JP2953466B2 - Pigment-dispersed aqueous ink composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment-dispersed aqueous ink composition preferably used for an ink-jet printer, which enables reliable printing and obtains a high-quality image.

2. Description of the Related Art Ink jet printing is a non-impact printing method in which a printer generates ink droplets in response to a digital signal such as a digital signal generated by a computer. The ink droplets adhere to a substrate such as paper or a transparent film. Ink jet printers have become widespread due to their print quality, low cost, relatively quiet operation, and graphics forming ability.
Thermal (bubble jet) and piezoelectric drop-on
Demand printers have been particularly successful in the marketplace and have been widely used as personal computer printers in offices and homes.

[0003] Inks used in ink jet printers can be classified into dye-based inks and pigment-based inks. Dye-based inks are satisfactory in various respects, but generally have poor light fastness and water fastness.
Since the printed matter is expected to have some durability, there is a problem that a printed image obtained with the dye-based ink is inferior in light fastness and water fastness. On the other hand, pigment inks are excellent in light resistance and water resistance. Therefore, pigment-based inks are generally preferred over dye-based inks in printed matter requiring durability.

[0004] In ink jet recording, the following three matters are important. That is, (1) reliability,
(2) drying speed, and (3) print quality. Reliability is generally evaluated based on the following four criteria. The first is durability under continuous printing conditions, which means that the weight of ink droplets does not change with time and good directional properties are maintained. Good directionality means that the deviation of the angle of the ink droplet ejected from the nozzle is within about ± 0.5 ° from the perpendicular to the nozzle surface. The second is durability under intermittent printing conditions, which means that the nozzles do not block while printing is stopped. Thirdly, a print head that recovers a printing operation (ink droplet weight and good directionality) that is the same as the initial printing operation by performing a limited amount of suction operation on the nozzles. The long-term storage durability of the ink inside. The fourth is that the ink retains its chemical and physical stability over a long period of time when stored under two extreme temperature conditions and even when repeatedly exposed to the extreme temperature. Storage stability.

[0005] Still further, the drying speed of the ink is an important factor that determines the processing speed of the printer. In page printers, the ink on the printed paper must be dry before the next paper comes in contact. If the ink does not dry, smudges will form.

[0006] Print quality is generally defined by two factors: (1) color characteristics and (2) non-color image characteristics. The color characteristics of an ink are measured by optical density and color coordinates that determine the hue. The non-color characteristics that determine the definition of an image include resolution (number of droplets per unit area), coverage area per droplet, sharpness or sharpness of an edge, and satellite (stray droplets around printed characters). ) Or a defect around the dot such as a beard.

What is important in ink jet recording is that a printed matter having a sharp edge or sharp image and having as little bleeding as possible is called "plain paper".
Whether it can be obtained at As used herein, "plain paper" refers to a wide variety of commercially available papers, especially papers used for electrostatic copying. Such commercially available papers do not have a unique structure, composition, or narrow properties adapted to inkjet printers. Recently, there is an increasing demand for an ink jet printer capable of realizing excellent print quality on plain paper.

[0008] Pigment-based inks that are properly configured to obtain good quality printed matter on plain paper are preferred over conventional pigment-based and dye-based inks. When an ink drop is applied by ink jet printing and contacts the paper surface, the ink spreads from the point of contact and penetrates the paper. Cellulose fibers present in most plain papers, by capillary action, act as a wick that draws liquid along the length of individual fibers.

In the case of a dye-based ink in which a colorant is uniformly dissolved in a solvent, the colorant spreads and penetrates, and the colorant is sucked to the same extent as the solvent along the length of the cellulose fiber. When a dye-based ink is used, the edges of the obtained colored dots are poor in clarity and may be accompanied by mustaches.

In the case of a pigment-based ink in which a colorant is uniformly dispersed in a liquid, the colorant spreads and penetrates in the longitudinal direction of the cellulose fiber as long as the dispersion stability of the colorant is not lost by contact with paper. Along with the solvent. When a normal pigment-based ink is used, the clarity of the edges of the obtained colored dots is poor, and the color dots may be accompanied by mustaches. In contrast, in a pigment-based ink configured so that the dispersion stability of the colorant is lost by contact with paper, the colorant does not spread and does not penetrate, that is, in the length direction of the cellulose fiber. Not sucked along. In this type of ink, the colorant effectively separates from the solvent. As a result, colored dots with sharp edges and negligible whiskers are obtained.

Dispersants for dispersing pigments in water are well known to those skilled in the art and have been used to apply coatings, such as paints, to various substrates. Stable pigment dispersions can be obtained either by steric stabilization alone or by using pigment dispersants that provide stability by a combination of both steric stabilization and ionic stabilization.

Examples of the polymer dispersant which imparts only three-dimensional stabilization include those belonging to nonionic water-soluble polymers, such as polyvinyl alcohol, cellulose resin, ethylene oxide-modified phenol and ethylene oxide / propylene oxide polymer. Is mentioned. Pigment dispersions containing such polymers do not lose their dispersion stability on contact with paper. Therefore, a printed image with poor edge clarity and whiskers may be obtained.

Examples of the polymer dispersant that provides both steric stabilization and ionic stabilization include those composed of neutralized acrylic acid, maleic acid or vinyl sulfonic acid monomers. Pigment dispersions containing this type of polymer dispersant, which are suitably configured,
Contact with paper results in loss of dispersion stability, resulting in a printed image with sharp edge boundaries and negligible whiskers. The mechanism by which this type of polymer dispersion loses dispersion stability when in contact with paper is described below.

Such polymers have partially or completely neutralized acid functions and can be classified as anionic polyelectrolytes. Typically, the anionic polyelectrolyte is
Binds to multivalent cations such as magnesium, calcium, and aluminum. The strength and sensitivity of the binding of the polyvalent cation depend on the linear charge density and the structure of the polyelectrolyte. In a suitably configured pigment dispersion containing a polymer with partially or fully neutralized acid functionality, the polymer will generally bind to multivalent cations present on the surface of plain paper. If the binding of the polyvalent cation is sufficient, the anionic charge density of the dispersant is partially or completely neutralized. Neutralization of the charge results in loss of ionic stabilization and loss of colorant dispersion stability. As described above, when the dispersion stability of the colorant is lost, the colorant separates from the solvent. As a result, a printed image with no whiskers and a clear edge boundary can be obtained.

The strength and sensitivity at which polyvalent cations are bound to the polymer electrolyte depend on the linear charge density and structure of the polymer electrolyte. Generally, the higher the linear charge density of the polyelectrolyte, the greater the binding interaction between the polyelectrolyte and the polyvalent cation. The linear charge density of polymers with neutralized acid functionality on adjacent monomer units is greater than polymers with neutralized acid functionality on monomer units interspersed with nonionic monomer units. For example, the linear charge density of polyacrylic acid is higher than a random polymer of acrylic acid and styrene. The structure of the polyelectrolyte also affects the strength and sensitivity of the binding of the polyvalent cation. If the binding site on the polyelectrolyte has a shape and coordination environment that optimally matches the ionic radius of the polyvalent cation, then the binding interaction between the polyelectrolyte and the polyvalent cation is a special structure. Larger than similar polyelectrolytes without the above characteristics. The optimal binding site for Ca ²⁺ (ionic radius: 1.14 Å; hexacoordination) is Mg ²⁺ (ionic radius: 0.86 Å;
Obviously, it is not always optimal for (6-coordination). On the other hand, the optimal binding site for Ca ²⁺ (ionic radius: 1.14 angstroms; hexacoordinate) is
Monovalent Na ⁺ (ionic radius: 1.16 Å;
It is easily understood that it binds well to the (coordination).

However, polymeric dispersants consisting solely of hydrophilic, neutralized acrylic, maleic, or vinyl sulfonic acid monomers do not produce stable pigment dispersions. The reason is that the hydrophilic functional group does not sufficiently adhere to the surface of the ordinary pigment. A stable pigment dispersion can only be obtained if the polymer dispersant also contains one or more hydrophobic moieties that adsorb and adhere to the surface of the pigment. Therefore, a polymer dispersant that provides both steric stabilization and ionic stabilization must contain both hydrophobic and hydrophilic moieties.

In US Pat. No. 4,597,794, a pigment is prepared using a random polymer having a carboxylic acid functional group neutralized hydrophilically and a hydrophobic aromatic ring functional group attached to the pigment surface. Dispersed aqueous ink dispersions for inkjet printers are described. Since this polymer is a random copolymer, it has a low linear charge density and appears to be less sensitive to polyvalent cations on the surface of typical plain paper.

US Pat. No. 5,085,698 describes an aqueous ink dispersion for an ink jet printer in which a pigment is dispersed using an AB or BAB block copolymer. Part A of this block copolymer is
Hydrophobic water-insoluble homopolymers or copolymers of acrylates or amides. The portion B of the block copolymer is a hydrophilic water-soluble homopolymer or copolymer of an acrylic acid ester in which the alcohol portion of acrylic acid, acrylic acid amide or ester has hydrophilicity. In a block copolymer having a moiety B with acrylic acid, the acid functionality is an organic base,
Neutralized with a neutralizing agent selected from the group consisting of alkanolamines, alkali metal hydroxides and mixtures thereof. Examples and comparative examples described in this publication are:
An ink formulated with an AB or BAB block copolymer pigment dispersion having independent hydrophobic and hydrophilic moieties, is better than an ink formulated with a random copolymer of a hydrophobic monomer and a hydrophilic monomer. This indicates that the printing performance is excellent. Further, since the block copolymer has a high linear charge density on the hydrophobic portion B, it is considered that the above random copolymer is more sensitive to polyvalent cations on the surface of general plain paper. However, while the hydrophilic portion B has a high linear charge density, it does not have any special structural features that favor binding to polyvalent cations.

[0019]

SUMMARY OF THE INVENTION The present inventor has now found that a novel polyuronic acid derivative is excellent as a pigment dispersant, and that an ink composition containing this derivative can realize good images.

Accordingly, an object of the present invention is to provide a pigment-dispersed aqueous ink composition that can provide reliable printing performance and, in particular, can provide excellent quality images on plain paper.

Another object of the present invention is to provide a novel polyuronic acid derivative and a dispersant containing the same.

The pigment-dispersed aqueous ink composition according to the present invention comprises water as a main solvent, a pigment, and a polyuronic acid derivative in which a hydrophobic polymer is covalently bonded to the reducing end of polyuronic acid. .

[0023]

DETAILED DESCRIPTION OF THE INVENTION Ink Composition The ink composition according to the present invention is used in a recording system using the ink composition. Examples of the recording method using the ink composition include an ink jet recording method, a recording method using a writing instrument such as a pen, and various other printing methods. In particular, the ink composition according to the present invention is preferably used for an ink jet recording method.

Polyuronic Acid Derivative The polyuronic acid derivative contained in the ink composition of the present invention comprises a polyuronic acid portion and a hydrophobic polymer covalently bonded to the reducing end of the polyuronic acid portion.

This polyuronic acid derivative is considered to have a function of dispersing the pigment in the ink composition of the present invention in a satisfactory manner. By the addition of the polyuronic acid derivative, the ink composition according to the present invention has good printing characteristics and realizes a high quality printed image. Although the reason is not clear, this polyuronic acid derivative has both a hydrophobic part and a hydrophilic part, and has the same mechanism as a conventionally known type of dispersant having two parts, It is expected that this is because the pigment is stably dispersed by a more improved mechanism and good dots without whiskers can be formed. More specifically,
First, the hydrophobic polymer portion is adsorbed on the pigment surface, and the pigment particles are well dispersed in the aqueous solvent. Further, it is considered that the polyuronic acid portion of the polyuronic acid derivative has a structure suitable for binding to a polyvalent cation. That is, the chain conformation of polyuronic acid has a buckle shape, and pockets in which carboxyl groups and hydroxy groups are arranged are formed. This pocket was found to be sized to accommodate divalent ions such as calcium. Therefore, it is considered that good dots without whiskers are formed because the ink is bonded to the polyvalent cations present on the plain paper, the dispersed state of the ink composition is destroyed, and the colorant does not spread. The above theory is only expected,
The present invention is not bound by this theory.

The polyuronic acid derivative used in the present invention is novel. Therefore, according to another aspect of the present invention, a novel polyuronic acid derivative and a dispersant comprising the same are provided.

The addition amount of the polyuronic acid derivative in the ink composition according to the present invention may be appropriately determined within the range where the effects of the present invention can be obtained, but is preferably about 0.1 to 30% by weight, more preferably. 0.1 to 20% by weight.

Polyuronic Acid Partial polyuronic acid contains 1,4-linked polygalacturonic acid, polyguluronic acid, polyiduronic acid or a mixture thereof as a main component. Polyuronic acids can be obtained from natural substances and may contain non-uronic saccharides. The uronic acid content of the polyuronic acids used in the present invention preferably exceeds 80% by weight. More preferably, 85% by weight
And most preferably more than 90% by weight.

Polygalacturonic acid includes lemon, lime,
It can be obtained by hydrolysis and de-esterification of pectin, a natural hydrocolloid obtained from fruits such as grapefruit, orange, mango, apple, sunflower and sugar beet. Polyguluronic acid can be obtained from a giant kelp (Macrocystis pyri).
fera), horsetail kelp (Laminaria)
Digita) and sugar kelp (Lami)
After partially hydrolyzing alginic acid, which is a natural polysaccharide obtained from seaweed such as Naria saccharina),
It can be obtained by selective precipitation. Polyiduronic acid can be obtained by hydrolysis of various animal polysaccharides.

The polyuronic acid used in the present invention has a number average molecular weight of about 700 to 10,000. More preferably from about 700 to about 7000.

Hydrophobic Polymer Part According to a preferred embodiment of the present invention, the hydrophobic polymer in the present invention can be preferably divided into four embodiments.

In a first embodiment of the present invention, the hydrophobic polymer part comprises styrene or a styrene derivative, vinylpyridine or a vinylpyridine derivative, methacrylate, acrylate, acrylonitrile, methacrylonitrile, butadiene and isoprene. A homopolymer or copolymer prepared from at least one monomer selected from the group. The monomer may be appropriately selected, and examples thereof include styrene and α.
-Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 3-nitrostyrene, 3-fluorostyrene, 4-fluorostyrene, 2-vinylpyridine, 4-vinylpyridine, methyl methacrylate, ethyl Methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethyl-hexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl methacrylate, 2-ethoxyethyl methacrylate, 2-trimethylsiloxyethyl methacrylate, Glycidyl methacrylate, p-tolyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate n- butyl acrylate, ter
t-butyl acrylate, hexyl acrylate, 2-
Ethyl-hexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate,
Examples include phenyl acrylate, 2-ethoxyethyl acrylate, 2-trimethylsiloxyethyl acrylate, glycidyl acrylate, p-tolyl acrylate, acrylonitrile, methacrylonitrile, butadiene and isoprene.

The hydrophobic polymer according to the first aspect of the present invention can be prepared by a usual anionic polymerization method. Since anionic polymerization uses a "living" polymeric carbanion, stringent conditions with respect to oxygen, moisture and other impurities must be maintained during the polymerization reaction. Therefore, solvents and monomers must be rigorously purified before polymerization.

The hydrophobic polymer prepared by the usual anionic polymerization method has a very narrow molecular weight distribution. A typical polymer has a dispersity of less than 1.5, typically in the range of 1.0 to 1.3, when expressed as the dispersity of the polymer weight average molecular weight divided by the number average molecular weight. . Both weight average and number average molecular weights of polymers can be obtained from size chromatography using columns calibrated with polymer standards of known molecular weight.

As is well known in the art for anionic polymerization, a number of electrophiles react with "living" polymeric carbanions to yield functional terminated polymers. Such a functional group-terminated polymer is desirable for the covalent attachment of a hydrophobic polymer moiety to the reducing end of polyuronic acid. Carboxy-, hydroxy- and amino-terminated polymers can be readily prepared by conventional methods.

In the second embodiment of the present invention, the hydrophobic polymer portion may be a hydrophobic polymer containing poly (dialkylsiloxane) as a main component. Preferred examples of the poly (dialkylsiloxane) include poly (dimethylsiloxane).

In a third embodiment of the invention, the hydrophobic polymer part is a polyamide. According to a preferred embodiment of the present invention, the polyamide hydrophobic polymer moiety comprises:
Preferred are N-acylated derivatives of polyamines wherein at least 50% of the amine functional groups on the polyamine are primary or secondary amines.

According to a preferred embodiment of the present invention, the polyamine from which the polyamide is derived is preferably from the polyamine group consisting of linear polyethyleneimine, branched polyethyleneimine, polyallylamine, poly-N-alkylallylamine and polyvinylamine. Selected.

Further, the acyl group R- (CO) of the polyamide
- preferably comprises at least one selected from the following acyl groups: _{i.e., C n H (2n + 1} ) - (C
O)-(where n is 3 or more, preferably 3 or more and 1
9 or less is); phenyl - (CO) -; substituted phenyl - (CO) -; phenyl -CH ₂ - (CO) -; substituted phenyl -CH ₂ - (CO) -; phenyl--C ₂ H ₄ - ( C
O) -; and substituted phenyl _{-C 2 H 4 - (CO)} - it is preferably selected from. Acyl group CH ₃ — (CO) —
And _{C 2 H 5 - (CO)} - with N- acylated polyamine is not a hydrophobic, soluble in water. Therefore, the polyamine N-acylated by the acyl group C _n H _{(2n + 1)} -(CO)-(where n is 3 or more) is hydrophobic. Similarly, an acyl group containing an aryl group
The acylated polyamine is hydrophobic;

[0040] In a fourth aspect of the invention, the hydrophobic polymer moiety is a hydrophobic polyamine. According to a preferred embodiment of the present invention, the hydrophobic polyamine polymer moiety is a poly-N-alkylated derivative of a water-soluble polyamine. Further according to a preferred embodiment of the present invention, the water-soluble polyamine from which the hydrophobic poly-N-alkylated polyamine is derived is selected from polyethyleneimine, polyallylamine, polyvinylamine, poly (propyleneimine) dendrimer, and poly (amidoamine) dendrimer. It is preferably selected from the group consisting of water-soluble polyamines.

The alkyl group of the poly-N-alkylated derivative of the water-soluble polyamine is represented by the general formula -CHX ₁ X ₂ . Here, the group X ₁ represents a hydrogen atom, alkyl, substituted alkyl, aryl, or substituted aryl, and the group X 1
₂ is a hydrogen atom, alkyl, substituted alkyl, aryl,
Or a substituted aryl. The choice of X ₁ and X ₂ is made in view of the polyamine covalently attached to the reducing end of the polyuronic acid. For example, tris (2-aminoethyl) amine (H, a low molecular weight branched polyethylimine)
_When producing ₂ NCH ₂ CH ₂ ) ₃ N), X ₁ and X ₂ are preferably selected so that the molecular weight of the hydrophobic polymer portion is 300 or more. That is, fully alkylated tris (2-aminoethyl) amine-form, X ₁ and X ₂ are the same, that X ₁ and X ₂ represent each of 3 or more groups carbon, molecular weight 300 The above hydrophobic polymer portion is obtained. Similarly, a partially alkylated tris (2-aminoethyl) amine has a hydrophobic property having a molecular weight of 300 or more, where X ₁ is a hydrogen atom and X ₂ is a group having 4 or more carbon atoms. A polymer moiety is obtained. Further, in the case of a water-soluble polyamine having a molecular weight of 300 or more, the number of carbon atoms is not particularly limited in selecting X ₁ and X ₂ . In addition to the selection of the water-soluble polyamine, the selection of X ₁ and X ₂ is made in consideration of the molecular weight of the polyuronic acid. If the hydrophobicity of the hydrophobic polymer is large,
This is because in order to obtain a water-soluble polyuronic acid derivative, the molecular weight of polyuronic acid must be large.

The degree of N-alkylation of the covalently bound water-soluble polyamine is preferably more than 10%, more preferably more than 20%, even more preferably more than 30% of the total amine functionality on the water-soluble polyamine. is there.

According to a preferred embodiment of the present invention, the number average molecular weight of the hydrophobic polymer in the present invention is 15,000.
Or less, more preferably 10,000 or less. In the present invention, the number average molecular weight of the hydrophobic polymer is preferably 300 or more, more preferably 4 or more.
00 to 5000.

Preparation of Polyuronic Acid Derivatives As mentioned above, US Pat. No. 5,085,698 discloses AB having a hydrophobic (A) portion and a hydrophilic (B) portion.
Alternatively, the use of a pigment dispersant consisting of a BAB block copolymer is clearly shown to be advantageous when compared to a random copolymer. By covalently attaching one type of hydrophobic polymer to one end of the polyuronic acid, AB is classified according to US Pat. No. 5,085,698.
A polyuronic acid derivative which can be classified as a block copolymer is obtained. Similarly, by covalently bonding two types of hydrophobic polymers to both ends of polyuronic acid, B
A polyuronic acid derivative which can be classified as an AB block copolymer is obtained. Polyuronic acid derivatives that cannot be classified by the above-mentioned patent classification can be obtained by polycovalently bonding several hydrophobic polymers to polyfunctional groups on polyuronic acid. The polyuronic acid derivative having a structure in which a kind of hydrophobic polymer is bonded to one end of polyuronic acid, which is used in the present invention, can be preferably produced by the method described below.

The polyuronic acids described above have several functional groups that can chemically bind hydrophobic polymers.
That is, a hydroxy group (two per uronic acid, but three for the non-reducing end of polyuronic acid), a carboxy group (one per uronic acid), and a reducing end of polyuronic acid It has the above terminal aldehyde group. Here, the binding of the hydrophobic polymer to the hydroxyl group or the carboxy group is expected to adversely affect the binding of the polyuronic acid to the polyvalent cation. In support of this, Schweiger has shown that partially acetylating the hydroxyl groups of polyuronic acid reduces the gel-forming ability of polyuronic acid and calcium ions (J. Org. Chem., Vol. 27, 1789, 1962, and
Vol.27,2973,1964). Since the carboxy group is essential for the binding of the polyvalent cation, it is clear that binding of the hydrophobic polymer to the carboxy group results in the loss of this binding ability. In support of this, Kohn
And Furda show that increasing the degree of esterification of the carboxy groups of polygalacturonic acid decreases the stability constant of calcium polygalacturonic acid (Co
ll. Czech. Chem. Commun., Vol. 32, 4470, 1967).

Thus, the only functional group to which the hydrophobic polymer may be attached is the terminal aldehyde group. Accordingly, the polyuronic acid derivative used in the present invention is produced by covalently bonding one type of hydrophobic polymer to a terminal aldehyde or a derivative of the terminal aldehyde. Since the aldehyde group is on the reducing end of the polyuronic acid, the covalent bonding of the hydrophobic polymer does not block the binding interaction between the polyuronic acid moiety and the polyvalent cation present on the surface of plain paper.

Although a number of methods are effective for covalently attaching the hydrophobic polymer to the terminal aldehyde of polyuronic acid or a derivative thereof, preferred methods in the present invention are:
Reductive amination using an amino-terminated hydrophobic polymer and unmodified polyuronic acid. As is well known for polysaccharides such as polyuronic acids, the aldehyde group on the reducing end is present in solution primarily as a cyclic hemiacetal. Specifically, for polyuronic acids, the reducing end is present as a 6-membered cyclic hemiacetal called "pyranose". Reductive amination with primary or secondary amines results in ring opening and disruption of the pyranose ring structure. The destruction of one polyuronic acid unit at the terminal position does not appear to have a significant adverse effect on the binding interaction between the polyuronic acid moiety and the polyvalent cation.

Reductive amination with a primary amine-terminated hydrophobic polymer gives a secondary amine. Similarly,
Reductive amination with a secondary amine terminated hydrophobic polymer gives a tertiary amine. Both potential amine products are chemically robust and hydrolytically stable. Thus, inks containing pigment dispersants prepared by reductive amination appear to be chemically stable.

The reductive amination is preferably carried out in an aqueous or alcoholic aqueous solution using a salt of borohydride or a salt of cyanoborohydride. Typically used salts of borohydride include sodium borohydride, potassium borohydride, lithium borohydride, tetramethylammonium borohydride and tetrabutylammonium borohydride. Typically used salts of cyanoborohydride include sodium cyanoborohydride, potassium cyanoborohydride, lithium cyanoborohydride and tetrabutylammonium cyanoborohydride. Preferably, the salt of borohydride is used at a pH value above about 7. Salts of cyanoborohydride can be used at a low pH of about 3. Borohydride or cyanoborohydride salts are highly selective and do not reduce any carboxy groups present in the polyuronic acid. Less selective reagents for reductive amination that can be used include hydrogen and catalysts, zinc and hydrochloric acid, iron pentacarbonyl and alcoholic potassium hydroxide, and formic acid.

The polyuronic acid derivative according to the third aspect of the present invention is obtained by first obtaining a polyamide as a hydrophobic polymer portion and bonding the polyamide to the reducing end of the polyuronic acid as described above. be able to. However, according to a preferred embodiment of the present invention, the polyamine is first attached to the reducing end of the polyuronic acid via one of its amine functions, and then the plurality of amine functions of the polyamine moiety are selectively N-acylated. It is preferably manufactured by More specifically, multiple amine functional groups on a polyamine covalently bonded to the reducing end of polyuronic acid are selectively N-acylated using an acylating reagent such as an organic acid halide or organic acid anhydride. Is preferred. In this step, the N-acylated primary amine gives a primary amide, and the N-acylated secondary amine gives a secondary amide. Tertiary amines are not acylated.

A polyuronic acid having a covalently linked polyamine moiety, such that the amine function of the polyamine moiety is converted to an amide (N-acylation) and the hydroxyl group of the polyuronic acid moiety is converted to an ester (O-acylation). Non-selective acylation of must be avoided. It appears that partial acetylacylation of the hydroxyl group of polyuronic acid reduces its ability to form gels with calcium ions.
That is, polyuronic acids with non-selectively acylated covalently bound polyamine moieties do not have high affinity for multivalent cation binding. Therefore, it is not possible to obtain a printed image of excellent quality by the pigment-dispersed aqueous ink composition containing such a non-selective acylating dispersant.

Several processes for the selective N-acylation of amine functions in the presence of hydroxyl groups have already been described. For example, Katsutoshi Inoue et al. (Adv. Chitin Scienc
e, Vol. 1, 271, 1996) disclose the use of chitosan, a natural polymer obtained from the shell of a crustacean containing one primary amine and two hydroxyl groups per monomer unit, in anhydrous diethylenetriamine in pyridine. It is selectively N-acylated using pentaacetic acid (65 ° C; 24 hours). This reaction is general in that other organic anhydrides can be used in place of diethylenetriaminepentaacetic anhydride. Gunda I. Georg et al. (Bioorganic and Medicinal Che
mistry Letters, Vol. 4, 335, 1994) disclose a complex diterpene, N-debenzoyltaxol, containing one primary amine and three hydroxyl groups, using Schotten-Bau using sodium bicarbonate as a pH buffer.
Selective N-selection by various organic acid chlorides under man conditions
It is acylated; Both of these two methods can be preferably used to selectively N-acylate the polyuronic acid having a covalently bonded polyamine moiety in the present invention.

Commercially available organic acid halide type acylating reagents which can be preferably used in the present invention include butyryl chloride, isobutyryl chloride, valeryl chloride, isovaleryl chloride, trimethylacetyl chloride, and the like.
Hexanoyl chloride, tert-butylacetyl chloride, heptanoyl chloride, octanoyl chloride, 2-ethylhexanoyl chloride, nonanoyl chloride, decanoyl chloride, undecanoyl chloride, lauroyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride, benzoyl chloride,
Phenylacetyl chloride, o-toluoyl chloride, m-chloride
Toluoyl, p-toluoyl chloride, 4-ethylbenzoyl chloride, hydrocinnamoyl chloride, 4-propylbenzoyl chloride, 4-butylbenzoyl chloride, tert-chloride
Butylbenzoyl, 4-pentylbenzoyl chloride, 4-hexylbenzoyl chloride, 4-heptylbenzoyl chloride and the like. Further, commercially available and organic anhydride type acylating reagents that can be preferably used in the present invention include butyric anhydride, isobutyric anhydride, valeric anhydride, trimethylacetic anhydride, hexanoic anhydride, heptanoic anhydride, heptanoic anhydride,
Decanoic anhydride and benzoic anhydride are exemplified.

In the third embodiment of the present invention, the above-mentioned linear polyethyleneimine is obtained from Takeo Saegusa et al.
ecules, Vol 5, 4470, 1972). Branched polyethyleneimines of various molecular weights are commercially available from BASF and Nippon Shokubai. Polyallylamine and poly (N
-Alkyl) allylamine is commercially available from Nitto Boseki. Various molecular weight polyvinylamines are commercially available from Mitsubishi Kasei.

In the polyuronic acid derivative according to the fourth aspect of the present invention, similarly to the polyuronic acid derivative according to the third aspect, first, a polyamine as a hydrophobic polymer portion is first obtained, and this polyamine is converted as described above. To the reducing end of polyuronic acid. However, according to a preferred embodiment of the present invention, the polyamine is first attached to the reducing end of the polyuronic acid via one of its amine functions, and then the plurality of amine functions of the polyamine moiety are selectively N-alkylated. It is preferably manufactured by N-alkylation is, specifically,
Reductive amination performed with aldehydes and / or ketones as the source of alkyl groups selectively N-alkylates the polyamine groups of the covalently linked polyamine moiety.
Here, the reductive amination is conveniently carried out using a borohydride salt or a cyanoborohydride salt as described above. Also, if an excess of aldehyde is used, tertiary amine functionality is obtained by reductive amination of primary and secondary amine functions on covalently bound water-soluble polyamine moieties. If an excess of ketone is used, reductive amination of the primary and secondary amine functions on the covalently bound water-soluble polyamine moiety will result in secondary and tertiary amine functions, respectively.

In the fourth aspect of the present invention, as described above, branched polyethyleneimines having various molecular weights are commercially available from BASF and Nippon Shokubai. Polyallylamine is commercially available from Nitto Boseki, and polyvinylamine is commercially available from Mitsubishi Kasei. Poly (propylene imine) dendrimer is available from DSM FineC
Commercially available from chemicals. Poly (amidoamine) dendrimers are available from Aldrich Chemical
al Company, Inc. From Starburs
It can be purchased under the trade name of t ™ dendrimer.

As described above, in the third and fourth embodiments of the present invention, the polyamine is covalently attached to the reducing end of the polyuronic acid via the amine function. In this case, this covalent bond is easily achieved by the above-mentioned reductive amination. In the reductive amination, one covalent bond of polyuronic acid occurs per polyamine, and no covalent bond of multiple polyuronic acids occurs per polyamine.
It is preferred to use an excess of polyamine relative to polyuronic acid. Preferably, the stoichiometric ratio of polyamine to polyuronic acid in the reductive amination reaction is greater than about 2: 1. For most linear and branched polyamines, there are several chemically distinct amine functions that result in a covalent bond to the polyuronic acid. Which amine function selectively binds to the polyuronic acid by reductive amination can be controlled to some extent by changing the pH. However, it is common to obtain a mixture of linked amines with different structures. In the case of dendrimer polyamines having a single amine function, the covalent attachment of the polyamine through one of the amine functions will result in a single compound if the polyuronic acid polydispersity is ignored.

The polyuronic acid derivative used in the present invention can be produced by a synthesis method other than reductive amination in which one hydrophobic polymer is single-covalently bonded to the reducing end of polyuronic acid.

For example, hydrophobic polymers functionalized with terminal phenylhydrazine groups are believed to selectively react with terminal aldehydes in aqueous or alcoholic aqueous solutions to form phenylhydrazone derivatives. In addition, techniques that have been used for the synthesis and screening of glycoconjugates can also be applied to polyuronic acids. Therefore, the polyuronic acid derivative used in the present invention can be produced by the following method. First, in the first step, the hemiacetal at the reducing end is converted into a glycosylamine derivative by stirring a solution obtained by adding the polysaccharide to a saturated aqueous solution of ammonium carbonate for several days. This reaction is
Works well for ionized polysaccharides. Then, in the second step, the glycosylamine derivative is selectively amidated using a large excess of a homobifunctional reagent, disuccinimidyl suberate (DSS). As a result of this derivatization, one N-hydroxysuccinimidyl ester remains as it is and can be further derivatized. Then, in the third step, the DSS-modified glycosylamine derivative is selectively amidated using an amine-functionalized hydrophobic polymer. Finally, the 8-carbon spacer group results in a single covalent bond of one hydrophobic polymer to the reducing end of the polysaccharide.

Pigments The pigments used in the present invention may be either organic or inorganic pigments or mixtures thereof. The term "pigment" as used herein means an insoluble pigment.

[0061] The pigment particles are prepared by dispersing the pigment-dispersed ink in an ink-jet printing apparatus, in particular, typically having a diameter of 10 to 50 µm.
It is desirably small enough to flow freely through the discharge nozzle. The particle size of the pigment is preferably 10 μm or less, more preferably 1.0 μm or less.

The selected pigment can be used in dry or undried form. Usually, the pigment is produced in an aqueous medium and the pigment is obtained as a water wet presscake. In this presscake form, the pigment does not aggregate to some extent in dry form. Pigments in the form of undried presscakes do not require as much deagglomeration as dried pigments in the ink manufacturing process.

The pigments usable in the present invention include:
The following are mentioned: Shimla First Yellow GF (manufactured by Dainippon Ink and Chemicals, Inc .; CI.
Pigment Yellow 12), Shimla First Yellow GFR (manufactured by Dainippon Ink and Chemicals, Inc .; CI.
Pigment Yellow 13), Shimla First Yellow 5GF (manufactured by Dainippon Ink and Chemicals, Inc .; CI.
Pigment Yellow 14), Irgalite Yel
low CG (manufactured by Ciba-Geigy; CI Pigment Yellow 16), Shimla First Yellow HGF (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Yellow 17), Shimla First Yellow 4117 (Dainippon Ink and Chemical) Industrial Co., Ltd .;
Pigment Yellow-73), Shimla First Yellow 4191N (manufactured by Dainippon Ink and Chemicals, Inc .; C.I.
I. Pigment Yellow 74), Shimla First Yellow 4181 (manufactured by Dainippon Ink and Chemicals, Inc .;
C. I. Pigment Yellow 83), Chromoph
thal Yellow 3G (Ciba-Geigy
C .; I. Pigment Yellow 93), Chrom
ophthal Yellow GR (Ciba-Ge
igy; C.I. I. Pigment Yellow 95), Shimla First Yellow 4186 (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Yellow 97), H
ansa Brilliant Yellow 10G
X (manufactured by Hoechst Celanese);
Pigment Yellow 98), Permanent Ye
llowG3R-01 (Hoechst Celane
se Co .; I. Pigment Yellow 114), Ch
romophtal Yellow 8G (Ciba
-Geigy; C.I. I. Pigment Yellow 12
8), Irgazin Yellow 5GT (Cib
a-Geigy; C.I. I. Pigment Yellow 12
9), Hostaperm Yellow H4G (H
oechst Celanese; C.I. I. Pigment Yellow 151), Shimla First Yellow 4
192 (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Yellow 154), Hostaperm Or
angel GR (manufactured by Hoechst Celanese; CI Pigment Orange 43), Paliog
en Orange (manufactured by BASF; CI Pigment Orange 51), Shimla Brilliant Carmine (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Red 57: 1), Fast Gen Super Magenta (Dainippon Ink and Chemicals) Co., Ltd .; CI Pigment Red 122), Paliogen Red L38
70 (manufactured by BASF; CI Pigment Red 12)
3), Hostaperm Scarlet GO (H
oechst Celanese; C.I. I. Pigment Red 168), Permanent Rubin
e F6B (Hoechst Celanese);
C. I. Pigment Red 184), Monastra
l Magenta (Ciba-Geigy; C.I.
I. Pigment Red 202), Monastral
Scarlet (manufactured by Ciba-Geigy; CI.
Pigment Red 207), Fast Gen Blue GP
-100 (manufactured by Dainippon Ink and Chemicals, Inc .; CI.
Pigment Blue 15: 2), Fast Gen Blue G
NPR (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Blue 15: 3), Fast Gen Blue GN
PS (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Blue 15: 4), Microcrate Blue
R (manufactured by Ciba-Geigy; CI Pigment Blue 60), Fast Gen Green S (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Green 7), Fast Gen Green 2YK (dainippon Ink and Chemicals, Inc.) Co., Ltd .; CI Pigment Green 3
6), First Gen Super Red (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Violet 1)
9), First Gen Super Violet (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Violet 23), Monastral Maroon RT
-229-D (manufactured by Ciba-Geigy; CI Pigment Violet 42), Raven 1170
(C.C.
I. Pigment Black 7), Special Black 4A
(Manufactured by Degussa; CI Pigment Black 7), FW18 (manufactured by Degussa; CI Pigment Black 7), and color black S160 (D
egussa; C.I. I. Pigment black 7).

The amount of the pigment in the composition of the present invention is about 0.1 to 20% by weight, more preferably 0.1 to 10% by weight.

[0065] Water Water is the principal solvent for the pigment dispersed aqueous ink composition of the present invention. Preferably, the amount of aqueous carrier medium in the ink composition according to the invention is between 70 and 99.8% by weight. Additional components that can be included in the ink composition are further described below.

In order to solubilize the polyuronic acid portion of the basic pigment dispersant in aqueous media, it may be necessary to neutralize some or all of the carboxylic acid functional groups. Suitable bases for this include organic bases, alkanolamines, alkali metal hydroxides and mixtures thereof and the like. Suitable bases include, for example: methylamine, dimethylamine, trimethylamine, morpholine, N-methylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyl-monoethanolamine, N, N-dimethyl-monoethanolamine, N-methyl-diethanolamine, tetramethylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.

Water-Soluble Auxiliary Solvents In addition to the components described above, the inks can optionally contain one or more water-soluble organic solvents. Water-soluble organic solvents are well known and include (1) alcohols such as isopropyl alcohol and butyl alcohol, (2) ketones such as acetone and methyl ethyl ketone, (3) ethers such as tetrahydrofuran and dioxane, and (4) Esters such as ethyl acetate and propylene carbonate, (5) ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, polypropylene glycol,
Polyhydric alcohols such as 1,5-pentanediol, 1,2,6-hexanetriol, thiodiglycol, glycerol, (6) ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether , Ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether,
Ethylene glycol mono-sec-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol mono-n-amyl ether, ethylene glycol mono-n-hexyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether , Propylene glycol monoethyl ether, propylene glycol diethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-sec-butyl ether, propylene glycol mono-isobutyl ether , Propylene glycol mono-tert-butyl Ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether and dipropylene glycol mono-n Lower alkyl ethers of polyhydric alcohols such as -butyl ether; (7) nitrogen-containing compounds such as urea, pyrrolidone and N-methyl-2-pyrrolidone; and (8) sulfur-containing compounds such as dimethyl sulfoxide and tetramethylene sulfoxide. . The total amount of the auxiliary solvent used in the ink is not particularly limited, but preferably, the auxiliary solvent is present in the range of 0.5 to 40% by weight.

Other Ingredients In addition to the ingredients described above, the ink may optionally contain one or more penetrating surfactants selected from the group consisting of anionic or nonionic surfactants. . Examples of the anionic surfactant include a fatty acid salt, a higher alcohol sulfate ester salt, an alkylbenzene sulfonate, and a higher alcohol phosphate ester salt. As the nonionic surfactant, for example, ethylene oxide adduct of acetylene diol, ethylene oxide adduct of higher alcohol, ethylene oxide adduct of alkylphenol, aliphatic ethylene oxide adduct,
Ethylene oxide adducts of higher alcohol fatty acid esters, ethylene oxide adducts of higher alkylamines, ethylene oxide adducts of fatty acid amides, ethylene oxide adducts of polypropylene glycol, fatty acid esters of polyhydric alcohols, alkanolamine fatty acid amides and ethylene oxide-propylene oxide copolymers No. Air Products, Allentown, PA, 18195, USA
d An ethylene oxide adduct of an acetylene-based diol available from Chemicals is preferably used. Examples of these include Surfynol 465 (ethoxylated tetramethyldecine diol), Surfynol CT-136 (a blend of acetylenic diol and anionic surfactant), Surfynol GA (an acetylenic diol blend) and Surfynol GA Nol TG (a blend of acetylenic diol with ethylene glycol). The amount of the surfactant for imparting permeability in the ink is not particularly limited, but is preferably 0.01 to 5%.
% By weight. In addition to the above-described surfactant for imparting permeability, additives such as a pH buffer, a biocide, a viscosity modifier, an ultraviolet absorber and an antioxidant may be contained. The amount of all compositions of the ink is such that the viscosity of the ink is 10 cps at 20 ° C.
Is selected to be less than.

Preparation of Ink The ink composition of the present invention can be prepared in one step by dispersing and mixing the above-mentioned components using an appropriate method.
In addition, the ink composition 1) disperses and mixes a part of the above-mentioned components, and 2) then adds the remaining components to the dispersion.
By mixing, it can be prepared in two steps.
The dispersion process is performed by a ball mill, sand mill, attritor,
The operation can be performed using a roll mill, an agitator mill, a Henshel mixer, a colloid mill, an ultrasonic homogenizer, a jet mill, an ong mill, or other pulverizing apparatuses known to those skilled in the art so as to obtain a uniform dispersion.

First, after preparing a colored ink in a concentrated form,
This concentrated dispersion may be diluted to a concentration suitable for use in an ink jet printer. Also, in general,
It is desirable to filter the pigment-dispersed aqueous ink composition, preferably using a metal mesh filter or a membrane filter. Filtration may be performed by applying pressure to the ink composition being filtered or by reducing the pressure at the receiving end of the filtration device. Also, centrifugation may be used to remove large particles that may cause nozzle failure in the printhead of an inkjet printer.

[0071]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Preparation of Polygalacturonic Acid The polygalacturonic acid used in the following examples was prepared using the following general method. Pectin (BA-KI
NG, The Copenhagen Pectin
Factory Co., Ltd.) with isopropanol and water (6
0:40) was slurried at 10% by weight. Sodium hydroxide, half the weight of pectin,
Added to the slurry. Next, the mixed slurry was heated to 40 ° C.
For 3 days. The solid was collected by filtration and washed thoroughly with a solution consisting of isopropanol and water (60:40). Next, the solid was suspended in an excess amount of water, and the pH of the suspension was adjusted to about 1.5 by slowly adding a 1 M aqueous oxalic acid solution. After stirring the acidified suspension for 24 hours,
The solid polygalacturonic acid was collected by filtration. The solid was thoroughly washed with a solution consisting of ethanol and water (60:40), then washed with ethanol, and then dried in vacuum. The dried polygalacturonic acid was then converted to its sodium salt by neutralizing with a dilute sodium hydroxide solution such that a 1% by weight solution of neutralized polygalacturonic acid was prepared. The pH of the resulting solution was adjusted to about 3.3 by adding dilute sulfuric acid dropwise. Next, the solution was heated to 100 ° C.
For 4 hours. At this time, the pH was maintained at 3.3 by periodically adding a small amount of dilute sulfuric acid. After filtering the cooled solution, it was concentrated to one-third of its original volume using a rotary evaporator. Four volumes of ethanol were added and the precipitated material was removed by filtration. The solid collected by filtration was dissolved in water to make a 10% by weight solution, and then the pH of the solution was adjusted to 1.5 by slowly adding a 1M oxalic acid aqueous solution. After stirring the acidified suspension for 24 hours, the solid polygalacturonic acid was filtered off. The solid was thoroughly washed with a solution consisting of ethanol and water (60:40), then washed with ethanol, and then dried in vacuum.

Preparation of Polyglucuronic Acid The polyglucuronic acid used in the following examples was prepared using the following general method. Alginic acid (eg, I
-3G, manufactured by Kimitsu Chemical Industry Co., Ltd.) was slurried at 5% by weight in a 1 molar oxalic acid aqueous solution. The slurry was vigorously stirred for 10 minutes to obtain a viscous suspension. next,
The suspension was heated to reflux in a boiling water bath. The mixture was refluxed for 20 hours while passing a stream of nitrogen through the mixture. After cooling to room temperature, the mixture was placed in a 100 ml centrifuge tube for 3 hours.
Centrifuged at 000 rpm for 1 hour. The supernatant was discarded and the precipitate was suspended in deionized water in an amount of 60% by weight of the original aqueous oxalic acid solution. A 40% by weight sodium hydroxide solution was added dropwise to the stirred mixture until the precipitate just dissolved. One-ninth of the total solution weight of solid oxalic acid dihydrate was added to the resulting solution with stirring. The partially hydrolyzed alginic acid precipitated to give a viscous suspension. The suspension was heated to reflux in a boiling water bath. The mixture was refluxed for 20 hours while passing a stream of nitrogen through the mixture. After cooling down to room temperature, the mixture was placed in a 100 ml centrifuge tube at 3000
Centrifuged for 1 hour at rpm. The supernatant was discarded, and the precipitate was dried under vacuum to a constant weight. Dry solids are 0.1% so that a 0.5% by weight solution of partially hydrolyzed alginic acid is obtained.
It was suspended in a molar sodium chloride aqueous solution. Solution pH
A 10% by weight sodium hydroxide solution was added dropwise to the stirred mixture until the pH rose to a value of about 6. With vigorous stirring,
The mixture was acidified to pH 2.85 by dropwise addition of a 1 molar aqueous hydrochloric acid solution. After stirring for 4 hours, the mixture was centrifuged at 3000 rpm in a 100 ml centrifuge tube.
For 1 hour. The supernatant was discarded, and the precipitated solid polyguluronic acid was added to a 50 wt.
It was suspended in an aqueous solution of ethanol by weight. This suspension is
After stirring for an hour, the solid polyguluronic acid was collected by filtration. The solid was sufficiently washed with ethanol and dried in vacuum.

Polyuronic acid derivative A 1- [4-polystyrenecarboxamide-butylamido
[D] Dihydropolygalacturonic acid 5.0 g of polygalacturonic acid and 3.3 g of N, N-diisopropylethylamine are dissolved in 100 mL of a 50% by weight aqueous methanol solution with stirring. 4-polystyrylcarboxamido-butylamine (amino-terminated polystyrene, Mn = 2600, Polymer Sourc
e) and 5.0 g of tetramethylammonium borohydride. After flushing the reaction flask with argon gas for 3 minutes, seal with a serum cap. The reaction mixture is stirred at room temperature for 96 hours. Concentrated HCl while cooling the mixture with stirring using an ice bath
(10 ml) are added and after stirring at room temperature for 1 hour, the mixture is evaporated to dryness. The residue is then ground and washed several times with anhydrous methanol. The washing liquid is discarded, and the remaining solid matter is vacuum-dried to a constant weight. Put the dry solids in deionized water,
A suspension containing 40% by weight of the polyuronic acid derivative is obtained. The mixture is stirred vigorously and N, N-dimethylethanolamine is added dropwise over 2-3 hours with vigorous stirring until the pH of the mixture does not change to 8.0. A small amount of insoluble material is filtered off. Add deionized water to obtain a solution of about 25% solids by weight.

Polyuronic acid derivative B 1- [4-poly (2-vinylpyridine) carboxyamido
[D-butylamino] dihydropolygalacturonic acid 4-poly (2-vinylpyridine) carboxamido-butylamine (amino-terminated poly- (2-vinylpyridine), Mn = 1500, Polymer Source
Polyuronic Acid Derivative A except that
Prepared in the same manner as in the preparation of

Polyuronic acid derivative C 1- [4-polystyrenecarboxamide-butylamido
[ D] Dihydropolyguluronic acid It is produced in the same manner as in the preparation of the polyuronic acid derivative A except that polyguluronic acid is used instead of polygalacturonic acid.

Polyuronic acid derivative D 1- [4-poly (2-vinylpyridine) carboxyamido
[ D -butylamino] dihydropolyguluronic acid It is produced in the same manner as in the preparation of the polyuronic acid derivative B, except that polyguluronic acid is used instead of polygalacturonic acid.

[0078]Polyuronic acid derivative E [Poly (N-4-ethylbenzoyl) alkyleneimi
] -Dihydropolygalacturonic acid 10.0 g of polygalacturonic acid and lithium hydroxide monohydrate
Of an aqueous solution (15% by weight) with deionized water 3
Dissolve with stirring into 00 mL. This solution has a branched chain
Polyethyleneimine (SP-003, manufactured by Nippon Shokubai; molecule
70 g) are added with stirring. Violently disrupt
While stirring, a 6N hydrochloric acid solution is added dropwise to adjust the pH of the mixed solution.
Adjust to 10.1. Power the argon gas flow into the flask
While flashing well, lithium borohydride 1.0g
Is added slowly with vigorous stirring. Reaction flask
With a serum cap vented to the oil bubbler
Seal and stir the reaction mixture at room temperature for 48 hours. mixture
The temperature of the product was raised to 40 ° C. using a water bath and the mixture was
The residual lithium borohydride is hydrolyzed by stirring for
Decomposes to lithium metaborate and hydrogen. Then, low
Water is removed using a tarie evaporator to obtain an oily solid.
You. This solid is washed with 5% N, N-dimethylethanolamide.
Wash several times with anhydrous methanol solution (by weight)
Remove excess polyethyleneimine. Discard the washing solution,
The remaining solid is vacuum dried to constant weight. Dry solid
And aqueous solution of lithium hydroxide monohydrate (15% by weight).
5 g with stirring to 300 mL of deionized water
You. A slightly cloudy solution was obtained, containing lithium carbonate
Add 18 g. Next, vigorously stir the resulting mixture
While dropping 20 g of 4-ethylbenzoyl chloride
You. After addition of the organic acid chloride, the mixture is continued for a further 4 hours
And stir. Cool the stirred mixture using an ice bath.
Then slowly add the concentrated hydrochloric acid solution. At this time,
Significant foaming occurs as lithium carbonate is neutralized
You. Add acid until the pH of the mixture reaches a value of 1.5.
Continue adding. This acidified mixture is placed on a rotary evaporator.
Evaporate to dryness using a filter. Next, the residue is
Wash several times to remove excess 4-ethylbenzoic acid
You. Discard the washing solution and dry the remaining solid under vacuum to constant weight.
Dry. Put the dried solid in deionized water and induce polyuronic acid
A mixture of 40% by weight of conductor is obtained. PH of the mixture is 8.0
2-3 hours with vigorous stirring until no longer changes
Then, N, N-dimethylethanolamine is added dropwise.
A small amount of undissolved material is removed by filtration. Deionized water
Is further added to obtain a solution having a solid content of about 25% by weight.

Polyuronic acid derivative F [poly (N-octanoyl) alkyleneimine ] -dihi
Mud polygalacturonic acid polygalacturonic acid 10.0 g, in the same manner as described above polyuronic acid derivative E, branched polyethyleneimine (SP-003, manufactured by Nippon Shokubai Co., molecular weight: 300) by reductive amination. The isolated solid is vacuum dried to constant weight. The resulting dry solid and 0.5 g of aqueous solution of lithium hydroxide monohydrate (15% by weight) are added to 300 mL of deionized water with stirring. A slightly cloudy solution is obtained, to which 18 g of lithium carbonate are added.
Next, 19.5 g of octanoyl chloride is added dropwise while vigorously stirring the resulting mixture. After addition of the organic acid chloride, the mixture is continuously stirred for a further 4 hours. The concentrated hydrochloric acid solution is added slowly while cooling the stirred mixture using an ice bath. At this time, considerable foaming occurs as the excess lithium carbonate is neutralized. PH of the mixture is 1.5
The addition of acid is continued until the value of is reached. The acidified mixture is evaporated to dryness using a rotary evaporator. The residue is then washed several times with dichloromethane to remove excess octanoic acid. Discard the washings and vacuum dry the remaining solid to constant weight. The dried solid is placed in deionized water to give a mixture of 40% by weight of polyuronic acid derivative. N, N-Dimethylethanolamine is added dropwise over 2-3 hours with vigorous stirring until the pH of the mixture does not change at 8.0. A small amount of undissolved material is removed by filtration. Deionized water is further added to a solution having a solids content of about 25% by weight.

Polyuronic acid derivative G [poly (N-isobutyryl) allylamine] -dihydro
Polygalacturonic acid polygalacturonic acid 10.0g of lithium monohydrate hydroxide aqueous solution (15 wt%) 11.0 g, deionized water 3
Dissolve with stirring into 00 mL. In another flask, 16 g of lithium hydroxide monohydrate was added to 100 g of a polyallylamine hydrochloride solution (Danfix-723, manufactured by Nitto Boseki; free amine molecular weight: 960; solid content 35% by weight)
While stirring. The flask is cooled in an ice bath during the addition and dissolution of the lithium hydroxide monohydrate. Next, an aqueous solution of polyallylamine and lithium chloride is added to the neutralized polygalacturonic acid solution. By dripping 6N hydrochloric acid solution with vigorous stirring,
Adjust the pH of the mixed solution to 10.2. While vigorously flushing the flask with a stream of argon gas, 1.0 g of lithium borohydride is slowly added with vigorous stirring. The reaction flask is sealed with a serum cap vented to an oil bubbler and the reaction mixture is stirred at room temperature for 48 hours. The temperature of the mixture is raised to 40 ° C. using a water bath, and the mixture is stirred for 2 hours to hydrolyze residual lithium borohydride to lithium metaborate and hydrogen. Next, water is removed using a rotary evaporator to obtain an oily solid. The solid is washed several times with 5% triethylamine (by weight) in anhydrous methanol to remove excess polyallylamine. Discard the washings and vacuum dry the remaining solid to constant weight. The obtained dry solid and lithium hydroxide monohydrate aqueous solution (15% by weight)
0 g is added to 300 mL of deionized water with stirring. A slightly cloudy solution is obtained, to which 26 g of lithium carbonate are added. Next, 29 g of isobutyryl chloride is added dropwise while vigorously stirring the resulting mixture. After addition of the organic acid chloride, the mixture is continuously stirred for a further 4 hours. The concentrated hydrochloric acid solution is added slowly while cooling the stirred mixture using an ice bath. At this time, considerable foaming occurs as the excess lithium carbonate is neutralized. The addition of acid is continued until the pH of the mixture reaches a value of 1.5. The acidified mixture is evaporated to dryness using a rotary evaporator. The residue is then washed several times with dichloromethane to remove excess isobutyric acid. Discard the washings and vacuum dry the remaining solid to constant weight. The dried solid is placed in deionized water and the polyuronic acid derivative 40% by weight
To obtain a mixture of The mixture is stirred vigorously for 2-3 hours until the pH of the mixture no longer changes at 8.0.
Dimethylethanolamine is added dropwise. A small amount of undissolved material is removed by filtration. Deionized water is further added to a solution having a solids content of about 25% by weight.

Polyuronic acid derivative H [hexa (N-4-tert-butylbenzoyl) pen
Taethylene hexaamine] -dihydropolygalacturon
Acid polygalacturonic acid 10.0 g and lithium hydroxide monohydrate aqueous solution (15% by weight) 11.0 g were mixed with deionized water 3
Dissolve with stirring into 00 mL. 60 g of pentaethylenehexamine (Aldrich Japan; catalog number: 29,275-3) is added to this solution with stirring. The pH of the mixed solution is adjusted to 10.1 by dropping a 6N hydrochloric acid solution with vigorous stirring. While vigorously flushing the flask with a stream of argon gas, 1.0 g of lithium borohydride is slowly added with vigorous stirring. The reaction flask is sealed with a serum cap vented to an oil bubbler and the reaction mixture is stirred at room temperature for 48 hours. The temperature of the mixture to 40 ° C. using a water bath
And the mixture is stirred for 2 hours to hydrolyze the residual lithium borohydride to form lithium metaborate and hydrogen. Next, water is removed using a rotary evaporator to obtain an oily solid. The solid is washed several times with a 5% solution of N, N-dimethylethanolamine (by weight) in anhydrous methanol to remove excess pentaethylenehexamine. Discard the washings and vacuum dry the remaining solid to constant weight. The resulting dry solid and 0.5 g of aqueous solution of lithium hydroxide monohydrate (15% by weight) are added to 300 mL of deionized water with stirring. A slightly cloudy solution is obtained, to which 17 g of lithium carbonate are added.
The resulting mixture was then stirred vigorously while stirring
17.7 g of tert-butylbenzoyl are added dropwise. After addition of the organic acid chloride, the mixture is continuously stirred for a further 4 hours. The concentrated hydrochloric acid solution is added slowly while cooling the stirred mixture using an ice bath. At this time, considerable foaming occurs as the excess lithium carbonate is neutralized. The addition of acid is continued until the pH of the mixture reaches a value of 1.5. The acidified mixture is evaporated to dryness using a rotary evaporator. Next, the residue is washed several times with toluene to remove excess 4-tert-butylbenzoic acid. Discard the washings and vacuum dry the remaining solid to constant weight. The dried solid is placed in deionized water to give a mixture of 40% by weight of polyuronic acid derivative. PH of the mixture is 8.0
N, N-dimethylethanolamine is added dropwise over 2 to 3 hours with vigorous stirring until no longer changes.
A small amount of undissolved material is removed by filtration. Deionized water is further added to a solution having a solids content of about 25% by weight.

Polyuronic acid derivative I [hexa (N-hydrocinamoyl ) pentaethylenehexene
Saamine] -dihydropolygalacturonic acid 10.0 g of polygalacturonic acid was prepared in the same manner as the above polyuronic acid derivative H, using pentaethylene hexaamine (manufactured by Aldrich Japan; catalog number: 29,275).
-3) for reductive amination. The isolated solid is
Vacuum dry until constant weight. The resulting dry solid and 0.5 g of aqueous solution of lithium hydroxide monohydrate (15% by weight) are added to 300 mL of deionized water with stirring. A slightly cloudy solution was obtained, which contained 17 g of lithium carbonate.
Is added. Next, 15.0 g of chlorinated hydrocinnamic acid is added dropwise while vigorously stirring the resulting mixture. After addition of the organic acid chloride, the mixture is continuously stirred for a further 4 hours. The concentrated hydrochloric acid solution is added slowly while cooling the stirred mixture using an ice bath. At this time, considerable foaming occurs as the excess lithium carbonate is neutralized. The addition of acid is continued until the pH of the mixture reaches a value of 1.5. The acidified mixture is evaporated to dryness using a rotary evaporator. The residue is then washed several times with toluene to remove excess hydrocinnamic acid. Discard the washing solution,
The remaining solid is vacuum dried to constant weight. The dried solid is placed in deionized water to give a mixture of 40% by weight of polyuronic acid derivative. N, N-Dimethylethanolamine is added dropwise over 2-3 hours with vigorous stirring until the pH of the mixture does not change at 8.0. A small amount of undissolved material is removed by filtration. Deionized water is further added to a solution having a solids content of about 25% by weight.

[0083]Returned with polyethyleneimine (MW = 800)
Originally aminated polyguluronic acid [PGA-PE
I ₈₀₀ ] 100.0 g of polyguluronic acid and polyethyleneimine (trade name)
Product name: Lupasol FG; BASF; MW = 800) 3
5.0 g of deionized water in a 1 liter beaker
Dissolved in 300 mL with stirring. Same polyethylene
Add 165.0 g of imine to the solution while stirring
did. Next, a 12N hydrochloric acid solution was added dropwise with vigorous stirring.
To adjust the pH of the mixed solution to 8.95.
Was. Add deionized water to bring the total volume of the solution to 900 mL
After doing so, the solution was left at room temperature for 10 days. 10 days
After standing, the solution was transferred to a 2 liter beaker. Intensify the solution
While stirring vigorously, 5.0 g of sodium borohydride was added.
1.0 g was added to the solution over 5 hours in 5 portions.
The solution was left overnight. Stir solution vigorously again
Then, apply 1.0 g of lithium borohydride five times in 0.2 g increments.
And added over 6 hours. Leave the solution again overnight
did. After transferring the solution to a 3 liter beaker,
330 g of lithium trihydrate are added to the solution with stirring.
Was. After dissolution of sodium acetate trihydrate, methanol 1.
Five liters were added with stirring. Add methanol
The addition resulted in an off-white solid precipitate. This
The mixture was left overnight. Next, 3000 rpm, about
Several batches of centrifugation (100 mL centrifugation) for 20 minutes
The solid was isolated from the mixture by carrying out (tube).
Transfer this solid to a 2 liter beaker and add deionized water
Was added to bring the total volume of the mixture to 1300 mL. this
The mixture was stirred for 6 hours while warming to 50 ° C. and then overnight
I left it. Next, the 12N hydrochloric acid solution was stirred vigorously.
To adjust the pH of the mixture to 0.90
did. This acidification caused the product to precipitate. Solids
Filtration and several times with 70% methanol-containing methanol aqueous solution
Washed. The resulting off-white solid is allowed to dry naturally.
After drying, it was vacuum dried. The dry solid weight was 52 g.
Was.

N, N, N ′, N′-tetrakis (2-A
Minoethyl) ethylene-diamine
Ligururonic acid [PGA-pentene] branched-chain polyethyleneimine, N, N, N ', N'-tetrakis (2-aminoethyl) ethylenediamine (abbreviation: pentene), about 90 g, was added to Wagnon and Ja.
The method of ckels (Inorganic Chemis
try, vol. 89, p. 1924 (1989)). 100g of polyguluronic acid and 40.0 of pentene
g was dissolved in 300 mL of deionized water in a 1 liter beaker with stirring. 48.0 g of penten
Was further added to the solution with stirring. Next, 12N
By adding the hydrochloric acid solution dropwise with vigorous stirring,
The pH of the mixed solution was adjusted to 9.00. After adding deionized water to bring the total volume of the solution to 900 mL, the solution was left at room temperature for 8 days. After standing for 8 days, the solution was transferred to a 2 liter beaker. Subsequent operations are PGA-PEI
The preparation and isolation of ₈₀₀ were performed in the same manner. The weight of the dry solid obtained by this operation was 54 g.

Polyethylene imine (MW = 1,300)
Polyauronic acid [PGA-PEI]
₁₃₀₀ ] polyguluronic acid 100.0 g and polyethyleneimine (trade name: Lupasol G-20 (anhydrous); BASF; MW =
(1,300) was dissolved in 300 mL of deionized water in a 2 L beaker with stirring. 270.0 g of the same polyethyleneimine were further added to the solution with stirring. Next, the pH of the mixed solution was adjusted to 8.95 by dropping a 12N hydrochloric acid solution with vigorous stirring. After addition of the hydrochloric acid solution, the solution was left at room temperature for 10 days. Since the solution was already in a 2 liter beaker, there was no need to transfer the solution before adding the borohydride. Subsequent operations are performed on PGA-PEI ₈₀₀
Preparation and isolation of The weight of the dry solid obtained by this operation was 57 g.

[0086] Starburst (PAMAM) Dend
Polyguluronic acid reductively aminated with limmer [PGA-
Starburst G1] Poly (amidoamine) dendrimer, Starburs
t (trade name) (PAMAM) dendrimer (first generation)
To Aldrich Chemical Company
y, Inc. Was purchased as a 20% by weight methanol solution. The molecular formula of this dendrimer is as follows:
[—CH ₂ N ｛CH ₂ CH ₂ CONHCH ₂ CH ₂ N (CH ₂ N
CH ₂ CONHCH ₂ CH ₂ NH ₂ ) ₂ ｝ ₂ ] ₂ . The methanol was removed using a rotary evaporator to give about 150 g of oily free amine. 100g of polyguluronic acid and St
55.0 g of arburst (trade name) (PAMAM) dendrimer (first generation) was dissolved with stirring in 300 mL of deionized water in a 2 liter beaker. S
92.0 g of tarburst (PAMAM) dendrimer (first generation) was further added to the solution with stirring. Next, the pH of the mixed solution was adjusted to 9.05 by dropwise adding a 12N hydrochloric acid solution with vigorous stirring. Add deionized water to bring the total volume of the solution to 100
After 0 mL, the solution was left at room temperature for 9 days. Since the solution was already in a 2 liter beaker, there was no need to transfer the solution before adding the borohydride. Subsequent operations were carried out in analogy to the preparation and isolation of PGA-PEI _800. The weight of the dry solid obtained by this operation was 53 g.

Polyuronic Acid Derivative J PGA-P Reductively Aminated with Propionaldehyde
_{EI 800 [PGA-PEI 800 -} ( propyl) _x] PGA-PEI ₈₀₀ 40.0g of N, and N- dimethylethanolamine 18.2 g, was added with stirring to deionized water 450mL were placed in a 1-liter flask . 3
The pH of the mixture was adjusted to 6.0 by dropwise addition of a N hydrochloric acid solution. Next, propionaldehyde 30.
0 g was added to the mixture. With vigorous stirring of the mixture, 27.0 g of sodium cyanoborohydride were added.
The mixture was added to the mixture over a period of 18 hours.
Each time 3.0 g of sodium cyanoborohydride is added, the pH of the mixture is adjusted by dropping 3N hydrochloric acid solution.
Was adjusted to 5.5. After the first addition of sodium cyanoborohydride, the mixture emulsified. After all of the sodium cyanoborohydride was added, the mixture was left for 12 hours. The mixture was then cooled with an ice bath while
The hydrochloric acid solution was added dropwise to the stirred mixture placed in a well ventilated fume hood. The addition was continued until the pH of the mixture reached 1.0. The addition of hydrochloric acid precipitated an off-white solid. 1 acidified mixture
After standing for 2 hours, the solid was collected by filtration. Wet solids,
Washed several times with 95% ethanol. This wet solid is
Transferred to a 1 liter flask with 450 mL of deionized water. N, N-dimethylethanolamine was added dropwise to the stirred mixture until the pH of the resulting solution was 9.0. Next, while cooling the solution using an ice bath, a 12N hydrochloric acid solution was added dropwise to the stirred solution until the pH of the solution became 1.0. As before, this acidification resulted in an off-white solid precipitate. This solid is collected by filtration,
Washed several times with 95% ethanol. The solid was air-dried and then dried under vacuum to constant weight. In a 250 mL flask, 30.0 g of this dry solid and 90.0 g of deionized water
g. While stirring the mixture vigorously, N, N-
Dimethylethanolamine was added in small portions. After most of the solids had dissolved, N, N-dimethylethanolamine was added dropwise while simultaneously monitoring the pH of the solution. When the pH of the solution reaches a constant value of 6.0, N, N-
The addition of dimethylethanolamine was stopped. Additional water was added to bring the total solution weight to 136 g. Finally, the resulting solution was filtered through a 3 μm Teflon membrane filter. PGA-PEI ₈₀₀ reductively aminated with polyuronic acid derivative K acetone [P
GA-PEI ₈₀₀ - (isopropyl) _x] PGA-PEI ₈₀₀ 40.0g of N, and N- dimethylethanolamine 18.2 g, was added with stirring to deionized water 450mL were placed into a 1 liter flask. 3
The pH of the mixture was adjusted to 6.0 by dropwise addition of a N hydrochloric acid solution. Next, 30.0 g of acetone was added to the mixture. While the mixture was being vigorously stirred, 27.0 g of sodium cyanoborohydride was added to the mixture over a period of 18 hours in nine 3.0 g portions. Each time 3.0 g of sodium cyanoborohydride was added, the pH of the mixture was adjusted to 5.5 by dropping a 3N hydrochloric acid solution. Shortly after the first addition of sodium cyanoborohydride, the mixture emulsified. After all of the sodium cyanoborohydride was added, the mixture was left for 12 hours. For further operations, PGA-PEI ₈₀₀ - (propyl) _x Isolation and N, was carried out in analogy to the preparation of N- dimethyl ethanol ammonium salt solution (136 g). Finally,
PGA-PEI ₈₀₀ - (isopropyl) _x in N, N- dimethyl ethanol ammonium salt solution and filtered through a 3μm Teflon membrane filter.

Polyuronic Acid Derivative L 2-Aminone and then octanal
PGA-pentene [PGA-pentene- (1-
Methylheptyl ) _x (1-octyl) _y ] 40.0 g of PGA-pentene and 18.2 g of N, N-dimethylethanolamine were added with stirring to 450 mL of deionized water in a 1 liter flask. 3N
The pH of the mixture is adjusted to 6. by dropwise addition of a hydrochloric acid solution.
Adjusted to zero. Next, 2-octanone (purity: 98%)
17.0 g was added to the mixture. A two-phase mixture was obtained in which 2-octanone was in a poorly water-soluble state. While stirring the mixture vigorously, 7.2 g of sodium cyanoborohydride
Was added to the mixture in 4 portions of 1.8 g over 8 hours. Each time 1.8 g of sodium cyanoborohydride was added, the pH of the mixture was adjusted to 5.5 by adding a 3N hydrochloric acid solution dropwise. Shortly after the first addition of sodium cyanoborohydride, the two-phase mixture emulsified.
After addition of all of the sodium cyanoborohydride (7.2 g), the mixture was left for 12 hours. Next, 20.0 g of octanal (purity: 99%) was added to the emulsified mixture. While stirring the mixture vigorously, 5.4 g of sodium cyanoborohydride was divided into three 1.8 g portions, 6 times.
Added to the mixture over time. Each time 1.8 g of sodium cyanoborohydride was added, the pH of the mixture was adjusted to 5.5 by adding a 3N hydrochloric acid solution dropwise. After addition of all of the sodium cyanoborohydride (5.4 g), the mixture was left for 12 hours. Subsequent operations are PGA
-PEI ₈₀₀ - (propyl) Isolation of _x and N, N-
Dimethylethanol ammonium salt aqueous solution (136 g)
Was performed in the same manner as in the preparation of Finally, N, N of PGA-pentene- (1-methylheptyl) _x (1-octyl) _y
-The dimethylethanol ammonium salt solution was filtered through a 3 μm Teflon membrane filter.

Polyuronic acid derivative M PGA-pen reductively aminated with cinnamaldehyde
Ten [PGA-pentene- (cinnamyl) _x ] 40.0 g of PGA-pentene and 18.2 g of N, N-dimethylethanolamine were added with stirring to 450 mL of deionized water in a 1 liter flask. 3N
The pH of the mixture is adjusted to 6. by dropwise addition of a hydrochloric acid solution.
Adjusted to zero. Next, 31.0 g of transcinnamaldehyde (purity: 99%) was added to the mixture. A two-phase mixture was obtained in which cinnamaldehyde was poorly soluble in water.
While the mixture was being vigorously stirred, 12.5 g of sodium cyanoborohydride was added to the mixture in 2.5 g portions in 5 portions over 10 hours. Each time 2.5 g of sodium cyanoborohydride was added, the pH of the mixture was adjusted to 5.5 by dropping a 3N hydrochloric acid solution. Shortly after the first addition of sodium cyanoborohydride, the two-phase mixture emulsified. After all of the sodium cyanoborohydride was added, the mixture was left for 12 hours. For further operations, PGA-PEI ₈₀₀ - (propyl) _x Isolation and N, was carried out in analogy to the preparation of N- dimethyl ethanol ammonium salt solution (136 g). Finally, PG
A solution of A-pentene- (cinnamyl) _x in N, N-dimethylethanol ammonium salt was filtered through a 3 μm Teflon membrane filter.

PGA-PEI reductively aminated with polyuronic acid derivative N- formaldehyde
₁₃₀₀ [PGA-PEI ₁₃₀₀ - (methyl) _n] PGA-PEI ₁₃₀₀ 40.0g of N, and N- dimethylethanolamine 18.2 g, was added with stirring to deionized water 450mL were placed into a 1 liter flask. 3
The pH of the mixture was adjusted to 6.0 by dropwise addition of a N hydrochloric acid solution. Next, 56.0 g of formalin (formaldehyde content: 37%) was added to the mixture.
While the mixture was vigorously stirred, 36.0 g of sodium cyanoborohydride was added to the mixture over 9 hours in 9 portions of 4.0 g. Each time 4.0 g of sodium cyanoborohydride was added, the pH of the mixture was adjusted to 5.5 by dropping a 3N hydrochloric acid solution. After all of the sodium cyanoborohydride has been added, the mixture is
Left for hours. For further operations, PGA-PEI ₈₀₀ -
Isolation of (propyl) _x and preparation of its N, N-dimethylethanol ammonium salt aqueous solution (136 g) were performed in the same manner. Finally, a solution of PGA-PEI _1300- (methyl) _n in N, N-dimethylethanol ammonium salt was filtered through a 3 μm Teflon membrane filter.

[0091]Polyuronic acid derivative O PGA-star reductively aminated with acetaldehyde
Burst G1 [PGA-Starburst G1- (Echi
Le) _n ] 40.0 g of PGA-starburst G1 and N, N-di
Add 18.2 g of methylethanolamine to 1 liter
Add to 450 mL of deionized water in Lasco with stirring
Added. The mixture is added dropwise by dropping a 3N hydrochloric acid solution.
Was adjusted to 6.0. Next, cool the solution to 5 ° C.
15.0 g of toaldehyde were added to the mixture. The mixture
While stirring vigorously, sodium cyanoborohydride 1
8.0 g is divided into six 3.0 g portions and mixed for 12 hours.
Added to the mixture. 2. sodium cyanoborohydride;
Each time 0 g is added, a 3N hydrochloric acid solution is added dropwise.
The pH of the mixture was adjusted to 5.5. Cyano hydrogenated e
After adding all of the sodium iodide, leave the mixture for 12 hours
did. Subsequent operations are PGA-PEI₈₀₀-(Prop.
Le)_xAnd its N, N-dimethylethanol alcohol
Perform the same procedure as in the preparation of the aqueous ammonium salt solution (136 g).
Was. Finally, PGA-starburst G1- (ethyl
Le)_nOf N, N-dimethylethanol ammonium salt
The solution is filtered through a 3 μm Teflon membrane filter
did.

Example 1 The following components were mixed, and this mixture was mixed with glass beads (1.7 mm in diameter) 1.5 times the total weight of this mixture.
With a sand mill (manufactured by Yasukawa Seisakusho). Milling is carried out for 2 hours. Raven 1170 carbon black (manufactured by Columbia Chemicals; CI Pigment Black 7) 5% by weight Polyuronic acid derivative A (solid content 25% by weight) 10% by weight glycerin 15% by weight diethylene glycol 5% by weight triethylene glycol mono-n- Butyl ether 2% by weight Deionized water 63% by weight The glass beads are filtered off with a coarse stainless steel mesh. Next, the undispersed particles are filtered off from the mixture with a 3 micron membrane filter to obtain an ink for inkjet printing.

Example 2 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. Raven 1170 carbon black (manufactured by Columbian Chemicals; CI Pigment Black 7) 5% by weight Polyuronic acid derivative C (solid content 25% by weight) 10% by weight glycerin 12% by weight Diethylene glycol 10% by weight 1-propanol 3% by weight removal 60% by weight ion water

Example 3 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. Special Black 4A (manufactured by Degussa; CI Pigment Black 7) 5% by weight Polyuronic acid derivative B (solid content 25% by weight) 10% by weight Glycerin 15% by weight 1,5-pentanediol 4% by weight Diethylene glycol 4% by weight tert -Amyl alcohol 1% by weight Deionized water 61% by weight

Example 4 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. Special Black 4A (manufactured by Degussa; CI Pigment Black 7) 5% by weight Polyuronic acid derivative D (solid content 25% by weight) 10% by weight Diethylene glycol 20% by weight 2-pyrrolidone 4% by weight Deionized water 61% by weight

Example 5 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. Shimla First Yellow 4191N (Dainippon Ink & Chemicals, Inc .; CI Pigment Yellow 74) 2% by weight Polyuronic acid derivative C (solid content 25% by weight) 4% by weight Glycerol 15% by weight Diethylene glycol 10% by weight Ethanol 3% by weight 66% by weight of deionized water

Example 6 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. FIRSTGEN S (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Green 7) 2.5% by weight Polyuronic acid derivative D (solid content 25% by weight) 5% by weight Diethylene glycol 20% by weight 2-propanol 3.5% by weight % Deionized water 69% by weight

Example 7 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. Shimla brilliant carmine (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Red 57: 1) 2% by weight Polyuronic acid derivative A (solid content 25% by weight) 4% by weight Glycerol 15% by weight 1,4-butanediol 5 Weight% diethylene glycol mono-n-butyl ether 1.5 weight% deionized water 72.5 weight%

Example 8 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. 3% by weight of polyuronic acid derivative B (solid content: 25% by weight) 6% by weight of diurethane glycol 18% by weight 1-propanol 4% by weight 69% by weight of deionized water

Example 9 The following components were mixed, and the mixture was dispersed by a sand mill (manufactured by Yasukawa Seisakusho) containing glass beads (1.7 mm in diameter) 1.5 times the total weight of the mixture. Milling is carried out for 2 hours. Raven 1170 carbon black (manufactured by Columbian Chemicals; CI Pigment Black 7) 4% by weight Polyuronic acid derivative E (solid content 25% by weight) 8% by weight glycerol 15% by weight Diethylene glycol 5% by weight Deionized water 68% by weight Fine After crushing, the glass beads are filtered off with a coarse stainless mesh. Transfer 97 parts of the resulting mixture to a beaker and dilute with 3 parts of 1-propanol. The dilution is stirred for 2 hours. Next, the undispersed particles are removed from the mixture with a 3 micron membrane filter to obtain an ink suitable for inkjet printing.

Example 10 The components shown below were mixed, and the mixture was dispersed using a sand mill described in Example 9. Post-milling treatment is performed as in Example 9 to obtain an ink suitable for inkjet printing. Raven 1170 carbon black (manufactured by Columbian Chemicals; CI Pigment Black 7) 4% by weight Polyuronic acid derivative F (solid content 25% by weight) 8% by weight Glycerol 15% by weight Diethylene glycol 5% by weight Deionized water 68% by weight

Example 11 The components shown below were mixed, and the mixture was dispersed using a sand mill described in Example 9. Post-milling treatment is performed as in Example 9 to obtain an ink suitable for inkjet printing. Raven 1170 carbon black (manufactured by Columbian Chemicals; CI Pigment Black 7) 4% by weight Polyuronic acid derivative G (solid content 25% by weight) 8% by weight Glycerol 15% by weight Diethylene glycol 5% by weight Deionized water 68% by weight

Example 12 The components shown below were mixed, and the mixture was dispersed using a sand mill described in Example 9. Post-milling treatment is performed as in Example 9 to obtain an ink suitable for inkjet printing. Raven 1170 carbon black (manufactured by Columbian Chemicals; CI Pigment Black 7) 4% by weight Polyuronic acid derivative H (solid content 25% by weight) 8% by weight Glycerol 15% by weight Diethylene glycol 5% by weight Deionized water 68% by weight

Example 13 The components shown below are mixed, and the mixture is dispersed by a sand mill described in Example 9. Post-milling treatment is performed as in Example 9 to obtain an ink suitable for inkjet printing. Raven 1170 carbon black (manufactured by Columbian Chemicals; CI Pigment Black 7) 4% by weight Polyuronic acid derivative I (solid content 25% by weight) 8% by weight Glycerol 15% by weight Diethylene glycol 5% by weight Deionized water 68% by weight

Example 14 The components shown below were mixed, and the mixture was dispersed using a sand mill described in Example 9. Shimla brilliant carmine (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Red 57: 1) 2% by weight Polyuronic acid derivative G (solid content 25% by weight) 4% by weight Glycerol 15% by weight 1,4-butanediol 5 % By weight Deionized water 74% by weight After fine grinding, the glass beads are filtered off with a coarse stainless steel mesh. Transfer 97 parts of the resulting mixture to a beaker and dilute with 3 parts of ethanol. Stir the dilution for 2 hours. next,
Undispersed particles are removed from the mixture by a 3 micron membrane filter to obtain an ink suitable for inkjet printing.

Example 15 The following components were mixed, and the mixture was dispersed using a sand mill described in Example 9. Fast Gen Blue GNPR (Dainippon Ink & Chemicals, Inc .; CI Pigment Blue 15: 3) 3% by weight Polyuronic acid derivative F (solid content 25% by weight) 6% by weight Glycerol 15% by weight Diethylene glycol 5% by weight Water 71% by weight After fine grinding, the glass beads are filtered off with a coarse stainless steel mesh. Transfer 97 parts of the resulting mixture to a beaker and dilute with 3 parts of 2-propanol. Stir the dilution for 2 hours.
Next, the undispersed particles are removed from the mixture by a 3 micron membrane filter to obtain an ink suitable for inkjet printing.

Example 16 The following components were mixed, and the mixture was dispersed using a sand mill described in Example 9. Fast Gen Blue GNPR (manufactured by Dainippon Ink and Chemicals, Inc .; CI Pigment Blue 15: 3) 3% by weight Polyuronic acid derivative E (solid content 25% by weight) 6% by weight Glycerol 12% by weight Diethylene glycol 8% by weight Deionization Water 71% by weight After fine grinding, the glass beads are filtered off with a coarse stainless steel mesh. Transfer 97 parts of the resulting mixture to a beaker and dilute with 3 parts of 1-propanol. Stir the dilution for 2 hours.
Next, the undispersed particles are filtered from the mixture through a 3 micron membrane filter to obtain an ink suitable for ink jet printing.

Example 17 The following components were mixed, and the mixture was dispersed using a sand mill described in Example 9. Example 16 after fine grinding
To obtain an ink suitable for inkjet printing. Shimla First Yellow 4191N (Dainippon Ink & Chemicals, Inc .; CI Pigment Yellow 74) 2% by weight Polyuronic acid derivative H (solid content 25% by weight) 4% by weight Glycerol 13% by weight Diethylene glycol 8% by weight Deionized water 73 weight%

Example 18 The following components were mixed, and the mixture was dispersed using a sand mill described in Example 9. Example 14 after fine grinding
To obtain an ink suitable for inkjet printing. Shimla First Yellow 4191N (Dainippon Ink & Chemicals, Inc .; CI Pigment Yellow 74) 2% by weight Polyuronic acid derivative I (solid content 25% by weight) 4% by weight Glycerol 13% by weight Diethylene glycol 8% by weight Deionized water 73 weight%

Example 19 The following components were mixed, and the mixture was mixed with Eiger Mo.
tormill M250 VSE-EXJ (Eige
r Japan, Tokyo, Japan). Glass beads (diameter: 1.0 mm) (total volume 175 mL)
Was used as the finely ground media. Milling 4000
Performed at rpm for 4 hours. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38 g polyuronic acid derivative J (solid content 22% by weight) 130 g deionized water 82 g After finely pulverizing, 100 g of the dispersion was transferred to a beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Example 20 The following ingredients were mixed, and the mixture was mixed with the Eiger Motormill M250 VSE described in Example 19.
-Dispersed by EXJ. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38 g Polyuronic acid derivative K (solid content 22% by weight) 130 g Deionized water 82 g After finely pulverizing, 100 g of the dispersion was transferred to a beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Example 21 The following ingredients were mixed, and the mixture was mixed with the Eiger Motormill M250 VSE described in Example 19.
-Dispersed by EXJ. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38 g Polyuronic acid derivative L (solid content 22% by weight) 130 g Deionized water 82 g After finely pulverizing, 100 g of the dispersion was transferred to a beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Example 22 The following ingredients were mixed, and the mixture was mixed with the Eiger Motormill M250 VSE described in Example 19.
-Dispersed by EXJ. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38 g polyuronic acid derivative M (solid content 22% by weight) 130 g deionized water 82 g After finely pulverizing, 100 g of the dispersion was transferred to a beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Example 23 The following ingredients were mixed, and the mixture was mixed with the Eiger Motormill M250 VSE described in Example 19.
-Dispersed by EXJ. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38 g polyuronic acid derivative N (solid content 22% by weight) 130 g deionized water 82 g After finely pulverizing, 100 g of the dispersion was transferred to a beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Example 24 The following ingredients were mixed, and the mixture was mixed with the Eiger Motormill M250 VSE described in Example 19.
-Dispersed by EXJ. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38 g polyuronic acid derivative O (solid content 22% by weight) 130 g deionized water 82 g After finely pulverizing, 100 g of the dispersion was transferred to a beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Comparative Example 1 The components shown below were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The treatment after the pulverization is also performed in the same manner as in Example 1 to obtain an ink suitable for inkjet printing. Raven 1170 carbon black (manufactured by Columbia Chemicals; CI Pigment Black 7) 5% by weight Joncryl 62 (manufactured by SC Johnson Polymer; acrylic resin solution; solids content 34% by weight) 12% by weight glycerin 15% by weight diethylene glycol 5% by weight 1-propanol 3% by weight Deionized water 60% by weight

Comparative Example 2 The following components were mixed, and the mixture was dispersed in the same sand mill as in Example 1. The polymer dispersant used in this example was a methyl methacrylate // methyl methacrylate / methacrylic acid block copolymer (MMA // M) prepared by the method described in US Pat.
MA / MA). The block copolymer is converted to N, N-
Neutralize with dimethylethanolamine and solids 25
Dilute to obtain a weight percent solution. Raven 1170 Carbon Black (manufactured by Columbia Chemicals; CI Pigment Black 7) 20% by weight MMA // MMA / MA block copolymer (see above; solids content 25% by weight) 40% by weight Diethylene glycol 14% by weight deionized water 26 The weight% glass beads are filtered off with a coarse stainless steel mesh.
One part of the dispersion is transferred to a beaker and diluted with 3 parts of a 20% by weight aqueous diethylene glycol solution. The resulting mixture is
Stir for 2 hours. Next, the ink for ink-jet printing is obtained by filtering off the undispersed particles from the mixture with a 3-micron membrane filter.

Comparative Example 3 The components shown below were mixed, and the mixture was mixed with the Eiger Motormill M250 VSE described in Example 19.
-Dispersed by EXJ. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38 g Joncryl 62 (SC Johnson Polymer; acrylic resin solution; solid content 34% by weight) 84 g deionized water 128 g , Transferred to beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Comparative Example 4 The following components were mixed, and the mixture was mixed with the Eiger Motormill M250 VSE described in Example 19.
-Dispersed by EXJ. The polymer dispersion used in this example was butyl methacrylate / methacrylic acid prepared by the method of Preparation Example 3 described in U.S. Pat. No. 5,085,698, except that n-butyl methacrylate was removed from Feed II. Block copolymer (BMA / MA;
(10/10). This block copolymer is
Neutralized with N, N-dimethylethanolamine, diluted according to the method of method A of the patent, and solid content 25% by weight, p
A solution of H8.4 was obtained. FW18 (carbon black pigment; manufactured by Degussa; CI Pigment Black 7) 38.0 g BMA / MA block copolymer (solid content 25% by weight) 110.5 g deionized water 101.5 g , Transferred to beaker. The following components were added sequentially with stirring. Glycerol 30.0 g 2-Pyrrolidone 15.0 g Diethylene glycol mono-n-butyl ether 20.0 g Surfynol 465 2.5 g Deionized water 82.5 g The resulting mixture was stirred for 2 hours. Next, the mixture is
Filtration through a 3 μm membrane filter provided an ink suitable for inkjet printing.

Continuous Printing Test The reliability of the above ink under continuous printing conditions is evaluated as follows. First, the ink is defoamed and sealed in a heat-sealable aluminum pack. Next, apply the ink to MJ-80.
It is loaded into a print head of a 0C printer (manufactured by Seiko Epson Corporation). First, a line pattern using all of the nozzles is printed so that ink is ejected from all of the nozzles in a favorable direction. The printing pattern is changed to one having intermittent solid blocks and line patterns ejected from all nozzles. The combination pattern is continuously printed on the entire surface of A4 size paper. For every 100 printed sheets, flight skew, clogged nozzles, and reduced solid block optical density (less than 5%)
Evaluate for For all of the tested inks except Comparative Example 1, no flying skew, nozzle clogging, and reduced optical density are expected to be observed for the 10,000 printed sheets. With respect to Comparative Example 1, it is expected that a flight bend will occur when less than 5000 sheets are used. Further, in Examples 19 to 24, 1
No skew or nozzle clogging was observed up to 000 sheets of paper. On the other hand, in Examples 3 and 4, flight bending occurred when less than 5000 sheets were used.

Intermittent Printing Test The reliability of the above ink under intermittent printing conditions is evaluated as follows. First, the ink is defoamed and sealed in a heat-sealable aluminum pack. Next, the ink was applied to MJ-
Load the print head of the 800C printer. A line pattern that uses all of the nozzles is printed first so that ink is ejected from all of the nozzles in a favorable direction. After one drop of ink is sequentially discharged from each nozzle, the print pattern is changed to a print pattern in which the print head is not capped and a pause time during which no ink is discharged is provided. This pattern, in which one dot is ejected from all the nozzles and then becomes a pause time, is continuously repeated while increasing the length of the pause time in units of 5 seconds. For example, the first pause time is 5
Seconds, second pause 10 seconds, third pause 1
Do it for 5 seconds. The time interval of the downtime in which the nozzle first causes a discharge failure is recorded. For all tested inks except Comparative Example 1, the minimum time interval before the first nozzle failure occurs is expected to be greater than 90 seconds. For Comparative Example 1, the minimum time interval before a discharge failure is expected to be less than 60 seconds.

Long-term storage test The reliability of the ink for long-term storage in a print head is evaluated as follows. First, the ink is defoamed and sealed in a heat-sealable aluminum pack. Next, the ink is loaded into the print head of the MJ-800C printer. First, a line pattern using all of the nozzles is printed so that ink is ejected from all of the nozzles in a favorable direction. Next, the ink supply source is disconnected from the print head, and the print head is removed from the printer. The print head is stored without capping in a constant temperature oven at 40 ° C. for 7 days. Reattach the printhead to the printer and reattach the ink supply to the printhead. After performing the cleaning operation of the printer, a line pattern using all of the nozzles is printed. The cleaning operation and the subsequent printing of the line pattern are repeated until all the nozzles can be printed in a good direction (no flight bending), and the number of cleanings until all the nozzles recover is recorded. For all of the tested inks except Comparative Example 1, the number of cleanings required to fully recover is expected to be 3 or less. For Comparative Example 1, it is expected that complete recovery of all nozzles will not be achieved even after performing the cleaning operation 10 times. In Examples 19 to 24 and Comparative Examples 3 and 4, MJ-510 was used as a printer.
Using C (manufactured by Seiko Epson Corporation), the ink composition was filled in a cartridge dedicated to MJ-510C, and the evaluation was performed in the same manner as above except that the cartridge of the ink supply source was not removed from the print head. As a result, in Examples 19 to 24, the number of times of cleaning until completely returning was 3 or less. On the other hand, Comparative Examples 3 and 4
Regarding the above, complete recovery of all nozzles was not achieved even after performing the cleaning operation 10 times.

Heat cycle test Two extreme temperatures of the above ink (-30 ° C and 60 ° C)
Is evaluated as follows. First, the ink is degassed and sealed in a 30 mL glass sample bottle. 60 sample bottles
It puts it in a constant temperature oven of ° C, and preserve | saves for 24 hours under this temperature condition. The sample is taken out of the oven, transferred to a constant temperature freezer at −30 ° C., and stored at this temperature condition for 24 hours. This two temperature cycle is repeated until a total of 10 cycles are completed. After the last cycle, the ink is thawed to room temperature and the glass vial is inverted without shaking to check for deposits at the bottom of the vial. No precipitate is expected to be observed for all of the tested inks except Comparative Example 1. It is expected that a precipitate is observed in Comparative Example 1. In Examples 19 to 24, no precipitate was actually observed. On the other hand, precipitates were observed in Comparative Examples 3 and 4.

Drying time test A solid block pattern was printed, and the printed pattern was
The drying time of the ink is evaluated by wiping at intervals of 0 second while increasing the interval. Printing is performed using an MJ-800C printer, and the recording paper is recorded using Xerox 4024 paper to record the time during which the printed ink is not stained. Drying time for all tested inks is 3
Expected to be less than 0 seconds.

Print Quality Test The print quality was measured using an MJ-800C printer for the ink compositions of Examples 1 to 18 and Comparative Examples 1 and 2, and MJ-930C for Examples 19 to 24 and Comparative Examples 3 and 4. (Manufactured by Seiko Epson Corporation) is evaluated as follows. Standard kanji in 4 point character size using Gothic and Mincho, and 720 characters
Print at dpi. Four types of plain paper are used as recording paper, namely, Xerox 4024, Xerox R, Yamayuri, and Conqueror Laid. The print sample is observed using an optical microscope, and the print quality is evaluated according to the following criteria. Evaluation A: Kanji is clear and there is no ink in the internal space in the character. Evaluation B: The kanji is clear, but in the kanji having more than about 15 strokes, some ink enters the internal space. Evaluation NG: The kanji is not clear, and in the kanji having more than about 10 strokes, remarkable ink penetration into the internal space is observed. The results of the print quality test are expected as shown in Table 1 below. Examples 19 to 24 and Comparative Examples 3 and 4
Is an actual experimental result.

[0126]

[Table 1]

Claims (23)

(57) [Claims] 1. A pigment-dispersed aqueous ink composition, comprising: (a) water as a main solvent; (b) a pigment; and (c) a polyuronic acid having a hydrophobic polymer covalently bonded to a reducing end of polyuronic acid. And an acid derivative;
Ink composition. 2. The ink composition according to claim 1, wherein the polyuronic acid is mainly composed of 1,4-bonded polygalacturonic acid, polyguluronic acid, polyiduronic acid, or a mixed polymer thereof. 3. The hydrophobic polymer according to claim 1, wherein the hydrophobic polymer is at least one selected from the group consisting of styrene or a styrene derivative, vinylpyridine or a vinylpyridine derivative, methacrylate, acrylate, acrylonitrile, methacrylonitrile, butadiene, and isoprene. The ink composition according to claim 1, wherein the ink composition is a homopolymer or a copolymer manufactured from the following. 4. The ink composition according to claim 1, wherein the hydrophobic polymer contains poly (dialkylsiloxane) as a main component. 5. The ink composition according to claim 1, wherein the hydrophobic polymer is a polyamide. 6. The polyamide as claimed in claim 1, wherein the polyamide is an N-acylated derivative of a polyamine, the polyamide having an amine functionality of 50%.
% Or more is a primary or secondary amine.
3. The ink composition according to claim 1. 7. The polyamine of claim 6, wherein the polyamine providing the polyamide is selected from the group consisting of linear polyethyleneimine, branched polyethyleneimine, polyallylamine, poly-N-alkylallylamine, and polyvinylamine. The ink composition as described in the above. 8. The acyl group R- (CO)-of the polyamide.
_{There, C n H (2n + 1} ) - (CO) - ( wherein, n is 3 or more); phenyl - (CO) -; substituted phenyl - (CO)
-; Phenyl-CH _2- (CO)-; substituted phenyl-C
H ₂ - (CO) -; _{phenyl--C 2 H 4 - (CO)} -; and substituted phenyl _{-C 2 H 4 - (CO)} - is selected from the group consisting of claims 5-7 The ink composition according to claim 1. 9. The ink composition according to claim 1, wherein the hydrophobic polymer is a hydrophobic polyamine. 10. The ink composition according to claim 9, wherein said hydrophobic polyamine is a poly-N-alkylated derivative of a water-soluble polyamine. 11. The method of claim 10, wherein said water-soluble polyamine is selected from the group consisting of polyethyleneimine, polyallylamine, polyvinylamine, poly (propyleneimine) dendrimer, and poly (amidoamine) dendrimer. Ink composition. 12. An aqueous carrier medium comprising 0.1 to 10% by weight of a pigment, 0.1 to 20% by weight of a polyuronic acid derivative.
The ink composition according to any one of claims 1 to 11, wherein the ink composition comprises from 9 to 99.8% by weight. 13. The ink composition according to claim 1, wherein the polyuronic acid moiety has a number average molecular weight of 700 or more. 14. The ink composition according to claim 1, wherein the number average molecular weight of the hydrophobic polymer portion is 300 or more. 15. The polyuronic acid moiety is neutralized with a neutralizing agent selected from the group consisting of organic bases, alkanolamines, alkali metal hydroxides, and mixtures thereof. 15. The ink composition according to any one of 14. 16. An ink jet recording method comprising:
The ink composition according to claim 1. 17. A recording method for printing on a recording medium by attaching an ink composition, wherein the ink composition according to claim 1 is used as the ink composition. 18. An ink jet recording method for discharging ink droplets of an ink composition and attaching the liquid droplets to a recording medium to perform printing, wherein the ink composition is any one of claims 1 to 15. An ink jet recording method using the ink composition described in the above. 19. A recorded matter recorded by the recording method according to claim 17. 20. A polyuronic acid derivative comprising a hydrophobic polymer covalently bonded to the reducing end of polyuronic acid. 21. The polyuronic acid derivative according to claim 20, wherein the number average molecular weight of the polyuronic acid moiety is 700 or more. 22. The polyuronic acid derivative according to claim 20, wherein the number average molecular weight of the hydrophobic polymer portion is 300 or more. 23. A dispersant comprising the polyuronic acid derivative according to claim 20.