JP2002080742A - Water-based ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-soluble dye which has excellent water resistance, alkali resistance, acid resistance, light resistance, and solubility in solvents, to provide a water-based ink which has a good color tone, can impart excellent water resistance, light resistance and weather resistance to printed articles, and has excellent storage stability, and to provide a water-based ink which hardly clogs printing heads and is used for ink jet recording. SOLUTION: This oil-soluble dye obtained by the amidation treatment of a water-soluble dye having one or more groups selected from sulfo group and carboxy group in the molecule. The water-based ink containing the oil-soluble dye. And the method for producing the oil-soluble dye, comprising halogenating the water-soluble dye having one or more groups selected from sulfo group and carboxy group in the molecule and then amidating the halogenated compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-soluble dye which can be suitably used for an ink jet recording liquid, ink for a ballpoint pen, ink for a marker, toner, paint, paint for lacquer spray, magic ink and the like. In addition, the oil-soluble dye referred to in this specification means all water-insoluble dyes.

[0002] The present invention also relates to a water-based ink. More specifically, it relates to a water-based ink that can be suitably used as a water-based ink for ink-jet recording.

[0003]

2. Description of the Related Art Oil-soluble dyes are used in the above-mentioned various applications by being dissolved in an organic solvent or the like, dispersed in water, or contained in a polymer and then dispersed in water.

Various oil-soluble dyes have been produced, but they have excellent color tone, good light and weather resistance, have acid and alkali resistance, and are sufficiently soluble in organic solvents. At present, there is almost no oil-soluble dye.

For example, as oil-soluble magenta dyes, monoazo dyes (CI Solvent Red 1, 3 etc.) and disazo dyes (CI Solvent Red 18, 24, 27)
Etc.), metal complex dyes (CI Solvent Red 8, 13
2), anthraquinone dyes (CI Solvent Red 52, 111, 145, 146, 149, 150, 151, 155 etc.), xanthene dyes (CI Solvent Red 49, 218 etc.),
Amino ketone dyes (CI Solvent Red 109, 17
9, 180, etc.), perinone dyes (CI Solvent Red)
135, 176 etc.) are known. Of these, monoazo, disazo, metal complex, anthraquinone,
Aminoketone-based and perinone-based oil-soluble dyes have low solubility in low-polarity organic solvents such as toluene and are often poor in color tone. In addition, xanthene-based oil-soluble dyes have a disadvantage that they are inferior in light resistance.

In the case of a yellow dye, an azo dye (CI Solvent Yellow 14, 16, 29, 33, 44, 56, 77, 79,
82, 93, 114, 116, 117) are commercially available, but all have the disadvantage of low solubility in low-polarity organic solvents and poor handling properties. As cyan dyes, metal phthalocyanine dyes, triphenylmethane dyes and anthraquinone dyes (CI Solvent Blue 14, 25,
35, 38, 70, 83, 94, 105, etc.), but have the same disadvantages as yellow dyes.

[0007] Disperse dyes having water resistance, acid resistance and alkali resistance also generally have low solubility in organic solvents.

On the other hand, among water-soluble dyes such as acid dyes, there are dyes excellent in color tone and fastness. When such a dye is neutralized with a highly hydrophobic basic compound such as octylamine, it is possible to impart solubility to an organic solvent while maintaining the characteristics of the dye. However, such dyes are poor in acid resistance and alkali resistance.

Carbon black-dispersed inks are partially used as black inks in water-based inks for printers for personal use, office use, etc. excluding industrial uses, and most of them use water-soluble dyes. In color inks, water-soluble dyes are mainly used.

However, water-based inks using a water-soluble dye have the disadvantage that the water resistance is extremely poor.

In order to improve the water resistance, pigment-dispersed inks have been developed. However, in particular, color inks are not suitable in terms of dispersibility, color tone for high color reproducibility, print density and reliability. It is enough.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oil-soluble dye having excellent water resistance, alkali resistance, acid resistance, light resistance and solvent solubility.

Another object of the present invention is to provide a water-based ink which has good color tone, imparts excellent water resistance, light resistance and weather resistance to printed matter, and has excellent storage stability.
Further, the present invention is less likely to cause clogging in the print head,
It is an object to provide a water-based ink for inkjet recording.

[0014]

The gist of the present invention is to provide (1)
1 selected from a sulfone group and a carboxyl group in the molecule
Amidation treatment of an oil-soluble dye obtained by amidating a water-soluble dye having at least one group, and (2) amidation treatment of a water-soluble dye having at least one group selected from a sulfone group and a carboxyl group in a molecule. Aqueous ink containing an oil-soluble dye,
And (3) a method for producing an oil-soluble dye which is obtained by halogenating a water-soluble dye having at least one group selected from a sulfone group and a carboxyl group in a molecule and then amidating the halogenated dye.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION As a water-soluble dye having one or more groups selected from a sulfone group and a carboxyl group in the molecule, one or more groups selected from a sulfone group and a carboxyl group in the molecule are used. Acid dyes, reactive dyes, direct dyes and food dyes.

Examples of the acid dye include CI Acid Yellow 1, 2, 5, 7, 16, 17, 23, 24, 26, 28, 29,
31, 41,44, 48, 50, 51, 52, 52: 1, 58, 60, 62, 63,
64, 67, 72, 76, 77, 94, 107, 108, 109, 110, 112, 11
5, 118, 119, 121, 122, 131, 132, 139, 140, 155, 15
6, 157, 158, 159, 172, 191 etc., preferably CI Acid Yellow 5, 17, 23;

[0017] CI Acid Black 1, 3, 4, 7, 11,
12, 13, 14, 17, 18, 19, 23, 25, 29, 34, 36, 38, 3
9, 40, 41, 42, 44, 49, 50, 53, 55, 59, 61, 64, 70,
71, 72, 75, 76, 78, 79, 98, 99, 110, 111, 112, 11
4, 116, 118, 119, 122, 127,128, 131, 135, 141, 14
2, 143, 151, 159, 161, 162, 163, 164, 165, 169, 17
2, 174, 190, 195, 196, 197, 199, 218, 219, 222, 22
7th magnitude; CI Acid Orange 7, 8, 10, 19, 20, 24,
28, 33, 41, 45, 51, 56, 64 etc .;

[0018] CI Acid Red 1, 4, 6, 8, 9, 1
3, 14, 15, 18, 19, 21, 26, 27, 30, 32, 34, 35, 37,
40, 42, 44, 51, 52, 54, 57, 62, 75, 77, 80, 82, 8
3, 85,87, 88, 89, 92, 94, 97, 106, 108, 110, 111,
114, 115, 117, 118, 119, 127, 128, 129, 130, 131,
133, 134, 135, 138, 143, 144, 145, 151, 152, 154,1
55, 158, 168, 172, 176, 180, 183, 184, 186, 187, 1
94, 198, 199, 209, 211, 215, 216, 217, 219, 249, 2
52, 254, 256, 257, 261, 262, 263, 265, 266,274, 27
6, 282, 283, 289, 299, 301, 305, 317, 318, 320, 32
1, 322, 336, 337, 361, 396, 397 etc., preferably CI
Acid Red 35, 37, 40, 52, 87,92, 265, 289;

[0019] CI Acid Violet 5, 7, 11, 1
5, 34, 35, 41, 43, 47, 48, 49, 51, 75, 90, 103, 126
etc;

[0020] CI Acid Blue 1, 7, 9, 15, 22,
23, 25, 27, 29, 40, 41, 43, 45, 51, 53, 54, 55, 5
6, 59, 60, 62, 72, 74, 76, 78, 80, 81, 82, 83, 90,
92, 93, 100, 102, 103, 104, 106, 111, 112, 113, 1
17, 120, 124, 126, 127, 129,130, 131, 138, 140, 14
2, 143, 145, 151, 154, 158, 161, 166, 167, 168, 17
0, 171, 175, 181, 182, 183, 184, 187, 192, 199, 20
3, 204, 205, 207, 220,221, 229, 230, 232, 234, 23
6, 247, 249, 258, 260, 264, 271, 277, 278, 279, 28
0, 288, 290, 326, etc., preferably CI Acid Blue
9;

CI Acid Green 3, 9, 12, 16, 1
9, 20, 25, 27, 41, 44 etc .; CI Acid Brown 4,
14 etc .;

As the reactive dye, for example, CI Reactive Black 1, 3, 4, 5, 6, 8, 12, 14, 21, 23, 2
6, 31, 32,34, 37 etc., preferably CI Reactive
Black 37; CI Reactive Yellow 1, 2, 3, 12,
13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 3
7, 41, 42 etc .; CI Reactive Orange 2, 5, 7, 1
6, 20, 24 etc .;

CI Reactive Red 3, 6, 7, 11,
12, 13, 15, 17, 19, 21, 22, 23, 24, 29, 35, 36, 3
7, 40, 41, 42, 43, 45, 49, 55, 63, 66, 84, 120, 18
0, 184, preferably CI Reactive Red 23, 2
4, 120, 180; CI Reactive Violet 1, 2, 3,
4, 5, 6, 7, 8, 9, 16, 17, 22, 23,24, 26, 27, 33,
34 etc .;

CI Reactive Blue 2, 3, 5, 7, 8,
10, 12, 13, 14, 15, 17, 18, 19, 20, 21, 25, 26, 2
7, 28, 29, 37, 38, 40, 41 etc .; CI Reactive Green 5, 7 etc .; CI Reactive Brown 1, 7, 16
And the like.

Examples of the direct dye include CI Direct Black 2, 4, 9, 11, 14, 17, 19, 22, 27, 32, 3
6, 38, 41,48, 51, 56, 62, 69, 71, 74, 75, 77, 78,
80, 91, 94, 97, 105, 106, 107, 108, 112, 113, 114,
117, 118, 121, 122, 125, 132, 133, 146, 154, 166,
168, 171, 173, 194, 199 etc.

CI Direct Yellow 1, 2, 4, 8,
9, 11, 12, 24, 26, 27, 28, 29, 33,34, 35, 39, 41,
42, 44, 48, 50, 51, 53, 58, 59, 68, 72, 85, 86, 8
7, 88,89, 93, 95, 96, 98, 100, 106, 108, 109, 110,
127, 130, 132, 135, 141, 142, 144, 161, 163, etc., preferably CI Direct Yellow 86, 132;

CI Direct Orange 6, 8, 10, 26,
29, 39, 41, 49, 51, 62, 102 etc .; CI Direct Red 1, 2, 4, 8, 9, 11, 13, 15, 17, 20, 23, 24, 26,
28,31, 33, 37, 39, 44, 46, 47, 48, 51, 59, 62, 6
3, 72, 73, 75, 76, 77, 79, 80, 81, 83, 84, 85, 87,
89, 90, 92, 94, 95, 99, 101, 108, 110, 111, 113, 1
45, 173, 184, 189, 197, 201, 207, 211, 212, 214, 2
18, 220, 221, 223,224, 225, 226, 227, 228, 229, 23
0, 232, 233, 240, 241, 242, 243, 247, 250, 256, 25
7, 321 etc .;

CI Direct Violet 1, 7, 9,
12, 35, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 1
01 etc .; CI Direct Blue 1, 2, 6, 8, 10, 12, 1
5, 22, 25, 34, 41, 55, 67, 68, 69, 70, 71, 72, 75,
76, 77, 78, 80, 81, 82, 83, 84, 86, 87, 90, 98, 1
06, 108, 109, 110, 120, 123, 151, 156, 158, 159, 1
60, 163, 165, 168, 189, 192, 193, 194, 195, 196, 1
99, 200, 201, 202, 203, 207, 211, 213, 214,218, 22
5, 226, 229, 236, 237, 239, 244, 246, 248, 249, 25
1, 252, 258, 264, 270, 280, 287, 288, 289, 291
Etc., preferably CI Direct Blue 86,199;

CI Direct Green 1, 6, 8, 28, 3
3, 37, 63, 64 etc .; CI Direct Brown 1A, 2, 6,
25, 27, 44, 58, 95, 100, 101, 106, 112, 173, 194,
195, 209, 210, 211 and the like.

Examples of food coloring agents include CI Food Black 1, 2 and the like; CI Food Yellow 3, 4, 5 and the like;
CI Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94,
102, 104, 105, 106 etc .; CI Food Violet 2
CI Food Blue 1, 2 etc .; CI Food Green 2, 3 etc.

Among these, CI Acid Red 2
89, CI Acid Yellow 23, CI Acid Yellow 17, CI Direct Yellow 86 and CI Direct Yellow 132 have excellent color reproducibility, and are excellent in color tone, light resistance and weather resistance. preferable.

The oil-soluble dye of the present invention can be produced by amidating a sulfone group and / or a carboxyl group of the water-soluble dye. Before the amidation, it is preferred to halogenate, and among the halogenations, chlorination is more preferred.

The halogenation of the water-soluble dye can be performed in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the water-soluble dye. Examples of the organic solvent include halogen solvents such as chloroform, methylene chloride and dichloroethane, and aprotic solvents such as thionyl chloride, toluene, methyl ethyl ketone, 1,3-dimethyl-2-imidazolidinone, and 2-pyrrolidone. Among these, 1,3-dimethyl-2-imidazozolidinone and chloroform can be suitably used from the viewpoints of dye solubility, inertness to a halogenating agent, cost, and the like. The amount of the organic solvent is not particularly limited, but is usually 500 parts by weight based on 100 parts by weight of the water-soluble dye.
It is preferably about 100,000 parts by weight.

In halogenating the water-soluble dye, it is preferable to use a catalyst. Such a catalyst includes a compound represented by the formula: HCONR ¹ R ² (wherein R ¹ and R ² each independently represent a carbon atom of 1
To 5 to 5). Among R ¹ and R ² , a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
Among the catalysts, N, N-dimethylformamide can be suitably used.

The amount of the catalyst is 0.001 to 100 mol, preferably 1 mol to 1 mol of the water-soluble dye, from the viewpoint of the reaction rate, the yield, the cost and the like and the yield at the time of isolation and purification such as washing with water. Is preferably from 0.1 to 50 mol, more preferably from 1 to 50 mol.

By dissolving the water-soluble dye and the catalyst in an organic solvent in advance and adding a halogenating agent to the obtained water-soluble dye solution, the water-soluble dye can be easily halogenated.

When the water-soluble dye is halogenated, it is preferable to replace the inside of the reaction system with an inert gas in advance and to create an inert gas atmosphere. Examples of such an inert gas include a nitrogen gas and an argon gas.
Of these, nitrogen gas is preferred.

The solution temperature at the time of adding the halogenating agent to the water-soluble dye solution is determined from the viewpoints of stabilization of the reaction, safety, suppression of side reactions, and the like, and reaction speed, yield, cost, and the like. The temperature is desirably 0 to 80 ° C, preferably 0 to 60 ° C, and more preferably 10 to 40 ° C.

As the halogenating agent, for example, thionyl chloride, chlorine gas, hydrochloric acid, phosphorus pentachloride, phosphonyl chloride,
Sulfonyl chloride, phosgene and the like can be mentioned, and among these, thionyl chloride is preferred from the viewpoint of reaction yield, safety and cost. The amount of the halogenating agent is preferably such that the sulfone group and / or carboxyl group present in the water-soluble dye can be sufficiently halogenated. Usually, the amount of the halogenating agent is preferably 1 to 100 mol per 1 mol of the total amount of the sulfone groups and carboxyl groups present in the water-soluble dye.

After the addition of the halogenating agent, it is desirable to carry out aging at a temperature of 15 to 85 ° C., preferably 15 to 35 ° C. for about 1 to 24 hours in order to allow the halogenation reaction to proceed sufficiently. If necessary, the catalyst may be further added and aging may be performed. After the halogenation reaction has sufficiently proceeded, the amidation can usually be performed after removing the halogenating agent, for example, thionyl chloride, by a water washing step. In addition, amidation can be immediately performed without performing the water washing step.

Next, amidation of the halogenated water-soluble dye can be carried out by subsequently adding an amidating agent to the obtained reaction solution. As the amidating agent, it is preferable to use a primary amine, a secondary amine, or a basic dye having an amino group in the molecule, from the viewpoints of solubility of the product in a solvent, absorbance of the product, and the like.

The primary amine is represented by the formula: NH ₂ R ^{3 wherein} R ³ is an alkyl group having 8 to 24 carbon atoms, particularly preferably an alkyl group having 12 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and 3 carbon atoms. To a trialkylsilyl group of 1 to 14 and a fluoroalkyl group having an alkyl group of 1 to 12 carbon atoms]. The number of carbon atoms of the primary amine is preferably 6 or more from the viewpoint of water insolubility. Further, from the viewpoint of improving the color developing properties of the dye, it is preferable to use a basic dye having an amino group in the molecule (CI Basic Red 9, CI Basic Blue 5, etc.) as an amidating agent.

The secondary amine is represented by the formula: HNR ⁴ R ^{5 wherein} R ⁴ and R ⁵ are each independently 2 carbon atoms.
To 12, preferably 4 to 10 alkyl groups, 6 to 6 carbon atoms
An aryl group having 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms in the alkyl group, or R ⁴ and R ^{5 taken} together to form a heterocyclic ring; And the like. Examples of the alkyl group having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms include a butyl group, a pentyl group, a hexyl group, an n-octyl group, and a 2-ethylhexyl group. Among them, a hexyl group, an n-octyl group and a 2-ethylhexyl group are preferred. The carbon number of the alkyl group is desirably 12 or less, preferably 10 or less, since the absorbance becomes appropriate. Among the aryl groups having 6 to 10 carbon atoms, a phenyl group, a benzyl group and the like are preferable.
The trialkylsilyl group having 3 to 10 carbon atoms is preferably a trimethylsilyl group. As the tris (trifluoroalkyl) alkyl group, a tris (trifluoromethyl) methyl group is preferable. When R ⁴ and R ⁵ together form a heterocyclic ring, the heterocyclic ring is preferably a 5- or 6-membered ring.

Among the amidating agents, a formula represented by hexamethyldisilazane from the viewpoint of solubility of the product in a solvent, absorbance of the product, and the like:

[0045]

Embedded image

Wherein R ^a , R ^b , R ^c , R ^d , R ^e and R ^f each independently represent an alkyl group having 1 to 6 carbon atoms; Dibutylamine, dioctylamine, dihexylamine and di-2-ethylhexylamine are preferred. In particular, di-2-
Ethylhexylamine is preferred. The primary amine is preferably a secondary amine because a low molecular weight may result in insufficient water insolubility and a high molecular weight may result in insufficient alkali resistance and absorbance.

The amount of the amidating agent is from 1.2 to 20 moles, preferably 1 to 20 moles, per mole of the total amount of sulfone groups and carboxyl groups, from the viewpoints of the reaction rate and the yield and the yield at the time of washing with water. Desirably, it is 2 to 10 mol.

When the amidating agent is added, the temperature of the reaction solution is from 0 to 60 ° C., preferably from 10 to 60 ° C. in consideration of the reaction rate and the yield, and the boiling points of the amidating agent and the solvent. Desirably, the temperature is -20 ° C.

The atmosphere during the amidation is preferably the same inert gas atmosphere as described above from the viewpoint of the stability of the reaction intermediate (halide).

After the addition of the amidating agent, in order to allow the amidation to proceed sufficiently, the temperature is preferably 20 to 80 ° C., preferably 2 to 80 ° C.
It is desirable to perform aging at a temperature of 0 to 60 ° C for about 1 to 24 hours.

Thus, an oil-soluble dye is obtained. The obtained reaction solution containing the oil-soluble dye is washed with water, alkaline water, etc., precipitated with hexane or the like, and filtered to recover the oil-soluble dye. can do. The recovered oil-soluble dye can be dried or further washed, if necessary.

In the molecule, -SO ₂ NR ⁴ R ⁵ (wherein R ⁴
And R ⁵ are the same as defined above) and —CONR ⁴
An oil-soluble dye having at least one group selected from the group consisting of groups represented by R ⁵ (wherein R ⁴ and R ⁵ are the same as described above) is preferable.

In the water-soluble dye having at least one group selected from a sulfone group and a carboxyl group in a molecule which can be suitably used in the present invention, CI Acid Red 289, CI Acid Yellow 23, CI Acid Yellow 23・ Yellow 17 and CI Direct Yellow 132
Each of formula (I):

[0054]

Embedded image

Wherein R ⁶ and R ⁷ each independently represent —SO ₂ NR ⁴ R ⁵ (R ⁴ and R ⁵ are as defined above), and a compound represented by the formula (II): :

[0056]

Embedded image

Wherein R ⁶ and R ⁷ are as defined above. R ⁸
Oil-soluble dye represented by -CONR ⁴ R ⁵ (R ⁴ and R ⁵ are as defined above) shows a], Formula (III):

[0058]

Embedded image

Wherein R ⁶ and R ⁷ are the same as described above, and a compound represented by the formula (IV):

[0060]

Embedded image

(Wherein R ⁸ is —SO ₂ NR ⁴ R ⁵ (R ⁴
And R ⁵ are the same as those described above)).

The oil-soluble dyes represented by the formulas (I) to (IV)
It may not be produced from a water-soluble dye.

The oil-soluble dye of the present invention is, as described above,
Because it has excellent water resistance, alkali resistance, acid resistance, light resistance and solvent solubility, for example, ink jet recording liquid, ballpoint pen ink, marker ink, toner,
It can be suitably used for paint, lacquer spray paint, magic ink, and the like.

Emulsions containing oil-soluble dyes include: A dispersion in which the oil-soluble dye alone is dispersed in the emulsion; and II. Oil-soluble dyes refer to both the dispersions contained in the polymer particles in the emulsion. Among these embodiments, the latter (II)
Is preferable from the viewpoint of the dispersion stability and the ejection stability of the ink.

The dispersion in which the oil-soluble dye alone is dispersed in the emulsion may be an aqueous dispersion in which the oil-soluble dye is dispersed in water with a dispersant or a surfactant, or an oil-soluble dye which has been subjected to a self-dispersing treatment. It is an aqueous dispersion of a dye.

The polymer component of the polymer emulsion containing an oil-soluble dye includes polyester-based polymers,
Examples thereof include a vinyl polymer, a polyurethane polymer, and a polyamide polymer. Among them, a vinyl polymer is preferable. Examples of the vinyl polymer include (a) at least one vinyl monomer selected from the group consisting of acrylate, methacrylate and styrene monomers, and (b) a polymerizable unsaturated monomer having a salt-forming group. And (c) a polymer obtained by copolymerizing a monomer composition containing a vinyl monomer and a polymerizable unsaturated monomer having a salt-forming group and a copolymerizable monomer.

Examples of the vinyl monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-amyl acrylate, and n-acrylate.
Acrylates such as hexyl, n-octyl acrylate, dodecyl acrylate; methyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, methacrylic acid 2 -Ethylhexyl,
Methacrylic esters such as lauryl methacrylate and polyethylene glycol methacrylate; and styrene monomers such as styrene, vinyltoluene and 2-methylstyrene.

Examples of the polymerizable unsaturated monomer having a salt-forming group include a cationic monomer having a salt-forming group and an anionic monomer having a salt-forming group.

Examples of the cationic monomer having a salt-forming group include unsaturated tertiary amine-containing monomers, unsaturated ammonium salt-containing monomers, and the like. Preferred examples thereof include N, N-diethylaminoethyl acrylate,
N- (N ', N'-dimethylaminoethyl) acrylamide, vinylpyridine, 2-methyl-5-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like can be mentioned.

Examples of the anionic monomer having a salt-forming group include unsaturated carboxylic acid monomers, unsaturated sulfonic acid monomers, unsaturated phosphoric acid monomers and the like. Preferred examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.

The monomers copolymerizable with the vinyl monomer and the polymerizable unsaturated monomer having a salt-forming group include:
Acrylamide monomer, methacrylamide monomer, silicone macromer having a polymerizable functional group at one end, methacrylic acid ester macromer having a polymerizable functional group at one end, styrene macromer having a polymerizable functional group at one end, piece Polyester macromer having a polymerizable functional group at one end, polyurethane macromer having a polymerizable functional group at one end, polyalkyl ether macromer having a polymerizable functional group at one end, a hydroxyl group-containing monomer, formula (V): CH ₂ ＣC (R ⁷ ) COO (R ⁸ O) _p R ⁹ (V) (wherein, R ⁷ may be a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and R ⁸ may have a hetero atom. Carbon number 1
A divalent hydrocarbon group of 30; R ⁹ is a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom;
And the like can be used alone or as a mixture of two or more. In addition, these monomers are illustrations, and this invention is not limited only to such illustrations.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, polyethylene glycol (n = 2 to 30) acrylate, 2-hydroxyethyl methacrylate,
-Hydroxypropyl methacrylate, polyethylene glycol (n = 2 to 30) methacrylate, poly (ethylene glycol (n = 1 to 15) / propylene glycol (n = 1 to 15)) acrylate, poly (ethylene glycol (n = 1 to 15) ) ・ Propylene glycol (n
= 1 to 15)) methacrylate and the like. Among them, 2-hydroxyethyl acrylate and 2-hydroxyethyl acrylate
Hydroxyethyl methacrylate is preferred.

The monomer represented by the formula (V) exerts an excellent effect of improving the ejection stability of the aqueous ink of the present invention and suppressing the occurrence of warpage even in continuous printing.

Specific examples of the monomer represented by the formula (V) include methoxypolyethylene glycol (1 to 30: the value of p in the formula (V); the same applies hereinafter) (meth) acrylate, methoxypolytetramethylene Glycol (1-3
0) (meth) acrylate, ethoxy polyethylene glycol (1-30) (meth) acrylate, (iso) propoxy polyethylene glycol (1-30) (meth)
Acrylate, butoxy polyethylene glycol (1 to
30) (meth) acrylate, methoxy polypropylene glycol (1 to 30) (meth) acrylate, methoxy (ethylene glycol / propylene glycol copolymerization) (1 to 30, ethylene glycol therein: 1 to 2)
9) (meth) acrylates and the like, which can be used alone or in combination of two or more. Among these, methoxypolyethylene glycol (1-30) (meth) acrylate is preferred. In addition,
“(Meth) acrylate” in the present specification indicates acrylate or methacrylate. “(Iso) propoxy” indicates n-propoxy or isopropoxy.

Among the above copolymerizable monomers, silicone macromers, methacrylate macromers and styrene macromers are preferred.

The content of the vinyl monomer in the monomer composition is from 1 to 40% by weight, preferably from 2 to 20% by weight, from the viewpoint of improving the dispersion stability of the polymer emulsion and avoiding scorching of the ink jet printer head. It is desirable.

The content of the polymerizable unsaturated monomer having a salt-forming group in the monomer composition is from 2 to 40% by weight, preferably from 2 to 40% by weight, from the viewpoint of improving the dispersion stability of the polymer emulsion and avoiding the scorching of the ink jet printer head. It is desirably 5 to 20% by weight.

The content of the monomer which can be copolymerized with the vinyl monomer and the polymerizable unsaturated monomer having a salt-forming group in the monomer composition depends on the viewpoint of improving the dispersion stability of the polymer emulsion and avoiding scorching of the ink jet printer head. Therefore, the content is desirably 60 to 90% by weight, preferably 70 to 85% by weight.

The monomer composition may optionally contain a polymerization chain transfer agent.

The polymer can be obtained by copolymerizing the monomer composition by a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these methods, a solution polymerization method is particularly preferable.

Solvents used in the solution polymerization method include aliphatic alcohols such as ethanol and propanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; aromatic solvents such as benzene and toluene. And the like, and these can be used alone or in combination of two or more.

The weight average molecular weight of the polymer was 3,000 to 3,000 when measured by gel permeation chromatography according to Examples 6 to 10 and Comparative Examples 16 to 22 described below.
It is desirably 100,000, preferably 3,000 to 50,000, from the viewpoint of avoiding scorching of the printer head, the durability of the ink after printing, and the stability of the dispersion.

In order to incorporate the oil-soluble dye into the polymer particles in the emulsion, known emulsification methods such as forced emulsification, phase inversion emulsification, dispersion polymerization and emulsion polymerization can be used. Forced emulsification is preferred.

The amount of the oil-soluble dye in the polymer emulsion is from 5 to 900 parts by weight, preferably from 10 to 90 parts by weight, per 100 parts by weight of the solid content of the polymer, from the viewpoint of the printing density and the ease of inclusion in the polymer fine particles. Desirably 400 parts by weight.

The solid content of the polymer emulsion in the aqueous ink is 0.5 to 30% by weight, preferably 1 to 20% by weight, from the viewpoint of ejection stability and print density.
% By weight.

The average particle size of the oil-soluble dye-containing polymer particles contained in the polymer emulsion is preferably from 20 to 200 nm from the viewpoint of dispersion stability.

When a polymer emulsion using a polymer in which an anionic monomer is copolymerized is used, an anionic surfactant or an amphoteric surfactant must be used in order to maintain dispersion stability in an aqueous ink. Is preferred. On the other hand, when using a polymer emulsion in which a polymer in which a cationic monomer is copolymerized is used, from the viewpoint of maintaining the dispersion stability in an aqueous ink, a cationic surfactant or an amphoteric surfactant may be used. preferable.

Further, the water-based ink of the present invention may contain a wetting agent, if necessary. Examples of the wetting agent include glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and glycerin, and urea, ethylene urea, 2-pyrrolidone,
Nitrogen-containing compounds such as amino acids such as N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, formamide, trimethylglycine, methylglycine, and 6-amino-n-caproic acid. These wetting agents can be used alone or in combination of two or more.

If necessary, additives such as an antifoaming agent, a pH adjuster, a preservative, an ultraviolet absorber, an oxygen absorber, and a chelating agent may be added to the water-based ink within a range that does not impair the object of the present invention. It can be contained.

[0090]

EXAMPLES Example 1 Preparation of Oil-Soluble Dye A A magenta acid dye [C.
I. Acid Red 289, manufactured by Chugai Kasei Co., Ltd., Trade name:
Chugai Aminol Fast Pink RH / C] (5 g) was added and the atmosphere was sufficiently replaced with nitrogen.

Next, 1.3 g of N, N-dimethylformamide and 300 g of chloroform were added to the flask and stirred sufficiently. Thereafter, the flask was placed in an ice bath, and 2.2 g of thionyl chloride was added dropwise at 3 ° C. After completion of the dropwise addition, the mixture was aged at room temperature (25 ° C.) for 3 hours to obtain a chlorination reaction solution.

To the obtained chlorination reaction solution, 10 g of N, N-dimethylformamide was added. The flask was again immersed in an ice bath, and 7.4 g of dioctylamine was added dropwise at 3 ° C. to cause an amidation reaction, followed by aging at room temperature (25 ° C.) for 3 hours. After aging, washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the obtained reaction solution was reprecipitated by dropping in hexane, filtered, and dried. The obtained dried product is washed three times with hexane, dried again and recovered, and has the formula:

[0093]

Embedded image

An oil-soluble dye A represented by the following formula was obtained. The yield is
74%.

Example 2 [Preparation of oil-soluble dye B] A yellow acid dye [C.
I. Acid Yellow 23, manufactured by Orient Chemical Co., Ltd.
Trade Name: Water Yellow 1] (15 g) was sufficiently purged with nitrogen.

Next, 4.64 g of N, N-dimethylformamide and 300 g of chloroform were added to the flask, and the mixture was sufficiently stirred. Thereafter, the flask was placed in an ice bath, and 7.55 g of thionyl chloride was added dropwise at 3 ° C. After completion of the dropwise addition, the mixture was aged at room temperature (25 ° C.) for 3 hours to obtain a chlorination reaction solution.

10 g of N, N-dimethylformamide was added to the obtained chlorination reaction solution. The flask was immersed again in an ice bath, 20.49 g of dibutylamine was added dropwise at 3 ° C., and the mixture was aged at room temperature (about 25 ° C.) for 3 hours. After aging,
Washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the obtained reaction solution was dropped into hexane to reprecipitate, filtered, and dried. The obtained dried product is washed three times with hexane, dried again and collected,
formula:

[0098]

Embedded image

An oil-soluble dye B represented by the formula was obtained. The yield is
It was 81%.

Example 3 [Preparation of Oil-Soluble Dye C] A yellow acid dye [C.
I. Acid Yellow 17, manufactured by Nippon Kayaku Co., Ltd., trade name: Kayacyl Yellow GG] (15 g), and sufficiently purged with nitrogen.

Next, 2.65 g of N, N-dimethylformamide and 300 g of chloroform were added to the flask and stirred sufficiently. Thereafter, the flask was placed in an ice bath and 4.32 g of thionyl chloride was added dropwise at 3 ° C.

After completion of the dropping, the mixture was aged at room temperature (about 25 ° C.) for 3 hours, then dropped into ice water, and washed three times with water to give 0.01
It was washed three times with an aqueous solution of N sodium hydroxide. After washing
The obtained reaction solution was again charged in the flask, immersed in an ice bath, and 16.82 g of dihexylamine was added dropwise at 3 ° C. After completion of the dropwise addition, the mixture was aged at room temperature (about 25 ° C.) for 3 hours.
After aging, washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the solution was re-precipitated by dropping in hexane, filtered and dried. The obtained dried product is washed three times with hexane, dried again and recovered, and has the formula:

[0103]

Embedded image

An oil-soluble dye C represented by the following formula was obtained. The yield is 7
0.89%.

Example 4 [Preparation of Oil-Soluble Dye D] A yellow direct dye [C.
I. Direct Yellow 86, manufactured by Daiwa Kasei Co., Ltd., trade name: Daiwa IJ Yellow 214H], and sufficiently purged with nitrogen.

Next, 0.26 g of N, N-dimethylformamide and 300 g of chloroform were added to the flask, and the mixture was sufficiently stirred. Thereafter, the flask was placed in an ice bath, and 5.06 g of thionyl chloride was added dropwise at 3 ° C.

After completion of the dropwise addition, the mixture was aged at room temperature (about 25 ° C.) for 3 hours, then dropped into ice water, and washed three times with water. After washing, the obtained reaction solution was again charged into the flask, immersed in an ice bath, and 7.77 g of diethylamine was added dropwise at 3 ° C. After completion of dropping, the mixture was aged at room temperature (about 25 ° C.) for 3 hours.
After aging, washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the solution was re-precipitated by dropping in hexane, filtered and dried. The obtained dried product was washed three times with hexane, dried again, and recovered to obtain an oil-soluble dye D. The yield was 75.98%.

Example 5 [Preparation of oil-soluble dye E] A yellow direct dye [C.
I. Direct Yellow 132, manufactured by Daiwa Kasei Co., Ltd., trade name: Daiwa IJ Yellow 306H], and sufficiently purged with nitrogen.

Next, 0.20 g of N, N-dimethylformamide and 300 g of chloroform were added to the flask, and the mixture was sufficiently stirred. Thereafter, the flask was placed in an ice bath and 4.50 g of thionyl chloride was added dropwise at 3 ° C.

After completion of the dropping, the mixture was aged at room temperature (about 25 ° C.) for 3 hours, dropped into ice water, and washed three times with water. After washing, the obtained reaction solution was again charged into the flask, immersed in an ice bath, and 11.76 g of diethylamine was added dropwise at 3 ° C. After completion of the dropwise addition, the mixture was aged at room temperature (about 25 ° C.) for 3 hours. After aging, washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the solution was re-precipitated by dropping in hexane, filtered and dried. The obtained dried product is washed three times with hexane, dried again and recovered, and has the formula:

[0111]

Embedded image

An oil-soluble dye E represented by the following formula was obtained. Yield 8
2.32%.

Comparative Examples 1 to 13 As a dye, dye a (manufactured by Chugai Kasei Co., Ltd., trade name: Chu
gai Aminol Fast Pink RH / C], dye b [manufactured by Orient Chemical Co., Ltd., trade name: Water Yellow 1], dye c [manufactured by Nippon Kayaku, trade name: Kayacyl Yellow GG], dye d [Daiwa Chemical Co., Ltd. Product name: Daiwa IJ Yellow 214H
], Dye e [manufactured by Daiwa Kasei Co., Ltd., trade name: Daiwa IJ
Yellow 306H], dye f [Chugai Aminol Fast Pi
nk RH / C neutralized with dioctylamine], dye g
[Water Yellow 1 neutralized with dibutylamine], Dye h [Kayacyl Yellow GG neutralized with dihexylamine], Dye i [Daiwa Chemical Co., Ltd.
And trade name: Daiwa IJ Yellow 214H neutralized with diethylamine], dye j [manufactured by Daiwa Kasei Co., Ltd., trade name: Daiwa IJ Yellow 306H neutralized with diethylamine], dye k [manufactured by BASF, product Name: Neozapon Magent
a525], dye 1 (CI Solvent Red 49, manufactured by Orient Chemical Co., Ltd., trade name: Oil Pink 312) or dye m (manufactured by BASF, trade name: Neopen Yellow 075) was used.

The physical properties of the dyes in the examples and comparative examples were evaluated according to the following methods. Table 1 shows the results.

A. 0.1 g of water-, alkali-, and acid-resistant dye is dissolved in 10 ml of tetrahydrofuran,
Add plain paper [Xerox 40, trade name: XEROX 40] to this solution.
24] was immersed for 10 minutes, then taken out for 24 hours at 25 ° C
And air dried. After drying, it is immersed in water (water resistance), 1N-sodium hydroxide aqueous solution (alkali resistance) or 1N-hydrochloric acid aqueous solution (acid resistance) for 10 minutes to check whether or not the dye is dissolved, and evaluated based on the following evaluation criteria. did.

(Evaluation Criteria) な し: No dissolution of dye ×: Dissolution of dye

B. Light fastness The dye was dissolved in tetrahydrofuran (concentration: 1.0% by weight), and plain paper (trade name: XEROX 4024, manufactured by Xerox Co., Ltd.) was immersed in this solution for 10 minutes.
Air-dried for 4 hours. After drying, use a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd., trade name: low temperature cycle xenon long life fade meter) at 1000
After the irradiation at 0 kJ / m ² , the presence or absence of fading was examined and evaluated based on the following evaluation criteria. (Evaluation criteria) ○: No fading ×: Fading

C. Solvent Solubility To 100 parts by weight of the solvent shown in Table 1, 20 parts by weight of the dye was added, and at 20 ° C., whether or not the dye was dissolved in the solvent was observed and evaluated based on the following evaluation criteria. (Evaluation criteria) ○: Dye dissolved ×: Dye not dissolved

[0119]

[Table 1]

From the results shown in Table 1, all the oil-soluble dyes obtained in Examples 1 to 5 have excellent water resistance, alkali resistance, acid resistance, light resistance and solvent solubility at the same time. It turns out to be something.

Comparative Example 14 When the chlorination reaction solution obtained in the same manner as in Example 1 was dropped into ice water for washing with water, all the products gelled, and the amidation reaction could be performed. could not.

Comparative Example 15 When the chlorination reaction solution obtained in the same manner as in Example 2 was dropped into ice water for washing with water, it was completely dissolved in water and could not be recovered.

Production Example 1 [Preparation of Oil-Soluble Dye IA] A water-soluble dye a [magenta acid dye: CI Acid Red 289, manufactured by Chugai Kasei Co., Ltd., trade name: Chugai Aminol Fast, was placed in a 1 L separable flask. Pink RH / C)
5 g was added, and the atmosphere was sufficiently replaced with nitrogen in a warm bath (60 ° C.).

Next, 1.3 g of N, N-dimethylformamide and 300 g of 1,3-dimethyl-2-imidazolidinone were added to the flask, and the mixture was sufficiently stirred. The flask was then ice bathed and thionyl chloride at 3 ° C.
2 g were added dropwise. After completion of the dropwise addition, the mixture was aged at room temperature (25 ° C.) for 3 hours to obtain a chlorination reaction solution.

To the obtained chlorination reaction solution, 10 g of triethylamine was added and aged for 1 hour. The flask was again immersed in an ice bath, and 7.4 g of dioctylamine was added dropwise at 3 ° C. to cause an amidation reaction, followed by aging at room temperature (25 ° C.) for 3 hours. After aging, washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the obtained reaction solution was reprecipitated by dropping in hexane, filtered, and dried. The obtained dried product is washed three times with hexane, dried again and recovered, and has the formula:

[0126]

Embedded image

An oil-soluble dye IA represented by the following formula was obtained. The yield was 74.5%.

Production Example 2 [Preparation of Oil-Soluble Dye IB] A water-soluble dye b [Yellow acid dye: CI Acid Yellow 23, manufactured by Orient Chemical Co., Ltd., trade name: Water Yellow 1] 5 g, and sufficiently purged with nitrogen.

Next, 4.64 g of N, N-dimethylformamide and 300 g of chloroform were added to the flask and stirred sufficiently. Thereafter, the flask was placed in an ice bath, and 7.55 g of thionyl chloride was added dropwise at 3 ° C. After completion of the dropwise addition, the mixture was aged at room temperature (25 ° C.) for 3 hours to obtain a chlorination reaction solution.

[0130] To the obtained chlorination reaction solution, 10 g of triethylamine was added, and the mixture was aged for 1 hour. The flask was immersed again in an ice bath, 20.49 g of dibutylamine was added dropwise at 3 ° C., and the mixture was aged at room temperature (about 25 ° C.) for 3 hours. After aging, washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the obtained reaction solution was dropped into hexane to reprecipitate, filtered, and dried. The obtained dried product is washed three times with hexane, dried again and recovered, and has the formula:

[0131]

Embedded image

An oil-soluble dye IB represented by the following formula was obtained. The yield was 81.2%.

Production Example 3 [Preparation of Oil-Soluble Dye IC] A water-soluble dye c [yellow acid dye: CI Acid Yellow 17, manufactured by Nippon Kayaku Co., Ltd., trade name: Kayacyl Yellow GG] and 15 g, and sufficiently purged with nitrogen.

Next, 2.65 g of N, N-dimethylformamide and 300 g of chloroform were added to the flask and sufficiently stirred. Thereafter, the flask was placed in an ice bath and 4.32 g of thionyl chloride was added dropwise at 3 ° C.

After completion of the dropping, the mixture was aged at room temperature (about 25 ° C.) for 3 hours, dropped into ice water, washed three times with water, and the obtained reaction solution was again charged into the flask and immersed in an ice bath. ,
At 3.degree. C., 16.82 g of dihexylamine was added dropwise. After completion of the dropwise addition, the mixture was aged at room temperature (about 25 ° C.) for 3 hours. After aging,
Washing with water was performed three times, and washing was performed three times with a 0.01 N aqueous sodium hydroxide solution. After washing, the solution was re-precipitated by dropping in hexane, filtered and dried. The obtained dried product is washed with hexane for 3 hours.
Washed twice, dried again and collected, formula:

[0136]

Embedded image

An oil-soluble dye IC represented by the following formula was obtained. The yield was 70.9%.

Production Example 4 [Preparation of Oil-soluble Dye ID] A water-soluble dye d [yellow direct dye: C.I. I. Direct Yellow 132, manufactured by Daiwa Kasei Co., Ltd., trade name: Daiwa IJ Yellow 306H] 5 g
And the atmosphere was sufficiently replaced with nitrogen. 0.2 g of N, N-dimethylformamide and 300 g of 1,3-dimethyl-2-imidazolidinone were added, and the mixture was sufficiently stirred. Thereafter, the flask was placed in an ice bath, and 4.2 g of thionyl chloride was added dropwise. After completion of the dropwise addition, the mixture was aged at room temperature (about 25 ° C.) for 3 hours, and washed three times with water. The reaction solution was put again in a separable flask, immersed in an ice bath, and 7.5 g of dibutylamine was added dropwise. After completion of the dropwise addition, the mixture was aged at room temperature (about 25 ° C.) for 3 hours. After aging, washing with water was performed three times, and washing was performed three times with a 0.01 N sodium hydroxide aqueous solution. After washing, the obtained general-purpose solution was dropped into hexane to reprecipitate, filtered, and dried. The obtained dried product is washed three times with hexane, dried and collected again, and has the formula:

[0139]

Embedded image

An oil-soluble dye ID represented by the following formula was obtained. The yield was 92.5%.

Production Example 5 [Preparation of Oil-Soluble Dye IE] A water-soluble dye e [Yellow direct dye: CI Direct Yellow 86, manufactured by Daiwa Kasei Co., Ltd., trade name: Daiwa IJ Yellow] 214H], and sufficiently purged with nitrogen.

Next, 1.87 g of N, N-dimethylformamide and 300 g of 2-pyrrolidone were placed in the flask.
Was added and stirred well. Thereafter, the flask was placed in an ice bath and 3.05 g of thionyl chloride was added dropwise at 3 ° C.

After completion of the dropping, the mixture was aged at room temperature (about 25 ° C.) for 3 hours, dropped into ice water, washed three times with water, charged again in the flask, immersed in an ice bath, and added diethylamine 2
0.67 g was added dropwise. After completion of the dropwise addition, the mixture was aged at room temperature (about 25 ° C.) for 3 hours, washed three times with water, and washed three times with a 0.01N aqueous sodium hydroxide solution. After washing, the obtained reaction solution was reprecipitated by dropping in hexane, filtered, and dried. The obtained dried product was washed three times with hexane, dried again and collected to obtain an oil-soluble dye IE. The yield is 86.
3%.

Reference Examples 1 to 7 Water-soluble dyes a to e and oil-soluble dye f used in Production Examples 1 to 5 [CI Solvent Red 49, manufactured by Orient Chemical Co., Ltd., trade name: Oil Pink 312] Or an oil-soluble dye g (manufactured by BASF, trade name: Neopen Magenta 525). The oil-soluble dyes f and g have no sulfone group or carboxyl group in the molecule.

Examples 6 to 10 and Comparative Examples 16 to 22 (1) Preparation of vinyl polymer A dropping funnel was attached to a separable flask having a capacity of 500 ml, and after sufficient purging with nitrogen, methyl methacrylate 30
g, acrylic acid 2 g, methoxypolyethylene glycol methacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: N
K ester M-40G] (8 g), 0.4 g of 2-mercaptoethanol and 10 g of 2-butanone were added, and the temperature was raised to 60 ° C. while refluxing.

Methyl methacrylate 120 was added to the dropping funnel.
g, acrylic acid 8 g, methoxy polyethylene glycol methacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: N
[K ester M-40G] 32 g, 1.6 g of 2-mercaptoethanol, 1.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and 40 g of 2-butanone were added and added dropwise over 3 hours.

After dropping, the mixture was aged for 2 hours, 0.4 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was further aged for 2 hours to obtain a vinyl polymer solution. A part of the solution was dried at 105 ° C. under reduced pressure for 2 hours, and isolated by removing the solvent. The weight average molecular weight was measured by gel permeation chromatography using polystyrene as a standard substance and tetrahydrofuran as a solvent. However, it was 6,500.

(2) Preparation of Coloring Material-Containing Emulsion In 10 g of toluene, 0.6 g of the dye obtained in Production Examples 1 to 5 or the dye described in Reference Examples 6 to 7 was dissolved. 1.40 g of the obtained vinyl polymer solution was added, and the mixture was sufficiently stirred and dissolved.

Next, 5.21 g of a 1N aqueous solution of potassium hydroxide and 50 g of purified water were added to the obtained solution, and the mixture was sufficiently stirred. After stirring, use an ultrasonic homogenizer for 40 minutes.
Emulsification was performed at 0 μA for 20 minutes. Thereafter, the toluene was removed by heating under reduced pressure to remove toluene, followed by filtration through a 0.8 μm filter to obtain a coloring material-containing emulsion containing a dye in a vinyl polymer.

(3) Preparation of ink 8 parts by weight of 30% aqueous solution of the colorant-containing emulsion or the dyes of Reference Examples 1 to 5 obtained in (2) above, 10 parts by weight of trimethylglycine, 5 parts by weight of urea, An ink was prepared by mixing 1 part by weight of sodium ethylhexyl sulfosuccinate and 76 parts by weight of purified water.

(4) Measurement of Physical Properties of Ink Storage stability of ink A 100 mL fluororesin bottle is filled with the ink, and the bottle is stored in the air at 60 ° C. for 3 months, and as physical properties, the particle size before and after storage [Otsuka Electronics Co., Ltd. Particle size distribution analyzer: measured with ELS-8000], viscosity [manufactured by Toki Sangyo Co., Ltd., trade name: VISCOMETER ELS-80L, measured at 25 ° C]
And surface tension [manufactured by Kyowa Interface Science Co., Ltd., trade name: AUTOMA
Check the TIC Surface Tensiometer CBVP-Z at 25 ° C] and determine the retention by the formula: [Retention] = [Physical properties after storage / Physical properties before storage] x 100
(%).

B. Physical Properties of Printing Paper The ink was charged into a cartridge for an inkjet printer (trade name: BCI-21e, manufactured by Canon Inc.), and this was loaded into a bubble jet printer [trade name: BJC-430J, manufactured by Canon Inc.] Plain paper [manufactured by Canon Inc., trade name: inkjet paper P
B Paper] or inkjet-only paper [manufactured by Canon Inc., trade name: inkjet-only paper HR-10]
After printing on [1] and drying sufficiently, the following physical properties were evaluated using the printing paper. Table 2 shows the results.

Color Tone (L) of printed matter of PB paper (manufactured by Canon Inc.)
* A * b *) with a colorimeter [manufactured by Nippon Denshoku Co., Ltd., trade name: S
E2000].

Water resistance: A printed matter of plain paper is immersed in purified water (25 ° C.) for 10 minutes, sufficiently removed of water, air-dried, and printed density at the same place before and after immersion (hereinafter referred to as OD). Is a print density measurement device [Macbeth, reflection densitometer R
D-914], and the OD residual ratio is calculated by the formula: [OD residual ratio] = [OD after immersion] ÷ [OD before immersion]
× 100.

Light fastness A printed matter of PB paper (manufactured by Canon Inc.) was irradiated with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd., trade name: low-temperature cycle xenon long life fade meter) at 10,000 kJ / m ^2. Then, the print density (OD) of the same place before and after irradiation is measured by the same print density measuring device as above, and the OD residual ratio is calculated by the formula: OD residual ratio = [OD after irradiation] ÷ [OD before irradiation] × 1
00.

Ozone resistance A printed matter of plain paper was exposed to an air stream having an ozone concentration of 3 ppm for 2 hours, and the color tone (L * a * b *) before and after the exposure was measured with a colorimeter [manufactured by Nippon Denshoku Co., Ltd.] And trade name: SE2000], and indicated by ΔE.

C. Print head clogging After printing, remove the print head from the printer, leave it under normal temperature and normal pressure environment for 24 hours, then mount it on the printer again, and when it is possible to discharge from all nozzles, evaluate ○,
When discharge was impossible with one or more nozzles, the evaluation of x was made.

[0158]

[Table 2]

From the results shown in Table 2, Examples 6 to 10 were obtained.
It can be seen that the ink obtained in (1) is excellent in storage stability and hardly causes clogging in the print head.

The printed matter using the inks obtained in Examples 6 to 10 had good color tone and excellent water resistance, light resistance and ozone resistance. I understand.

As described above, the oil-soluble dye of the present invention has excellent water resistance, alkali resistance, acid resistance, light resistance and solvent solubility at the same time.

The aqueous ink of the present invention has excellent storage stability, imparts good color tone, excellent water resistance, light resistance and ozone resistance to printed matter, and is used as an aqueous ink for inkjet recording. In addition, there are various excellent effects that the print head is hardly clogged.

[0163]

The oil-soluble dye of the present invention can be suitably used in ink jet recording liquids, inks for ballpoint pens, inks for markers, toners, paints, paints for lacquer spraying, magic inks and the like.

The water-based ink of the present invention can be suitably used as a water-based ink for ink-jet recording.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/09 G03G 9/08 361 (72) Inventor Kenji Aida 1334 Minato, Wakayama City Kao Corporation Research Laboratory (72) Inventor Makoto Sakakibara 1334 Minato, Wakayama City F-term within Kao Corporation Research Laboratory (Reference) 2C056 EA13 FC01 2H005 AA06 AA21 AB02 CA21 2H086 BA56 4J039 AD03 AD10 BC05 BC06 BC12 BC31 BC33 BC36 BC40 BC41 BC44 BC51 BC54 BC68 BE07 BE22 CA06 EA15 EA17 EA34 EA35 EA38 EA41 EA44 GA24 GA26 GA27

Claims (6)

[Claims] 1. An oil-soluble dye obtained by amidating a water-soluble dye having at least one group selected from a sulfone group and a carboxyl group in a molecule. 2. The method according to claim 1, wherein the water-soluble dye is CI Acid Red 28.
9. The oil-soluble dye according to claim 1, which is CI Acid Yellow 23, CI Acid Yellow 17, CI Direct Yellow 86 or CI Direct Yellow 132. 3. The oil-soluble dye according to claim 1, which is amidated with a secondary amine. 4. The oil-soluble dye according to claim 1, which is subjected to amidation treatment with a basic dye having an amino group in the molecule. 5. An aqueous ink containing the oil-soluble dye according to claim 1. 6. A method for producing an oil-soluble dye, which comprises halogenating a water-soluble dye having at least one group selected from a sulfone group and a carboxyl group in a molecule and then amidating the halogenated dye.