JP2002371087A - Organic phosphonic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound to be a surface modifier which can excellently disperse inorganic solid ultrafine particles into an aqueous or alcoholic solvent and has excellent safety. SOLUTION: This organic phosphonic acid has 200-1,000 molecular weight and contains >=3 hydroxy groups at an organic residue part. The organic phosphonic acid is a dendronphosphonic acid containing an aliphatic polyether or polyester skeleton. The organic phosphonic acid contains a glucide residue and a glycoside bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to organic phosphonic acids. More specifically, the present invention relates to an organic phosphonic acid having a plurality of hydroxyl groups in a molecular structure. INDUSTRIAL APPLICABILITY The organic phosphonic acid of the present invention is excellent in safety and can bind to the surface of an inorganic solid having a wide range of compositions in an aqueous or alcoholic solvent having a small burden on the natural environment to hydrophilize the surface. In particular, when the inorganic solid is ultrafine particles, the ultrafine particles acquire water solubility (non-aggregation and dispersibility in water) by the above-mentioned hydrophilicity. Therefore, it is very suitably used for the production of an aqueous dispersion of inorganic solid ultrafine particles characterized by safety and non-aggregation properties, and such an aqueous dispersion is used, for example, as an inkjet ink composition or paint. .

[0002]

2. Description of the Related Art Generally, in a liquid coloring material such as ink or paint, it is desirable that the coloring material raw material particles contained therein are non-precipitating. To this end, it is effective to reduce the particle size of the coloring material particles, but this has a problem that the inorganic solid particles are likely to aggregate. As a means for solving such conflicting problems, use of a surfactant has been conventionally performed. For example, ultrafine particles having an average particle diameter of less than about 50 nm, which are highly safe colored inorganic solids such as iron oxide and cobalt blue, are commercially available as a slurry dispersed in a protic solvent such as ethanol. Such a slurry can be directly used as a paint or the like depending on the application, but a large amount of a surfactant is added so that the ultrafine particles do not aggregate and precipitate, thereby coating and stabilizing the surface of the inorganic solid. . Therefore, there is a possibility that the problem of the toxicity of the surfactant may occur, and there has been a demand for an improved coating organic material technology for coating the surface of an inorganic solid (nanoparticle).

[0003] As a recent color material technology which is attracting attention from such a viewpoint, Japanese Patent Application Laid-Open No. 11-228860 and WO2000
No. 020519, wherein the particle size is from 1 to 1.
An ink composition in which the surface of an inorganic crystal having a thickness of 100 nm is coated with an organic substance having a molecular weight of 1,000 or more (for example, a biodegradable polymer such as polyaspartic acid) and dispersed in a solvent is disclosed. According to this technique, for example, a low-toxicity colored oxide crystal such as iron oxide is easily decomposed in nature like a biodegradable polymer, and the decomposed product is converted into an aqueous or alcoholic solvent by a coated organic substance having low toxicity. It can be dispersed.
However, since the molecular weight of the coated organic substance needs to be at least 1000 in order to obtain the above-mentioned dispersibility, the effect of improving the dispersibility is not always sufficient for the amount of the coated organic substance used. This generally means a molecular weight of 1000
This is because it is difficult to effectively fix the above-mentioned polymer conformation on the surface of the inorganic solid (that is, to give the dispersibility most efficiently). Also,
Because of the use of a coated organic material such as polyaspartic acid, which has a relatively weak binding force to an inorganic crystal surface such as a carboxyl group or an amide bond, there was a limit that the fixation of the conformation became more difficult. .

As a technique for coating the surface of a colored inorganic crystal such as iron oxide with a low organic molecule having a molecular weight of less than 1000, for example, JP-A-2000-327948 discloses a technique selected from fluoroalkylsilanes and alkoxysilanes.
The use of organosilane compounds formed from one or more hydrophobizing agents is disclosed. However, all of these techniques have an effect of improving dispersibility in a hydrophobic organic medium (synthetic resin, organic solvent, etc.), but rather deteriorate dispersibility in an aqueous or alcoholic solvent.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is a surface modifier which is capable of dispersing inorganic solid ultrafine particles well in an aqueous or alcoholic solvent and has excellent safety. It is an object to provide a compound which can be:

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied the reactivity of an organic compound to the surface of an inorganic solid and the effect of imparting hydrophilicity, and as a result, the effect of imparting hydrophilicity has been significantly improved. To achieve this, it has been found that it is extremely effective to have a molecular structure in which a plurality of hydroxyl groups are effectively spatially arranged, and furthermore, a phosphonic acid group [-P
(O) (OH) ₂ ], this phosphonic acid group reacts with a wide range of inorganic solid surfaces to form a strong bond, and the molecular structure of phosphonic acid for realizing it was studied. As a result, the present invention has been achieved. That is, the gist of the present invention resides in an organic phosphonic acid having a molecular weight of 200 to 1,000 and having three or more hydroxyl groups in an organic residue portion.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. [Organic phosphonic acid] The organic phosphonic acid of the present invention has a molecular weight of 200 to 1,000, contains a phosphonic acid group [-P (O) (OH) ₂ ] as an essential structure in its molecular structure, and has an organic residue. It is a molecule having three or more hydroxyl groups in its part. The number of phosphonic acid groups in the molecular structure is not limited, but usually 1
From 5 to 5, particularly preferably 1 for the purpose of suppressing crosslinking between ultrafine particles in the case of bonding to the surface of inorganic solid ultrafine particles.
３3, most preferably 1. The organic phosphonic acids of the present invention are preferably aliphatic phosphonic acids. The aliphatic phosphonic acid may have an aromatic substituent, but it is desirable that the aliphatic phosphonic acid does not contain an aromatic ring in the molecular structure in view of its water solubility.

If the molecular weight is less than 200, the effect of effectively arranging hydroxyl groups is reduced, while if it exceeds 1,000, an unnecessarily large amount of organic components is required to impart necessary hydrophilicity to the surface of the inorganic solid. And the effect of imparting hydrophilicity per unit molecular weight is reduced. Thus, the preferred molecular weight range is 240-900, more preferably 27
0 to 800. The molecular weight may have a distribution, but in terms of the role, the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is usually 1 to 10, preferably 1 to 7, more preferably 1 to 7. It is preferable to control to 1 to 5, most preferably 1 to 3.

When the number of hydroxyl groups in the organic residue of the organic phosphonic acid molecule of the present invention is less than 3, the effect of imparting hydrophilicity becomes insufficient. This number is preferably 4 or more,
More preferably, the number is 8 or more, and it is preferable that the number is as large as possible in principle.
The usual upper limit is about ten. When a dispersion (preferably aqueous or alcoholic) of colored inorganic solid ultrafine particles such as iron oxides or cobalt blue having the organic phosphonic acid of the present invention bonded to the surface thereof is printed on paper by, for example, an inkjet method, the plurality of dispersions are reduced. As a practical effect of the hydroxyl group, excellent fixing property and low bleeding property of the printed surface may be exhibited. This is presumed to be due to the effect of being appropriately adsorbed and immobilized on the surface hydroxyl groups of the cellulose (poly-β-D-glucose) fiber, which is the main component of the paper, due to the strong hydrogen bonding ability of the hydroxyl groups and the like. Specific examples of the organic phosphonic acid of the present invention satisfying the above conditions include a pentaerythritol derivative represented by the following formula (1).

[0010]

Embedded image This is synthesized, for example, by the following procedure. That is, commercially available peracyl pentaerythritols such as pentaerythritol tetrabenzoate are first mixed with 1/4 equivalent of alkali hydroxide (pulverized as needed or used as a concentrated aqueous solution) using an alcohol such as ethanol as a solvent. When activated, only one acyl group is hydrolyzed to obtain triacylpentaerythritols such as pentaerythritol tribenzoate. Next, a conventional method of converting alcohols to alkyl bromide (for example, a method of reacting carbon tetrabromide with triphenylphosphine, a method of reacting phosphorus tribromide, or a method of reacting a hydrogen bromide acetic acid solution) Replaces the deprotected hydroxyl group with a bromine atom to obtain triacylpentaerythrityl bromide.
Further, a method in which a trialkyl phosphite (for example, triethyl phosphite, tri-t-butyl phosphite, or the like) is allowed to act on an alkyl halide while heating is applied.
The bromine atom is converted into a corresponding dialkyl phosphonate group by a lis-Arbuzov rearrangement reaction, and finally the dialkyl ester and an acyl group such as a benzoyl group are all hydrolyzed under acidic or alkaline conditions to obtain the above-mentioned formula (1) A compound can be obtained.

In the molecular structure of the organic phosphonic acid according to the present invention, in order to suitably exhibit the effect of imparting the hydrophilicity of the hydroxyl group, the hydroxyl group is oriented outward as much as possible when the molecule is bonded to the surface of the inorganic solid. It is desirable to be present. Excessive mobility (flexibility) of the molecular structure is not always preferable in terms of the effect due to burying of hydroxyl groups in the molecular structure and hydrogen bonding between hydroxyl groups. Therefore, it is effective to design a fixed conformation to fix the effective spatial arrangement of hydroxyl groups to some extent. From this viewpoint, preferred molecular structures are a dendrimer structure and a carbohydrate residue described later.

The dendrimer structure has a dendritic regular branching structure, as described later, so that the branches rapidly become denser toward the branch end. Due to this effect, the molecule has extremely small conformational freedom as compared to a molecule having a straight-chain polymer or a molecule having a short-chain branch. On the other hand, carbohydrate residues have the characteristic that they take a 5- or 6-membered ring and the conformation is fixed to, for example, a chair or boat. [Dendron] The dendron in the present invention is a molecule having a dendrimer structure. For example, D. A. To
Maria et al; Angew. Chem. Int. Ed.
Engl. 29, pp. 138-175 (1990),
Or Kakimoto; Chemistry, 50, 608-612 (19
The regular dendritic branched structure described in 95) corresponds to the dendrimer structure in the present invention. As schematically shown in FIG. 1, the starting point of such a dendrimer structure is called a focal point (hereinafter abbreviated as FP).
Another feature of the dendrimer is that, in principle, its molecular structure can be strictly controlled and a compound having no molecular weight distribution (that is, the value of Mw / Mn is 1) can be synthesized. As schematically shown in FIG. 1, the order of branching of the dendrimer structure is referred to as "generation", and the branch-side terminals other than the FP terminal are referred to as branch terminals.

Dendrons, which are the molecular structures most preferably used in the present invention, are described, for example, in US Pat. R. Newkome et al .;
“Dendritic Molecules: Conc
epts, Synthesis, Perspectiv
es "; VCH Verlags GmbH (We
As described on page 110 of Inheim, Germany, 1996), a structure used in the meaning of "part" of a dendrimer structure obtained mainly by a synthesis strategy that is assembled from constituent units on the branch terminal side called the Convergent method. Synonymous with concept.

In general, when a structural formula is written on a sheet of paper, a dendron is represented by a form in which dendritic branches are sequentially spread in a fan shape (or a wedge shape; also called a wedge). In addition, actually taking such a conformation is, for example, the structural study of a monomolecular film (LB film) on the water surface of a polybenzyl ether dendron having an alcoholic hydroxyl group in FP. M. Saville et al .; J. Phys. C
Chem., 99, 8283 (1995).

When the organic phosphonic acid of the present invention is a dendron, it is very preferable to bond a phosphonic acid group to its FP. This is because it is preferable to bond to the surface of the inorganic solid via FP. FIG. 2 schematically shows such a state. It is presumed that one of the factors of the excellent effect is that the wedge-shaped conformation of the dendron effectively covers the surface of the inorganic solid. In addition, the dendron having a hydroxyl group at a branch end is expected to assume a state in which the hydroxyl group is arranged outside the wedge-shaped conformation (arc portion) of the dendron in FIG. Very preferred in that respect.

Examples of dendrimer structures usable in the present invention include, for example, E.C. Buhleier et al .; Synth
esis, 1978, p. 155; M.
M. de Brabander-van den Be
Ang et al .; Angew. Chem. Int. Ed. Eng
l. 32, p. 1308 (1993); J. Hawker
J. et al. Am. Chem. Soc. , 112, 763
8 (1990), A.I. Morikawa et al .; Macromole
cures, 26, 6324-6329 (199)
3). M. Miller et al .; Am. Chem.
Soc. 115, 356-357 (1993);
C. J. Hawker et al; Macromolecule
s, 29, 4370-4380 (1996);
Morikawa; Macromolecules, 3
1, 5999-6009 (1998), etc .; J. H
awker et al .; Am. Chem. Soc. , 113
Vol., P.4583 (1991), the aromatic polyester structure described in E.C. Malmstrom et al; Macr
omolecules, 28, 1698 (199
5) The poly [2,2-bis (hydroxymethyl) propionic acid] structure reported in 5); Morikawa
Polymer J. et al. , 24, p. 573 (199
2) The polysiloxane structure reported in 2); Roo
Vers et al .; Polym. Preprints, 33
Vol., P. 182 (1992). R. Newcome et al .; Org.
Chem. , 50, p. 2003 (1985), a polyamidoamine structure identical to the PAMAM dendrimer commercially available from Aldrich, or M.I. Jayaraman et al .; A
m. Chem. Soc. 120, 12996 (1
998), an aliphatic polyether structure,
H. Ihr et al; Macromolecules, 31.
Vol., P. 4061 (1998).

Among the above-mentioned structural examples of the hyperbranched molecule, the polypropyleneimine structure, the polyamidoamine structure, the aliphatic polyether structure, the polybenzylether structure, and the H . Preferred are aliphatic polyester structures and the like according to Ihr et al. Among these, more preferred in terms of hydrophilicity are the polyamidoamine structure, the aliphatic polyether structure,
H. And the like. The aliphatic polyester structure and the H.I. Ihr
The aliphatic polyester structure is more preferable in terms of water solubility, and the above-mentioned aliphatic polyether structure is particularly preferable in terms of chemical stability. Specific structural examples of the aliphatic polyether dendron are shown in the following formulas (2) and (3).

[0018]

Embedded image

[0019]

Embedded image The phosphonic acid groups of the formulas (2) and (3) are the same as those of the Jay
A dendron (hereinafter abbreviated as "alcohol dendron") having an alcoholic hydroxyl group in the FP and having a branched terminal hydroxyl group protected by, for example, a benzyl group, described in a document by Araman et al., is converted to a bromine atom by the bromination reaction. To a dendron (abbreviated as “bromide dendron”), and then to the Michaelis-Arb
It is converted to the corresponding phosphonic acid dialkyl ester by uzov rearrangement reaction, and the benzyl group at the branch end is further reduced by a conventional hydrogen gas catalytic method (using a catalyst such as palladium-carbon).
And finally the dialkyl ester is hydrolyzed to convert it to a phosphonic acid group. [Saccharide residue] The saccharide residue used as the structural unit of the phosphonic acid in the present invention is a monosaccharide or an oligosaccharide residue in which a plurality of monosaccharide residues are glycosidically bonded.

Such a saccharide may be an alkyl group such as a methyl group, an ethyl group, an isopropyl group or a benzyl group, or an acetyl group, if necessary, as long as the conditions for the number of hydroxyl groups are satisfied and the hydrophilicity and water solubility are not extremely reduced. Any chemical structure such as a group, an acyl group such as an acryloyl group or a methacryloyl group, or a residue of an amino acid such as asparagine, serine or threonine can be bonded to the hydroxyl group. When a radical polymerizable group such as an acryloyl group, a methacryloyl group, or a vinylphenyl group is bonded, it may be suitable for use in an ink composition characterized by fixability or solidification by light or heat.

Such a saccharide residue preferably has a non-reducing terminal having a glycosidic bond in terms of chemical stability. The reason for this is that the non-reducing end of the monosaccharide or oligosaccharide is not glycosidated, and the hemiacetal structure (equivalent to aldehyde) with high chemical reactivity is used.
Therefore, an undesired chemical change such as air oxidation due to heating is easily caused. In addition, as the kind of such a glycoside bond, an O-glycoside bond via an oxygen atom, a C-glycoside bond via a carbon atom,
Examples include an S-glycoside bond via a sulfur atom, an N-glycoside bond via a nitrogen atom, and a P-glycoside bond via a phosphorus atom. Of these, O-glycoside bond and C-glycoside are preferable in terms of chemical stability. O-glycoside bond is the most preferable in view of ease of synthesis and low toxicity.

When the molecular structure of the organic phosphonic acid of the present invention contains a preferred saccharide residue having a glycosidic bond at the non-reducing end, the phosphonic acid group may be aglycone (Aglyc).
More preferably, it is bonded to a carbon atom of the (on) moiety, ie, the moiety that is not the saccharide moiety (Glycon). To further explain the aglycone portion by way of example, for example, in the case of methyl α-D-glucopyranoside, the aglycone portion is a methyl group, and the other glucose residues are glycones,
The molecule in which the methyl group which is the aglycone moiety is bonded to the phosphonic acid group corresponds to the preferred organic phosphonic acid of the present invention.

In the case where a phosphonic acid group is preferably bonded to the carbon atom of the aglycone part, the number of carbon atoms of the aglycone part is usually 1 to 10, and preferably 1 to 10 in terms of hydrophilicity.
6, more preferably 1-4, while the lower limit is preferably 2, more preferably 3, in terms of the effect of shielding the inorganic solid from the outside. A specific example of a molecular structure containing a D-glucose residue is represented by the following general formula (4).

[0024]

Embedded image (In the formula, m is a natural number of 1 to 10, and a wavy line indicates that the glycosidic bond may be any of α-type and β-type isomers.) The compound represented by the general formula (4) is, for example, a commercially available compound. 2,3,4,6- obtained by bromination of peracetylated D-glucose by a conventional method (for example, using a solution of hydrobromic acid in acetic acid)
Glycosyl halides (hereinafter abbreviated as Glyco-X) of peracetyl sugar such as tetra-O-acetyl-α-D-glucopyranosyl bromide are used as a common raw material, and for example, the following two synthetic routes are possible. is there.

The first synthetic route is as follows: Glyco-X
An excess equivalent of a glycol having m carbon atoms (e.g., ethylene glycol having m = 2, 1,4-dihydroxybutane having m = 4, 1,8-dihydroxyoctane having m = 8) is added to silver carbonate or trifluoromethane. In the presence of a dehalogenating agent such as silver sulfonate (silver triflate), methylene chloride or the like is used as a solvent to convert the bromine atom into a glycol glycoside in which the glycol is substituted. In the glycol glycoside thus obtained, the hydroxyl groups of the carbohydrate residues are all protected with acetyl groups, and only the hydroxyl group at the terminal of the glycol is unprotected, so that the unprotected hydroxyl group is converted to a bromine atom by the bromination reaction. Substitution, followed by conversion to the corresponding dialkyl phosphonate by Michaelis-Arbuzov rearrangement as before, and finally hydrolysis of all ester linkages to completion.

In the second synthetic route, one of the two hydroxyl groups of the glycols used in the first synthetic route is previously converted to a dialkylphosphonate group, which is then glycosidized in the same manner as described above, and finally deprotected. How to As a method of converting one of the two hydroxyl groups of the glycols into a dialkylphosphonate group in advance, first, one of the two hydroxyl groups of the glycols is protected with an appropriate protecting group such as an acetyl group, and then the other is protected. Is substituted with a bromine atom by the bromination reaction, and then the bromine atom is converted to a phosphonic acid dialkyl ester group by the Michaelis-Arbuzov rearrangement reaction,
Finally, all ester bonds are hydrolyzed to complete. Instead of Glyco-X, a peracetyl sugar is treated with benzylamine, hydrazineacetic acid, or the like, and the non-reducing end (1
1) is converted to a free hydroxyl group and then added to trichloroacetonitrile in the presence of a base such as DBU in a solvent such as methylene chloride to obtain a 1-imidate sugar, ie, -C (N
H) -CCl ₃ group (hereinafter simply referred to as “imidate group”)
O-glycosides can also be used. When the imidate group at the 1-position is, for example, an acetyl group at the 2-position, it is an excellent leaving group via an intramolecular ring-closure intermediate which has reacted with the adjacent group, and thus, for example, an acid catalyst (eg, methylene chloride) Glycosidation by condensing a reagent having an alcoholic hydroxyl group such as the glycols described above using a boron trifluoride ether complex or trimethylsilyltrifluoromethanesulfonate (TMSOTf) under cooling conditions of about −20 ° C. is possible. An advantage of such an imidate method, which is a common method of sugar chemistry, is that there is no need to use expensive and toxic silver compounds as the dehalogenating agent.

When the carbohydrate residue to be used has a biological activity such as a sugar chain antigen activity, the inorganic solid ultrafine particles to which the carbohydrate residue is bound, and a dispersion or ink composition obtained by dispersing the ultrafine inorganic particles in a solvent also have the biological activity. In such a case, it can be applied to a special printing application utilizing the biological activity, for example, an analysis chip utilizing selective binding of a biological substance to a substrate. [Monosaccharides and Oligosaccharides that Form Carbohydrate Residues] Examples of the monosaccharides that are constituent units of the carbohydrate residues are as follows. Although the D-form and L-form optical isomers of all the exemplified monosaccharides can be used as the constitutional unit of the saccharide residue, those which are naturally preferred in terms of low toxicity and biological activity of the saccharide residue are naturally occurring. The use of existing optical isomers. The optical isomers of naturally occurring monosaccharides may be different between animals and plants. In the following examples, naturally-occurring optical isomers in which a particularly important type is evident are indicated by adding the type. The nomenclature used here is “Polysaccharide Biochemistry 1, Chemistry,” p. 5 (supervised by Fujio Egami, Kyoritsu Shuppan Co., Ltd.
1969). Org. C
hem. 28, p. 281 (1963), with revisions made in 1965, prepared by a joint committee of the Union of Applied Chemistry (IUPAC) and the International Union of Biochemistry (IUB).

Examples of aldoses include aldosteroses such as glyceraldehyde, aldotetroses such as erythrose and threose, D-ribose, D- and L-.
Aldopentoses such as arabinose, lyxose, D-xylose, D-glucose, D- and L-galactose, D-mannose, aldohexoses such as gulose, idose, D-talose, allose, altrose, and aldoheptose such as glucoheptose And the like.

Examples of the ketoses include ketotrioses such as dioxyacetone, ketotetroses such as glycerotetolulose, D-erythropentulose (common name: ribulose), and D- and L-threopentulose (common names:
Ketopentoses such as xylulose), ribohexulose (common name: psicose), D-arabinohexulose (common name: fructose, DL type common name: α-aculose), D- and L-xylohexulose (common name: sorbose) ), Ketohexoses such as D-lyxohexulose (common name: tagatose), and ketoheptoses such as glucoheptulose.

Important deoxysaccharides include 6-deoxy-L-mannose (common name: rhamnose), 6-deoxy-L-galactose and 6-deoxy-D-galactose (common name: fucose, L-type is an animal polysaccharide) Important as a common component of quality), 2-deoxyribose and the like. As amino sugars, D-glucosamine, D-
2-amino-2-deoxy sugars such as galactosamine, D-mannosamine, grosamine, idosamine, talosamine, allosamine, fructosamine, fucosamine, arabinosamine and xylosamine, 2-amino- such as glucosaminitol, galactosaminitol and mannosaminitol. 2
Sugar alcohols which are deoxy sugar derivatives, N-acetylglucosamine, N-acetylgalactosamine, N-acetylmannosamine, N-acetylglosamine, N-acetylidosamine, N-acetyltalosamine, N-acetylallosamine , N-acetylfructosamine, N-acetylfucosamine, N-acetylarabinosamine, N-
2-acetylamino-2-deoxy sugars such as acetylxylosamine, 2-acetylamino- such as N-acetylglucosaminitol and N-acetylgalactosaminitol
Sugar alcohols that are 2-deoxy sugar derivatives, sialic acids (or nonulosamic acid) such as neuraminic acid, N
- acetylneuraminic acid, N- glycolylneuraminic acid, N, O ₄ - di-acetylneuraminic acid, N, O ₇ - di-acetylneuraminic _{acid, N, O 4, O 7} - tri acetylneuraminic sialic such neuraminic acid Acids and the like are exemplified.

As sugar alcohols, erythritol, ethylene glycol, glycerol, D-inositol, L-inositol, myo-inositol, silitol, laminitol, D-sorbitol, D-mannitol, fucitol, galactitol (common name: dulcitol or dulcitol) ), D-glucitol, D-arabitol, xylitol, ribitol (common name: Adonitol or Adonitol), glucohepitol and the like.

Examples of carboxylic acid derivatives of monosaccharides include uronic acids such as glucuronic acid, D-galacturonic acid, D-mannuronic acid, guluronic acid, iduronic acid, taluronic acid, aronic acid, and arturonic acid; gluconic acid and galactonic acid. Aldonic acids, muramic acid and the like. Other examples include sulfur-containing monosaccharides such as glucothiose.

[0033] Although illustrated monosaccharides are typically not applicable to, those a general formula CnH _2n O _n carbon atoms n
Is 2 to 10, or a compound in which a part of these hydroxyl groups is substituted with an amino group or a carboxyl group. The structure of the oligosaccharide is not limited,
Sucrose, maltose, lactose, galactinol, laminaribiose, nigerose, sophorose, α, α-trehalose, which are naturally occurring oligosaccharide units,
Disaccharides such as melibiose, kojibiose, gentibiose, cellobiose, glucoxylose, and glucuronoglucose, and trisaccharides such as meletitose, raffinose, and manninotriose are also units usable in the present invention.

[0034] The organic phosphonic acid of the present invention may contain a plurality of types of the aforementioned carbohydrate residues in the molecular structure. Further, a carbohydrate residue at the branch end of any of the above dendrons may be bound. [Method of Bonding to Inorganic Solid Surface] The method of bonding the organic phosphonic acid of the present invention to the surface of inorganic solid ultrafine particles such as a metal oxide is not limited, but the following three possible methods are exemplified.

The first method is a method in which the organic phosphonic acid of the present invention coexists in a reaction system in which the inorganic solid ultrafine particles are formed in a liquid phase. For example, when producing ultrafine particles of yellow iron oxide (goethite) by the iron carbonate hydrolysis method,
When the ultrafine particles have grown to a desired particle size, the method of adding the organic phosphonic acid of the present invention for coordination corresponds to this. By such an operation, the inorganic solid ultrafine particles during crystal growth are coated on the surface with the organic phosphonic acid of the present invention,
It is presumed that further crystal growth is practically impossible, and that the grain size is stabilized. There is no limitation on the timing of coexistence of the organic phosphonic acid of the present invention. Usually, the latter method is preferred in terms of controllability of the particle size.

In the second method, the surface of the inorganic solid ultrafine particles synthesized to a desired particle size is coated with a temporary ligand (hereinafter, referred to as a “temporary ligand”) capable of ligand exchange later. And then performing a ligand exchange reaction in the liquid phase in which part or all of the temporary ligand is substituted with the organic phosphonic acid of the present invention. For example, B. O. Dabbousi et al .; Phys
s. Chem. B, 101, 9463-9475 (1
997) Ultrafine particles of a II-VI compound semiconductor such as CdSe bonded to the surface as a temporary ligand of an organic ligand such as trioctylphosphine oxide (abbreviated as TOPO) obtained by a so-called hot soap method. Is purified and isolated by a known method (for example, a combination of reprecipitation by addition of a toluene solution in methanol and centrifugation), which is then brought into contact with the phosphonic acid of the present invention while heating and refluxing in a solvent such as ethanol. The method of performing the ligand exchange reaction corresponds to this.

The third method is the above-mentioned various dry methods (gas phase method).
Or, such as solid phase synthesis method, while introducing and dispersing the inorganic solid ultrafine particles generated by non-liquid phase reaction into the liquid phase while maintaining the required particle size, the organic phosphonic acid of the present invention in the liquid phase It is a method of bonding to the surface. For example, an aqueous solution containing goethite ultrafine particles having a particle size of about 10 nm produced by the iron carbonate hydrolysis method is sprayed into air at a temperature of 200 ° C. or higher, and the water is evaporated to leave the remaining goethite ultrafine particles in air. In the gas phase synthesis for obtaining red iron oxide (hematite) ultrafine particles by heat oxidation, an air stream containing the hematite ultrafine particles is introduced into an aqueous solution in which the organic phosphonic acid of the present invention is dissolved, whereby the hematite ultrafine particles are dissolved. A method of coating the surface in an aqueous solution corresponds to this. In such a method, there is no limitation on the method of causing the organic phosphonic acid of the present invention to act in the liquid phase. A method in which the particles are first dispersed in a liquid phase and then the organic phosphonic acid of the present invention is added is possible, but the former method is usually preferred. As in the above-described example, by using the aqueous phase in which the organic phosphonic acid of the present invention acts as an aqueous solution, by-products such as salts that become impurities of the inorganic solid synthesized in the gas phase are dissolved in the aqueous solution. There is an advantage that can be separated.

[0038]

The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. [Measurement device] (1) Nuclear Magnetic Resonance (NMR) spectrum: JEOL Ltd. JNM-EX270 type FT-NMR ⁽¹ H: 2
70 MHz, ¹³ C: 67.8 MHz). Unless otherwise specified, deuterated chloroform was used as a solvent, and tetramethylsilane was measured at 23 ° C. with 0 ppm as a control. (2) Infrared absorption (IR) spectrum: FT / IR-8000 type FT-IR manufactured by JASCO Corporation. Measured at 23 ° C. (3) Transmission electron microscope (TEM): Hitachi, Ltd.
H-9000UHR transmission electron microscope (acceleration voltage 3
00 kV, degree of vacuum at the time of observation about 7.6 × 10 ⁻⁹ Torr
r). (4) Absorption spectrum: Hewlett-Packard H
P8453 UV / visible absorption spectrophotometer. EXAMPLES Example 1 Synthesis of Aliphatic Polyether Dendron Having Phosphonic Acid Group in FP First, a second-generation alcohol dendron was synthesized according to the above-mentioned literature by Jayaraman et al. However, a benzyl group was used at the branch end for ease of deprotection. This will be described below. The reaction of adding two molecules of benzyl alcohol to one molecule of epichlorohydrin is carried out using a combined system of potassium hydroxide and tetrabutylammonium iodide as a base catalyst, and using hydrated benzyl alcohol as a solvent. Dibenzyloxy-2-hydroxypropane was obtained. An etherification reaction of condensing two molecules of the first generation dendron with one molecule of methallyl dichloride (that is, 2-chloromethyl-allyl chloride) is performed using sodium hydride as a base, and a second generation having a vinyl group at a focal point (FP). Get a dendron. A second-generation alcohol dendron (hereinafter abbreviated as Bn-G2-OH) having a benzyl group at the branch end by a reaction with a borane complex intended for hydroboration to the vinyl group, followed by oxidation with hydrogen peroxide. Can be obtained. Purification of the product in each step is performed by silica gel column chromatography. Bn-G2-OH
Is confirmed by the integral value of the signal of each proton at the phenyl group at the branch end, the benzyl position, the methylene group of the dendron skeleton and the branch point in the proton NMR spectrum, and the presence of the hydroxyl group absorption band in the IR spectrum.

Next, the hydroxyl group of FP is converted to a phosphonic acid group. First, Bn-G2-OH (1 eq.) And carbon tetrabromide (1.25 eq.) Are dissolved in tetrahydrofuran, and triphenylphosphine (1.25 eq.) Is added thereto. Convert to atoms. Post-treatment of this reaction is carried out by separating and washing between two layers of water and methylene chloride. Then, the Michaelis-Arbuzo mixed with tri-t-butyl phosphite and heated.
The bromine atom is converted to a di-t-butylphosphonate group by a v rearrangement reaction. Purification of this product is performed by silica gel column chromatography. All benzyl groups were removed by catalytic reduction with hydrogen gas over a palladium-carbon catalyst, and finally de-butylated with trifluoroacetic acid to convert the di-t-butylphosphonate group to a phosphonic acid group, and Second generation dendron having a phosphonic acid group of (2) in FP (hereinafter abbreviated as HO-G2-Phos)
Can be obtained. Example 2: Synthesis of D-glucopyranoside having a phosphonic acid group in the aglycon moiety
Glucopyranose is synthesized in which the hydroxyl groups at positions 3, 4 and 6 are protected with an acetyl group and the position 1 is imidate. That is, 1,2,3,4,6-penta-O-acetyl-β-D-glucopyranose supplied by Tokyo Chemical Industry is dissolved in methylene chloride and benzylamine (1.6 equivalents) is added at room temperature.
2,3,4 selectively deacetylated at position 1 by adding
6-Tetra-O-acetyl-D-glucopyranose is obtained. This was dissolved in methylene chloride and cooled to -20 ° C.
Trichloroacetonitrile and the base, commonly known as DBU (i.e., 1,8-diazabicyclo [5.4.0] undec-7
Imidate) to convert to 1-imidate sugar.

Next, glycosidation of the 1-imidate sugar (1 equivalent) with an alcohol having a phosphonic acid diester group is carried out by using a conventional method of sugar chemistry. That is, Ald
excess equivalent of diethyl (hydroxymethyl) phosphonate (diethyl phosphonoyl methanol in another nomenclature) supplied by Rich Co. in the presence of trimethylsilyl trifluoromethanesulfonate (1 equivalent) at -20 ° C.
To give diethylphosphonoylmethyl 2,3,4,6-tetra-O-acetyl-D-glucopyranoside. This is treated in a methanolic potassium hydroxide solution to decompose the acetyl group and the phosphonic acid diethyl ester, and then acidified to obtain the desired compound of formula (4) wherein the natural number m is 1. It is possible. Purification is possible by gel filtration. This compound is abbreviated as “Glu-C-Phos” below. [Application example] Application example 1: Ultra-fine goethite particles bonded with hydrophilic dendrons Dissolve iron (II) sulfate (1 equivalent) in water in which nitrogen gas has been bubbled and the dissolved air has been sufficiently replaced, followed by stirring and nitrogen gas. Sodium hydroxide (1 equivalent) is added to the aqueous solution while bubbling is continued to obtain a neutral Fe (OH) ₂ colloid aqueous solution. Next, sodium bicarbonate (1 equivalent) was added to form a colloidal aqueous solution of ferrous carbonate FeCO ₃ , and while maintaining the temperature at room temperature to 40 ° C., the bubbling was switched to air, and stirring was continued to obtain a goethite (α-FeO 3). (O
H)). Here, HO-G2 obtained in Example 1
-Phos was added in an excess amount, and dilute hydrochloric acid was added dropwise to make the pH acidic, thereby controlling the number average particle size of the goethite ultrafine particles having HO-G2-Phos bound as the organic phosphonic acid of the present invention to about 10 nm. Can be generated. This aqueous solution can be dialyzed with a commercially available dialysis membrane to perform purification in which desalting and removal of an excessive amount of HO-G2-Phos are simultaneously performed. The aqueous dispersion of goethite ultrafine particles obtained by dialysis and purification in this way has a turbid yellow color,
It has an absorption band in the wavelength range of 0 to 680 nm, and does not cause precipitation even when concentrated. Application Example 2: Goethite ultrafine particles having glucose residue bonded The same operation as in Application Example 1 except that the Glu-C-Phos obtained in Example 2 was used in an excessive equivalent amount instead of HO-G2-Phos. Perform Glu-CP
Goss ultra-fine particles having hos bonded as the organic phosphonic acid of the present invention can be produced by controlling the number average particle diameter to about 10 nm. This aqueous solution can be dialyzed with a commercially available dialysis membrane to perform purification in which desalting and removal of excess Glu-C-Phos are simultaneously performed. The aqueous dispersion of goethite ultrafine particles obtained by dialysis and purification in this manner has a turbid yellow color, has an absorption band in the wavelength range of 380 to 680 nm, and does not generate a precipitate even when concentrated. [Evaluation of printability] When the aqueous dispersion of the inorganic solid of the above application example was charged into a commercially available ink jet cartridge and printing was performed on paper, the printed surface having excellent hue and fixability, and low bleeding property was obtained. Obtainable.

With such fixing property and low bleeding property, the surface of the inorganic solid ultrafine particles is strongly adsorbed and fixed to the hydroxyl groups on the surface of the cellulose fiber which is the main component of paper due to the strong hydrogen bonding ability of the hydroxyl groups of the organic phosphonic acid of the present invention. It is presumed to be due to the effect of In addition, the excellent hue of the printed surface is as follows: the inorganic solid of the above-mentioned application example has a smaller number average particle diameter of 10 nm than ever before, which is 2
It is presumed that because the secondary aggregation is suppressed, the hue that the inorganic solid originally has as a substance appears effectively.

[0042]

(1) The organic phosphonic acid of the present invention binds to the surface of an inorganic solid ultrafine particle such as a metal oxide, and has a hydrophilic (preferably water-soluble), non-aggregating property in an aqueous solvent. , Excellent hue and safety. (2) When the aqueous solvent dispersion of the colored inorganic solid ultrafine particles having the organic phosphonic acid bonded to the surface thereof of the present invention is used as, for example, an ink composition for an ink-jet method, it can be applied to paper caused by the hydroxyl group of the organic phosphonic acid of the present invention. Printing that exhibits excellent print fixability and low bleeding property due to the strong adsorption effect of the organic fine particles, and furthermore, because of the surface coating with the organic phosphonic acid of the present invention, the secondary aggregation of the ultrafine particles is suppressed and an excellent hue is exhibited. Shows the effect on performance.

[Brief description of the drawings]

Fig. 1 Generation of dendron and focal point (F
It is a schematic diagram which shows P).

FIG. 2 is a schematic diagram showing a state of binding of a dendron to an inorganic solid surface.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 11/00 C09D 11/00

Claims (5)

[Claims] 1. An organic phosphonic acid having a molecular weight of 200 to 1000 and having three or more hydroxyl groups in an organic residue portion. 2. The organic phosphonic acid according to claim 1, wherein the organic phosphonic acid has a molecular structure in which a phosphonic acid group is bonded to a focal point of a dendron. 3. The organic phosphonic acid according to claim 2, wherein the chemical structure of the dendron contains an aliphatic polyether skeleton or an aliphatic polyester skeleton. 4. The organic phosphonic acid according to claim 1, which has a carbohydrate residue in the molecular structure. 5. The organic phosphonic acid according to claim 4, wherein the non-reducing end of the carbohydrate residue has a glycosidic bond and the aglycon portion has a phosphonic acid group.