JP2001048934A - Agent for imparting water resistance, ink composition and reaction liquid and method for ink jet recording with two liquids - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water resistance-imparting agent which can realize images which scarcely blot and have excellent water resistance, when added to an ink composition, by including a cationic water-soluble resin having a specific structure. SOLUTION: This water resistance-imparting agent contains a cationic water- soluble resin comprising a (co)polymer which comprises repeating units of formula I (R1 is H or methyl; R2 and R3 are each a 1 to 3C alkyl in an amount of 100 to 0 mol.% and repeating units of formula II [R4 is H or methyl; R5 to R7 are each a 1 to 3C alkyl; Z-is a counter ion; (k) and (l) are each 1, 2 or 3] and contains a carboxyl group at one of molecular terminals and an aromatic ring at the other. The agent for imparting water resistance preferably has a number-average mol.wt. of 1,000 to 10,000 by gel permeation chromatography, and is preferably added to an ink composition in an amount of 0.2 to 20 wt.%. When added to a reaction liquid for an ink jet recording method, images having high color concentrations and reduced printing irregularity can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-resistance imparting agent which is a cationic water-soluble resin having a specific structure, an ink composition and a reaction liquid containing the same, and an ink jet recording method using the same.

2. Description of the Related Art It is important that printed images obtained by using ink compositions have good water resistance and light fastness and can realize images with less bleeding.

In order to realize good water resistance, a combination of a cationic resin and an anionic dye has conventionally been used as exemplified below.

[0004] For example, Japanese Patent Application Laid-Open No. Sho 62-119280 discloses an ink comprising a hydroxyethylated polyethyleneimine polymer and a dye component, and it is stated that such a combination exhibits water resistance. Japanese Patent Publication No. Hei 7-91494 discloses an ink comprising a hydroxyalkylated polyallylamine polymer and a dye, and it is stated that this combination exhibits water resistance. However, in the two inks described above, since the polymer used contains a hydroxyalkyl group having high hydrophilicity, further improvement is required in terms of securing sufficient water resistance of an image.

Further, JP-A-2-255876, JP-A-2-296778, and JP-A-3-188174 each disclose a polyamine having a primary amino group having a molecular weight of 300 or more, an anionic dye, and a stabilizing agent. An ink composition comprising an agent is disclosed. Here, it is stated that the combination of a primary amino group and an anionic dye exhibits water resistance. However, the resins used in these publications have a strong attack on the dye. For example, when the ink is left at a high temperature, the dye is decomposed, or the photodecomposition of the printed matter is promoted, and the light resistance is higher than that of the dye alone. The present inventors have confirmed that the concentration may be reduced.

Further, JP-A-7-305011 discloses an aqueous ink comprising a basic water-soluble polymer, an anionic dye having a volatile base as a counter ion, and a buffer having a volatile base as a counter ion. Is disclosed. It is said that the volatile base suppresses the dissociation of the polymer in the ink, and on paper, the volatile base is evaporated to promote a salt-forming reaction between the polymer and the dye, thereby obtaining water resistance.

JP-A-62-238873 discloses an ink jet recording paper containing a homopolymer of diallylamine and monoallylamine or a copolymer of both. On this recording medium,
It is said that an insolubilization reaction between the polymer and the dye occurs to obtain water resistance. However, in the recording method using a recording medium containing a cationic resin disclosed in this publication, the ink does not have water resistance in the first place, and therefore, when other recording medium is used, the image does not exhibit water resistance.

[0008] The ink jet recording method is a printing method in which droplets of an ink composition are made to fly and adhere to a recording medium such as paper to perform printing. This method has a feature that high-resolution and high-quality images can be printed at a high speed with a relatively inexpensive device. In general, an ink composition used for ink jet recording contains water as a main component, and further contains a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.

On the other hand, as an ink jet recording method, a method has recently been proposed in which a polyvalent metal salt solution is applied to a recording medium and then an ink composition containing a dye having at least one carboxyl group is applied ( For example, JP-A-5-202328). In this method,
It is stated that an insoluble complex is formed from the polyvalent metal ion and the dye, and the presence of this complex makes it possible to obtain a high-quality image having water resistance and no color bleed.

[0010] Further, by using a color ink containing at least a surfactant or a penetrating solvent for imparting permeability and a salt, and a black ink which thickens or aggregates by the action of the salt, an image is formed. It has been proposed that a high-quality color image having a high density and no color bleed can be obtained (Japanese Patent Laid-Open No. 6-10673).
No. 5). That is, an ink jet recording method has been proposed in which a good image can be obtained by printing two liquids of a first liquid containing a salt and an ink composition.

In addition, an ink jet recording method for printing two liquids has been proposed (for example, Japanese Patent Application Laid-Open No.
240557, JP-A-3-240558).

[0012]

SUMMARY OF THE INVENTION The present inventors have recently proposed a cationic aqueous solution having a specific structure in an ink composition and a reaction liquid used in an ink jet recording method for adhering two liquids of the ink composition and the reaction liquid to a recording medium. It has been found that by adding a resin, a good image, in particular, an image excellent in water resistance and light resistance and with little bleeding can be realized. The present invention is based on this finding.

Accordingly, the present invention relates to an ink composition which is excellent in water resistance and light resistance and can form an image with little bleeding, and an ink jet recording method for adhering two liquids of an ink composition and a reaction liquid to a recording medium. It is an object of the present invention to provide a water resistance imparting agent for realizing a reaction solution to be used.

Another object of the present invention is to provide an ink composition which is excellent in water resistance and light resistance and can realize an image with less blur.

Further, the present invention is excellent in water resistance and light resistance,
It is an object of the present invention to provide a reaction liquid used in an ink jet recording method using two liquids and an ink jet recording method using the same, which can realize an image with less bleeding, particularly, less color bleed.

According to a first aspect of the present invention, there is provided a water resistance imparting agent, wherein the water resistance imparting agent comprises a repeating unit represented by the following formula (I): A (co) polymer with a) and a repeating unit (b) represented by the formula (b), comprising the unit (a) in the range of 100 to 0 mol%, and one end group of a molecule. Is a group containing a carboxyl group, and the other terminal group is a group containing an aromatic ring, and comprises a cationic water-soluble resin made of a (co) polymer.

Embedded image (In the above formula, R ₁ represents a hydrogen atom or a methyl group;
R ₂ and R ₃ may be the same or different and C _1-3
It represents an alkyl group, R ₄ represents a hydrogen atom or a methyl group, R _5, R _6, and R _7, which may be the same or different, represent a C _1-3 alkyl group, Z ^- is a counter Represents an ion, and k and l may be the same or different and represent 1, 2, or 3. Also, according to a second aspect of the present invention, there is provided an ink composition, the ink composition comprising at least a cationic water-soluble resin as defined above.

Further, according to a third aspect of the present invention, there is provided a reaction liquid used in an ink jet recording method for performing printing by adhering a reaction liquid and an ink composition to a recording medium, wherein the reaction liquid is as described above. It comprises at least a defined cationic water-soluble resin.

Further, according to a fourth aspect of the present invention, there is provided an ink jet recording method, wherein the ink jet recording method performs printing by adhering an ink composition and a reaction liquid to a recording medium. In a method, the reaction solution comprises a water-resistance imparting agent which is a cationic water-soluble resin having the above specific structure.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The water-resistance imparting agent represented by the formula (I) which is a cationic water-soluble resin having a specific structure according to the present invention (hereinafter referred to as "water-resistance imparting agent") is as described above. A repeating unit (a) represented by the formula (a) in the formula (I)
And a (co) polymer of the repeating unit (b) represented by the formula (b), wherein the unit (a) is contained in the range of 100 to 0 mol%, and one terminal group of the molecule is a carboxyl group. And the other terminal group is a group containing an aromatic ring. In the present invention, the “water resistance imparting agent” refers to an additive that is added to a solution requiring water resistance in a dry state and that imparts at least water resistance to a dried product of the solution. A preferred specific example is an additive which is added to the ink composition to impart at least water resistance to an image obtained by the ink composition. Is an additive that imparts at least water resistance to the obtained image by being added to a reaction solution used in an ink jet recording method of performing printing by adhering to a recording medium.

According to the ink composition of the present invention to which the water resistance imparting agent is added, an image having less bleeding and excellent water resistance can be realized. In addition, as a result of the colorant being fixed to the recording medium satisfactorily, a remarkable effect that an image with less bleeding can be realized is obtained.

When the reaction liquid containing the water resistance imparting agent according to the present invention is brought into contact with the ink composition, the reaction liquid dissolves the colorant in the ink composition, the resin emulsion optionally contained below, and other components. And / or disrupt the dispersed state and cause it to aggregate. Therefore, by adding this water resistance imparting agent to the reaction liquid in a so-called two-liquid inkjet recording method, these aggregates suppress the penetration of the colorant into the recording medium, and as a result,
It is considered that an image with high color density, less blur, and less printing unevenness is realized. Further, in a color image, there is an advantage that uneven color mixing in a boundary region of different colors, that is, color bleeding can be effectively prevented.

In the water-resistance imparting agent represented by the formula (I) used in the present invention, R ₁ and R ₄ may be the same or different and represent a hydrogen atom or a methyl group. Also R
₂ , R ₃ , R ₅ , R ₆ and R ₇ may be the same or different and represent a C _1-3 alkyl group, preferably a methyl group. Most preferably, R ₁ represents a hydrogen atom, R ₂ represents a methyl group, R ₃ represents a methyl group, R ₄ represents a hydrogen atom, R ₅ represents a methyl group, and R ₆ represents a methyl group. Represents, R ₇
Is a combination representing a methyl group.

[0023] In addition, Z ^- represents a counter ion,
Preferably Z represents a halogen atom, ie, a fluorine, chlorine, bromine or iodine atom, more preferably a chlorine atom.

In the formula (I), k and l are 1, 2,
Or, it represents 3, but preferably represents 3.

Examples of the terminal group containing a carboxyl group include groups represented by the following formulas (II) to (V).

Embedded image Examples of the terminal group containing an aromatic ring include the following formula (VI)
To (XVII).

Embedded image When added to the ink composition according to the second aspect of the present invention, the unit (a) in formula (I) is 100 to 8
0 mol%, preferably 100 to 90 mo
1%, more preferably 100-95 mol
% Range. In addition, the existence form of these two repeating units may be a block or a random form.

When added to the reaction solution according to the third aspect of the present invention, in formula (I), the unit (a) is 10 units.
0 to 0 mol%, preferably 80 to 0 mol.
1%, more preferably 45 to 0 mol%. In addition, the existence form of these two repeating units may be a block or a random form.

Further, according to a preferred embodiment of the present invention,
The number average molecular weight of the water resistance imparting agent is a value determined by gel permeation chromatography (hereinafter abbreviated as GPC), and is preferably in the range of about 1,000 to 10,000.

Ink Composition The ink composition according to the second embodiment of the present invention is used in a recording method 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 recording methods. In particular, the ink composition according to the present invention is preferably used for an ink jet recording method.

The ink composition according to the present invention basically comprises
An alkali-soluble coloring agent, a water-soluble organic solvent, and water,
A water-resistance imparting agent which is a cationic water-soluble resin having a specific structure represented by the above formula (I). As described above, according to the ink composition of the present invention to which the above is added, an image with less bleeding and excellent water resistance can be realized. In addition, as a result of the colorant being fixed to the recording medium satisfactorily, a remarkable effect that an image with less bleeding can be realized is obtained.

The amount of the water resistance-imparting agent represented by the above formula (I) may be appropriately determined within the range where the above effects can be obtained, but is preferably about 0.2 to 20% by weight based on the ink composition. And more preferably about 0.5 to 10% by weight. More preferably, it is about 0.5 to 5% by weight.

The alkali-soluble coloring agent contained in the ink composition according to the present invention may be a dye or a pigment. Here, alkali-soluble means that the compound is dissolved in an alkaline medium, and the water-soluble group contained in the molecule is an acidic or basic dissociable group, or a non-dissociable functional group, and a plurality of such groups are used. May be included. Further, a coloring agent that dissolves in an acidic solution may be used as long as it dissolves in an alkali.

The amount of the colorant may be determined as appropriate,
For example, 0.5 to 20% by weight based on the total weight of the ink composition
It is preferable to add in the range of. This is because a print image having a sufficient optical density can be realized in this range, and the viscosity can be easily adjusted to a value suitable for the ink jet recording method.

[0033] The colorant is more preferably selected from organic dyes or organic pigments. These are suitable because they have high color density per weight and vivid colors.

Dyes are organic colored substances that dissolve in water, and are acidic dyes, direct dyes,
Those that are classified as reactive dyes, soluble vat dyes, or food dyes are useful. In addition, colorants classified as oil-soluble dyes and basic dyes in the color index can be used as long as they are insoluble in neutral water but soluble in alkaline water.

The pigment may be selected from those generally classified as pigments in the color index. Pigments are generally organic colored substances that are insoluble in water, but some are alkali-soluble and can be used.

Examples of dyes and pigments include, for example, C.I. I. Acid Yellow 1, 3, 11, 17,
19, 23, 25, 29, 36, 38, 40, 42, 4
4, 49, 59, 61, 70, 72, 75, 76, 7
8, 79, 98, 99, 110, 111, 127, 13
1, 135, 142, 162, 164, 165, C.I.
I. Direct Yellow 1, 8, 11, 12, 24, 2
6, 27, 33, 39, 44, 50, 55, 58, 8
5, 86, 87, 88, 89, 98, 110, 132,
142, 144, C.I. I. Reactive Yellow 1,
2, 3, 4, 6, 7, 11, 12, 13, 14, 15,
16, 17, 18, 22, 23, 24, 25, 26, 2,
7, 37, 42, C.I. I. Food yellow 3, 4, C.I.
I. Solvent Yellow 15, 19, 21, 30, 10
9, C.I. I. Pigment Yellow 23 and the like.
Further, as a reddish color, C.I. I. Acid Red 1, 6,
8, 9, 13, 14, 18, 26, 27, 32, 35,
37, 42, 51, 52, 57, 75, 77, 80, 8
2, 85, 87, 88, 89, 92, 94, 97, 10
6, 111, 114, 115, 117, 118, 11
9, 129, 130, 131, 133, 134, 13
8,143,145,154,155,158,16
8, 180, 183, 184, 186, 194, 19
8, 209, 211, 215, 219, 249, 25
2, 254, 262, 265, 274, 282, 28
9, 303, 317, 320, 321, 322, C.I.
I. Direct Red 1, 2, 4, 9, 11, 13, 1
7, 20, 23, 24, 28, 31, 33, 37, 3,
9, 44, 46, 62, 63, 75, 79, 80, 8
1, 83, 84, 89, 95, 99, 113, 197,
201, 218, 220, 224, 225, 226, 2
27, 228, 229, 230, 231, C.I. I. Reactive Red 1,2,3,4,5,6,7,8,1
1, 12, 13, 15, 16, 17, 19, 20, 2
1, 22, 23, 24, 28, 29, 31, 32, 3
3, 34, 35, 36, 37, 38, 39, 40, 4,
1, 42, 43, 45, 46, 49, 50, 58, 5,
9, 63, 64, C.I. I. Sorbilize Red 1,
C. I. Food red 7, 9, 14, C.I. I. Pigment Red 41, 48, 54, 57, 58, 63, 68,
81 and the like. Further, as a blue color, C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 2
7, 29, 40, 41, 43, 45, 54, 59, 6
0, 62, 72, 74, 78, 80, 82, 83, 9
0, 92, 93, 100, 102, 103, 104, 1
12, 113, 117, 120, 126, 127, 12
9, 130, 131, 138, 140, 142, 14
3,151,154,158,161,166,16
7, 168, 170, 171, 182, 183, 18
4,187,192,199,203,204,20
5, 229, 234, 236, 249, C.I. I. Direct Blue 1, 2, 6, 15, 22, 25, 41, 7
1, 76, 77, 78, 80, 86, 87, 90, 9
8, 106, 108, 120, 123, 158, 16
0, 163, 165, 168, 192, 193, 19
4, 195, 196, 199, 200, 201, 20
2, 203, 207, 225, 226, 236, 23
7, 246, 248, 249, C.I. I. Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 1
5, 17, 18, 19, 20, 21, 25, 26, 2,
7, 28, 29, 31, 32, 33, 34, 37, 3
8, 39, 40, 41, 43, 44, 46, C.I. I. Solubiliz Bat Blue 1, 5, 41, C.I. I. Bat blue 29, C.I. I. Food blue 1, 2, C.I. I. Basic Blue 9, 25, 28, 29, 44, C.I. I.
Pigment Blue 1, 17 and the like. Further, C.I. I. Acid Black 1, 2, 7, 2
4, 26, 29, 31, 48, 50, 51, 52, 5
8, 60, 62, 63, 64, 67, 72, 76, 7
7, 94, 107, 108, 109, 110, 112,
115, 118, 119, 121, 122, 131, 1
32, 139, 140, 155, 156, 157, 15
8, 159, 191, C.I. I. Direct Black 1
7, 19, 22, 32, 35, 38, 51, 56, 6
2, 71, 74, 75, 77, 94, 105, 106,
107, 108, 112, 113, 117, 118, 1
32, 133, 146, 154, 168, 171, 19
5, C.I. I. Reactive Black 1, 3, 4, 5,
6, 8, 9, 10, 12, 13, 14, 18, C.I. I.
Sorbilize Butt Black 1, C.I. I. Food Black 2 and the like. These colorants can be used alone or in combination of two or more.

In the ink composition according to the present invention, water is the main solvent. As the water, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, or distilled water, or ultrapure water can be used. In addition, it is preferable to use water sterilized by ultraviolet irradiation, addition of hydrogen peroxide, or the like, since the generation of mold and bacteria can be prevented when the ink composition is stored for a long period of time.

Further, the ink composition according to the present invention may comprise an acidic substance. Examples of the acidic substance include inorganic acids such as hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, and nitric acid, or acetic acid, propionic acid, n-butyric acid, i
so-butyric acid, n-valeric acid, glycolic acid, gluconic acid,
Organic acids such as lactic acid and toluenesulfonic acid can be mentioned. Water resistance can be further improved by adding these acidic substances to the ink.

Further, the ink composition according to the present invention may comprise a basic substance.

Examples of the basic substance include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, radium hydroxide, beryllium hydroxide, magnesium hydroxide,
Inorganic bases such as ammonia; mono-, di- or tri-amines such as ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, diisopropylamine, tert-butylamine, dibutylamine, diisobutylamine, isopropylamine, sec-butylamine, and pentylamine Lower alkylamines, 3
Lower alkyl lower hydroxyalkoxyamines such as -ethoxypropylamine or 3-methoxypropylamine, lower alkyl lower alkoxyamines such as 3-ethoxypropylamine or 3-methoxypropylamine, 2-aminoethanol, 2- ( Dimethylamino) ethanol, 2- (diethylamino) ethanol,
Diethanolamine, N-butyldiethanolamine,
Mono-, di- or tri-lower hydroxyalkylamines such as triethanolamine, aminomethylpropanol or triisopropanolamine, iminobispropylamine, 3-diethylaminopropylamine, dibutylaminopropylamine, methylaminopropylamine, dimethyl Organic amines such as aminopropanediamine and methyliminobispropylamine can be exemplified. These basic substances have an effect of stably dissolving the water resistance imparting agent and the colorant in the ink composition and retaining them. For example, when an ink is prepared by combining the water-resistance imparting agent of the present invention with a specific colorant, the ink may not be dissolved by simple mixing, but may be stably dissolved by adding these basic substances. Can be.

In the ink composition according to the present invention, the water-soluble organic solvent means a medium capable of dissolving solutes such as a colorant, and is preferably selected from water-soluble solvents having a vapor pressure lower than water. Further, the form at room temperature is not limited to only liquid ones, and those which are solid at room temperature but function as a solvent during heating and melting, and those which function as a solvent when used in combination with an aqueous solution or another solvent are also included in the present invention. It can be used as a solvent. Examples of water-soluble organic solvents include:
Ethylene glycol, propylene glycol, butanediol, pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 1,2,6-hexanetriol, diethylene glycol, dipropylene glycol, etc. Polyhydric alcohols, ketones such as acetonylacetone, γ-butyrolactone, diacetin, esters such as triethyl phosphate,
Lower alkoxy lower alcohols such as 2-methoxyethanol and 2-ethoxyethanol, thiodiglycol,
Sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, nitrogen-containing compounds such as ethylene urea, prorylene urea, 1,3-dimethyl-2-imidazolidinone, ethylene carbonate, propylene carbonate, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc. Is mentioned. Since the vapor pressure of the organic solvent is lower than that of the pure water, the ratio of the organic solvent in the ink does not decrease even if the drying of the ink proceeds at the tip of the inkjet head. As a result, the dissolving power of the organic solvent does not decrease, and the ink can be stably held.

The amount of the water-soluble organic solvent may be determined as appropriate, but is preferably added, for example, in the range of 5 to 50% by weight based on the total amount of the ink.

According to a preferred embodiment of the present invention, the ink composition according to the present invention comprises (1) a water-soluble hydroxypyridine derivative, (2) a linear or cyclic amide compound, (3) an imidazole derivative, and (4) a hydroxycyclic compound. Amine compounds, (5) azole compounds, (6) azine compounds,
(7) An anti-clogging agent selected from an amidine derivative and (8) a purine derivative.

By the addition of these clogging preventive agents, for example, even in an extreme situation where the ink jet recording apparatus is left under a high temperature and a low humidity for a long time, ink drying at the nozzle tip can be prevented. Further, even if the ink is dried and solidified as the drying proceeds, the tip portion can be redissolved with the ink supplied from the rear of the nozzle. Therefore, printing can be normally resumed early even after being left for a long time.

According to a preferred embodiment of the present invention, the anti-clogging agent is preferably contained in an amount of about 1 to 40% by weight based on the ink.

(1) Water-soluble hydroxypyridine derivative The water-soluble hydroxypyridine derivative used in the present invention means a water-soluble compound in which a hydroxyl group is bonded to a pyridine ring directly or via a methylene chain. Specific examples thereof include 2-pyridinol, 3-pyridinol, 4-pyridinol, 3-methyl-2-pyridinol, 4-methyl-2-pyridinol, 6-methyl-2-pyridinol, 2-pyridinemethanol, 3-pyridine Methanol, 4-pyridinemethanol, 2-pyridineethanol, 3-pyridineethanol, 4-pyridineethanol, 2-pyridinepropanol, 3-pyridinepropanol, 4-pyridinepropanol, α-methyl-2-pyridinemethanol, 2,3- Pyridinediol. These can be used alone or in combination.

(2) Linear or Cyclic Amide Compound The water-soluble linear or cyclic amide compound used in the present invention is a linear amide derivative having 1 to 8 carbon atoms in the molecule, preferably 1 to 3 carbon atoms. A chain amide derivative having 6 and a cyclic amide derivative having 4 to 8 carbon atoms, preferably a cyclic amide derivative having 4 to 6 carbon atoms are meant. Specific examples of these include lactamide, methyl carbamate, ethyl carbamate, propyl carbamate, formamide, N-methylformamide, N, N-diethylformamide, N, N
-Dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, N-methylpropionamide, nicotinamide, 6-aminonicotinamide, N, N-diethylnicotinamide, N-ethylnicotinamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidone, 5-hydroxymethyl-2-pyrrolidone, δ
-Valerolactam, ε-caprolactam, heptactam, pyroglutamic acid, N-methyl-ε-caprolactam, β-propiolactam. These can be used alone or in combination.

(3) Imidazole derivative The imidazole derivative used in the present invention is water-soluble, and has a hydroxyl group, carboxyl group, lower alkyl (for example, C1-6 alkyl group, preferably C1
-4 alkyl) bound to a water-soluble compound. Specific examples thereof include imidazole, N-methylimidazole, 2-methylimidazole, 2-hydroxyimidazole, 4-hydroxyimidazole, 5-hydroxyimidazole, pyrimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples include histamine, histidine, imidazoleacetic acid, 4-methylimidazole, 4-imidazoleacrylic acid, 4,5-imidazoledicarboxylic acid, and pilocarpine. These can be used alone or in combination.

(4) Hydroxycyclic amine compound The hydroxycyclic amine compound used in the present invention is water-soluble, and a hydroxyl group is bonded directly or via a methylene chain to a cyclic amine (preferably a 5- or 6-membered cyclic amine). Means a water-soluble compound. Specific examples thereof include 4-hydroxypiperidine, 3-hydroxypiperidine, 2-hydroxypiperidine, N-methyl-3.
-Hydroxypiperidine, N-ethyl-3-hydroxypiperidine, N-methyl-3-hydroxymethylpiperidine, N-methyl-2-hydroxymethylpiperidine,
N- (2-hydroxyethyl) piperidine, 2- (2-
(Hydroxyethyl) piperidine, 4- (2-hydroxyethyl) piperidine, N- (2-hydroxyethyl) piperazine, N- (2-hydroxyethyl) morpholine,
N- (2-hydroxypropyl) morpholine, N- (2-
Hydroxyethyl) pyrrole, pyrrolinol, N- (2
-Hydroxyethyl) pyrrolidine, N-methyl-2-
(2-Hydroxyethyl) pyrrolidine, N- (2-hydroxyethyl) ethyleneimine, 3-oxypyrazole, and 5-oxypyrazole. These can be used alone or in combination.

(5) Azole compound The azole compound used in the present invention is water-soluble, is a 5-membered heterocyclic ring, has at least two or more heteroatoms in the ring, and has at least one heteroatom as nitrogen. Refers to a certain compound. In particular, two or three hetero atoms are preferable, and those in which the hetero atom is selected from nitrogen, oxygen, and sulfur are preferable. Specific examples of the azole compound include 1,2,3-triazole,
1,2,4-triazole, 1,2,3-triazole-4,5-dicarboxylic acid, 1H-1,2,4-triazole-3-thiol, benzotriazole, benzotriazole-5-carboxylic acid, 1H- Benzotriazole-1-methanol, pyrazole, tetrazole, oxazole, N1- (4,5-dimethyl-2-oxazolyl) sulfanilamide, thiazole, 2-aminothiazole, 2-thiazolecarboxaldehyde, 5-thiazolemethanol, 1,2 , 3-thiadiazole, benzimidazole, benzimidazole-2-carbamic acid, (2-benzimidazolyl) acetonitrile, 5
-Benzimidazolecarboxylic acid, 2-benzimidazoleethanol, 2-benzimidazolepropionic acid, 2-mercaptobenzimidazole.
These can be used alone or in combination.

(6) Azine compound The azine compound used in the present invention is water-soluble, is a 6-membered heterocyclic ring, has at least two or more heteroatoms in the ring, and at least one heteroatom is nitrogen. Refers to a certain compound. In particular, two or three hetero atoms are preferable, and those in which the hetero atom is selected from nitrogen, oxygen, and sulfur are preferable. Moreover, it may have a carboxyl group and a lower alkyl (for example, a C1-C6, preferably C1-C4 alkyl) as a substituent. Specific examples thereof include pyrazine, pyrazinamide, hexahydropyrazine, 3-ethyl-2,6
Dimethylpyrazine, pyrazine-2,3-dicarboxylic acid, pyrazinecarbonitrile, 2,3-pyrazinedicarbonitrile, 2,3-pyrazinecarboxamide, 2,
Examples include 3-pyrazine dicarboxylic anhydride, pyrazineethanethiol, triazine, cyanuric acid, methyl cyanurate, melamine, trithiocyanuric acid, pyridazine, 4-pyridazinecarboxylic acid, cytosine, and cytosine-5-carboxylic acid. These can be used alone or in combination.

(7) Amidine derivative The amidine derivative used in the present invention is water-soluble, and preferably means a guanidine derivative. Specific examples of the amidine derivative include guanidine, 1-methyl-3
-Nitro-1-nitrosoguanidine, 1-amyl-3-
Nitro-1-nitrosoguanidine, nitroguanidine,
Sulfaguanidine, guanidinoacetic acid, guanitidine,
Aminoguanidine, canavanine, argininosuccinic acid,
Arginine and biguanide. These can be used alone or in combination.

(8) Purine Derivative The purine derivative used in the present invention is water-soluble, and specific examples thereof include purine, purine riboside, 2-amino-6-mercaptopurine, 6- (methylthio) purine riboside, and 6-benzylamino. Purine, xanthosine, guanine, 2'-deoxyguanosine, guanosine, O-methylguanine, methylguanine, caffeine, xanthine, theophylline, theobromine, adenine, adenosine, 2'-deoxyadenosine, N-benzyl-9- (2 -Tetrahydropyranyl) adenine and adenosine triphosphate. These can be used alone or in combination.

The ink composition according to the present invention may further contain, if necessary, an auxiliary generally used in ink jet recording inks. For example, a penetration enhancer, a viscosity adjuster, a surface tension adjuster, a hydrotrope, a humectant, a pH adjuster, a fungicide, a chelating agent, a preservative, a rust inhibitor and the like can be added.

Examples of the penetration enhancer include lower alcohols such as ethanol, isopropanol, butanol and pentanol; cellosols such as ethylene glycol monobutyl ether; carbitols such as diethylene glycol monobutyl ether and triethylene glycol monobutyl ether; And the like.

Examples of the surface tension adjuster include alcohols such as diethanolamine, triethanolamine, glycerin and diethylene glycol, nonionic, cationic, anionic and amphoteric surfactants.

As the hydrotrope, urea,
Alkyl urea, ethylene urea, propylene urea, thiourea, guanidates, tetraalkyl ammonium halides and the like are preferred.

As a humectant, glycerin, diethylene glycol or the like may be added as a water-soluble organic solvent. Further, sugars such as maltitol, sorbitol, gluconolactone, maltose and the like can be added.

As the pH adjusting agent, the above-mentioned basic substance can be added.

Further, according to a preferred embodiment of the present invention, the ink composition according to the present invention may comprise a water-soluble resin other than the above-mentioned water resistance imparting agent. As such a water-soluble resin, a nonionic water-soluble resin is preferable. For example, polymethacrylic acid hydroxyesters such as polyacrylamide and polyhydroxyethyl methacrylate, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and the like are used. By adding these water-soluble resins, the ink composition can be further stabilized.

Ink jet recording method using two liquids The ink jet recording method according to the fourth aspect of the present invention comprises:
And printing the reaction liquid and the ink composition on a recording medium.

In the ink jet recording method according to the present invention, a good image can be realized by contact between the reaction liquid and the ink composition. The following is a hypothesis, and the reason is as follows, provided that the present invention is not interpreted in a limited manner. When the reaction liquid comes into contact with the ink composition, as described above, the water resistance imparting agent destroys the dissolved and / or dispersed state of the colorant in the ink composition, the resin emulsion optionally contained later, and other components. And agglomerate it. It is considered that these aggregates suppress the penetration of the coloring agent into the recording medium. As a result, it is considered that an image having high color density, bleeding, and less printing unevenness is realized. Further, in a color image, there is an advantage that uneven color mixing in a boundary region of different colors, that is, color bleeding can be effectively prevented.

Further, the water resistance imparting agent is stably dissolved in the reaction liquid, but when the reaction liquid is adhered to a recording medium together with the ink composition, the water resistance imparting agent is contained in the ink composition. This resin causes an electrostatic interaction with the coloring agent, while the resin also interacts with the recording medium and can be stably fixed on the recording medium. It is considered that, with the fixation of the resin to the recording medium, the colorant is also fixed to the recording medium together with the resin, thereby imparting water resistance to the image. Further, it is considered that an image with less bleeding and color bleed can be realized as a result of the colorant being fixed well to the recording medium. More preferably, the combination of the reaction liquid containing the water resistance imparting agent represented by the formula (I) and the ink composition containing the dye greatly improved the light fastness. Conventionally, a combination of a polyallylamine and a dye, which has been used as a cationic water-soluble resin, is disadvantageous in that its light resistance deteriorates more than the unique characteristics of the dye. However, in the present invention, the use of the water-resistance imparting agent represented by the formula (I) can prevent the dye alone from maintaining the light resistance of an image while maintaining the water resistance of an image. This is to improve the points that were not obtained.

The order in which the reaction liquid and the ink composition are applied to the recording medium may be any order, that is, a method in which the reaction liquid is applied to the recording medium, and then the ink composition is applied to the recording medium. A method of adhering the reaction liquid after the ink composition is adhered, and a method of mixing the reaction liquid and the ink composition immediately before or immediately after the ejection can be suitably performed.

Regarding the adhesion of the reaction liquid to the recording medium, there are either a method in which the reaction liquid is selectively applied only to the place where the ink composition is to be applied, or a method in which the reaction liquid is applied to the entire surface of the paper. You may. The former is economical because it can minimize the consumption of the reaction solution,
A certain degree of accuracy is required for the position where both the reaction liquid and the ink composition are attached. On the other hand, in the latter, the requirement for the accuracy of the adhesion position of the reaction liquid and the ink composition is relaxed as compared with the former, but a large amount of the reaction liquid adheres to the entire surface of the paper, and the paper is easily curled during drying. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the reaction liquid. When the former method is adopted, the reaction liquid can be attached by an ink jet recording method.

(A) Reaction liquid The reaction liquid used in the fourth embodiment of the present invention basically contains the above-mentioned water resistance imparting agent which forms aggregates when it comes into contact with the ink composition. As described above, the reaction liquid in the present invention is a liquid capable of destroying and aggregating the dispersed and / or dissolved state of the dye or pigment, and in some cases, the resin emulsion and other components in the ink composition.

The amount of the water resistance imparting agent to be added to the reaction solution may be appropriately determined within the range where the above effects can be obtained, but is preferably about 0.2 to 20% by weight, more preferably 0 to 20% by weight, based on the reaction solution. It is about 0.5 to 10% by weight.

According to a preferred embodiment of the present invention, the composition may contain an acidic substance. Examples of the acidic substance include inorganic acids such as hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, and nitric acid, or acetic acid, propionic acid, n-butyric acid, is
Organic acids such as o-butyric acid, n-valeric acid, glycolic acid, gluconic acid, lactic acid, and toluenesulfonic acid can be mentioned.

[0069] According to a preferred embodiment of the present invention, the composition may comprise a basic substance. Examples of the basic substance include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, radium hydroxide, beryllium hydroxide, magnesium hydroxide, and ammonia; Mono-, di- or tri- such as ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, diisopropylamine, tert-butylamine, dibutylamine, diisobutylamine, isopropylamine, sec-butylamine and pentylamine
Lower alkylamines, 3-ethoxypropylamine,
Or lower alkyl lower hydroxyalkoxyamines such as 3-methoxypropylamine, lower alkyl lower alkoxyamines such as 3-ethoxypropylamine or 3-methoxypropylamine, 2-aminoethanol, 2- (dimethylamino) ethanol, Mono-, di- or tri-lower hydroxyalkylamines such as 2- (diethylamino) ethanol, diethanolamine, N-butyldiethanolamine, triethanolamine, aminomethylpropanol or triisopropanolamine, iminobispropylamine, 3-diethylamino Organic amines such as propylamine, dibutylaminopropylamine, methylaminopropylamine, dimethylaminopropanediamine, and methyliminobispropylamine Door can be.

Further, according to a preferred embodiment of the present invention, the reaction solution according to the present invention can contain a water-soluble resin other than the above-mentioned water resistance imparting agent. As such a water-soluble resin, a nonionic water-soluble resin is preferable. For example, polymethacrylic acid hydroxyesters such as polyacrylamide and polyhydroxyethyl methacrylate, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and the like are used. The reaction solution can be further stabilized by adding these water-soluble resins.

Further, the ink jet recording method according to the present invention
The reaction solution in the method may contain a polyvalent metal salt.
it can. Preferred examples thereof include divalent or higher-valent polyvalent metals.
Ions and anions binding to these polyvalent metal ions
And salts soluble in water. Polyvalent metal ion
Examples of the components include Ca²⁺, Cu²⁺, Ni²⁺, M
g ²⁺, Zn²⁺, Ba²⁺Divalent metal ions such as Al³⁺,
Fe³⁺, Cr³⁺And other trivalent metal ions. shadow
As the ion, Cl^-, Nitrate ion, I^-, Br^-, C
10_Three ^-And carboxylate ions.

In particular, a metal salt composed of Ca ²⁺ or Mg ²⁺ gives favorable results from the two viewpoints of the pH of the reaction solution and the quality of the printed matter obtained.

The concentration of these polyvalent metal salts in the reaction solution may be appropriately determined within a range in which the effect of preventing printing quality and clogging can be obtained, but is preferably about 0.1 to 40% by weight, more preferably. Is about 5 to 25% by weight.

In a preferred embodiment of the present invention, the polyvalent metal salt contained in the reaction solution is composed of divalent or higher polyvalent metal ions and nitrate ions or carboxylate ions bound to these polyvalent metal ions. It is soluble in water.

Here, the carboxylate ion is preferably derived from a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms or a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms. Preferred examples of the saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid,
Isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid and the like. Particularly, formic acid and acetic acid are preferable.

A hydrogen atom on the saturated aliphatic hydrocarbon group of the monocarboxylic acid may be substituted with a hydroxyl group. A preferred example of such a carboxylic acid is lactic acid.

Further, preferred examples of the carbocyclic monocarboxylic acid having 6 to 10 carbon atoms include benzoic acid and naphthoic acid, and more preferably benzoic acid.

According to a preferred embodiment of the present invention, the reaction solution may contain a wetting agent comprising a high-boiling organic solvent. The high boiling point organic solvent prevents clogging of the head by preventing the reaction solution from drying. Preferred examples of the high-boiling organic solvent include ethylene glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, glycerin,
Polyhydric alcohols such as trimethylolethane and trimethylolpropane; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether,
Alkyl ethers of polyhydric alcohols such as triethylene glycol monobutyl ether, urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-
2-imidazolidinone, triethanolamine and the like.

The amount of the high-boiling organic solvent is not particularly limited, but is preferably about 0.5 to 40% by weight, more preferably about 2 to 20% by weight.

According to a preferred embodiment of the present invention, the reaction solution may contain a low-boiling organic solvent. Preferred examples of the low boiling organic solvent include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol and n-
Butanol, sec-butanol, tert-butanol, iso-butanol, n-pentanol and the like. Particularly, a monohydric alcohol is preferable. The low-boiling organic solvent has the effect of shortening the drying time of the reaction liquid on the recording medium. 0.5 to 10% by weight of low boiling organic solvent
And more preferably in the range of 1.5 to 6% by weight.

According to a preferred embodiment of the present invention, the reaction solution may contain a penetrant. Examples of the penetrant include various surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, alcohols such as methanol, ethanol, and iso-propyl alcohol, and ethylene glycol monomethyl ether. And lower alkyl ethers of polyhydric alcohols such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether.

(B) Ink Composition The ink composition used in the fourth embodiment of the present invention means a black ink composition when performing monochrome printing, and a color ink when performing color printing. A composition, specifically, a yellow ink composition, a magenta ink composition, and a cyan ink composition, and in some cases, a black ink composition.

The ink composition used in the present invention contains at least a colorant and water.

The colorant contained in the ink composition used in the present invention may be either a dye or a pigment.

Dyes are organic colored substances that dissolve in water, and include acid dyes, direct dyes,
Those classified as reactive dyes, soluble vat dyes, or food grade dyes are useful. Further, a coloring agent classified as an oil-soluble dye, a basic dye or a pigment in the color index can be used as long as it is insoluble in neutral water but soluble in alkaline water.

Specific examples of the dye and the alkali-soluble pigment include those described for the ink composition according to the second embodiment of the present invention.

As the pigment, inorganic pigments and organic pigments can be used without any particular limitation. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method can be used. Examples of organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines) Pigments, thioindico pigments, isoindolinone pigments, quinoflurone pigments, etc., dye chelate pigments (eg, basic dye type chelate pigments, acid dye type chelate pigments, etc.), nitro pigments, nitroso pigments, aniline black, etc. it can.

The amount of the colorant may be determined as appropriate.
For example, 0.5 to 20% by weight based on the total weight of the ink composition
It is preferable to add in the range of. This is because a print image having a sufficient optical density can be realized in this range, and the viscosity can be easily adjusted to a value suitable for the ink jet recording method.

According to a preferred embodiment of the present invention, of these colorants, a pigment is introduced with a dispersant or a surfactant, or an anionic functional group is introduced by a surface treatment so that the pigment can be dispersed in an aqueous medium. Is preferred. Thereby, the pigment particles can be stably dispersed in the ink composition, and on the other hand, on the recording medium, an electrostatic interaction between the water resistance imparting agent in the reaction liquid and the introduced functional group is developed, A clear image with little bleeding or color bleed can be realized.

According to a preferred embodiment of the present invention, the ink composition preferably comprises a resin emulsion. Here, the resin emulsion means an emulsion in which the continuous phase is water and the dispersed phase is the following resin component. As the resin component of the dispersed phase, acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acryl-styrene resin, butadiene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin, Benzoguanamine resin, phenol resin, silicone resin, epoxy resin and the like can be mentioned.

According to a preferred embodiment of the present invention, the resin is preferably a polymer having both a hydrophilic part and a hydrophobic part. Further, the particle size of these resin components is not particularly limited as long as an emulsion is formed.
Or less, more preferably about 5 to 100 nm.

These resin emulsions can be obtained by dispersion polymerization of a resin monomer in water together with a surfactant, if necessary. For example, an emulsion of an acrylic resin or a styrene-acrylic resin can be obtained by dispersing and polymerizing a (meth) acrylate or a (meth) acrylate and styrene together with a surfactant in water.
The mixing ratio of the resin component and the surfactant is usually 10: 1.
It is preferable to set it to about 5: 1.

When the amount of the surfactant used is within the above range, better water resistance and permeability of the ink can be obtained. Although the surfactant is not particularly limited, preferred examples thereof include anionic surfactants (for example, sodium dodecylbenzenesulfonate, sodium laurate, ammonium salts of polyoxyethylene alkyl ether sulfate, etc.), and nonionic surfactants (for example, , Polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkyl amides, etc. These can be used in combination. It is also possible to use acetylene glycol (olefin Y and Surfynol 82, 104, 440, 465, and 485 (all manufactured by Air Products and Chemicals Inc.)).

It is also possible to use a commercially available resin emulsion, for example, Microgel E-100.
2, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001
(Acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.) Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, ZEON Corporation) Made), Cybinol S
K-200 (acrylic resin emulsion, manufactured by Seiden Chemical Co., Ltd.).

The ink used in the present invention preferably contains a resin emulsion such that the resin component is 0.1 to 40% by weight of the ink, more preferably 1 to 2%.
It is in the range of 5% by weight.

The resin emulsion has the effect of suppressing the penetration of the coloring component and promoting the fixation to the recording medium by interacting with the water resistance imparting agent. Further, depending on the type of the resin emulsion, a film is formed on the recording medium, which has the effect of improving the abrasion resistance of the printed matter.

According to a preferred embodiment of the present invention, the ink composition preferably contains a thermoplastic resin in the form of a resin emulsion. Here, the thermoplastic resin has a softening temperature of 50C to 250C, preferably 60C to 200C. Here, the term "softening temperature" refers to the glass transition point, melting point, and temperature at which the viscosity of the thermoplastic resin becomes 10 ¹¹ to 10 ¹² poise, the pour point, and the minimum film formation temperature (MFT) when in the form of a resin emulsion. Means the lowest temperature. In the heating step of the method according to the present invention, the recording medium is heated at a temperature equal to or higher than the softening temperature of the thermoplastic resin.

Further, it is preferable that these resins form a film having strong water resistance and abrasion resistance when heated and cooled to a temperature higher than the softening or melting temperature.

Specific examples of the water-insoluble thermoplastic resin include polyacrylic acid, polymethacrylic acid, polymethacrylate, polyethylacrylic acid, styrene-
Butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, chloroprene copolymer, fluororesin, vinylidene fluoride, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, polystyrene, Styrene-acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl acetal, polyamide, rosin resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose resin, vinyl acetate resin, ethylene-vinyl acetate copolymer ,
Examples include, but are not limited to, vinyl acetate-acrylic copolymers, vinyl chloride resins, polyurethanes, rosin esters, and the like.

Specific examples of the low molecular weight thermoplastic resin include animal and plant waxes such as polyethylene wax, montan wax, alcohol wax, synthetic oxide wax, α-olefin-maleic anhydride copolymer, carnauba wax, lanolin, paraffin wax. And microcrystalline wax.

As such a resin emulsion, known resin emulsions can also be used. For example, Japanese Patent Publication No. 62-1426, Japanese Patent Application Laid-Open No. 3-56573, Japanese Patent Application Laid-Open No. 3-79678, and Japanese Patent Application Laid-Open No. 3-201668. The resin emulsion described in JP-A-4-18462 can be used as it is.

According to a preferred embodiment of the present invention, the ink composition preferably contains an alginic acid derivative. Preferred examples of the alginic acid derivative include alkali metal alginates (eg, sodium salts and potassium salts), organic alginates (eg, triethanolamine salts), and ammonium alginates.

The addition amount of this alginic acid derivative to the ink composition is preferably about 0.01 to 1% by weight.
More preferably, it is about 0.05 to 0.5% by weight.

The reason why a good image can be obtained by adding an alginic acid derivative cannot be determined, but the water resistance imparting agent present in the reaction solution reacts with the alginic acid derivative in the ink composition to change the dissolution or dispersion state of the colorant. This is considered to be caused by promoting the fixation of the colorant to the recording medium.

According to a preferred embodiment of the present invention, the ink composition preferably contains an organic solvent. This organic solvent is preferably a low-boiling organic solvent, and preferred examples thereof include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, tert-butanol, is
o-butanol, n-pentanol and the like.
Particularly, a monohydric alcohol is preferable. Low-boiling organic solvents have the effect of shortening the drying time of the ink.

According to a preferred embodiment of the present invention, the ink composition used in the method according to the fourth embodiment of the present invention preferably further comprises a wetting agent comprising a high-boiling organic solvent. Preferred examples of the high boiling organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, Polyhydric alcohols such as trimethylolethane and trimethylolpropane, ethylene glycol monoethyl ether,
Alkyl ethers of polyhydric alcohols such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; urea; -Pyrrolidone,
N-methyl-2-pyrrolidone, 1,3-dimethyl-2-
Examples include imidazolidinone and triethanolamine.

The wetting agent was added in an amount of 0.5
Preferably, it is in the range of 2 to 20% by weight. Further, the amount of the low-boiling organic solvent to be added is preferably 0.5 to 10% by weight of the ink, more preferably 1.5 to 6% by weight.

The ink composition used in the present invention can contain a dispersant and a surfactant. Examples of the surfactant include various surfactants described in the description of the resin emulsion.

According to a preferred embodiment of the present invention, the ink composition may contain a sugar. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucosyl , (Sorbit), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, polysaccharide means sugar in a broad sense, and alginic acid, α-cyclodextrin,
The term includes a substance widely existing in nature such as cellulose.

Examples of the derivatives of these saccharides include reducing sugars of the aforementioned saccharides (for example, sugar alcohols (formula H
OCH ₂ (CHOH) n CH ₂ OH (where n = 2-5
Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thiosugars and the like. In particular, sugar alcohols are preferred, and specific examples include maltitol and sorbitol.

The content of these saccharides is 0.1 to 0.1% of the ink.
A suitable range is 40% by weight, preferably 0.5 to 30% by weight.

In addition, if necessary, a pH adjuster, a preservative, a fungicide and the like may be added.

According to a preferred embodiment of the present invention, the ink composition according to the second embodiment of the present invention can be used as the ink composition in the ink jet recording method according to the fourth embodiment of the present invention. As a result, it is possible to obtain a high-quality image that is more excellent in water resistance and light resistance and has less blur.

(C) Ink Jet Recording Apparatus An ink jet recording apparatus for performing the ink jet recording method according to the fourth embodiment of the present invention will be described below with reference to the drawings.

The ink jet recording apparatus shown in FIG. 1 is a mode in which an ink composition and a reaction liquid are stored in a tank, and the ink composition and the reaction liquid are supplied to a recording head via an ink tube. That is, the recording head 1 and the ink tank 2 are connected by the ink tube 3. Here, the inside of the ink tank 2 is partitioned, and the ink composition,
In some cases, a room for a plurality of color ink compositions and a room for a reaction liquid are provided.

The recording head 1 moves along the carriage 4
It is moved by a timing belt 6 driven by a motor 5. On the other hand, the paper 7 as a recording medium is placed at a position facing the recording head 1 by the platen 8 and the guide 9. In this embodiment, a cap 10 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is supplied to the waste ink tank 13 via the tube 12.
Is stored.

FIG. 2 is an enlarged view of the nozzle surface of the recording head 1. The portion indicated by 1b is the nozzle surface of the reaction liquid, and the nozzle 21 for discharging the reaction liquid is provided in the vertical direction. On the other hand, the portion indicated by 1c is the nozzle surface of the ink composition, and from the nozzles 22, 23, 24, and 25, the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition are respectively provided. Discharged.

An ink jet recording method using the recording head shown in FIG. 2 will be described with reference to FIG. The recording head 1 moves in the direction of arrow A. During that move,
The reaction liquid is discharged from the nozzle surface 1b to form a band-like reaction liquid attachment region 31 on the recording medium 7. Next, the recording medium 7 is transported by a predetermined amount in the paper feed direction arrow B. During that time, the recording head 1 moves in the direction opposite to the arrow A in the figure, and returns to the position on the left end of the recording medium 7. Then, the ink composition is printed on the reaction liquid adhering area where the reaction liquid has already adhered to form a print area 32.

Further, as shown in FIG. 4, in the recording head 1, all the nozzles can be arranged in the horizontal direction. In the figure, 41a and 41b are discharge nozzles of a reaction liquid, respectively, from the nozzles 42, 43, 44 and 45, a yellow ink composition, a magenta ink composition,
A cyan ink composition and a black ink composition are ejected. In the recording head of such an aspect, the recording head 1 can perform printing both in the forward path and the return path in which the recording head 1 reciprocates on the carriage, so that the recording head can be printed at a higher speed than in the case of using the recording head shown in FIG. Printing can be expected.

Further, by adjusting the surface tension of the reaction liquid and the ink composition preferably as described above, a high-quality image can be obtained more irrespective of the order of attachment. In this case, the number of nozzles for discharging the reaction solution can be one (for example, the nozzle 41b can be omitted in the figure), and further downsizing of the head and high-speed printing can be achieved.

Further, in some ink jet recording apparatuses, replenishment of the ink composition is performed by replacing a cartridge which is an ink tank. This ink tank may be integrated with the recording head.

FIG. 5 shows a preferred example of an ink jet recording apparatus using such an ink tank. In the figure, the same members as those of the apparatus of FIG. 1 are denoted by the same reference numerals. In the embodiment of FIG. 5, the recording heads 1a and 1b
Are integrated with the ink tanks 2a and 2b.
The recording head 1a or 1b discharges the ink composition and the reaction liquid, respectively. The printing method may be basically the same as the apparatus of FIG. In this embodiment, the recording head 1a and the ink tank 2a and the recording head 1a and the ink tank 2b move on the carriage 4.

[0123]

The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto.

Example A Synthesis Example A1 : Preparation of Waterproofing Agent A1 15.0 g of N, N-dimethylaminopropylacrylamide was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 0.57 g of 2,4-diphenyl-4-methyl-1-pentene, n-acetic acid
After charging 20.0 g of butyl, dimethyl 2,2 ′
After adding 20.0 g of n-butyl acetate in which 0.44 g of -azobis (2-methylpropionate) was dissolved, the mixture was heated with stirring under a nitrogen atmosphere and kept at 80 ° C for 4 hours.
The temperature was raised to ℃, and the reaction was continued for another 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 13.0 g of a solid.

Further, water 1 was added to a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube.
5.0 g of the above solid substance was charged into 0.0 g, and the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 90 ° C. for 20 hours. The solvent was distilled off under reduced pressure, re-dissolved in methyl ethyl ketone, and re-precipitated repeatedly in a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 4.8 g of a solid content. As a result of the GPC measurement,
The weight average molecular weight is 9.4 in terms of polyethylene glycol.
The number average molecular weight was 5,100.

Synthesis Example A2 : Preparation of Waterproofing Agent A2 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 14.0 g of N, N-dimethylaminopropylacrylamide and trimethyl chloride were added. 1.3 g of a 75% by weight aqueous solution of aminopropylacrylamide, 0.90 g of 2,4-diphenyl-4-methyl-1-pentene and 2 g of N, N-dimethylformamide
After charging 0.0 g, 20.0 g of N, N-dimethylformamide in which 1.09 g of dimethyl 2,2′-azobis (2-methylpropionate) were dissolved was added, and the mixture was heated while stirring under a nitrogen atmosphere. After keeping at 80 ° C. for 4 hours, the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 57 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 12.3 g of a solid.

Further, water 2 was added to a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube.
After charging 0.0 g and 10.0 g of the above solid substance, the mixture was heated with stirring under a nitrogen atmosphere and kept at 90 ° C. for 20 hours, and then cooled to room temperature to obtain about 30 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in methyl ethyl ketone, and reprecipitated repeatedly with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 9.6 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 4,200 and the number average molecular weight was 2,800 in terms of polyethylene glycol.

Synthesis Example A3 : Preparation of Waterproofing Agent A3 In a 500 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 52.6 g of N, N-dimethylaminopropylacrylamide and trimethyl chloride were added. A 75% by weight aqueous solution of aminopropylacrylamide was added to 2
3.2 g, 2,4-diphenyl-4-methyl-1-pentene, 4.0 g, N, N-dimethylformamide, 13 g
After charging 0 g, dimethyl 2,2′-azobis (2-
20 g of N, N-dimethylformamide in which 5.0 g of methylpropionate was dissolved was added, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours. Then, the temperature was increased to 95 ° C. and the reaction was further performed for 2 hours. Continued. After cooling to room temperature, about 23
0 g of a pale yellow clear solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 40.3 g of a solid.

Further, in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, water 2 was added.
After charging 0.0 g and 10.0 g of the above solid substance, the mixture was heated with stirring under a nitrogen atmosphere and kept at 90 ° C. for 20 hours, and then cooled to room temperature to obtain about 30 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in methyl ethyl ketone, and re-precipitated repeatedly in a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 9.2 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 4,800 and the number average molecular weight was 3,200 in terms of polyethylene glycol.

Synthesis Example A4 : Preparation of Waterproofing Agent A4 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide, 2,2 After charging 0.57 g of 4-diphenyl-4-methyl-1-pentene and 20.0 g of methanol, 20.0 g of methanol in which 0.54 g of 4,4′-azobis (4-cyanopentanoic acid) was dissolved was added. The temperature was raised while stirring under a nitrogen atmosphere, and the reaction was carried out at the boiling point for 15 hours. After cooling to room temperature, about 5
0 g of a pale yellow clear solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 13.0 g of a solid. As a result of GPC measurement, the weight average molecular weight was 8,900 and the number average molecular weight was 4,700 in terms of polyethylene glycol.

Synthesis Example A5 : Preparation of Waterproofing Agent A5 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide, 0.50 g of mercaptopropionic acid and 60.0 g of n-butyl acetate
After charging g, 2.00 g of 1,1′-azobis (1-acetoxy-1-phenylethane) was added and dissolved by stirring. The temperature was raised while stirring under a nitrogen atmosphere and maintained at 80 ° C. for 4 hours, and then the temperature was raised to 95 ° C. and the reaction was continued for another 2 hours.
After cooling to room temperature, about 77 g of a pale yellow solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 13.5 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 6,000 and the number average molecular weight was 2,200 in terms of polyethylene glycol.

Synthesis Example A6 : Preparation of Waterproofing Agent A6 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 12.5 g of N, N-dimethylaminoethylacrylamide, 2,2 0.83 g of 4-diphenyl-4-methyl-1-pentene, n-acetic acid
After charging 20.0 g of butyl, 20.0 g of n-butyl acetate in which 0.41 g of dimethyl 2,2'-azobis (2-methylpropionate) was dissolved was added, and the temperature was increased while stirring under a nitrogen atmosphere. After the temperature was kept at 4 ° C. for 4 hours, the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent is distilled off under reduced pressure,
Dissolve the remaining viscous liquid in methyl ethyl ketone,
The reprecipitation was repeated with a methyl ethyl-hexane system, and the precipitate was dried to obtain 12.0 g of a solid content.

Further, water 2 was added to a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube.
10.0 g of the above solid substance was charged into 0.0 g, and the temperature was increased while stirring under a nitrogen atmosphere and maintained at 90 ° C. for 20 hours, followed by cooling to room temperature to obtain about 30 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in methyl ethyl ketone, and reprecipitated repeatedly with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 9.0 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 6,700 and the number average molecular weight was 3,800 in terms of polyethylene glycol.

Synthesis Example A7 : Preparation of Waterproofing Agent A7 The reaction and purification were carried out in the same manner as in Synthesis Example A1, except that the amount of 2,4-diphenyl-4-methyl-1-pentene was changed to 1.13 g. Was. The yield after drying was 4.5 g.
As a result of GPC measurement of the product, the weight average molecular weight was 4,600 in terms of polyethylene glycol, and the number average molecular weight was 2,7.
00.

Synthesis Example A8 : Preparation of Waterproofing Agent A8 15.0 g of N, N-dimethylaminopropylmethacrylamide was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. After charging 0.83 g of 2,4-diphenyl-4-methyl-1-pentene and 20.0 g of n-butyl acetate, dimethyl 2,2 was added.
2'-azobis (2-methylpropionate) 0.41
After adding 20.0 g of n-butyl acetate dissolved therein, the temperature was increased while stirring under a nitrogen atmosphere and maintained at 80 ° C. for 4 hours.
The temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 12.9 g of a solid content.

Further, water 2 was added to a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
10.0 g of the above solid substance was charged into 0.0 g, and the mixture was heated with stirring under a nitrogen atmosphere, kept at 90 ° C. for 20 hours, and then cooled to room temperature to obtain about 31 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in acetone, and re-precipitated with acetone-hexane system repeatedly. The precipitate was dried to obtain 9.4 g of solid content. As a result of GPC measurement, the weight average molecular weight was 7,000 and the number average molecular weight was 4,000 in terms of polyethylene glycol.

Synthesis Example A9 : Preparation of Waterproofing Agent A9 5.0 g of the product obtained in Synthesis Example A1 was charged into a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. Methyl ethyl ketone 10.0
g and methanol 10.0 g. While stirring the solution, 0.22 g of methyl iodide was gradually added.
After the addition, the temperature was raised and the reaction was carried out at 60 ° C. for 8 hours. After cooling to room temperature, about 24 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, dissolved in methanol, and reprecipitated repeatedly in a methanol-acetone system, and the precipitate was dried to obtain 3.5 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 8,600 in terms of polyethylene glycol, and the number average molecular weight was 5,3.
00.

Example A1 : Preparation of Ink Set A1 2.0 g of the water resistance imparting agent A1 prepared in Synthesis Example A1 was added to
C. I. 4 g of Acid Black 24 and 1 of glycerin
1 g, 5 g of 2-pyrrolidinone, and 10 g of diethylene glycol monobutyl ether were added, and ultrapure water was further added to make the total amount 100 g, thereby obtaining a black ink A1.

Further, the above dye is C.I. I. Acid Yellow 23 to 3 g, C.I. I. Acid Red 1
3 as 2 g, or C.I. I. A yellow ink A1, a magenta ink A1, and a cyan ink A1 were obtained in the same manner as above except that Acid Blue 9 was changed to 2.5 g.

The four inks are combined to form an ink set A1.

Example A2 : Preparation of Ink Set A2 To 3.0 g of the water-resistance imparting agent A2 prepared in Synthesis Example A2,
C. I. Acid Black 1 is 3.5 g, diethylene glycol is 12 g, 1,3-dimethyl-2-imidazolidinone is 5 g, urea is 5 g, triethylene glycol monobutyl ether is 7 g, and potassium hydroxide is 0.1 g.
1 g was added, and ultrapure water was added to make the total amount 100 g, whereby a black ink A2 was obtained.

Further, the above dye is C.I. I. Acid Yellow 17 to 3.0 g, C.I. I. Acid Red 1 to 2.5 g or C.I. I. A yellow ink A2, a magenta ink A2, and a cyan ink A2 were obtained in the same manner as described above except that the direct blue 86 was changed to 4.0 g.

The four inks are combined to form an ink set A2.

Example A3 : Preparation of Ink Set A3 2.0 g of the water resistance imparting agent A3 prepared in Synthesis Example A3 was added to
C. I. 4.5 g of Direct Black 32, 9 g of glycerin, 5 g of thiodiglycol, 5 g of diethylene glycol monobutyl ether, 10 g of N-methylimidazole, 0.9 g of triethanolamine, 0.2 g of sodium hydroxide, and Surfynol 465
(Trade name, manufactured by Air Products and Chemicals) was added to 1 g, and ultrapure water was added to make a total amount of 100 g, thereby obtaining a black ink A3.

Further, the above dye was used in Daiwa IJ Yellow 21.
4 HL (trade name, manufactured by Daiwa Kasei Co., Ltd., CI Direct Yellow 86) in 2 g, palatin first pink-BNI in 6 g, or C.I. I. 3.5 g of this as Direct Blue 199
Except that the yellow ink A
3. Magenta ink A3 and cyan ink A3 were obtained.

The four inks are combined to form an ink set A3.

Example A4 : Preparation of Ink Set A4 1.8 g of Waterproofing Agent A4 prepared in Synthesis Example A4
And C. I. 4.5 g of Direct Black 32, 9 g of glycerin, 5 g of triethylene glycol, 5 g of maltitol, 3 g of L-histidine, 0.6 g of triethanolamine, 2.5 g of ethanol, and Surfynol 465 (trade name) , Air Products and Chemicals Co., Ltd.), and ultrapure water was added to make the total amount 100 g, to obtain a black ink A4.

Further, the above dye was used in Daiwa IJ Yellow 21.
4 HL (trade name, manufactured by Daiwa Kasei Co., Ltd., CI Direct Yellow 86) in 2 g, palatin first pink-BNI in 6 g, or C.I. I. 3.5 g of this as Direct Blue 199
Except that the yellow ink A
4. Magenta ink A4 and cyan ink A4 were obtained.

The four inks are combined to form an ink set A4.

Example A5 : Preparation of ink set A5 2.7 g of the water resistance imparting agent A5 prepared in Synthesis Example A5 was added to
C. I. 6 g of Direct Black 19 was dissolved, 10 g each of thiodiglycol and diethylene glycol monoethyl ether were added, and ultrapure water was further added to make a total amount of 100 g, whereby a black ink A5 was obtained.

Further, the above dye was used as MY123 (trade name,
Arimoto Chemical Co., Ltd.) to 3.2 g, Savinyl Pink 6BLS (trade name, Clariant Japan Co., Ltd.) to 3.2 g, or Bali Fast Blue 1605
As above, except that this was changed to 3 g,
Yellow ink A5, magenta ink A5 and cyan ink A5 were prepared.

The four inks are combined to form an ink set A5.

Example A6 : Preparation of Ink Set A6 To 3.2 g of the water-resistance imparting agent A6 prepared in Synthesis Example A6,
C. I. 6 g of food black 2 and 12 of glycerin
g, 10 g of triethylene glycol monobutyl ether
g, diethylene glycol 5 g, guanidine 3.0
g, and the nonionic surfactant Surfynol 465
Was mixed, and ultrapure water was added to make a total amount of 100 g, whereby a black ink A6 was obtained.

Further, the above dye is C.I. I. Acid Yellow 23 to 5 g, or C.I. I. Acid Red 249 to 2.5 g or C.I. I. A yellow ink A6, a magenta ink A6, and a cyan ink A6 were prepared in the same manner as described above except that 4 g of Direct Blue 86 was used. These four inks are combined to form an ink set A6.

Example A7 : Preparation of Ink Set A7 5.0 g of the water resistance imparting agent A7 prepared in Synthesis Example A7 was added to
C. I. Acid Black 1 (5.0 g), glycerin (10 g), 2-pyrrolidinone (5 g), triethylene glycol monobutyl ether (10 g) were added, and ultrapure water was added to make a total amount of 100 g, whereby a black ink A7 was obtained.

Further, the above dye is C.I. I. Acid Yellow 17 to 3.0 g, C.I. I. Acid Red 1 to 2.5 g or C.I. I. A yellow ink A7, a magenta ink A7, and a cyan ink A7 were obtained in the same manner as described above except that the direct blue 86 was changed to 4.0 g.

The four inks are combined to form an ink set A7.

Example A8 : Preparation of Ink Set A8 2.8 g of the water resistance imparting agent A8 prepared in Synthesis Example A8 was used, and 5 g of thiourea and 5 g of diethylene glycol were added as humectants in the same manner as in Example A1. Black ink A8, yellow ink A8, magenta ink A8,
Cyan ink A8 was prepared.

The four inks are combined to form an ink set A8.

Example A9 : Preparation of Ink Set A9 As the water resistance imparting agent, 1.0 g of the water resistance imparting agent A1 prepared in Synthesis Example A1 and 2.2 g of the water resistance imparting agent A7 prepared in Synthesis Example A7 were used. Other than the above, in the same manner as in Example A7,
Black ink A9, yellow ink A9, magenta ink A9, and cyan ink A9 were prepared.

The four inks are combined to form an ink set A9.

Example A10 Preparation of Ink Set A10 As a water-resistance imparting agent, 2.7 g of the water-resistance imparting agent A9 prepared in Synthesis Example A9 was used, except that 5 g of urea was changed to 5 g of 2- (dimethylamino) ethanol. In the same manner as in Example A2, black ink A10, yellow ink A1
0, magenta ink A10 and cyan ink A10 were prepared.

The four inks are combined to form an ink set A10.

Example A11 : Preparation of Ink Set A11 The water-resistance imparting agent A7 prepared in Synthesis Example A7 was added to 3.5 g.
C. I. 6 g of direct black 195, 12 g of glycerin, 10 g of triethylene glycol monobutyl ether, 5 g of tetraethylene glycol, 1,3-
Dimethyl-2-imidazolidinone (4 g), nonionic surfactant Surfynol 465 (1 g), and ultrapure water were added to make a total amount of 100 g, whereby a black ink A11 was obtained.

Further, the dye is C.I. I. Acid Yellow 23 to 5 g, or C.I. I. Acid Red 249 to 2.5 g or C.I. I. A yellow ink A11, a magenta ink A11, and a cyan ink A11 were prepared in the same manner as described above except that the amount of Direct Blue 86 was changed to 4 g.

The four inks are combined to form an ink set A11.

Example A12 (Comparative Example) : Ink set A12
Preparation of black ink A12 and yellow ink A1 in the same manner as in Example A1 except that no water resistance imparting agent A1 was used.
2, magenta ink A12 and cyan ink A12
I got Ink set A combining these four types of ink
It is assumed to be 12.

Example A13 (Comparative Example) : Ink set A13
Example A except that the water resistance imparting agent A1 was changed to SP-200 (trade name, polyethyleneimine, manufactured by Nippon Shokubai Co., Ltd.)
In the same manner as in Example 1, a black ink A13, a yellow ink A13, a magenta ink A13, and a cyan ink A13 were obtained. The four inks are combined to form a color ink set A13.

Example A14 (Comparative Example) : Waterproofing agent A10
And preparation of ink set A14 In a 500 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 19.7 g of N, N-dimethylaminopropylacrylamide and a 75% by weight aqueous solution of trimethylaminopropylacrylamide chloride were placed. 8
1.3 g, 4.0 g of 2,4-diphenyl-4-methyl-1-pentene and 13 g of N, N-dimethylformamide
After charging 0 g, dimethyl 2,2′-azobis (2-
20 g of N, N-dimethylformamide in which 5.0 g of methylpropionate was dissolved was added, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C for 4 hours. Continued. After cooling to room temperature, about 26
0 g of a pale yellow solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methanol, and reprecipitation was repeated with a methanol-acetone system.
0.1 g of solid was obtained. In addition, thermometer, stirrer,
In a 100 ml flask equipped with a nitrogen inlet tube and a reflux condenser, 10.0 g of the above solid substance was charged into 20.0 g of water, the temperature was raised while stirring under a nitrogen atmosphere, and the temperature was maintained at 90 ° C. for 20 hours. Upon cooling, about 30 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, redissolved in methanol,
Reprecipitation was repeated with a methanol-acetone system, and the precipitate was dried to obtain 8.1 g of a solid content. As a result of the GPC measurement,
The weight average molecular weight is 4,6 in terms of polyethylene glycol.
The number average molecular weight was 3,100.

According to the above synthesis method, the unit (a) was 30 mol.
% Of a water-resistance imparting agent A10. A black ink A14, a yellow ink A14, a magenta ink A14, and a cyan ink A14 were obtained in the same manner as in Example A3, except that 2.0 g of the water resistance imparting agent was used. These four inks are combined to form an ink set A14.

Ink composition performance evaluation test The ink composition prepared above was evaluated by the following method.

As the printer, an improved version of an ink jet recording system printer (color printer MJ-5000C manufactured by Seiko Epson Corporation) was used. The ink was used for evaluation after being filtered with a 5 μm filter.

Evaluation test A1 : Water resistance 3.5 c on A4 size acidic plain paper (trade name: Xerox-P, manufactured by Fuji Xerox Co., Ltd.) as a recording medium.
Full solid printing and character printing of 1.5 cm width for each color were performed every m (non-recording portion). The printed matter was allowed to stand naturally for one hour, and then immersed in 500 ml of water for one hour. After immersion, it was air-dried for 24 hours, and the ink transfer density of the non-recording portion and the remaining ink of the recording portion were visually evaluated. The results were evaluated according to the following criteria.

Evaluation A: The non-recording portion is not colored at all.
There is no change in the recording section. Evaluation B: Colored ink is present in the non-recording portion, but there is no practical problem. Evaluation C: Adhesion of the ink to the non-recording portion is noticeable. There is a density drop in the recording area. Evaluation D: Coloring of a non-recorded portion and a decrease in density of a recorded portion were remarkable, and in particular, characters sometimes disappeared and could not be read.

Evaluation test A2 : Light fastness A full-color image was printed using the same recording medium and printer as in Evaluation test 1.

The printed matter was evaluated for light fastness by the day and night method of the JIS0841 daylight test. The results were evaluated according to the following criteria.

Evaluation A: Grade change is less than first grade with respect to the ink without adding a water resistance imparting agent, based on the blue scale. Evaluation B: Grade change is primary or secondary. Evaluation C: Grade change exceeds third grade.

Evaluation test A3 : Environmental stability The container enclosing the ink was left at 60 ° C. for 1 day, and then
Exposure was performed 10 times in a cycle of leaving standing at 30 ° C. for 1 day. Thereafter, generation of precipitates and generation of discoloration of the ink were visually observed. The results were evaluated according to the following criteria.

Evaluation A: No change. Evaluation B: Precipitate or discoloration of practically sufficient level was observed. Evaluation C: A remarkable precipitate or discoloration which poses a practical problem was observed.

The above results are as shown in the following table.

[0181]

[Table 1]

Example B Synthesis Example B1 : Preparation of Waterproofing Agent B1 15.0 g of N, N-dimethylaminopropylacrylamide was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 0.57 g of 2,4-diphenyl-4-methyl-1-pentene, n-acetic acid
After charging 20.0 g of butyl, dimethyl 2,2 ′
After adding 20.0 g of n-butyl acetate in which 0.44 g of -azobis (2-methylpropionate) was dissolved, the mixture was heated with stirring under a nitrogen atmosphere and kept at 80 ° C for 4 hours.
The temperature was raised to ℃, and the reaction was continued for another 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 13.0 g of a solid.

Further, in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, water 1 was added.
0.0 g and 5.0 g of the above solid substance were charged, and the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 90 ° C. for 20 hours. The solvent was distilled off under reduced pressure, re-dissolved in methyl ethyl ketone, and re-precipitated repeatedly in a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 4.8 g of a solid content. As a result of the GPC measurement,
The weight average molecular weight is 9.4 in terms of polyethylene glycol.
The number average molecular weight was 5,100.

Synthesis Example B2 : Preparation of Waterproofing Agent B2 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 14.0 g of N, N-dimethylaminopropylacrylamide and trimethyl chloride were placed. 1.3 g of a 75% by weight aqueous solution of aminopropylacrylamide, 0.90 g of 2,4-diphenyl-4-methyl-1-pentene and 2 g of N, N-dimethylformamide
After charging 0.0 g, 20.0 g of N, N-dimethylformamide in which 1.09 g of dimethyl 2,2′-azobis (2-methylpropionate) were dissolved was added, and the mixture was heated while stirring under a nitrogen atmosphere. After keeping at 80 ° C. for 4 hours, the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 57 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 12.3 g of a solid.

In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, water 2 was added.
10.0 g of the above solid substance was charged to 0.0 g, and the temperature was increased while stirring under a nitrogen atmosphere and maintained at 90 ° C. for 20 hours, and then cooled to room temperature to obtain about 30 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in methyl ethyl ketone, and reprecipitated repeatedly with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 9.6 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 4,200 and the number average molecular weight was 2,800 in terms of polyethylene glycol.

Synthesis Example B3 : Preparation of Waterproofing Agent B3 In a 500 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 52.6 g of N, N-dimethylaminopropylacrylamide, trimethyl chloride A 75% by weight aqueous solution of aminopropylacrylamide was added to 2
3.2 g, 2,4-diphenyl-4-methyl-1-pentene, 4.0 g, N, N-dimethylformamide, 13 g
After charging 0 g, dimethyl 2,2′-azobis (2-
20 g of N, N-dimethylformamide in which 5.0 g of methylpropionate was dissolved was added, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C for 4 hours. Continued. After cooling to room temperature, about 23
0 g of a pale yellow clear solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 40.3 g of a solid.

Further, water 2 was added to a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube.
After charging 0.0 g and 10.0 g of the above solid substance, the mixture was heated with stirring under a nitrogen atmosphere and kept at 90 ° C. for 20 hours, and then cooled to room temperature to obtain about 30 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in methyl ethyl ketone, and re-precipitated repeatedly in a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 9.2 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 4,800 and the number average molecular weight was 3,200 in terms of polyethylene glycol.

Synthesis Example B4 : Preparation of Waterproofing Agent B4 The reaction and purification were carried out in the same manner as in Synthesis Example B1, except that the amount of 2,4-diphenyl-4-methyl-1-pentene was changed to 1.13 g. Was. The yield after drying was 4.5 g.
As a result of GPC measurement of the product, the weight average molecular weight was 4,600 in terms of polyethylene glycol, and the number average molecular weight was 2,7.
00.

Synthesis Example B5 Preparation of Waterproofing Agent B5 5.0 g of the product obtained in Synthesis Example B1 was charged into a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. Methyl ethyl ketone 10.0
g and methanol 10.0 g. While stirring this solution, 1.82 g of methyl iodide was gradually added.
After the addition, the temperature was raised and the reaction was carried out at 60 ° C. for 8 hours. After cooling to room temperature, about 26 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, dissolved in methanol, and reprecipitated repeatedly with a methanol-acetone system, and the precipitate was dried to obtain 5.2 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 9,900 in terms of polyethylene glycol, and the number average molecular weight was 6,
It was 100.

Synthesis Example B6 : Preparation of Waterproofing Agent B6 In a 500 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 19.7 g of N, N-dimethylaminopropylacrylamide and trimethyl chloride were placed. 8% by weight aqueous solution of aminopropylacrylamide
1.3 g, 4.0 g of 2,4-diphenyl-4-methyl-1-pentene and 13 g of N, N-dimethylformamide
After charging 0 g, dimethyl 2,2′-azobis (2-
20 g of N, N-dimethylformamide in which 5.0 g of methylpropionate was dissolved was added, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C for 4 hours. Continued. After cooling to room temperature, about 26
0 g of a pale yellow solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methanol, and reprecipitation was repeated with a methanol-acetone system.
0.1 g of solid was obtained.

Further, water 2 was added to a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube.
10.0 g of the above solid substance was charged to 0.0 g, and the temperature was increased while stirring under a nitrogen atmosphere and maintained at 90 ° C. for 20 hours, and then cooled to room temperature to obtain about 30 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in methanol, and re-precipitated repeatedly in a methanol-acetone system.
g of solids were obtained. As a result of GPC measurement, the weight average molecular weight was 4,600 and the number average molecular weight was 3,100 in terms of polyethylene glycol.

Synthesis Example B7 : Preparation of Waterproofing Agent B7 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, a 75% by weight aqueous solution of trimethylaminopropylacrylamide chloride was added to a 20.0% flask.
g, 2.26 g of 2,4-diphenyl-4-methyl-1-pentene, 20.0 g of N, N-dimethylformamide
After charging, 20.0 g of N, N-dimethylformamide in which 1.35 g of dimethyl 2,2′-azobis (2-methylpropionate) was dissolved, and the mixture was heated to 80 ° C. while stirring under a nitrogen atmosphere. After maintaining for 4 hours, the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 6
3 g of a pale yellow cloudy solution were obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methanol, and reprecipitation was repeated with a methanol-acetone system, and the precipitate was dried to obtain 12.3 g of a solid. 100 m with thermometer, stirrer, nitrogen inlet tube and reflux condenser tube
2 g of water and 10.0 g of the above solid substance
, And the mixture was heated at 90 ° C. for 20 hours while stirring under a nitrogen atmosphere, and then cooled to room temperature to obtain about 30 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, redissolved in methanol, and reprecipitated repeatedly with a methanol-acetone system, and the precipitate was dried to obtain 8.5 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 1 in terms of polyethylene glycol.
The number average molecular weight was 4,000 and the number average molecular weight was 5,700.

Color Ink Set B1 C.I. I. 6 g of Direct Black 195, 10 g of glycerin, 10 g of diethylene glycol, and 2-
5 g of pyrrolidone was mixed, and ultrapure water was added to make the total amount 100
As g, the mixture was filtered through a 5 μm filter to prepare a black ink B1.

Further, the above dye is C.I. I. 2.5 g of this as Direct Yellow 132, or C.I. I. Acid Red 249 in 2 g or C.I.
I. A yellow ink B1, a magenta ink B1, and a cyan ink B1 were prepared in the same manner as described above, except that Direct Blue 199 was changed to 4 g.

The four types of color inks are combined to form a color ink set B1.

Color Ink Set B2 C.I. I. 10 g of food flux 2 and 15 of glycerin
g, 5 g of diethylene glycol monobutyl ether,
Black ink 2 was obtained by mixing 5 g of diethylene glycol and 1 g of nonionic surfactant Surfynol 465 (trade name, manufactured by Air Products and Chemicals), and adding ultrapure water to make the total amount 100 g.

Further, the above dye is C.I. I. Acid Yellow 23 to 5 g, or C.I. I. 2.5 g of Direct Red 9 or C.I. I. A yellow ink B2, a magenta ink B2, and a cyan ink B2 were prepared in the same manner as above, except that Direct Blue 87 was changed to 4 g.

The four types of color inks are combined to form a color ink set B2.

5 g of a color ink set B3 carbon black MA7 (trade name, manufactured by Mitsubishi Kasei Corporation) and a styrene-acrylic acid copolymer (trade name:
1 g of Joncryl 679, Mw 7,000, acid value 200, manufactured by Johnson Polymer Co., Ltd.) and 0.3 g of triethanolamine were mixed, and glass beads (1.7 mm in diameter; 82.
(5 g used) for 2 hours. Thereafter, the glass beads were removed, and Boncoat 4001 (trade name,
50 g of acrylic resin emulsion, resin component 50% by weight, manufactured by Dainippon Ink Co., Ltd.), sucrose 0.7
g, maltitol 6.3 g, glycerin 10 g, 2
-Add 2 g of pyrrolidone, 4 g of ethanol, and ultrapure water so that the total amount becomes 100 g, and stir and mix;
The mixture was filtered through a 5 μm filter to prepare a black ink B3.

Further, the above-mentioned pigment is referred to as a pigment KETYELLOW.
403 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) in 2 g, or pigment KETRED309 (tradename, manufactured by Dainippon Ink and Chemicals, Inc.) in 2 g, or pigment KETBLUEEX-1 (trade name) ,
Dainippon Ink and Chemicals, Inc.), except that this was changed to 2 g.
3, magenta ink B3 and cyan ink B3 were prepared.

The four types of color inks are combined to form a color ink set B3.

Color Ink Set B4 C.I. I. 6 g of direct black 19, 10 g of glycerin, 10 g of diethylene glycol, 7 g of triethylene glycol monobutyl ether, 0.1 g of sodium alginate (manufactured by Kanto Kogyo KK), and Surfynol 465 which is a nonionic surfactant (trade name) , Air Products and Chemicals Co., Ltd.), mixed with ultrapure water to make the total amount 100 g, and filtered through a 5 μm filter to prepare a black ink B4.

The dye C.I. I. 2.5 g of this as Direct Yellow 144, or C.I. I. Direct Red 227 to 2 g or C.I.
I. A yellow ink B4, a magenta ink B4, and a cyan ink B4 were prepared in the same manner as above except that Acid Blue 9 was changed to 4 g.

The four types of color inks are combined to form a color ink set B4.

Color ink set B5 2.0 g of the water resistance imparting agent B1 prepared in Synthesis Example B1 was
C. I. 4 g of Acid Black 24 and 1 of glycerin
1 g, 5 g of 2-pyrrolidine, and 10 g of diethylene glycol monobutyl ether were added, and ultrapure water was further added to adjust the total amount to 100 g, thereby obtaining a black ink B5.

Further, the dye is C.I. I. 3 g of this as Direct Yellow 23, or C.I. I. Direct Red 13 to 2 g or C.I. I. A yellow ink B5, a magenta ink B5, and a cyan ink B5 were prepared in the same manner as above except that Acid Blue 9 was changed to 2.5 g.

The four types of color inks are combined to form a color ink set B5.

Reaction Solution B1 As a water-resistance imparting agent, 4 g of the water-resistance imparting agent B1 prepared in Synthesis Example B1, 10 g of glycerin, 10 g of diethylene glycol, and 5 g of diethylene glycol monobutyl ether were mixed, and ultrapure water was added to obtain a total amount. 100g
And filtered through a 5μ filter to prepare a reaction solution B1.

Reaction Solution B2 As the water resistance imparting agent, 7 g of the water resistance imparting agent B6 prepared in Synthesis Example B6 and 8 g of 35% hydrochloric acid were used.
Reaction solution B2 was prepared in the same manner as reaction solution B1.

Reaction Solution B3 The same procedure as in Reaction Solution B1 was carried out except that 6 g of the water resistance imparting agent B5 prepared in Synthesis Example B5 and 5 g of magnesium nitrate hexahydrate as a polyvalent metal salt were used as the water resistance imparting agent. Thus, a reaction solution B3 was prepared.

Reaction Solution B4 [0223] Except for using 5 g of the water resistance-imparting agent B7 prepared in Synthesis Example B7, 7 g of 35% hydrochloric acid, and 5 g of magnesium nitrate hexahydrate as a polyvalent metal salt, as the water-resistance imparting agent. Reaction solution B4 was prepared in the same manner as reaction solution B1.

Reaction solution B5 As a water-resistance imparting agent, 7 g of the water-resistance imparting agent B3 prepared in Synthesis Example B3, 8 g of 35% hydrochloric acid, 10 g of glycerin, and 10 g of diethylene glycol were mixed.
Ultrapure water was added to make the total amount 100 g, and the mixture was filtered through a 5 μm filter to prepare a reaction liquid B5.

Example B1 A performance evaluation test shown below was conducted by combining the color ink set B1 and the reaction liquid B2.

Example B2 The following performance evaluation test was conducted by combining the color ink set B2 and the reaction liquid B1.

Example B3 The following performance evaluation test was performed using the color ink set B3 and the reaction liquid B4 in combination.

Example B4 A performance evaluation test shown below was conducted by combining the color ink set B4 and the reaction liquid B3.

Example B5 The following performance evaluation test was conducted by combining the color ink set B1 and the reaction liquid B5.

Example B6 The following evaluation test was carried out using the color ink set B2 and the reaction liquid B5 in combination.

Example B7 The following evaluation test was conducted by combining the color ink set B5 and the reaction liquid B5.

Example B8 (Comparative Example) A performance evaluation test shown below was performed using only the color ink set B1.

Example B9 (Comparative Example) The following performance evaluation test was performed using only the color ink set B3.

Example B10 (Comparative Example) The same procedure as in the reaction liquid B1 was carried out except that 4 g (as solid content) of PAA-10C (trade name, Nitto Boseki, 10% aqueous solution of polyallylamine) was used as a water resistance imparting agent. Thus, a reaction solution B6 was prepared. This was combined with the color ink set B1, and the following performance evaluation tests were performed.

Performance Evaluation Test Each of the color ink set prepared above and the reaction liquid was combined and evaluated by the following method. In addition, what improved the inkjet recording system printer (the Seiko Epson Corporation; color printer PM-750C) was used as a printer.

Evaluation Test B1 : Print Quality (Bleeding and Color Bleed) Two types of A4 size plain paper (trade names: Xerox-P and Xerox-4024, both manufactured by Fuji Xerox Co., Ltd.) as recording media, and recycled paper ( Trade name: Xerox-R, manufactured by Fuji Xerox Co., Ltd.). For Examples B1 to B6 and Example B10, the case where the reaction liquid was printed first and then a full-color image was printed with the color ink set immediately thereafter, and the case where the reaction liquid was printed first with the color ink set and printed immediately thereafter And two types of evaluations. Then, the obtained full-color image was visually evaluated for bleeding and color freezing. The results were evaluated according to the following criteria.

Evaluation A: No bleeding or color bleeding was observed in any of the recording media. Evaluation B: There is a recording medium on which slight bleeding or color bleeding occurs. Evaluation C: In all the recording media, bleeding or color bleeding occurs remarkably.

Evaluation test B2 : Water resistance Using the same recording medium and printer as in Evaluation test 1, using the combination shown in the example, 1.5 for every 3.5 cm (non-recording portion)
Black, yellow, magenta, cyan, red, green and blue full solid prints and character prints of cm width were performed. After each printed matter was left naturally for 1 hour, it was immersed in 500 ml of water for 1 hour. After immersion, it was air-dried for 24 hours, and the ink transfer density of the non-recording portion and the remaining ink of the recording portion were visually evaluated. The results were evaluated according to the following criteria.

Evaluation A: The non-recorded portion is not colored at all.
There is no change in the recording section. Evaluation B: Coloring of a non-recording portion or a decrease in density of a recording portion may be indicated. Evaluation C: Coloring of the non-recorded area and a decrease in density of the recorded area were remarkable, and particularly, the characters disappeared and could not be read.

Evaluation test B3 : Light fastness Using the same recording medium and printer as in Evaluation test 1, full-color images were printed in the combinations shown in the examples. Using the printed matter, the O.D. of the printed matter before and after exposure for one day with a xenon weatherometer Ci35W (trade name, manufactured by Atlas Electric Devices Co., Ltd.). D. The value is entered in the color control system SPM50 (trade name,
GRETAG). The results were evaluated according to the following criteria.

Evaluation A: Discoloration and discoloration were O.D. D. The value is less than 5%. Evaluation B: Discoloration and discoloration were O. D. The value ranges from 5 to 20%. Evaluation C: Discoloration and discoloration were O. D. Value exceeds 20%.

The above results were as shown in the following table.

[0231]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a view showing an ink jet recording apparatus according to the present invention. In this embodiment, a recording head and an ink tank are independent of each other, and an ink composition and a reaction liquid are supplied to the recording head through an ink tube.

FIG. 2 is an enlarged view of a nozzle surface of a recording head,
Is the nozzle surface of the reaction liquid, and 1c is the nozzle surface of the ink composition.

FIG. 3 is a diagram illustrating inkjet recording using the recording head of FIG. 2; In the figure, reference numeral 31 denotes a reaction liquid adhering area, and reference numeral 32 denotes a printing area on which the ink is printed after the reaction liquid is adhering.

FIG. 4 is a diagram showing another embodiment of the recording head according to the present invention, in which all the ejection nozzles are arranged in the horizontal direction.

FIG. 5 is a view showing an ink jet recording apparatus according to the present invention. In this embodiment, a recording head and an ink tank are integrated.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Recording head 2 Ink tank 3 Ink tube 14 Heater 21 Reaction liquid discharge nozzle 22, 23, 24, 25 Ink composition discharge nozzle 31 Reaction liquid adhesion area 32 Printing area

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 11/00 B41J 3/04 101Y 101Z (72) Inventor Ota etc. 3-3 Yamato, Suwa City, Nagano Prefecture No. 5 Inside Seiko Epson Corporation (72) Inventor Tetsuya Aoyama 3-5-5 Yamato, Suwa City, Nagano Prefecture Inside Seiko Epson Corporation (72) Inventor Nobuo Uotani 1-Onodai, Midori-ku, Chiba City, Chiba Prefecture 1-1 Showa Denko KK Research Institute (72) Inventor Yuji Ito 1-1-1 Onodai Midori-ku, Chiba-shi, Chiba Prefecture Showa Denko KK Research Institute (72) Inventor Hiroshi Takahashi Chiba-shi, Chiba 1-1-1 Onodai, Midori-ku Showa Denko KK

Claims (49)

[Claims] 1. A (co) polymer of a repeating unit (a) represented by the formula (a) in the following formula (I) and a repeating unit (b) represented by the formula (b). And the unit (a) is 100 to
A cationic water-soluble resin comprising a (co) polymer comprising 0 mol% in one range and one terminal group of the molecule is a group containing a carboxyl group, and the other terminal group is a group containing an aromatic ring. A water resistance imparting agent. Embedded image (In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ may be the same or different, C _1-3
It represents an alkyl group, R ₄ represents a hydrogen atom or a methyl group, R _5, R _6, and R _7, which may be the same or different, represent a C _1-3 alkyl group, Z ^- is a counter Represents an ion, and k and l may be the same or different, 1, 2,
Or represents 3. ) 2. A compound having a number average molecular weight of 1,000 to 10,000.
The water-resistance imparting agent according to claim 1, wherein 3. The water-resistance imparting agent according to claim 1, wherein the terminal group containing a carboxyl group is a group selected from the group consisting of the following formulas (II) to (V). Embedded image 4. The method according to claim 1, wherein the terminal group containing an aromatic ring has the following formula (VI):
(XVII) is a group selected from the group consisting of
The water resistance imparting agent according to any one of the above. Embedded image 5. The unit (a) and the unit (b) are each formed by block or random polymerization.
The water resistance imparting agent according to any one of claims 1 to 4. 6. The water-resistance-imparting composition according to claim 1, wherein in the repeating unit represented by the formula (I), R ₁ represents a hydrogen atom and R ₄ represents a hydrogen atom. Agent. 7. The water resistance imparting agent according to claim 1, wherein k represents 3 and 1 represents 3 in the repeating unit represented by the formula (I). 8. The water resistance imparting agent according to claim 1, wherein Z represents a halogen atom in the repeating unit represented by the formula (I). 9. An alkali-soluble colorant, a water-soluble organic solvent, water, and a cationic water-soluble resin as defined in claim 1, wherein the unit (a) is contained in the range of 100 to 80 mol%. An ink composition comprising at least: 10. The cationic water-soluble resin according to claim 9, wherein the number average molecular weight is in the range of 1,000 to 10,000.
3. The ink composition according to claim 1. 11. The cationic water-soluble resin, wherein the terminal group containing a carboxyl group has the formula (II) to (II) defined in claim 3.
The ink composition according to claim 9, which is a group selected from the group consisting of (V). 12. The cationic water-soluble resin according to claim 9, wherein the terminal group containing an aromatic ring is a group selected from the group consisting of formulas (VI) to (XVII) defined in claim 4. The ink composition according to any one of the above. 13. The unit (a) of the cationic water-soluble resin.
The ink composition according to any one of claims 9 to 12, wherein the and the unit (b) are formed by block or random polymerization, respectively. 14. In the repeating unit represented by the formula (I), R ₁ represents a hydrogen atom, and R ₄ represents a hydrogen atom.
The ink composition according to any one of claims 9 to 13. 15. The repeating unit represented by the formula (I), wherein k represents 3 and 1 represents 3.
The ink composition according to any one of the above. 16. The ink composition according to claim 9, wherein in the repeating unit represented by the formula (I), Z represents a halogen atom. 17. The method according to claim 9, further comprising an acidic substance.
17. The ink composition according to any one of items 16 to 16. 18. The ink composition according to claim 9, further comprising a basic substance. 19. The ink composition according to claim 18, wherein the basic substance is a hydroxide of an alkali metal or an alkaline earth metal. 20. The ink composition according to claim 9, wherein the water-soluble organic solvent has a lower vapor pressure than water. 21. The ink composition according to claim 9, comprising the water-soluble organic solvent in a range of 5 to 50% by weight. 22. The method according to claim 9, further comprising a penetration enhancer selected from the group consisting of lower alcohols, cellosolves, carbitols, and nonionic surfactants.
22. The ink composition according to any one of claims 21 to 21. 23. The composition further comprising at least one selected from the group consisting of lower alcohols, cellosolves, and carbitols, and a nonionic surfactant.
An ink composition according to any one of claims 9 to 22. 24. The ink composition according to claim 9, wherein the colorant is a dye or a pigment. 25. The ink composition according to claim 9, further comprising a water-soluble resin other than the cationic water-soluble resin. 26. An anti-clogging agent selected from the group consisting of a water-soluble hydroxypyridine derivative, a linear or cyclic amide compound, an imidazole derivative, a hydroxycyclic amine compound, an azole compound, an azine compound, an amidine derivative and a purine derivative. The ink composition according to any one of claims 9 to 25, further comprising: 27. The ink composition according to claim 9, which is used for ink-jet recording. 28. A reaction liquid used in an ink jet recording method for performing printing by adhering a reaction liquid comprising at least the cationic water-soluble resin defined in claim 1 and an ink composition to a recording medium. 29. The cationic water-soluble resin according to claim 2, wherein the number-average molecular weight is in the range of 1,000 to 10,000.
9. The reaction liquid for inkjet recording according to 8. 30. The terminal group containing a carboxyl group of the cationic water-soluble resin is a compound represented by the formula (II)
30. The reaction liquid for inkjet recording according to claim 28, which is a group selected from the group consisting of (V). 31. The cationic water-soluble resin wherein the terminal group containing an aromatic ring is a group selected from the group consisting of formulas (VI) to (XVII) defined in claim 4. The reaction liquid for inkjet recording according to any one of the above. 32. The unit (a) of the cationic water-soluble resin
The reaction liquid for inkjet recording according to any one of claims 28 to 31, wherein the unit and the unit (b) are each formed by block or random polymerization. 33. The repeating unit represented by the formula (I) of the cationic water-soluble resin, wherein R ₁ represents a hydrogen atom, and R ₄ represents a hydrogen atom. The reaction liquid for inkjet recording according to item 1. 34. In the cationic water-soluble resin, in the repeating unit represented by the formula (I), k represents 3, and 1 represents 3
The reaction liquid for inkjet recording according to any one of claims 28 to 33, wherein 35. The reaction liquid for inkjet recording according to claim 28, wherein Z represents a halogen atom in the repeating unit represented by the formula (I) of the cationic water-soluble resin. 36. The method according to claim 2, further comprising an acidic substance.
The reaction liquid for inkjet recording according to any one of claims 8 to 35. 37. The reaction liquid for ink-jet recording according to claim 28, further comprising a basic substance. 38. The reaction liquid according to claim 37, wherein the basic substance is a hydroxide of an alkali metal or an alkaline earth metal. 39. The reaction liquid for inkjet recording according to claim 28, further comprising a water-soluble resin other than the cationic water-soluble resin. 40. The reaction liquid for inkjet recording according to claim 28, further comprising a polyvalent metal salt. 41. The reaction liquid according to claim 40, wherein the polyvalent metal salt is a nitrate or a carboxylate. 42. The composition according to claim 28, wherein the pH is 2 to 10.
The reaction liquid for inkjet recording according to any one of claims 1 to 7. 43. A recording medium comprising: an ink composition;
42. An ink jet recording method for performing printing by adhering the reaction liquid according to any one of items 8 to 41. 44. The ink jet recording method according to claim 43, wherein the ink composition comprises a pigment or a dye as a colorant. 45. The ink composition according to claim 43, wherein the ink composition comprises a pigment and a resin emulsion.
3. The inkjet recording method according to item 1. 46. The ink-jet recording according to claim 43, wherein the step of discharging the droplets of the ink composition onto the recording medium is performed after the step of attaching the reaction liquid to the recording medium. Method. 47. The ink-jet recording method according to claim 43, wherein the step of discharging the droplets of the ink composition onto the recording medium is performed before the step of attaching the reaction liquid to the recording medium. Recording method. 48. The ink composition according to claim 9, wherein the ink composition is the ink composition according to any one of claims 9 to 27.
48. The ink jet recording method according to any one of items 47 to 47. 49. A recorded matter recorded by the recording method according to any one of claims 43 to 48.