 18.4% were obtained, respectively. . FIG. 16 is a histogram of Example 4-1 and Example 4-7.

[Example 5]
<Coating of fluorescent polymer>
Using DHA as the first monomer and TA as the second monomer, nanosilica (Snowtex S (manufactured by Nissan Chemical Industries, Ltd., 30% aqueous dispersion, average particle size 50 nm)) was coated with a fluorescent polymer. The nanosilica was centrifuged under the conditions of 20,000 rpm for 15 minutes, and the precipitated component was redispersed in ethanol and used (silica content: 40 mg / mL). A mixed solution (5) was prepared by adding 2.6 mL of silica dispersion (105 mg of silica), 10.5 mg of DHA, and 6.45 mg of TA to ethanol. The mixture (5) was heated at 75 ° C. for 12 hours while stirring at 300 rpm on an oil bath, and the monomer was copolymerized on the nanosilica interface to obtain a dispersion solution (5) of the fluorescent polymer-coated silica particles. The dispersion (5) of the fluorescent polymer-coated silica particles was diluted with ethanol, centrifuged at 25,000 rpm for 30 minutes, the supernatant was removed, and the precipitate was collected. The precipitate was further dried at room temperature under reduced pressure to obtain fluorescent polymer-coated silica particles (5). FIG. 17 shows a state where the fluorescent polymer-coated silica particles (5) are dispersed in water and irradiated with ultraviolet light having a wavelength of 364 nm. FIG. 17 shows (a) a sample in which fluorescent polymer-coated silica particles (5) are dispersed in water, a few drops of 0.1N HCl added, (b) nothing added, (c) 0 A few drops of .1N NaOH were added. (A) shows a white color, (b) shows a red-orange color, and (c) shows a blue-green color, showing different fluorescent colors by changing pH conditions.

[Example 6] (2,2'-DHBP-TA)
A fluorescent polymer was produced using 2,2′-DHBP as the first monomer and TA as the second monomer. Using a mixed solvent of EtOH: water (volume ratio 9: 1), a monomer mixture (6) was prepared in which each of 2,2′-DHBP and TA had a concentration of 75 mM. The monomer mixture (6) was heated at 150 ° C. for 30 minutes while stirring at 300 rpm using a microwave synthesizer to copolymerize the monomers to obtain a polymer solution (6). This polymer solution was filtered through a membrane filter to recover a yellow polymer (6).

FIG. 18 is an SEM observation image of the obtained polymer (6). As shown in FIG. 18, spherical particles having a diameter of about 2.5 μm were obtained.

(Optical properties of polymer solution)
FIG. 19 shows UV-visible light absorption characteristics (FIG. 19 (a)) and excitation light-fluorescence characteristics (FIG. 19 (A)) of a solution obtained by adding 50 μL of a 0.1N aqueous sodium hydroxide solution to an ethanol dispersion solution of the polymer (6). b)) was confirmed. In the polymer dispersion medium, the intensity of the absorption band at 330 nm was increased as compared with the monomer solution. Excitation at 281 nm increased the emission intensity around 410 nm.

[Example 7] (4,4'-DHBP-TA)
A fluorescent polymer was produced using 4,4′-DHBP as the first monomer and TA as the second monomer. Using a mixed solvent of EtOH: water (volume ratio 9: 1), a monomer mixture (7) having a concentration of 4,4′-DHBP and TA of 75 mM was prepared. This monomer mixture (7) was heated at 200 ° C. for 30 minutes while stirring at 300 rpm using a microwave synthesizer to copolymerize the monomers to obtain a polymer solution (7). This polymer solution was filtered with a membrane filter to recover a yellow polymer (7).

FIG. 20 is an SEM observation image of the obtained polymer (7). As shown in FIG. 20, spherical particles having a diameter of about 2.5 μm were obtained.

(Optical properties of polymer solution)
FIG. 21 shows UV-visible absorption characteristics (FIG. 21 (a)) and excitation light-fluorescence characteristics (FIG. 21 (A)) of a solution obtained by adding 50 μL of a 0.1N aqueous sodium hydroxide solution to an ethanol dispersion solution of the polymer (7). b)) was confirmed. In addition, it was confirmed that when excited at 300 nm, the emission spectrum at 400 nm to 550 nm shifted to the longer wavelength side compared to the monomer solution.

Example 8 (2,2′-BHPP-TA)
A fluorescent polymer was produced using 2,2'-BHPP as the first monomer and TA as the second monomer. Using a mixed solvent of EtOH: water (volume ratio 9: 1), a monomer mixture (8) was prepared in which each of 2,2′-BHPP and TA had a concentration of 75 mM. The monomer mixture (8) was heated at 150 ° C. for 30 minutes while stirring at 300 rpm using a microwave synthesizer to copolymerize the monomers, thereby obtaining a polymer solution (8). This polymer solution was filtered with a membrane filter to recover a white polymer.

(Optical properties of polymer solution)
FIG. 22 shows UV-visible light absorption characteristics (FIG. 22 (a)) and excitation light-fluorescence characteristics (FIG. 22 (A)) of a solution obtained by adding 50 μL of a 0.1N aqueous sodium hydroxide solution to an ethanol dispersion solution of the polymer (8). b)) was confirmed. When excited at 295 nm in the polymer dispersion medium, an emission spectrum at 350 nm to 500 nm that was not observed in the monomer solution was observed.

蛍 光 The fluorescent polymer of the present invention can be used as a novel fluorescent substance. For example, it is possible to provide fluorescent particles, molded articles, liquids, and the like, and to use a fluorescent polymer as a bioanalytical marker or the like, which is industrially useful.

Claims (11)

1. A fluorescent polymer having a structural unit derived from the first monomer and a structural unit derived from a crosslinking agent,
   The first monomer is a polycyclic fluorescent compound having two or more hydroxy groups, an anthracene derivative, a fluorene derivative, a pyrene derivative, an anthraquinone derivative, a porphyrin derivative, a binaphthalene derivative, a bipyridine derivative, At least one selected from the group consisting of biphenyl derivatives, bisphenol derivatives, xanthene derivatives, dibenzofuran derivatives, and naphthalene derivatives;
   A fluorescent polymer in which the first monomer is at least a part of a structural unit of a main chain of the fluorescent polymer and is crosslinked by a crosslinking agent.
2. 蛍 光 The fluorescent polymer according to claim 1, wherein the crosslinking agent is a triazinan derivative and / or hexamethylenetetramine.
3. 請求 The fluorescent copolymer according to claim 1, wherein the crosslinking agent is hexamethylenetetramine.
4. The first monomer is a polycyclic fluorescent compound having two or more hydroxy groups, and is an anthracene derivative, a fluorene derivative, a pyrene derivative, an anthraquinone derivative, a porphyrin derivative, a bipyridine derivative, a biphenyl derivative. 4. The fluorescent copolymer according to claim 2, which is at least one selected from the group consisting of a bisphenol derivative, a xanthene derivative, a dibenzofuran derivative, and a naphthalene derivative.
5. 蛍 光 Fluorescent polymer particles containing the fluorescent polymer according to any one of claims 1 to 4 and having a diameter of 3 to 500 nm.
6. A dispersion comprising the fluorescent polymer according to any one of claims 1 to 4, wherein the dispersion is water and / or an organic solvent.
7. 複合 A composite of a fluorescent polymer having a site containing the fluorescent polymer according to any one of claims 1 to 4 on a carrier and / or a substrate.
8. A method for producing a fluorescent polymer in which the first monomer is crosslinked by a crosslinking agent,
   The first monomer is a polycyclic fluorescent compound having two or more hydroxy groups, an anthracene derivative, a fluorene derivative, a pyrene derivative, an anthraquinone derivative, a porphyrin derivative, a binaphthalene derivative, a bipyridine derivative, At least one selected from the group consisting of a biphenyl derivative, a bisphenol derivative, a xanthene derivative, and a naphthalene derivative;
   A method for producing a fluorescent polymer, wherein the first monomer is cross-linked by a cross-linking agent so that the first monomer is at least a part of a structural unit of a main chain of the fluorescent polymer.
9. A mixing step of mixing the first monomer, the crosslinking agent, and the polymerization solvent to prepare a monomer mixture,
   In the monomer mixture, a reaction step of polymerizing the first monomer and the crosslinking agent to form a polymer solution containing a fluorescent polymer,
   The method for producing a fluorescent polymer according to claim 8, further comprising a recovery step of recovering the fluorescent polymer from the polymer solution.
10. (10) The method for producing a fluorescent polymer according to (9), wherein the reaction step is a step of performing copolymerization by microwave heating.
11. The fluorescent polymer according to claim 1, wherein the fluorescent polymer according to any one of claims 1 to 4 is brought into contact with a carrier and / or a substrate to provide a portion containing the fluorescent polymer on the carrier and / or the substrate. Coating coating method.

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