JPH1160725A - Metal cationic complex and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject complex that inhibits the formation of cluster, when metal cations are dispersed in an organic polymer material in a high concentration, by arranging a branching polymer bearing diketonate groups through the statically mutual action or the covalent bond near the metal cations. SOLUTION: The objective metal cation complex is constructed according to the formula: M<n+> (RA<-> )n (M<n+> is a metal cation; n is the valance; RA<-> is a monovalent anion; R is an residue of branching polymer; A<-> is β-diketonate group). The branching polymer bearing the β-diketone group represented by the formula: RA corresponding to RA<-> simultaneously satisfies the relations of 300<=MN( GPC) <=50,000 and 1.0<=Mw( GPC) /Mn( GPC) <=15 between the number- average molecular weight Mn( GPC) and the weight-average molecular weight Mw( GPC) measured by the gel-permeation chromatography. In a preferred embodiment, a dendrimer is used as the branching polymer and the β-diketonate group is bonded to its focal point.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a metal cation and β
The present invention relates to a metal cation complex comprising a branched polymer having a diketonate group. The metal cation complex of the present invention has homogeneity, compatibility with solvents or various matrix materials, thermoplasticity, and is excellent in lightness and toughness. -A metal cation-containing material that has both lightness, toughness against bending displacement, and adhesion to a wide variety of substrates. Since the metal cation complex of the present invention can contain an element having a high atomic number in a wide concentration range, it is useful as an optical material having a controlled refractive index used for a lens, an optical waveguide, and the like, Since it is an ionic compound, a polymer composition or a coating agent using the same also has an electromagnetic wave shielding ability and an antistatic ability.

[0002] When the cation has a fluorescent ability,
Since it is a material that also has high fluorescence ability with suppressed concentration quenching, if dissolved in a solvent, it can be used as an X-ray intensifying screen, fluorescent lamp,
As a high-brightness fluorescent coating material with excellent storage stability that can be used for various molded articles including road signs and safety signs, or as a fluoroimmunoassay (fluoroimmuno).
As a material that can be used for a wide range of fluorescent light applications, such as fluorescent labeling agents used in assays and the like, optical communication members such as optical amplifiers, and laser transmitters. Further, when the cation has paramagnetism, it is useful as a contrast agent used for imaging (MRI) utilizing a nuclear magnetic resonance (NMR) phenomenon, an X-ray contrast agent, or the like.

[0003]

2. Description of the Related Art Metal cations have various functions such as excitation by light energy and fluorescence phenomenon by emission thereof, generation of X-rays by electron beam irradiation, magnetism, various catalytic actions, and redox action. In order to put these functions to practical use, it is necessary to control the state (for example, the oxidation number, the external environment such as ligands, the dispersed state of individual atoms, etc.), or to mold to a specific product form. It is necessary to provide workability. A common technique for this is to disperse the cations in a matrix material.

[0004] Taking as an example the case where the electromagnetic function of a metal cation, such as fluorescence, the property of changing the speed of light passing through a matrix (ie, change in refractive index), etc., is used, the matrix material used is It is usually necessary to be sufficiently transparent in the desired electromagnetic wave wavelength region. For example, in a technology utilizing a wavelength around the visible light region, inorganic glass such as silica glass has conventionally been an important matrix material. This is due to the properties of the inorganic glass such as excellent heat transmittance, chemical resistance, water resistance, surface hardness, abrasion resistance, and low coefficient of linear expansion, as well as excellent light transmittance in a wide wavelength range.

As a technique for dispersing a cation metal, particularly a lanthanoid cation having fluorescence, in an inorganic matrix, a method of melting and mixing at a temperature higher than the melting point, a method of dissolving raw materials in an acid or the like, mixing them, and then neutralizing the mixture. A so-called coprecipitation method of forming a precipitate, a solid-phase reaction method in which the raw material powder is mixed with a target composition and then heated at a high temperature to mutually diffuse ions, a method of injecting the element in a gas phase, a method of rapidly accelerating the Conventionally, a method of implanting an element, a so-called sol-gel method of hydrolyzing and condensing an alkoxide or the like of the element together with an alkoxide or the like serving as a precursor of an inorganic matrix have been used.
In some cases, these elements can be mixed in the inorganic matrix to a concentration of about several percent by weight,
Generally, since the solubility of the cation in the inorganic matrix is low, or it is difficult to control the chemical structure in the vicinity of the cation, there is a disadvantage that an aggregated state (cluster) is easily formed. In particular, in the case of utilizing the fluorescence of the cation, there is a disadvantage that the fluorescence intensity is rather lowered when the added concentration is set to a certain level or more due to concentration quenching caused by the transfer of the excitation energy in the cluster.

On the other hand, with the progress of the production technology of organic polymer materials, transparent resins such as acrylic resins, styrene resins, aromatic polycarbonate resins, aromatic polyarylate resins, polyimide resins, and amorphous polyolefin resins have been developed. Amorphous thermoplastic resin has been developed and features not found in inorganic glass, such as excellent moldability such as thermoplasticity and solution applicability, light weight, toughness, variety of monomer chemical structure selection, and other types Applications utilizing characteristics such as adhesion to materials and recyclability have been devised. For example, lenses for cameras and spectacles, headlamp covers for automobiles, transparent structural materials used for applications such as optical discs and compact discs,
Applications as a support medium for a polymer material for a photoresist, or a functional low-molecular compound such as a binder for an electrophotographic photosensitive member or a heat-sensitive transfer dye are increasing.

[0007] In view of the current state of such material technology, for example, in the technical field such as optical communication technology, which has mainly been mainly composed of inorganic materials, or in the case of conventional inorganic substances such as phosphor technology or organic complexes having a relatively low molecular weight, it is mainly used. In the technical field, the development of new materials that take advantage of the characteristics of organic polymer materials described above is one of the important issues. More specifically, for example, an organic polymer fluorescent material having a high fluorescence generating ability, or a controlled refractive index, an amplification function for compensating for a loss (lower signal intensity) during optical signal transmission, and a wavelength An organic polymer material having optical characteristics such as a conversion function is considered to be extremely useful.

As an application example of a cation of an element capable of generating fluorescence such as a lanthanoid to an inorganic matrix, for example, an inorganic glass to which a cation such as erbium is added is used as a material for an optical amplifier in optical communication technology. (Kimura et al., Optronics, November 1990)
No. 47, page 53, William J. et al. Minisc
alco; Lightwave Technology
gy, vol. 9, p. 234 (1991), and E
mmnural Desurvive; Erbium-
Doped Fiber Amplifiers: Pr
inclusions and Application
s, John Wiley & Sons, New Y
ork (1994)). This is the erbium f
Light in the visible to near-infrared region of orbital electrons (eg, wavelength 980)
nm) and the phenomenon of fluorescence generation at a wavelength of about 1500 nm. However, when an inorganic glass is used as a matrix, the solubility of erbium cations is relatively low, so that cluster formation occurs due to association of cations even with addition of at most several hundred ppm. As a result, the concentration quenching becomes remarkable, so that even if added more, the fluorescence generation efficiency is conversely reduced, that is, there is a drawback that the optical amplification function peaks out. In addition, because it is an inorganic glass material, its lightness, moldability, and toughness have not always been satisfactory.

For the purpose of improving these disadvantages, for example, Hoshino et al .; Proceedings of the Institute of Electronics, Information and Communication Engineers, 1991, 4-232
And the like disclose a method of obtaining a quartz film containing a rare earth element at a high concentration and uniformity by a hydrolysis-condensation reaction in a homogeneous solution using a metal alkoxide and a lanthanoid chloride as raw materials. However, in such a method, cracking and peeling of the quartz film from the substrate occur, so that there is a problem in the forming process such as difficulty in forming a thick quartz film on the substrate.

[0010] On the other hand, the addition of lanthanoid cations to organic polymer materials has been studied. For example, Okamot
o, Y. et al; Macromolecules,
14, p. 17 (1981), Heats, J. et al. et
al edition; “Metal Containing Po
lymphatic Systems ", PlenumPr
ess, New York (1985), and even Yoshi
iyuki Okamoto; Proceedings of the Society of Polymer Science, 19
In vol. 43 (1), p. 29, 1994, a lanthanoid salt of a polymerizable organic acid such as acrylic acid, methacrylic acid, styrene carboxylic acid, and styrene sulfonic acid was synthesized, and the lanthanoid cation-supporting monomer was polymerized or synthesized. A method has been reported in which the cation concentration is increased to about 10% by weight by copolymerization. JP-A-5-86189 discloses a polysiloxane obtained by using chlorosilanes having an organic group and a chloride of a rare earth element as raw materials and having a lanthanoid incorporated in a polymer chain. Furthermore,
JP-A-5-88026 discloses a material containing a complex excellent in solubility and oxidation resistance in an organic solvent, such as an acetylacetone complex of a lanthanoid, in a polyacrylate or polysiloxane.

Although these methods are certainly effective in increasing the concentration of the metal cation in the organic polymer material and give a material having apparently good transparency, the structure near the cation has a problem. The concentration quenching problem is not completely controlled because the cations are not precisely controlled and the association of the cations at structural levels smaller than the wavelength of light can still occur even if apparent transparency is achieved. Had not been resolved.

On the other hand, inorganic phosphors usually used for cathode ray tubes, fluorescent lamps, X-ray intensifying screens and the like include multi-step processes complicated in their production, such as mixing, sedimentation, filtration, drying, baking, and pulverization.・ A process such as classification is usually required, the dispersibility in a solvent or a binder polymer when applying it to a substrate may be insufficient, and a lanthanoid positive fluorescent species, as described above, may be used. There are drawbacks such as concentration quenching due to ion cluster formation. Also,
As a fluorescent labeling agent such as a fluoroimmunoassay fluorescent substance, a lanthanoid complex using a low-molecular organic ligand such as an acetylacetonate derivative has been conventionally used. I was

The X-ray contrast technique is a technique for injecting an element having a high atomic number having a high X-ray absorption capacity into a living body by any method and then performing X-ray irradiation to obtain an image. In order to perform good contrast imaging, a technique for stably dispersing such elements in the bloodstream, that is, in the aqueous electrolyte solution is essential. In the early days of X-ray imaging technology, a method of injecting a salt of iodide ion (I-) into blood was used. However, there was a problem of causing shock symptoms, pain, or thyroid disorders in a patient who received the salt. there were. For the purpose of alleviating such serious side effects, nonionic iodine compounds, for example, organic compounds containing iodine atoms at a high concentration and imparting hydrophilicity are widely used at present. However, even with such organic iodine compounds, side effects that are considered to be attributed to iodine have been reported, and the development of a new contrast agent for XRI using an element having a high atomic number other than iodine and having suppressed liberation has been desired. It is rare.

[0014]

As described above, various proposals have been made for a method of dispersing a metal cation and an organic polymer material in a high concentration and in a uniform manner. However, no method has yet been found that satisfactorily solves the problem of formation of clusters due to the association of the cations and consequently concentration quenching. An object of the present invention is to provide a metal cation complex that can extremely suppress cluster formation when a metal cation is dispersed in an organic polymer material at a high concentration. Another object of the present invention is to provide a metal cation complex that provides a means for stably dispersing a cation of an element having an arbitrary high atomic number in a blood stream.

[0015]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventor has conducted intensive systematic studies especially on the composite of a metal cation and an organic polymer material. By forming a complex in which a branched polymer having a β-diketonate group is disposed in the vicinity of a metal cation by an action or a coordination bond, the cation is solubilized in a wide range of solvents, and the obtained complex is heated. It has been found that it is possible to make it plastic. Such a complex also maintains the characteristics of the branched polymer, such as light weight, toughness against bending displacement, or adhesion to a wide variety of substrates. Furthermore, the cations are not exposed to the dendrimer surface and are hardly aggregated with each other in principle due to the large space exclusion effect (the effect of occupying a large space) of the branched polymer disposed near the metal cation. From this, it has also been found that when this is dispersed in various matrices, the cations are dispersed at the atomic level, and thus the formation of clusters is extremely suppressed. Therefore, they have found that high-concentration dispersion can be performed while suppressing concentration quenching due to cluster formation, and have completed the present invention.

That is, the gist of the present invention is based on the general formula M ^{n +} (RA
^-) metal cation complex represented by _n; (wherein, M n ⁺ represents a metal cation, n is an integer representing the valence of the cation, RA ^- represents a monovalent anion, R represents a branched polymer residues, a ^- is β- diketonate represents a group also, RA ^-. represented by the corresponding general formula RA to β
-The branched polymer having a diketone group has a number average molecular weight Mn _(GPC) measured by a gel permeation chromatography (GPC) method and a weight average molecular weight Mw _{(GPC) of} 300 ≦ Mn _(GPC) ≦ 50,000. And 1.0 ≦
Mw _(GPC) / Mn _{(GPC )} ≤15.

The branched polymer RA is, between the mass spectral method or the true weight average molecular weight measured by a light scattering method Mw and gel permeation chromatography weight average molecular weight is measured by gel permeation chromatography (GPC) Mw _(GPC) , Mw /
The metal cation complex satisfying the relationship of Mw _(GPC) >1; the metal cation complex in which the branched polymer RA is a dendrimer; the metal cation complex in which the dendrimer has an aromatic ring; β-diketonate group A Wherein the metal cation complex is bonded to the focal point of the dendrimer; the metal cation M ^{n +} is the metal cation complex having paramagnetism; the metal cation M ^{n +} is the metal cation complex having a fluorescence generating ability A cation complex; wherein the metal cation M ^{n +} is a lanthanoid cation; wherein the lanthanoid cation is Pr ³⁺ , Nd ³⁺ , Eu ³⁺ , G
the metal cation complex selected from the group consisting of d3 ⁺ , Tb3 ⁺ , Dy3 ⁺ , Ho3 ⁺ , Er3 ⁺ , Tm3 ⁺ , and Yb3 ⁺ ;
A contrast agent containing the metal cation complex as an essential component; a pharmaceutical composition for in-vivo diagnosis comprising the metal cation complex and a pharmaceutically acceptable carrier; wherein the metal cation complex is dispersed in a polymer matrix. A polymer composition characterized in that the metal cation concentration is 0.01 to 10% by weight; a molded article characterized by having the metal cation complex on the outer surface; A coating material comprising the molded article formed of a polymer composition; and the metal cation complex.

Due to such outstanding characteristics, various disadvantages of the prior art, such as poor dispersibility, brittleness, high specific gravity, lack of moldability and adhesion to other materials, and the like, or the conventional inorganic fluorescent light Not only does it significantly improve the disadvantages of materials, such as the need for multi-step manufacturing processes, insufficient dispersibility in solvents or binder polymers when applying, concentration quenching due to aggregation of metal cations, etc. By solubilizing in a wide range of solvents, application to applications utilizing its paramagnetism and the like can be expected.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (Metal Cation Complex) The metal cation complex of the present invention is generally
Formula M^{n +}(RA^-) A metal cation represented by n
M^{n +}And monovalent branched polymers having a β-diketonate group
Anion RA ^-And the electrostatic phase between both components
It is constituted by interaction or coordination bond.
Since the metal cation complex of the present invention becomes electrically neutral,
The number of anions RA equal to the valence n of the metal cation^-To
It takes a combined form, but contains coordination water (Pope,
G. FIG. W. et al; Inorg. Nucl. Ch
em. , 20, 304 (1961), Spring
er, C.E. S. et al; Inorg. Chem. ,
6, 1105 (1967)), one of RA-
Part of which is replaced with small anions such as hydroxide ion
(See the above-mentioned literature by Pope et al.), Alkali metal
Cations and onium ions (for example, ammonium ions
, Phosphonium ion, sulfonium ion, etc.)
Monovalent cations and RA^-Is added one by one
(The general formula is X⁺M^{n +}(RA^-) N RA^-Where X⁺Add
Represents the added monovalent cation. Melby, L .; R. e
tal; Am. Chem. Soc. , 86, 5
117 (1964), Horovitz, C .; T. Edition
Book "Scandium: Its Occuren"
ce, Chemistry, Physics, Meta
llurgy, Biology, and Techno
"logic" (Academic Press, London)
on, 1975). A. Author; Or
ganic Compounds, pp. 111-138
And pages 323-384), or one or two
(A general formula is M^{n +}(RA^-)
n · xL, where L represents an added ligand and x is an added ligand
Represents the number of ligands. The above Melby and Me
lson, Bauer, H .; et al;
J. Am. Chem. Soc. 86, 5125
(1964), and Selbin, J. et al. et al; I
norg. Chem. , 10, 1383 (197
Known variations such as 1) are also possible.
You.

(Metal cation) In the present invention, the metal cation
On is defined as hydrogen, boron, carbon, nitrogen in the periodic table.
1A (alkali metal), 2A (a
Lucari earth metal), 3A, 4A, 5A, 6A, 7A,
8, 1B, 2B (or more transition elements), 3B, 4B, and 5
It is a cation of an element belonging to each group of B. Such a cation
Li ⁺, Na⁺, K⁺, Rb⁺, Cs⁺,
Fr⁺Alkali metal cations such as Be²⁺, Mg²⁺, C
a²⁺, Sr²⁺, Ba²⁺, Ra²⁺Alkaline earth metal positive such as
Ion, Sc³⁺, Y³⁺Group cations such as T, T
i²⁺, Ti³⁺, Ti⁴⁺, Zr⁺, Zr²⁺, Zr³⁺, Zr
⁴⁺, Hf⁺, Hf²⁺, Hf³⁺, Hf⁴⁺Etc.
ON, V⁺, V²⁺, V³⁺, V⁴⁺, V⁵⁺, Nb⁺, N
b²⁺, Nb³⁺, Nb⁴⁺, Nb⁵⁺, Ta⁺, Ta²⁺, Ta
³⁺, Ta⁴⁺, Ta⁵⁺Cations such as vanadium, C
r⁺, Cr²⁺, Cr³⁺, Cr⁴⁺, Cr⁵⁺, Cr⁶⁺, Mo
⁺, Mo²⁺, Mo³⁺, Mo⁴⁺, Mo⁵⁺, Mo⁶⁺, W⁺,
W²⁺, W³⁺, W⁴⁺, W⁵⁺, W⁶⁺Chromium group cations such as,
, Mn⁺, Mn²⁺, Mn^Three+, Mn⁴⁺, Mn⁵⁺, M
n⁶⁺, Mn⁷⁺, Tc⁺, Tc²⁺, Tc³⁺, Tc⁴⁺, Tc
⁵⁺, Tc⁶⁺, Tc⁷⁺, Re⁺, Re²⁺, Re³⁺, R
e⁴⁺, Re⁵⁺, Re⁶⁺, Re⁷⁺Manganese group cations
, Fe⁺, Fe²⁺, Fe³⁺, Fe⁴⁺, Fe⁶⁺, R
u⁺, Ru²⁺, Ru³⁺, Ru⁴⁺, Ru⁵⁺, Ru⁶⁺, Ru
⁷⁺, Ru⁸⁺, Os⁺, Os²⁺, Os³⁺, Os⁴⁺, O
s⁵⁺, Os⁶⁺, Os⁷⁺, Os⁸⁺Iron group cations such as Co
⁺, Co²⁺, Co³⁺, Co⁴⁺, Co⁵⁺, Rh⁺, R
h²⁺, Rh³⁺, Rh⁴⁺, Rh⁵⁺, Rh⁶⁺, Ir⁺, Ir
²⁺, Ir³⁺, Ir⁴⁺, Ir⁵⁺, Ir⁶⁺Cobalt group positive
Ion, Ni⁺, Ni²⁺, Ni³⁺, Ni⁴⁺, Pd⁺, P
d²⁺, Pd³⁺, Pd⁴⁺, Pt²⁺, Pt³⁺, Pt⁴⁺, Pt
⁵⁺, Pt⁶⁺Nickel group cations such as Cu⁺, Cu²⁺,
Cu³⁺, Cu⁴⁺, Ag⁺, Ag²⁺, Ag³⁺, Au ⁺, A
u²⁺, Au³⁺, Au⁵⁺, Au⁷⁺Copper group cations such as Zn
²⁺, Cd⁺, Cd ²⁺, Hg⁺, Hg²⁺Zinc group cations
N, La²⁺, La³⁺, Ce²⁺, Ce³⁺, Ce⁴⁺, P
r²⁺, Pr³⁺, Pr⁴⁺, Nd²⁺, Nd³⁺, Nd⁴⁺, Pm
²⁺, Pm³⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, G
d²⁺, Gd³⁺, Tb²⁺, Tb³⁺, Tb⁴⁺, Dy²⁺, Dy
³⁺, Dy⁴⁺, Ho²⁺, Ho³⁺, Er²⁺, Er³⁺, T
m²⁺, Tm³⁺, Yb²⁺, Yb³⁺, Lu²⁺, Lu³⁺Etc.
Intermediate cation, Ac³⁺, Th⁴⁺, Pa³⁺, P
a⁴⁺, Pa⁵⁺, U³⁺, U⁴⁺, U⁵⁺, U⁶⁺, Np³⁺, Np
⁴⁺, Np⁵⁺, Np⁶⁺, Pu³⁺, Pu⁴⁺, Pu⁵⁺, P
u⁶⁺, Am²⁺, Am³⁺, Am⁴⁺, Am⁵⁺, Am⁶⁺, Cm
³⁺, Cm⁴⁺, Bk³⁺, Bk⁴⁺, Cf²⁺, Cf³⁺, C
f⁴⁺, Es²⁺, Es³⁺, Fm²⁺, Fm³⁺, Md²⁺, Md
³⁺, No²⁺, No³⁺Actinoid cations such as A
l³⁺, Ga²⁺, Ga³⁺, In +, In2 +, In3 +, Tl
⁺, Tl²⁺, Tl³⁺Group 3B cation such as Si²⁺, Si
⁴⁺, Ge²⁺, Ge⁴⁺, Sn²⁺, Sn⁴⁺, Pb²⁺, Pb⁴⁺
Group 4B cations such as³⁺, As⁵⁺, Sb⁺, S
b³⁺, Sb⁵⁺, Bi⁺, Bi³⁺, Bi⁵⁺5B group
ON and the like. Of these, Pr³⁺, Nd³⁺,
Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho^3+,Er³⁺, T
m³⁺, Yb³⁺Trivalent lanthanoid cations are visible ~
Fluorescence with features such as near-infrared region, long life, narrow wavelength width, etc.
It is preferable in that it emits cations such as MRI contrast agents.
When using magnetism, Pr³⁺, Nd³⁺, E
u³⁺, Gd³⁺, Tb³⁺, Dy ³⁺, Ho³⁺, Er³⁺, Tm
³⁺, Yb³⁺Trivalent lanthanoid cations such as
e²⁺, Fe³⁺And the like are preferred.
t²⁺, Pt³⁺, Au⁺, Au²⁺, Au³⁺, Pb²⁺, Bi
³⁺High atomic number cations such as
It is suitable in terms of the shielding effect, and Li⁺, Na⁺, K⁺, R
b⁺, Cs⁺Alkali metal cations such as Mg²⁺, Ca
²⁺, Sr²⁺, Ba²⁺Alkaline earth metal cations such as
It is suitable in terms of the antistatic effect.

[0021] (anion) monovalent anion which is a component of the metal cation complex of the present invention, RA ^- represented by consisting formula. Here, R is a branched polymer residue, and A ^- is β-
Represents a diketonate group. The term “branched polymer residue” as used herein means a polymer structure having a branch in the main chain structure.

The chemical structure of the monomer constituting the branched polymer residue impairs both the solvent solubility and the thermoplasticity essential for excellent moldability, which are the characteristics of the metal cation complex of the present invention. There are no particular restrictions unless otherwise specified. This is because the main reason for using a branched polymer residue in the present invention lies in its space exclusion effect. That is, for the space exclusion effect, which is one of the main points of the effect of the present invention, the spatial spread of the polymer residue is most important, and the contribution of the difference in chemical properties derived from the chemical structure is small. ,That's what it means.

Therefore, the chemical structure of the branched polymer residue R that can be used in the present invention is a necessary condition for ensuring excellent moldability, that is, compatibility with a solvent or various matrix materials. Or, it is to have thermoplastic, but specifically, aromatic polyether, aromatic polyester, aromatic or semi-aromatic polyamide, aromatic polycarbonate, aromatic polyester carbonate, aromatic polysulfide, aromatic polyimide, Aromatic polymers containing an element other than carbon, such as aromatic polyamide-imide, aromatic polyurethane, aromatic polyurethane urea, and aromatic polyurea, in the polymer main chain, aliphatic polyether, aliphatic polyester, aliphatic polyamide, and fat Aliphatic polycarbonate, aliphatic polyester carbonate, aliphatic polyurethane, aliphatic polycarbonate Aliphatic polymers containing elements other than carbon such as urethane urea and aliphatic polyurea in the polymer main chain, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polymethyl acrylate, polyphenylene, polyphenylacetylene, and carbon such as polyphenylene vinylene - polymer main chain carbon bond is formed, polysiloxanes, polytitanoxane, poly zirconocene hexane, silica (SiO _2), titania (Ti
O ₂ ), zirconia (ZrO ₂ ), etc., and a polymer composed of an oxygen atom and a 4A or 4B group element other than carbon.
Of these, a plurality of structures may coexist in the branched polymer residue R. Further, the metal cation complex of the present invention may be composed of a plurality of kinds of metal cations or a plurality of kinds of monovalent anions RA-.

As an additional effect of the present invention when the metal cation has a fluorescence generating ability, when the branched polymer residue R contains an aromatic structure, the structure absorbs excitation light mainly in the ultraviolet region. The mechanism of transmitting this energy to metal cations is to improve the fluorescence intensity. Such an effect is known as an antenna effect (eg, Ta
nner, S .; P. et al; Am. Chem.
Soc. 96, p. 706 (1974), Okamo.
to, Y. et al; Macromolecule
s, 14, 17 (1981), Sabbatin
i, N. et al; Coordination Ch
emistry Rev. 123, p. 201 (19
93) etc.), for example, it is effective in improving the fluorescence intensity of lanthanoid cations. Since the antenna effect is based on the properties of the metal cation complex itself, it is also effective in improving the fluorescence intensity at a low concentration at which concentration quenching does not pose a problem. The preferred structure of the branched polymer residue R from the viewpoint of the antenna effect is a structure absorbing in the ultraviolet region, for example, an aromatic polyether, an aromatic polyester, an aromatic or semi-aromatic polyamide, an aromatic polycarbonate, or an aromatic polyester carbonate. , Aromatic polysulfides, aromatic polyimides, aromatic polyamideimides, aromatic polyurethanes, aromatic polyurethaneureas, aromatic polyureas, aromatic polymers containing elements other than carbon in the polymer main chain, polyphenylene, polyphenylacetylene And aromatic conjugated polymers having a main chain composed of carbon-carbon bonds such as polyphenylenevinylene.

Further, when the metal cation complex of the present invention or the polymer composition containing the metal cation complex is used for utilizing near-infrared fluorescence, for example, as a material for an optical amplifier, carbon-carbon complex may be used.
In some cases, overtones of the vibration mode due to hydrogen bonding appear in the near-infrared region (for example, around 1.5 μm), and become noise components. For the purpose of avoiding such inconveniences, it is preferable to replace all hydrogen atoms bonded to carbon atoms in the structure of the branched polymer residue R with other elements, for example, halogen atoms such as fluorine and chlorine, deuterium and the like. There may be.

[0026] (degree of branching) anion RA 1 monovalent is a component of the metal cation complex of the present invention ^- has a specific molecular weight distribution as a branch polymer having a corresponding β- diketone group (general formula RA) It is necessary to have. That is, the number average molecular weight Mn _(GPC) and the weight average molecular weight Mw measured by the gel permeation chromatography (GPC) method.
_(GPC) , 300 ≦ Mn _(GPC) ≦ 5000
It is desirable that two relations of 0 and 1.0 ≦ Mw _(GPC) / Mn _{(GPC )} ≦ 15 be simultaneously satisfied. When the value of the Mn _(GPC) is less than 300, the spatial expansion of the RA is not sufficient, and the above-described spatial exclusion effect is low, and conversely, 50,000
It is thought that if the space exceeds this, the spatial spread is too large and it is impossible to place all of them in the vicinity of the metal cation.In each case, cluster formation is likely to occur, and the effect of improving the fluorescence intensity of the metal cation is insufficient. Undesirable effects may occur. The branched polymer having a β-diketone group represented by the general formula RA is obtained by treating a given metal cation complex with, for example, an acid.

Accordingly, the value of Mn _(GPC) is more preferably 400 or more and 40000 or less, further preferably 450 or more and 20000 or less, and most preferably 1500 or more and 100 or less.
00 or less. On the other hand, the above-mentioned Mw _(GPC) / Mn _(GPC)
Is larger than 15, it is considered that the dispersion of the spatial spread of the branched polymer RA becomes too large, and as a result, the dispersion of the space exclusion effect also becomes large. In some cases, the concentration quenching tends to occur in the case of having. Therefore, M
It can be said that the smaller the value of w _(GPC) / Mn _(GPC) , the more desirable the space exclusion effect. From this perspective,
The most suitable branched polymer structure for the present invention is a dendrimer. Dendrimers are, for example, Hawke
r, C.I. J. et al; Chem. Soc. , C
hem. Commun. , 1990, p. 1010, T
omalia, D .; A. et al; Angew. Ch
em. Int. Ed. Engl. 29, 138 (1990); Hawker, C .; J. et al;
J. Am. Chem. Soc. 112, 7638 (1990); Frechet, J .; M. J. ; Sci
ence, 263, 1710 (1994), or Kakimoto Masaaki; Chemistry, 50, 608 (1995). Since the dendrimer has a highly controlled dendritic branch structure, the value of Mw _(GPC) / Mn _(GPC) can be extremely small. For example, the above F
C described in rechet or Kakimoto's literature
According to the average method (a method of constructing a dendrimer molecule from the outer block toward the center), it can be set to 1.0 in principle.
Usually, the number can be about 1 or more and about 2 or less by the rgent method (a method of constructing dendrimer molecules from the center to the outside). Therefore, in the present invention, Mw
The value of _(GPC) / Mn _(GPC) is more preferably 1.0
It is set to 12 or more, more preferably 1.0 or more and 9 or less, and most preferably 1.0 or more and 5 or less. In particular, when the metal cation complex of the present invention is used as a contrast agent, by taking a dendrimer structure, the viscosity can be reduced and a contrast agent excellent in convenience at the time of use can be obtained.

When a dendrimer is used as the branched polymer, it is most preferable to link the β-diketonate group (A ⁻ ) to the focal point of the dendrimer (here, the foc of the dendrimer).
al point means the terminal end of the branch of the dendrimer, and is described in the above-mentioned literature on dendrimers). This is presumably because it is preferable that the branches of the branched polymer become more dense outward from the metal cation located at the center of the complex in order to exhibit an efficient space exclusion effect.

[0029] In the metal cation complex of the present invention, the anion RA ^- it should be monovalent. That is, it is necessary to use a branched polymer having one β-diketonate group A ⁻ in the molecule. If these conditions are not satisfied, cation aggregation may be observed, which is not preferable.

The branched polymer residue R desirably has as high a degree of branching as possible as long as the thermoplasticity of the metal cation complex of the present invention and the compatibility with a solvent or a matrix material are not impaired. This is because, when considering a polymer having the same monomer (repeating unit) structure and the same molecular weight, the larger the number of branch points, the higher the conformation with a spatial exclusion effect that hinders the approach of the cations. It is considered easy. In other words, as it approaches a linear polymer without branching, it becomes possible to change from a conformation that is aggregated in a filiform shape with a high space exclusion effect to a low conformation with the same effect that the polymer chain is extended. As a result, the probability that the cations approach each other increases.

As means for quantifying the degree of branching of the polymer,
For example, there is a method of measuring the relationship between the intrinsic viscosity and the absolute molecular weight in a dilute solution, or a method using an integral value of a signal assigned to each of a branched unit structure and an unbranched unit structure in a nuclear magnetic resonance (NMR) spectrum. As preferred conditions for the degree of branching in the present invention, the branched polymer RA may be a true weight average molecular weight Mw measured by a mass spectrum method or a light scattering method and a weight average molecular weight Mw _(GPC measured by a GPC method). _{) Satisfy the} relationship of Mw / Mw _(GPC) > 1.

An example in which Mw becomes larger than Mw _(GPC) is as follows.
Hawker, C .; J. et al; Am. Che
m. Soc. 112, 7638 (1990) and U.
hrich, K .; E. FIG. et al; Macromole
cules, vol. 25, p. 4583 (1992), which shows that as the absolute molecular weight (ie, Mw) as measured by mass spectrometry or light scattering is the same, as the degree of branching increases, It has been qualitatively interpreted that the spatial extent (ie, Mw _(GPC) ) of the polymer chains observed in a good solvent becomes smaller. There is no limitation on the method of the above mass spectrum as long as a molecular peak is given, and for example, a Matrix assisted laser which is suitably used for a relatively high molecular weight molecule having a molecular weight of about 1000 or more or an unstable molecule.
desorption ionization (MAL
DI) In some cases, it is preferable to apply a new method such as a mass spectrum or an Electrospray mass spectrum. Also, all GPC measurements in the description of the invention are:
It must be performed in a good solvent for the branched polymer RA. Mw
The value of / Mw _(GPC) is usually at most about 3 in the range of the number average molecular weight of the branched polymer RA suitable for the present invention, but is not particularly limited.

(Method for producing metal cation complex) The metal cation complex of the present invention can be prepared, for example, by the method of Springer, C .;
S. et al; Inorg. Chem. , Volume 6, 11
It is produced according to a known method such as a method described in page 05 (1967), for example, by a method of mixing equivalent amounts of the nitrate of the cation Mn + and the Na salt of β-diketonate. That is, in the case of the present invention, for example, RA ^- X is used for the nitrate of the metal cation Mn +.
⁺ (X ⁺ is an alkali metal cation) type salt of a branched polymer having a β-diketonate group. However, this is an example of a preferable production method, and the production method is not particularly limited as long as the metal cation complex of the present invention can be obtained.

In the metal cation complex of the present invention, it is desirable that all counter anions neutralizing the positive charge of the cation be the monovalent anion RA ⁻ . Because relatively small anions such as fluoride ions, chloride ions, bromide ions, halide ions such as iodide ions, sulfate ions, nitrate ions, formate ions,
Remaining anions generally used widely, such as acetate ions and oxalate ions, are to reduce the space exclusion effect. Therefore, when producing the metal cation complex of the present invention by the above-described complex formation reaction, one equivalent of the cation (M
It is desirable that exactly n equivalents of the above RA ^- X ⁺ act on (n ⁺ ) (n is the valence of the cation). However,
Even when an excess amount of RA-X + exceeding n equivalents is applied to Mn ⁺ , the effect of the present invention can be obtained since the product contains the desired metal cation complex of the present invention. In some cases.

(Contrast Agent) When the metal cation complex of the present invention is used as a contrast agent, parenteral administration such as intravenous administration is usually used, but oral administration is also possible. Examples of a preparation for parenteral administration, that is, a solvent or a suspending agent used for producing an injection or the like include water, propylene glycol, polyethylene glycol, benzyl alcohol, ethyl oleate, lecithin and the like. Preparation of the preparation may be performed by a conventional method. For oral administration, alone or in combination with a pharmaceutically acceptable carrier, for example, granules, fine granules, powders, tablets, hard syrups, soft capsules, syrups, emulsions, suspensions, liposomes Orally in the form of a liquid or the like. Examples of excipients used in producing a solid preparation include lactose, sucrose, starch, talc, cellulose, dextrin,
Kaolin, calcium carbonate and the like can be mentioned. Liquid preparations for oral administration, ie emulsions, syrups, suspensions, solutions and the like, contain commonly used inert diluents, such as vegetable oils. This formulation is not only an inert diluent, but also auxiliaries,
For example, wetting agents, suspending agents, sweetening agents, flavoring agents, coloring agents, preservatives and the like can be included. Liquid preparations may be included in capsules of absorbable substances such as gelatin.

The contrast agent according to the present invention is generally administered at a dose that provides the desired contrast effect without side effects. The specific value should be determined at the discretion of the physician, but is generally 0.1 mg per adult per diagnosis.
10 to 10 g, preferably 1 mg to 5 g. The compound of the present invention is used as an active ingredient in one diagnosis per adult.
mg to 5 g, more preferably 3 mg to 3 g, and may be administered.

(Polymer composition) The metal cation complex of the present invention can be dispersed in a polymer matrix to form a polymer composition. In this case, the cation concentration in such a polymer composition is, for the purpose of optical use,
There is no particular limitation as long as the transparency required for the use is maintained, but it is usually preferably 0.01 to 10% by weight based on the total of the polymer matrix and the metal cation complex. If the cation concentration is less than 0.01% by weight, the effect of the present invention such as an increase in refractive index or the ability to generate fluorescence becomes insufficient. May be significantly reduced in mechanical properties such as extreme brittleness, and both are not preferred. From such a viewpoint, the more preferable cation concentration is 0.05 to
7% by weight, more preferably 0.1-5% by weight, most preferably 0.5-4% by weight.

As a general feature of the polymer composition in which the metal cation complex of the present invention is dispersed in a polymer matrix, there is an extremely good dispersion of the cation which is not found in conventional materials. This is because the space exclusion effect of the metal cation complex of the present invention is maintained to some extent even in the process of producing such a polymer composition. Specifically, for example, it is observed by a transmission electron microscope. It is exemplified that the proportion of clusters in which the cations are in contact in the image is less than 20%, more preferably less than 10%, even more preferably less than 7% and most preferably less than 5%.

The types of the polymer matrix used in the polymer composition containing the metal cation complex of the present invention include:
There is no particular limitation. However, for the purpose of optical use, it is desirable that the compatibility with the metal cation complex is good in order to maintain the transparency required for the use. In other words, when the metal cation complex is dispersed, it is necessary to achieve a dispersion smaller than the wavelength of the light in order to achieve transparency for light in the ultraviolet to infrared region, which is considered to be practically important. is necessary. More specifically, for example, in observation with a transmission electron microscope, it is desirable that the size of the cation aggregate be 200 nm or less.

The term “aggregate” as used herein means a cluster in which metal cations are in direct contact with each other or a group formed by association of the metal cation complexes of the present invention.
This is a state in which they are close to each other at a distance of about m or less. From the viewpoint of the transparency of the polymer composition or the reduction of concentration quenching during the fluorescence generation process, such an aggregate is preferably as small as possible.Each cation is uniformly dispersed in the composition without formation of such an aggregate. Needless to say, this state is ideal for the purpose of the present invention.

[0041] Suitable polymeric matrices are monovalent anion RA constituting the metal cation complex is dispersed ^- depends on the chemical structure, if this is the organic compatibility, moldability, economical efficiency , And the transparency of the matrix itself, polystyrene, polymethyl methacrylate, aromatic polyesters, aromatic polycarbonates, aromatic polyester carbonates, semi-aromatic polyamides, amorphous polyolefins, aliphatic polyolefins such as polyethylene glycol Known resin materials such as ether, aromatic or aliphatic polyurethane, aromatic or aliphatic polyurethane urea, aromatic or aliphatic polyurea are suitably used. The molecular weight distribution and branched structure of such a matrix polymer are not particularly limited as long as excellent moldability is maintained.

The method for producing the polymer composition of the present invention by mixing the metal cation complex and the polymer matrix is not particularly limited. For example, a method of mixing and then drying the mixture in a solution to obtain a composition, a method of using a device for mixing in a molten state such as a single-screw extruder, a twin-screw extruder, or a Brabender can be exemplified. Among them, a method of mixing in a solution is effective in reducing the aggregate of the cations. Further, in the gold polymer composition of the present invention, a plurality of kinds of the cations, a plurality of kinds of metal cation complexes, or a plurality of kinds of polymer matrices can be used.

The metal cation complex of the present invention or the polymer composition containing the metal cation complex is used for a wide range of applications in which various functions of the cation are applied. For example, a solution is prepared by utilizing its excellent solvent solubility, and a problem such as generation of a precipitate in an inorganic phosphor dispersion liquid does not occur, and as a high-brightness fluorescent coating material having extremely stable storage stability. Available.

When this is applied to the outer surface of a molded article having an arbitrary shape such as a flat surface, a curved surface, or a pipe, various display plates such as a road sign, a safety sign, a license plate, and a safety display seal using fluorescence are used. (Paper), helmet, bumper,
Products such as protective parts and protective equipment for ensuring traffic safety, such as rain gear (rain flaps, umbrellas, etc.), lighting equipment such as fluorescent lamps, and intensifying screens such as X-ray intensifying screens can be advantageously obtained. In the use as such a coating material, there is no particular limitation on the type of solvent used, but in the case where a low-toxic solvent such as water or alcohol is required from the standpoint of environmental protection which has been particularly required in recent years. It is necessary to prepare a metal cation complex containing a monovalent anion RA- having good compatibility with such a solvent as a constituent.

Further, the metal cation complex of the present invention or a composition thereof is used as a fluorescent labeling agent for, for example, fluoroimmunoassay, a lens utilizing an increase in refractive index, or an optical waveguide material having a change in refractive index in the thickness direction. Alternatively, optical communication such as an optical amplifier using a lanthanoid such as Pr ³⁺ or Er ³⁺ having fluorescence in the near infrared region (eg, a wavelength of 1.3 μm or 1.5 μm) important in optical communication technology. It is also very useful to apply it as a member for use, a laser transmitter, or the like.

In practical use of the metal cation complex of the present invention or the polymer composition containing the same, any additive may be used as long as the purpose of the present invention is not significantly impaired, for example, an organic phosphorus compound such as trioctylphosphine oxide. As described above, it is also possible to use an additive or the like which suppresses a decrease in the fluorescence intensity by coordinating with the cation.

[0047]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. In addition, the raw material reagent and the solvent were used without purification, unless otherwise specified, manufactured by Tokyo Chemical Industry Co., Ltd.

[Measurement apparatus and conditions, etc.] (1) GPC: TSK gel manufactured by Tosoh Corporation (grade for molecular weight of about 10,000 or more: GMHXL, grade for molecular weight of about several hundred to 10,000: G-2000), developing solvent: tetrahydrofuran (THF), measurement temperature: 40 ° C., control: monodisperse polystyrene, detection: change in refractive index. (2) NMR: JNM-EX270 type FT manufactured by JEOL Ltd.
-NMR (1 H: 270 MHz, 13 C: 67.8 MH)
z), solvent: CDCl _3.

(3) FT-IR: FT manufactured by JASCO Corporation
/ IR-8000 type FT-IR, a cast film of a methylene chloride solution of a sample was prepared on a salt crystal and measured. (4) Mass spectrum: KOMPACT manufactured by Shimadzu Corporation
MALDI type III laser ionization TOF-MS was used. Cations were detected using 3-indoleacrylic acid as the matrix material. The measured values were used without any cation correction or the like. (MAL
In principle, DI measurement is observed in a form in which an alkali metal cation such as Na ⁺ or K ⁺ is added to a molecular peak, so that correction may be performed by subtracting this from the assumption of a reasonable cation atomic weight. is there. See, for example, Leon, J. et al. W.
et al; Polym. Bull. , 35, 449
See page (1995). (5) Fluorescence: F-3000 fluorometer manufactured by Hitachi, Ltd. (6) Proton relaxation measurement: JEOL MU-25 (2)
5MHz)

Example 1 Synthesis and Evaluation of Fluorescent Metal Cation Complex [Synthesis of Dendrimer as Raw Material] (1) Focal point having β-diketone structure
Preparation of t Constituent Unit 4'-Hydroxyacetophenone is dissolved in tetrahydrofuran (THF) and added thereto in the presence of a catalytic amount of hydrochloric acid.
A solution of 3,4-dihydro-21H0-pyran (5 equivalents) in the same volume of diethyl ether was added dropwise with stirring at room temperature over 30 minutes. Then, after stirring was continued at 40 ° C. for 1 hour, the mixture was poured into a large excess of 0.5N aqueous sodium hydroxide solution. This was extracted with diethyl ether, and the collected organic phases were washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue thus obtained is FT-
In IR, no absorption derived from the OH stretching vibration of the hydroxyl group is given, and 4'-P with a purity of 95% or more by ¹ H-NMR.
It was confirmed to be tetrahydropyranyloxyacetophenone. This is described in Springer, C.W.
S. et al; Inorg. Chem. , Volume 6, 11
Similarly to the method described on page 05 (1967), the mixture was reacted with ethyl heptafluorobutyrate in the presence of sodium methoxide, treated with an aqueous hydrochloric acid solution to remove the tetrahydropyranyl group, and then purified by silica gel column chromatography. 1,1,1,2,2,3,3-heptafluoro-6- (4′-hydroxyphenyl)-
4,6-hexanedione (hereinafter abbreviated as FHD) was obtained.

(2) The β-diketone structure is
Preparation of polybenzyl ether dendrimers with ointments Hawker, C .; J. et al; Am. Che
m. Soc. , 112, 7638 (1990) to synthesize first and third generation dendritic benzyl bromides (generic term for dendrimers having a benzyl bromide structure in a focal point). These 1.03 equivalents were respectively reacted with 1.0 equivalent of FHD by an etherification reaction using potassium carbonate and 18-crown-6 ether described in the literature to obtain the desired first and third generations. β-diketone structure is fo
A polybenzyl ether dendrimer (hereinafter, abbreviated as [G-1] -FHD and [G-3] -FHD, respectively) having a cal point was obtained. These products are:
Purified by silica gel column chromatography. The purified [G-1] -FHD and [G-3] -FHD consist of ¹
In the H and ¹³ C NMR spectra, the signal of the aromatic ring attributed to the FHD structure is given, and the absorption attributed to the β-diketone structure in the FT-IR spectrum, respectively.
Further, in the above mass spectrum measurement, substantially single signals assigned to the theoretical molecular weights (634.5 and 1908.0, respectively) were given.
It was confirmed that the desired product was obtained with high purity.

[Preparation of Metal Cation Complex] The above two types of dendrimers [G-1] -FHD and [G-3] -F
HD and the oxides of the various lanthanoid cations listed in Table 1 from Springer, C.I. S. et al; I
norg. Chem. , 6, 1105 (1967)
Lanthanoid cation complex (hereinafter abbreviated as [G-n] ₃ -Ln, where n is an integer of 1 or 3 representing the dendrimer generation, and Ln is the lanthanoid cation. (Representing an ion) was synthesized. In these complexes, it was confirmed that the β-diketone structure provided by the raw material dendrimer was converted to β-diketonate by FT-I
It was confirmed by the R spectrum. The ash weight was analyzed by the burn-off method. As shown in Table 1, all of the ash contents were in good agreement with the theoretical values.

[Preparation of Complex of Comparative Example] In the above-mentioned synthesis procedure of FHD, the same synthesis was carried out using 4′-methoxyacetophenone instead of 4′-hydroxyacetophenone, and 1,1,1,2,2,2 Thus, 3,3-heptafluoro-6- (4′-methoxyphenyl) -4,6-hexanedione (hereinafter abbreviated as FHMD) was obtained. Using this,
According to the procedure for synthesizing a complex using the above dendrimer,
Terbium cation (Tb ³⁺ ) and europium cation (Eu ³⁺ ) complexes were synthesized (hereinafter, abbreviated as FHMD ₃ -Tb and FHMD ₃ -Eu, respectively).

[Fluorescence Measurement] (1) Sample Preparation Of the lanthanoid cation complexes in Table 1 (including the complex of the comparative example), the terbium-based (containing Tb ³⁺ ) is Tb
^{The 3+} concentration was 0.05 μM, and the europium system (containing Eu ³⁺ ) was prepared by dissolving in anhydrous THF so that the Eu ³⁺ concentration was 5 μM. In addition, these solutions did not give deposits due to alteration and the like even when allowed to stand at room temperature for one month or more.

(2) Measurement of Fluorescence Intensity Using the above-mentioned fluorimeter, measurement was carried out using a quartz cell having an optical path length of 1 cm. The fluorescence wavelength is 5
The peak was around 45 nm and around 616 nm in the europium system, and the excitation wavelength was the wavelength of the maximum value of the excitation spectrum. All the measurement results were arranged by the ratio with the fluorescence intensity of the complex of the comparative example composed of the corresponding cation, and summarized in Table 1.

[Substrate Adhesion] Using the THF solution, the synthesized metal cation complex was cast on a glass plate and an aluminum foil, respectively, to form films. This was not possible because the film adhered strongly to the substrate.

[0057]

Table 1 Table 1 Results of analysis of fluorescent metal cation complex and evaluation of fluorescence intensity Complex ash (% by weight) ^c) Fluorescence intensity ratio Theoretical value Actual value [G-1] _3- Tb 8.88 8.97 2.4 [G-3] ₃ -Tb 3.11 3.12 5.1 [G-1] ₃ -Eu 8.57 8.64 1.5 [G-3] ₃ -Eu 3.00 3.10 1.9 [G-3] ₃ -Pr 2.81 2.72 --- [G-3] ₃ -Nd 2.87 2.96 --- [G-3] ₃ -Gd 3.08 3.00 --- [G-3] ₃ -Dy 3.17 3.30 --- [G-3] ₃ -Ho 3.21 3.11 --- [G-3] _3- Er 3.25 3.24 --- [G-3] ₃ -Tm 3.28 3.19 --- [G-3] ₃ -Yb 3.34 3.28 --- c) Ash is considered to exist in the form of Ln ₂ O ₃ Was. Example 2 Synthesis and Evaluation of Water-Soluble Metal Cation Complex [Synthesis of Focal Point Constituent Unit Having β-Diketone Group] Ethyl 4-acetyl obtained by reacting 4-acetylbenzonitrile with dry hydrogen chloride in ethanol Reacting the benzoate with a large excess of ethyl heptafluorobutyrate in the presence of sodium methoxide, and then reacting with sodium hydroxide to hydrolyze the ethyl ester;
Finally, the product was condensed with hydrochloric acid to obtain 4- (3′-heptafluoropropyl-1 ′, 3′-propanedionyl) benzoic acid (hereinafter abbreviated as β-DKF).

[Synthesis of Ligand] Newkome, G .;
R. , Et al; Macromolecules, 2
4, p. 1443 (1991), using tris (hydroxymethyl) aminomethane and acrylonitrile as starting materials for tris (2-cyanoethyl).
Oxymethyl @ aminomethane (hereinafter abbreviated as TCN) and tris {(2-ethoxycarbonylethyl) oxymethyl} aminomethane (hereinafter abbreviated as TEC) were synthesized. TE
The amino group of C is protected with a t-butoxycarbonyl group (BOC group) by a conventional method using di-t-butyl dicarbonate, and then the corresponding tricarboxylic acid (hereinafter BOC-T) is obtained by hydrolysis of the ester using sodium hydroxide.
C). Based on the above amide synthesis reaction, BOC
-TC is reacted with TCN to form one molecule of BOC-T
Compound in which three molecules of TCN are amide-bonded to C (hereinafter referred to as BO
C-TC-TCN ₃ substantially) was obtained. BOC-TC-TC
An amino group generated by removing the BOC group of N _{3 using} trifluoroacetic acid as a catalyst in THF is reacted with β-DKF by an amide synthesis reaction similar to the above, and a dendrimer skeleton having a β-diketone group at a focal point (hereinafter, referred to as a dendrimer skeleton) β-D
KF-CN ₉ ) was synthesized. The terminal nitrile group of β-DKF-CN ₉ is converted to the corresponding ethyl ester group by the procedure described in the literature, and then converted to an amide by heating with a large excess of 2-aminoethanol to give the dendrimer β.
-A dendrimer having a diketone group at the focal point and having a hydroxyl group at the terminal (hereinafter abbreviated as β-DKF-OH) was obtained.

[Synthesis and Evaluation of Gadolinium Complex]
Converting DKF-OH with sodium hydroxide to the corresponding sodium salt of β-diketonate cation;
A trivalent gadolinium cation (having a hydrophilic dendrimer having a β-diketonate group as a ligand) is reacted with three times the amount of an anhydrous salt obtained by heating a commercially available gadolinium (III) chloride hydrate as a ligand. An aqueous solution containing the (Gd ³⁺ ) complex was obtained. Next, this was filtered through a 0.8 μm glass fiber filter and further purified by dialysis to remove dissolved inorganic salts and low molecular weight impurities. The aqueous solution of this complex is 3
Since the longitudinal relaxation degree of the proton at 7 ° C. was much higher than the magnevist (manufactured by Schering, gadolinium (III) complex of DTPA) used as a control, strong MR was observed.
It is possible to obtain the I signal strength.

[0060]

The present invention has the following particularly advantageous effects, and its industrial value is extremely large. (1) Since the metal cation complex according to the present invention is formed by electrostatic interaction or coordination bond between the metal cation and a branched polymer having a β-diketonate group having a specific structure, homogeneity It has excellent compatibility with solvents and various matrix materials, thermoplasticity, light weight and toughness, so it has unprecedented excellent solvent application properties, thermoforming workability, light weight, toughness against bending displacement, wide range This is a metal cation-containing material that also has adhesion to various types of substrates. In addition, since it is possible to contain an element having a high atomic number, a material having a controlled refractive index, such as a lens or an optical waveguide having a refractive index change with a thickness direction, or an electromagnetic wave shielding material Further, since it is an ionic compound, a polymer composition or a coating agent using the compound also has an antistatic ability. It is also useful as an X-ray contrast agent utilizing the X-ray absorption ability of an element having a high atomic number. (2) In addition, when a material having a fluorescent ability is selected as a metal element, the material is also a material having a high fluorescence ability with suppressed concentration quenching, and thus has excellent storage stability when used as a solution. A wide range of fluorescent light applications, such as high-intensity fluorescent coating materials or fluorescent labeling agents for fluoroimmunoassay, optical communication members such as optical amplifiers using rare-earth elements having near-infrared fluorescence, laser transmitters, etc. It becomes a material that can be used for (3) Further, when the cation has paramagnetism, it is also useful as a contrast agent used for imaging (MRI) utilizing a nuclear magnetic resonance (NMR) phenomenon.

Claims (15)

[Claims] 1. A metal cation complex represented by the general formula M ^{n +} (RA ⁻ ) n. (Wherein, M ^{n +} represents a metal cation;
n is an integer representing the valency of the cation; RA- represents a monovalent anion; R represents a branched polymer residue;
^- represents a β- diketonate group. Furthermore, RA ^- branched polymer having a β- diketone group represented by the corresponding general formula RA, the number average molecular weight Mn _(GPC) and the weight average molecular weight Mw _(GPC, measured by gel permeation chromatography (GPC) ₎ And 300 ≦ Mn
_(GPC) ≦ 50,000 and 1.0 ≦ Mw _(GPC) / Mn _(GPC
) Satisfies two relations of ≤15 simultaneously) 2. A branched polymer RA is, the weight average molecular weight Mw is determined by mass spectrometry or true weight average molecular weight measured by a light scattering method Mw and gel permeation chromatography (GPC) _(GPC) In between, Mw
The metal cation complex according to claim 1, wherein the following relationship is satisfied: / Mw _(GPC) > 1. 3. The metal cation complex according to claim 1, wherein the branched polymer RA is a dendrimer. 4. The metal cation complex according to claim 3, wherein the dendrimer has an aromatic ring. 5. The metal cation complex according to claim 3, wherein the β-diketonate group A ⁻ is bonded to the focal point of the dendrimer. 6. The metal cation complex according to claim 1, wherein the metal cation M ^{n +} has paramagnetism. 7. The metal cation complex according to claim 1, wherein the metal cation M ^{n +} has a fluorescence generating ability. 8. The metal cation complex according to claim 1, wherein the metal cation M ^{n +} is a lanthanoid cation. 9. The lanthanoid cation is Pr ³⁺ , Nd
³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , E
The metal cation complex according to claim 8, which is selected from the group consisting of r3 ⁺ , Tm3 ⁺ , and Yb3 ⁺ . 10. A contrast agent comprising the metal cation complex according to claim 1 as an essential component. 11. A pharmaceutical composition for in vivo diagnosis comprising the metal cation complex according to claim 1 and a pharmaceutically acceptable carrier. 12. The metal cation complex according to claim 1, wherein the metal cation complex is dispersed in a polymer matrix, and the metal cation concentration is 0.01 to 10% by weight. Polymer composition. 13. A molded article having the metal cation complex according to claim 1 on an outer surface thereof. 14. The molded article according to claim 13, wherein the outer surface is formed of the polymer composition according to claim 12. A coating material comprising the metal cation complex according to any one of claims 1 to 9.