JP3463047B2 - Aqueous ink composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous ink composition. More specifically, it relates to a water-based ink composition that can be used in a water-based ink for inkjet recording and the like.

[0002]

2. Description of the Related Art An ink jet recording system is a recording system in which ink droplets are ejected directly from a very fine nozzle onto a recording member and adhered thereto to obtain characters and images. According to this method, not only has the advantage that the device used is low in noise and has good operability, but it also has the advantage that colorization is easy and plain paper can be used as a recording member. Widely used in recent years.

Inks used in ink jet printers include water-based inks, oil-based inks and solid inks. Water-based ink, which is the mainstream, uses water as a main component, and contains therein colorants such as dyes and pigment dispersions, moisturizers and surfactants as agents for adjusting ejection characteristics and image quality. ing. As the surfactant, polyethylene glycol lauryl ether, polyoxyethylene nonyl phenyl ether, etc. have been proposed as a landing accuracy improving agent (JP-A-60-32866, JP-A-4-39067).

However, when a surfactant is added to the water-based ink in an amount sufficient to improve the landing accuracy, the water-based ink spreads along the fibers of the paper, leading to a reduction in character quality and a reduction in print density. There are drawbacks.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a water-based ink exhibiting good water resistance, marker resistance and high print density, and more specifically, having excellent dischargeability when used in a water-based ink for inkjet recording. It is an object to provide a composition.

[0006]

The present invention comprises: (1) an aqueous medium, polymer particles in which a dye or a pigment is added to a water-insoluble polymer as a colorant, and / or a self-dispersible pigment; I):

[0007]

[Chemical 6]

[Wherein R ¹ , R ² , R ⁴ , R ⁶ and R ⁷
Each independently represent a hydrogen _{atom, -C n H 2n + 1 (} n is 1 to
6 integer) or _{-C n H 2n O (CH 2} CHYO) m H
(Y is a hydrogen atom or a methyl group, m is a number from 0 to 20, n is the same as the above); R ³ and R ⁵ are each independently a hetero atom, —C _n H _2n — (n is the same as the above). Or a divalent hydrocarbon group which may contain a hetero atom; a, e and i are each independently 0 or 1; b, f and j are each independently a number from 0 to 30; c, g and k is independently 1 to
An integer of 5; d and h each independently represent 0 or 1. However, the compound represented by the total number of -CH ₂ CHYO- units is 6-80] in the molecule,及 beauty formula (III):

[0009]

[Chemical 7]

[In the formula, R ⁹ is a hydrogen atom or —C _q H _{2q + 1.}
(Q is an integer of 0 to 4); Y is the same as above; r, s, t, and u each independently represent a number of 0 to 30. However, aqueous ink composition containing a -CH ₂ CHYO- compound of the total number of one or more selected from the group consisting of compounds represented by a 6-80] units A in one molecule, and ( 2) an aqueous medium, as a coloring agent, insoluble polymer over the water
Polymer particles in which a dye or pigment is contained and / or
Self-dispersion pigments and formula (I):

[0011]

[Chemical 8]

[ Wherein R ¹ , R ² , R ⁴ , R ⁶ and R ⁷
Each independently represent a hydrogen _{atom, -C n H 2n + 1 (} n is 1 to
6 integer) or _{-C n H 2n O (CH 2} CHYO) m H
(Y is a hydrogen atom or a methyl group, m is a number from 0 to 20, n is the previous
Same as above); R ³ and R ⁵ are each independently
Child, -C _n H _2n - a (n is as defined above) or a heteroatom
A divalent hydrocarbon group which may be contained; a, e and i are
0 or 1 independently of each other; b, f and j are each independent
Then 0 to 30; c, g and k are each independently 1 to
An integer of 5; d and h each independently represent 0 or 1.
You However, in one molecule, -CH ₂ CHYO- units
The total number is from 1 to 100], a compound of formula (II):

[0013]

[Chemical 9]

[In the formula, R ⁸ is — (CH ₂ CHYO) _k —
(Y is the same as above; k is a number from 0 to 25) ; X is a hydrogen atom,
_{Hydroxyl, -CH 2 O (CH 2 CHYO} ) k H (Y and k
Same) as _{above, - O (CH 2 CHYO)} k H (Y and
k is the same as the above) or -OM (M is an alkali metal); p
Represents an integer of 2 to 7. However, -CH in one molecule
₂ The total number of CHYO-units is 1 to 100]
Compound, and formula (III):

[0015]

[Chemical 10]

[In the formula, R ⁹ is a hydrogen atom or —C _q H _{2q + 1.}
(Q is an integer of 0 to 4); Y is the same as above; r, s, t and
And u each independently represent a number of 0 to 30. However, 1 minute
Is the total number of -CH ₂ CHYO- units in the child from 1 to 100
Is one selected from the group consisting of compounds represented by
More compound A, formula ^{(IV): R 10 O- (} CH 2 CHYO) v -H (IV) wherein, Y is as defined above. R ¹⁰ is a hydrogen atom or carbon number
Saturated or unsaturated, which may contain from 1 to 8 heteroatoms
Saturated monovalent hydrocarbon group, v represents a number from 1 to 100]
Compound represented by the formula _{(V): H (OCHYCH 2} ) W -O-R 11 O- (CH 2 CHYO) in _X -H (V) [wherein, Y is as defined above. R ¹¹ is C _y H _{2y +} 1 _(y is 3
10) or saturated or optionally containing heteroatoms
Or an unsaturated divalent hydrocarbon group, w and x are each independently
It stands up and shows the number of 1-99. However, CH in one molecule
₂ The total number of CHYO units is 2 to 100]
Compound and formula (VI): R ¹² — (OCHYCH ₂ ) _W —O—R ¹¹ O— (CH ₂ CHYO) _X —H (VI) [ wherein R ¹¹ , Y, w and x are the same as those defined above]. the same. R ¹² is carbon
Saturation optionally containing a heteroatom of the numbers 1 to 8 or
An unsaturated monovalent hydrocarbon group is shown. However, in one molecule
The total number of CH ₂ CHYO units is 1 to 100]
One or more compounds selected from the group consisting of
It relates to an aqueous ink composition containing B.

[0017]

The aqueous medium is water or a mixture of water and a water-soluble organic solvent excluding the polyalkoxyalkylene derivative. Deionized water is generally used as the water. Water-soluble organic solvents include U.S. Patent No. 5,085,698
Ethylene glycol, propylene glycol, glycerin, etc. described in the specification can be used.
A suitable mixture of water and a water-soluble organic solvent can be selected according to the required surface tension, viscosity and print image quality. An example thereof is a mixture of alkylene glycol having 2 to 6 carbon atoms and deionized water.

At least one compound A selected from the group consisting of the compound represented by the formula (I), the compound represented by the formula (II) and the compound represented by the formula (III) has an ejection property. Improve,
In addition, the excellent effect of maintaining or expressing high printing density is exhibited. In the compound represented by the formula (I), examples of the hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom.

Examples of the compound represented by the formula (I) include:
Glycerin, diglycerin, triglycerin, tetraglycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,6-hexanetriol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 2-methyl-2- (hydroxymethyl) -1,3-
Propanediol, pentaerythritol, erythritol, D-, L- and DL-threitol, adonitol, D-
And L-arabitol, xylitol, dulcitol, L-
Examples thereof include alkylene oxide (ethylene oxide and / or propylene oxide) adducts such as iditol, D-mannitol and D-sorbitol.

Commercially available examples include LiponicREG-1, Liponi
cRSO-20 (Lipo Chemicals Co., Paterson, NJ); PhotonolR
PHO-7149, Photonol PHO-7155 (Henkel Corporation; Amb
ler, PA); Voranal R230-660, Voranol R234-630 (Dow Chem
ical Co.,; Midland, MI); Fomrez R T-279, Fomred RT-31
5, Fomrez RET-190 and Fomrez RET-250 (Witco Corporati
on, Organics Division; New York, NY) and the like.

Examples of the compound represented by the formula (II) include aldose, ketose, aldonic acid, soluble metal aldonic acid salts and their polyalkoxyalkylene derivatives. Examples thereof include D- and L-forms of erythrose, threose, arabinose, ribose, lyxose, xylose, glucose, mannose, altrose, talose, galactose, idose, gulose and aldonic acids corresponding to the above, that is, D-glucone. Acid, D-
Examples of mannonic acid, D-altronic acid and D-alonic acid, and soluble metal aldonic acid include potassium gluconate, and alkylene oxide (ethylene oxide and / or propylene oxide) adducts thereof.

Examples of the compound represented by the formula (III) include:
Glucose, α-methyl glucoside and β-methyl-D
-Alloside alkylene oxide (ethylene oxide and / or propylene oxide) adducts.

The compound A represented by the formulas (I) to (III) is
Each may be used alone or as a mixture.

Further, --CH ₂ CHYO in the compound A
-The total number of units is from 1 to 100, preferably from 6 to 80, more preferably from 10 to 40 in view of dischargeability and print density. -CH
_When the total number of ₂ CHYO-units is 1 or more, excellent dischargeability and high print density, which are features of the present invention, can be obtained.
When it is 0 or less, the viscosity in the water-based ink composition becomes appropriate, which is preferable.

In order to improve the ejection property of the aqueous ink composition, it is desirable to use the compound A having a surface tension of 40 to 70 mN / m, preferably 50 to 70 mN / m in a 10% by weight aqueous solution.

The content of the compound A in the aqueous ink composition is not particularly limited, but is preferably 0.1 to 50% by weight, preferably 0.5 to 25% by weight, and more preferably 1 to 10% by weight. When the content is 0.1% by weight or more, the viscosity, dischargeability and print quality (printing density and sharpness of image quality) of the aqueous ink composition are well balanced, and when it is 50% by weight or less, the aqueous ink composition is It is preferable because the viscosity of is suitable.

For the purpose of further improving the dischargeability and the image quality,
Formula ^{(IV): R 10 O- (} CH 2 CHYO) v -H (IV) wherein, Y is as defined above. R ¹⁰ is a hydrogen atom or 1 carbon atom
A compound represented by the formula (V): H (OCH ₂ CHY), which is a saturated or unsaturated monovalent hydrocarbon group which may contain 8 to 8 hetero atoms, v represents a number of 1 to 100]. ^{_{W -O - R 11 O- (CH}} 2 cHYO) X -H (V) wherein, Y is as defined above. R ¹¹ is -C _y H _2y - _(y 3
An integer of 1 to 10) or a saturated or unsaturated divalent hydrocarbon group which may contain a hetero atom having 3 to 10 carbon atoms, w and x each independently represent a number of 1 to 99. However, the total number of —CH ₂ CHYO— units in one molecule is 2 to 100.
And a compound represented by the formula (VI): R ¹² — (OCH ₂ CHY) _W —O—R ¹¹ O— (CH ₂ CHYO) _X —H (VI) [wherein, R ¹¹ , Y , W and x are the same as above. R ¹² represents a saturated or unsaturated monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms. However, the total number of CH ₂ CHYO units in one molecule is 1 to 100], and at least one compound B selected from the group consisting of

Examples of the compound represented by the formula (IV) include monomethoxy, monoethoxy, mono (iso) propoxy,
Examples thereof include mono (iso) butoxy and monophenoxyethylene oxide / propylene oxide copolymers (ethylene oxide addition mole number = 5 to 30, propylene oxide addition mole number = 0 to 5).

Examples of the compound represented by the formula (V) include:
Ethylene oxide / propylene oxide copolymer of (iso) propylene glycol, di (iso) propylene glycol, (iso) butylene glycol, 1,3-phenylene glycol, and 1,4-phenylene glycol (ethylene oxide addition mole number = 5 to 30, the number of moles of propylene oxide added = 0 to 5) and the like.

Examples of the compound represented by the formula (VI) include:
Ethylene oxide / propylene oxide copolymer of (iso) propylene glycol, di (iso) propylene glycol, (iso) butylene glycol, 1,3-phenylene glycol, and 1,4-phenylene glycol (ethylene oxide addition mole number = 5 to 30, those in which one end of the propylene oxide addition mole number = 0 to 5) is etherified with methyl, ethyl, (iso) propyl, (iso) butyl, phenyl and the like can be mentioned.

In order to improve the ejection property of the aqueous ink composition, it is desirable to use the compound B having a surface tension of 40 to 70 mN / m, preferably 50 to 70 mN / m in a 10% by weight aqueous solution.

These compounds B have a smaller effect of increasing the print density than the compound A, but when they are used in combination with the compound A, they often improve the dischargeability without lowering the print density. It is preferable to use.

The content of the compound B in the aqueous ink composition is not particularly limited, but is preferably 0.1 to 50% by weight, preferably 0.5 to 25% by weight, more preferably 1 to 10% by weight. When the content is 0.1% by weight or more, the viscosity, ejection property and print quality (printing density and sharpness of image quality) of the aqueous ink composition are well balanced, and when it is 50% by weight or less, the aqueous ink composition is It is preferable because the viscosity becomes appropriate.

As the colorant, polymer particles in which a dye or pigment is contained in a water-insoluble polymer and / or a self-dispersion pigment can be used.

The polymer particles containing a dye or pigment in a water-insoluble polymer are very effective for imparting water resistance and marker resistance to a printed matter, and the self-dispersion pigment is effective for increasing the printing density. It is valid. One of these may be selected according to the purpose, or both may be mixed and used.

The dye that can be contained in the water-insoluble polymer particles is not particularly limited, but a hydrophobic dye is preferable. Examples thereof include oil dyes, disperse dyes, basic dyes and the like. Of these, oil dyes and disperse dyes are preferable because they can be favorably contained in the polymer particles.

The oily dye is not particularly limited, but for example, CI Solvent Black 3, 7,
27, 29, 34; CI Solvent Yellow 14, 16, 29, 5
6, 82; CI Solvent Red 1, 3, 8, 18, 24, 2
7, 43, 51, 72, 73; CI Solvent Violet
3; CI solvent blue 2, 11, 70; CI solvent green 3, 7; CI solvent orange 2 and the like.

The disperse dye is not particularly limited, but preferred examples include CI Disperse Yellow 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 11
9, 122, 124, 126, 160, 184: 1, 186, 198, 19
9, 204, 224, 237; CI Disperse Orange 1
3, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119, 1
63; CI Disperse Red 54, 60, 72, 73, 86, 8
8, 91, 93, 111, 126, 127, 134, 135, 143, 145
, 152, 153, 154, 159, 164, 167: 1, 177, 181
, 204, 206, 207, 221, 239, 240, 258, 277
, 278, 283, 311, 323, 343, 348, 356, 362
CI Dispers Violet 33; CI Dispers Blue 56, 60, 73, 87, 113, 128, 143, 148
, 154, 158, 165, 165: 1, 165: 2, 176, 183, 1
85, 197, 198, 201, 214, 224, 225, 257, 266
, 267, 287, 354, 358, 365, 368; CI Disperse Green 6: 1, 9 and the like.

The hydrophobic dye is added to the organic solvent from the viewpoint of efficiently encapsulating it in the water-insoluble polymer particles described later.
It is desirable to be able to dissolve g / L or more, preferably 20 to 500 g / L.

The pigment that can be contained in the water-insoluble polymer particles is also not particularly limited, and known inorganic pigments and organic pigments can be used. If necessary, an extender pigment may be used in combination therewith. Examples of the inorganic pigment include carbon black, metal oxides, metal sulfides, metal chlorides and the like, and carbon black is particularly preferable in the black aqueous ink composition. As carbon black, furnace black,
Lamp black, acetylene black, channel black and the like can be mentioned. Examples of organic pigments include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthoraquinone pigments, and quinophthalone pigments. Examples of extender pigments include silica, calcium carbonate, talc and the like.

Examples of the water-insoluble polymer used in the water dispersion of polymer particles containing a hydrophobic dye or pigment include vinyl polymers, ester polymers and urethane polymers. Of these polymers, vinyl polymers are preferred.

As an aqueous dispersion of vinyl polymer particles,
(A) a salt-forming group-containing monomer, (b) a macromer,
(C) An aqueous dispersion of vinyl polymer particles in which a pigment is contained in a vinyl polymer obtained by copolymerizing a monomer mixture containing a salt-forming group-containing monomer and a monomer copolymerizable with a macromer is preferable.

Examples of the component (a) include a cationic monomer, an anionic monomer and the like. Examples thereof include
Examples thereof include those described in JP-A 9-286939, page 5, column 7, line 24 to column 8, line 29.

Representative examples of the cationic monomer include unsaturated tertiary amine-containing monomers and unsaturated ammonium salt-containing monomers. Among these, N, N-dimethylaminoethyl (meth) acrylate, N-
(N ', N'-dimethylaminopropyl) (meth) acrylamide and vinylpyrrolidone are preferred.

Typical examples of the anionic monomer include unsaturated carboxylic acid monomers, unsaturated sulfonic acid monomers,
Unsaturated phosphoric acid monomers and the like can be mentioned. Among these,
Unsaturated carboxylic acid monomers such as acrylic acid and methacrylic acid are preferred.

As the component (b), a number average molecular weight of 500 to
Macromers, which are monomers having 100,000, preferably 100 to 10,000 polymerizable unsaturated groups, are mentioned. Among them, formula (VIII): X ¹ (Y ¹ ) _q1 Si (R ¹⁶ ) _3-r1 (Z ¹ ) _r1 (VIII) (In the formula, X ¹ is a polymerizable unsaturated group and Y ¹ is 2 A valent linking group, R ¹⁶ is independently a hydrogen atom, a lower alkyl group, an aryl group or an alkoxy group, Z ¹ is a residue of a monovalent siloxane polymer having a number average molecular weight of 500 or more,
q ₁ is 0 or 1 and r ₁ is an integer of ₁ to 3), and a silicone macromer and / or a styrene-based macromer having a polymerizable functional group at one end is preferable.

The number average molecular weight of the component (b) is measured by gel chromatography using chloroform containing 1 mmol / L of dodecyldimethylamine as a solvent and polystyrene as a standard substance.

The silicone macromer can be preferably used from the viewpoint of preventing charring of the head of an ink jet printer.

In the silicone macromer represented by the formula (VIII), as X ¹ , CH ₂ ═CH— group and CH ₂ ═
Examples thereof include monovalent unsaturated hydrocarbon groups having 2 to 6 carbon atoms such as C (CH ₃ ) -groups. Y ¹ is a -COO- group,-
A COOC _a1 H _2a1 -group (a ₁ represents an integer of ₁ to 5),
A divalent bonding group such as a phenylene group may be mentioned, and -COOC
₃ H ₆ − is preferred. R ¹⁶ is a hydrogen atom; a lower alkyl group having 1 to 5 carbon atoms such as methyl group or ethyl group; an aryl group having 6 to 20 carbon atoms such as phenyl group; an alkoxy group having 1 to 20 carbon atoms such as methoxy group. And the like, and of these, a methyl group is preferable. Z ¹ is preferably a monovalent residue of a dimethylsiloxane polymer having a number average molecular weight of 500 to 5000. q ₁ is 0 or 1, but is preferably 1. r ₁ is an integer of ₁ to 3, preferably 1.

As a typical example of the silicone macromer,
Formula _{(VIII-1): CH 2} = CR 17 -COOC 3 H 6 - [Si (R 18) 2 -O] b1 -Si (R 18) 3 (VIII-1) ( wherein, R ¹⁷ is a hydrogen atom Or a methyl group, R ¹⁸ are each independently a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms,
b ₁ is the silicone macromer represented by the number of 5 to 60), formula _{(VIII-2): CH 2} = CR 17 -COO- [Si (R 18) 2 -O] b1 -Si (R 18) Silicone macromer represented by ₃ (VIII-2) (wherein R ¹⁷ , R ¹⁸ and b ₁ are the same as above), Formula (VIII-3): CH ₂ = CR ¹⁷ -Ph- [Si (R ¹⁸ ) ₂ -O] _{b 1} -Si (R ¹⁸ ) ₃ (VIII-3) (wherein Ph is a phenylene group, R ¹⁷ , R ¹⁸ and b ₁ are the same as the above), a formula (VIII
^{_{-4): CH 2 = CR 17}} -COOC 3 H 6 -Si (OE) 3 (VIII-4) wherein, R ¹⁷ is as defined above. E is the formula:-[Si (R ¹⁷ ) ₂ O] _c1
And a silicone macromer represented by the formula: —Si (R ¹⁷ ) ₃ group (R ¹⁷ is the same as above. C ₁ is a number of 5 to 65).

Among these, the silicone macromer represented by the formula (VIII-1) is preferable, and particularly, the silicone macromer represented by the formula (VIII-
1a): CH ₂ = C (CH ₃ ) -COOC ₃ H _6- [Si (CH ₃ ) _2- O] _d1- CH ₃ (VIII-1a) (wherein d ₁ represents a number from 8 to 40) ) Silicone macromers represented by An example thereof is FM-0711 [trade name, manufactured by Chisso Corporation].

The styrenic macromer can be preferably used from the viewpoint of sufficiently containing the pigment in the vinyl polymer.

Examples of the styrene-based macromer include a styrene homopolymer having a polymerizable functional group at one end or a copolymer of styrene and another monomer. Among these, those having an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group at one end are preferable. The styrene content in the copolymer is 60 from the viewpoint that the pigment is sufficiently contained in the vinyl polymer.
It is desirable that the content is not less than wt%, preferably not less than 70 wt%. Examples of the other monomer include acrylonitrile and the like.

As the component (c), methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary)
Butyl (meth) acrylate, (iso) amyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, (iso) stearyl (meth) acrylate, etc. (Meth) acrylic acid ester of styrene; styrene-based monomers such as styrene, vinyltoluene, 2-methylstyrene, chlorostyrene, and the like, and these can be used alone or in admixture of two or more. The above (iso or tertiary) and (iso) mean both cases where these groups are present and cases where they are not present, and when these groups are not present, normal is shown.

The component (c) preferably contains a styrene-based monomer from the viewpoint of improving print density and marker resistance. As the styrene-based monomer, styrene and 2-methylstyrene are preferable, and these may be used alone or in combination. In this case, the content of the styrenic monomer in the component (c) is preferably 10 to 100% by weight, and more preferably 40 to 100% by weight, from the viewpoint of improving the printing density and the resistance to markers.

The monomer mixture is composed of (d) hydroxyl group-containing monomer [hereinafter referred to as (d) component] and (e) formula (V
II): CH ₂ ═C (R ¹³ ) COO (R ¹⁴ O) _p1 R ¹⁵ (VII) (In the formula, R ¹³ is a hydrogen atom or a lower alkyl group, and R ¹⁴ is a carbon which may have a hetero atom. A divalent hydrocarbon group having 1 to 30 carbon atoms, R ¹⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom, and p ₁ represents ₁ to 60
It may contain one or more kinds selected from the group consisting of monomers (hereinafter referred to as component (e)) represented by

As the component (d), 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene glycol (n = 2 to
30) (meth) acrylate, poly (ethylene glycol (n = 1 to 15) / propylene glycol (n = 1 to 1)
5)) (Meth) acrylate and the like. Among them, 2-hydroxyethyl (meth) acrylate is preferable.

The component (e) enhances the ejection stability of the water-based ink composition of the present invention, and exerts an excellent effect of suppressing the occurrence of twisting even during continuous printing.

In the formula (VII), R ¹³ is a hydrogen atom or a lower alkyl group. Examples of the lower alkyl group include alkyl groups having 1 to 4 carbon atoms.

R ¹⁴ is a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a halogen atom and a sulfur atom.

As typical examples of R ¹⁴ , an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a hetero ring having 3 to 30 carbon atoms which may have a substituent, and a substituent There may be mentioned an alkylene group having 1 to 30 carbon atoms which may have, and these rings or groups may be a combination of two or more kinds. Examples of the substituent include an aromatic ring having 6 to 29 carbon atoms, a hetero ring having 3 to 29 carbon atoms, an alkyl group having 1 to 29 carbon atoms, a halogen atom and an amino group.

Preferable examples of R ¹⁴ include a phenylene group having 1 to 24 carbon atoms and optionally having a substituent, and 1 to 3 carbon atoms.
0, preferably an aliphatic alkylene group having 1 to 20 carbon atoms, an alkylene group having 7 to 30 carbon atoms having an aromatic ring, and an alkylene group having 4 to 30 carbon atoms having a hetero ring.

Preferable examples of R ¹⁴ O group include ethylene oxide group, (iso) propylene oxide group,
A tetramethylene oxide group, a heptamethylene oxide group, a hexamethylene oxide group and a carbon number of 2 to 7 consisting of a combination of one or more of these alkylene oxides.
The alkylene oxide group and the phenylene oxide group of are mentioned.

R ¹⁵ is a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom. Examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom.

As a typical example of R ¹⁵ , an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a hetero ring having 3 to 30 carbon atoms which may have a substituent, or a substituted ring. Examples thereof include an alkyl group having 1 to 30 carbon atoms which may have a group. Examples of the substituent include an aromatic ring having 6 to 29 carbon atoms, a hetero ring having 4 to 29 carbon atoms, a halogen atom and an amino group.

Preferable examples of R ¹⁵ include a phenyl group, an aliphatic alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an alkyl group having 7 to 30 carbon atoms having an aromatic ring, and a heterocycle. And an alkyl group having 4 to 30 carbon atoms.

A more preferred example of R ¹⁵ is a methyl group,
Ethyl group, (iso) propyl group, (iso) butyl group,
1 carbon atom such as (iso) pentyl group and (iso) hexyl group
~ 6 alkyl groups, phenyl groups and the like. p ₁ is a number of ₁ to 60, but a number of 1 to 30 is preferable.

Specific examples of the component (e) include methoxypolyethylene glycol (1 to 30: the value of p ₁ in the formula (VII). The same applies hereinafter) (meth) acrylate, methoxypolytetramethylene glycol (1 to 30) (meth) acrylate, ethoxy polyethylene glycol (1-30)
(Meth) acrylate, (iso) propoxy polyethylene glycol (1-30) (meth) acrylate, butoxy polyethylene glycol (1-30) (meth) acrylate, methoxy polypropylene glycol (1-30)
(Meth) acrylate, methoxy (ethylene glycol / propylene glycol copolymerization) (1 to 30, ethylene glycol: 1 to 29 therein) (meth) acrylate and the like, each of which may be used alone or in combination of two or more. Can be used. Among these, methoxy polyethylene glycol (1-30) (meth) acrylate is preferable. In addition, in this specification, "(meth) acrylate" shows an acrylate or a methacrylate. Further, "(iso) propoxy" means n-propoxy or isopropoxy.

The content of the component (a) in the vinyl polymer is 1 to 50% by weight, preferably 2 to 40% by weight, from the viewpoint of dispersion stability of the resulting dispersion.

The content of the component (b) in the vinyl polymer is 1 to 25% by weight, from the viewpoint of suppressing charring of the heater surface of the ink jet printer and stability.
It is preferably 5 to 20% by weight.

The content of the component (c) in the vinyl polymer is 5 to 93% by weight from the viewpoint of suppressing the sticking of the heater surface of the ink jet printer and the stability.
It is preferably 10 to 80% by weight. When the component (c) containing a styrene-based monomer is used, the content of the component (c) in the vinyl polymer is preferably 10 to 60% by weight.

The content of the component (d) in the vinyl polymer is 5 to 40% by weight, preferably 7 to 20% by weight, from the viewpoint of ejection stability and print density. Also, (a)
From the viewpoint of stability in water and water resistance, the total content of the component and the component (d) is 6 to 60% by weight, preferably 10 to 50% by weight.

The content of the component (e) in the vinyl polymer is 5 to 50% by weight, preferably 10 to 40% by weight, from the viewpoint of ejection stability and dispersion stability.

The total content of the components (a) and (e) in the vinyl polymer is preferably 6 to 75% by weight from the viewpoint of dispersion stability in water and ejection stability.

The total content of the components (a), (d) and (e) in the vinyl polymer is 6 to 60% by weight, preferably from the viewpoint of dispersion stability and discharge stability in water. 7 to 50% by weight is desirable.

The vinyl polymer can be obtained by a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method.
It is produced by copolymerizing a monomer mixture. Among these polymerization methods, the solution polymerization method is preferable.

The solvent used in the solution polymerization method is preferably a polar organic solvent, and a water-miscible organic solvent may be mixed with water. Examples of the organic solvent include aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate. Among these, methanol, ethanol, acetone, methyl ethyl ketone or a mixed solution of these and water is preferable.

A radical polymerization initiator can be used in the polymerization. As the radical polymerization initiator,
2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisbutyrate, 2,2'-azobis (2-methyl) Azo compounds such as butyronitrile) and 1,1'-azobis (1-cyclohexanecarbonitrile) are preferable. Further, organic peroxides such as t-butyl peroxyoctoate, di-t-butyl peroxide, dibenzoyl oxide and the like can also be used.

The amount of the polymerization initiator is preferably 0.001 to 5 mol%, particularly 0.01 to 2 mol% based on the monomer mixture.

A polymerization chain transfer agent may be added during the polymerization. Specific examples of the polymerization chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan and mercaptoethanol;
Xanthogen disulfides such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide; thiuram disulfides such as tetramethylthiuram disulfide and tetrabutylthiuram disulfide; halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide; hydrocarbons such as pentaphenylethane And acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycolate, terbinolene, α-terpinene, γ-terpinene, diterpene, α-methylstyrene dimer, and further 9,10-dihydroanthracene,
Unsaturated cyclic hydrocarbon compounds such as 1,4-dihydronaphthalene, indene, and 1,4-cyclohexadiene;
-Unsaturated heterocyclic compounds such as dihydrofuran can be mentioned, and these can be used alone or in combination of two or more kinds.

The polymerization conditions of the monomer mixture will vary depending on the type of radical polymerization initiator, monomer, solvent, etc. used, but the polymerization temperature is usually 30 to 100 ° C., preferably 50 to 50 ° C.
The temperature is 80 ° C., and the polymerization time is 1 to 20 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas.

After completion of the polymerization reaction, reprecipitation from the reaction solution,
The copolymer can be isolated by a known method such as evaporation of the solvent. Further, the obtained copolymer can be purified by removing unreacted monomers and the like by repeating reprecipitation, membrane separation, chromatography, extraction and the like.

The weight average molecular weight of the polymer is 3000 to 1000.
A value of 00 is preferable in terms of durability after printing and dispersion stability.

An aqueous dispersion of polymer particles containing a hydrophobic dye can be produced by a known emulsification method.
For example, a polymer and a hydrophobic dye are dissolved in an organic solvent, a neutralizing agent is added if necessary to ionize a salt-forming group in the polymer, and water is added to the salt-forming group. It can be obtained by carrying out dispersion using a sonic emulsifier, distilling off the organic solvent and inversion into an aqueous system.

As a method for obtaining an aqueous dispersion of polymer particles containing a pigment, the polymer is dissolved in an organic solvent, and the pigment, water, a neutralizing agent and, if necessary, a surfactant are added and kneaded to obtain a paste. After that, a method is preferred in which the paste is diluted with water as necessary and the organic solvent is distilled off to form an aqueous system.

The amount of the hydrophobic dye or pigment in the polymer particles is preferably 20 to 400 parts by weight based on 100 parts by weight of the solid content of the polymer, from the viewpoint of print density and ease of inclusion in the polymer particles.

As the pigment aqueous dispersion, a self-dispersion pigment is also preferably used for the purpose of increasing the printing density.
For example, Cabot, a self-dispersing carbon black in which carbon black is dispersion-stabilized without a dispersant.
Examples include Cabo-Jet 200 (trade name) commercially available from the company.

Polymer particles in which a dye and a pigment are contained in a water-insoluble polymer are preferable to the self-dispersion pigment from the viewpoint of water resistance and marker resistance.

The particle size of the polymer particles containing these dyes and pigments, and the particle size of the self-dispersion pigment are from the viewpoint of dispersion stability.
It is preferably 0.01 to 0.5 μm.

The content of the colorant in the aqueous ink composition is not particularly limited as long as a sufficient print density can be obtained. Usually, the content is from 1 to 30% by weight, preferably from 2 to 10% by weight, more preferably from 4 to 8% by weight, from the viewpoint of providing sufficient ejection stability and print density.

In the water-based ink composition of the present invention, various conventionally known additives, for example, wetting agents such as polyhydric alcohols, dispersants, defoamers, antifungal agents and / or chelating agents, p
An H regulator and the like can be added.

[0092]

EXAMPLES Preparation Example (Colorant: Preparation of carbon black-containing polymer particle aqueous dispersion) (1) Preparation of water-insoluble polymer (1-1) Preparation of anionic polymer solution Mechanical stirrer, thermometer, nitrogen After thoroughly replacing the inside of a 1 L flask equipped with a gas inlet tube, a reflux tube and a dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, methoxy polyethylene glycol (n = 9) methacrylate 4.0 4.0 g of styrene macromer [trade name: AS-6 manufactured by Toagosei Co., Ltd.] and 0.4 g of mercaptoethanol were charged, and the temperature was raised to 65 ° C.

Next, 100.8 g of styrene and 25.2 g of acrylic acid.
, Lauryl methacrylate 108.0 g, methoxy polyethylene glycol (n = 9) methacrylate 36.0 g, hydroxyethyl methacrylate 60.0 g, styrene macromer [Toagosei Co., Ltd., trade name: AS-6] 36.0 g, mercaptoethanol 3.6 g, azo Bisdimethylvaleronitrile 2.
A mixed solution of 4 g and methyl ethyl ketone 18 g was dropped into the flask over 2.5 hours.

After the dropwise addition, 0.5 g of a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was added.
It dripped in the flask over time. After aging for 1 hour at 65 ° C, add 0.8 g of azobisdimethylvaleronitrile,
It was aged for another 1 hour.

After the reaction was completed, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50%.

A part of the obtained copolymer solution was put under reduced pressure to
Isolate by drying at 105 ° C for 2 hours and removing the solvent, using polystyrene as the standard and 1 mm as the solvent.
When the weight average molecular weight was measured by gel permeation chromatography using chloroform containing ol / L dodecyldimethylamine, it was 28,000.

(1-2) Preparation of Cationic Polymer Solution After thoroughly replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introducing tube, reflux tube and dropping funnel with nitrogen gas, styrene 50.0 g, lauryl methacrylate 1
2.0 g, N, N-dimethylaminoethyl methacrylate
40.0 g, methoxy polyethylene glycol (n = 4) methacrylate 60.0 g, styrene macromer [Toagosei Co., Ltd.
Product name: AS-6] 20.0 g and mercaptoethanol 0.
8 g was charged and the temperature was raised to 65 ° C.

Next, 40.0 g of styrene, 20.0 g of lauryl methacrylate, 60.0 g of N, N-dimethylaminoethyl methacrylate and methoxypolyethylene glycol (n = 4)
A mixed solution of 70.0 g of methacrylate, 20.0 g of styrene macromer (trade name: AS-6, manufactured by Toagosei Co., Ltd.), 7.2 g of mercaptoethanol, 2.4 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was placed in the flask for 2.5 hours. Dropped.

After the completion of dropping, 0.5% of a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was added.
It dripped in the flask over time. After aging for 1 hour at 65 ° C, add 0.8 g of azobisdimethylvaleronitrile,
It was aged for another 1 hour.

After the reaction was completed, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50%.

A part of the obtained copolymer solution was concentrated under reduced pressure.
It was dried at 105 ° C for 2 hours, isolated by removing the solvent, and the weight average molecular weight was measured by gel permeation chromatography using polystyrene as a standard substance and tetrahydrofuran as a solvent.
It was 000.

(2) Preparation of Aqueous Dispersion of Carbon Black-Containing Polymer Particles (2-1) Anionic Carbon Black-Containing Polymer Particles 28 g of the polymer solution obtained in the above (1-1), carbon black (Cabot) (Product name: Monarch880)
20 g, 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone and 30 g of ion-exchanged water were thoroughly stirred, and then 20 times using a 3-roll mill [Noritake Company, Ltd., trade name: NR-84A]. Kneaded

The obtained paste was put into 200 g of ion-exchanged water, and after sufficiently stirring, methyl ethyl ketone and water were distilled off using an evaporator, and the solid content was 20.0% by weight.
160 g of an aqueous dispersion of polymer particles containing anionic carbon black was obtained. The average particle size of the polymer particles was 110 nm as a result of measurement using a Coulter Counter N4 (manufactured by Coulter, trade name).

(2-2) Cationic carbon black-containing polymer particles 28 g of the polymer solution obtained in the above (1-2), carbon black (manufactured by Cabot, trade name: Monarch880)
16g, 1mol / L acetic acid aqueous solution 11.1g, methyl ethyl ketone
After thoroughly stirring 20 g and 30 g of ion-exchanged water, a three-roll mill [Noritake Company, Ltd., trade name: NR-8
4A] and kneaded 20 times.

The obtained paste was put into 200 g of ion-exchanged water, stirred sufficiently, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain a solid content of 20.0% by weight.
160 g of an aqueous dispersion of polymer particles containing cationic carbon black was obtained. The average particle size of the polymer particles was 138 nm as a result of measurement using Coulter Counter N4 (manufactured by Coulter, trade name).

(3) Preparation of Aqueous Dispersion of Polymer Particles Containing Oil Black To 28 g of the polymer solution obtained in (1-1) above, 20 g of methyl ethyl ketone and oil black as a hydrophobic dye [trade name, manufactured by Orient Co., Ltd., : Oil black 860] 10g
Was added and dissolved completely, 13.6 g of a 1 mol / L potassium hydroxide aqueous solution was added to neutralize the salt-forming groups of the polymer, 200 g of ion-exchanged water was added to this, and the mixture was stirred, followed by microfluidization. It was dispersed for 30 minutes using a Dizer (manufactured by Microfluidizer).

The obtained dispersion was concentrated by removing the organic solvent at 60 ° C. under reduced pressure and further removing water to obtain an aqueous dispersion of polymer particles containing oil black having a solid content of 20% by weight. It was The average particle diameter of the polymer particles was 82 nm as a result of measurement using a Coulter Counter N4 (manufactured by Coulter, trade name).

Examples 1 to 4 and Comparative Examples 1 and 2 (Preparation of aqueous ink composition) 2-pyrrolidone (10 g), glycerin (4 g), compound (8 g) shown below as a polyalkoxyalkylene derivative, isopropanol (1 g) and ion-exchanged water (47 g) were mixed. After that, 30 g of an aqueous dispersion of the polymer particles containing anionic carbon black obtained in (2-1) Preparation Example was added to the obtained mixed solution with stirring. The resulting mixture was filtered through a membrane filter having an average pore size of 0.8 μm [Fuji Photo Film Co., Ltd., trade name: Disk Capsule CALC80] to obtain an aqueous ink composition.

Examples 5-8 2-pyrrolidone (10 g), glycerin (4 g), compound (4 g) shown below as a polyalkoxyalkylene derivative, isopropanol (1 g) and ion-exchanged water (51 g) were mixed, and the resulting mixture was mixed with (2-2 ) 30 g of an aqueous dispersion of the polymer particles containing the cationic carbon black obtained in Preparation Example was added with stirring. The resulting mixture was filtered through a membrane filter having an average pore size of 0.8 μm [Fuji Photo Film Co., Ltd., trade name: Disk Capsule CALC80] to obtain an aqueous ink composition.

Example 9 In Example 1, instead of 30 g of the aqueous dispersion of polymer particles containing anionic carbon black, an aqueous dispersion of self-dispersing carbon black (trade name: Ca, manufactured by Cabot Corporation) was used.
(Bo-Jet 200, 20% concentration) 20 g and a polyalkoxyalkylene derivative 18 g shown below were used to obtain an aqueous ink composition in the same manner as in Example 1.

Example 10 Example 1 was repeated except that 30 g of the aqueous dispersion of polymer particles containing carbon black was replaced by 30 g of the aqueous dispersion of polymer particles containing oil black prepared in (3). An aqueous ink composition was obtained in the same manner as in.

In each of the examples and comparative examples, the polyalkoxyalkylene derivative compounded in the aqueous ink composition is as follows.

Example 1: EO / PO adduct of diglycerin (EO addition mole number = 18, PO addition mole number = 2) [compound of formula (I)]

Example 2: EO / PO adduct of α-methyl glucoside (number of moles of EO addition = 2)
0, number of moles of PO added = 3) [compound of formula (II)]

Example 3: EO adduct of α-methyl glucoside (EO addition mole number = 25) 6
g Compounding [compound of formula (III)] EO adduct of dipropylene glycol (EO addition mole number = 22)
2g formulation [compound of formula (IV)]

Example 4: EO adduct of pentaerythritol (EO addition mole number = 8) 4
g compound [compound of formula (I)] monophenoxypolyethylene oxide (number of moles of EO added)
= 23) 4g formulation [compound of formula (IV)]

Example 5: EO / PO adduct of pentaerythritol (mol of EO addition = 2)
5, PO addition mole number = 3) [compound of formula (I)]

Example 6: EO adduct of trimethylolpropane (EO addition mole number = 14)
[Compound of Formula (I)]

Example 7 EO / PO adduct of D-erythrose (EO addition mole number = 17, PO
Number of added moles = 3) [compound of formula (II)]

Example 8: EO adduct of 1,3,5-pentanetriol (EO addition mole number = 2)
0) [Compound of formula (I)]

Example 9: EO adduct of triglycerin (EO addition mole number = 25) [compound of formula (I)]

Example 10: EO / PO adduct of glycerin (EO addition mole number = 18, PO addition mole number = 3) [Compound of formula (I)] 4 g blended monobutoxy polyethylene oxide (EO addition mole number = 2
2) [Compound of formula (IV)] 4 g

Comparative Example 1: No polyalkoxyalkylene derivative is blended in the aqueous ink composition.

Comparative Example 2: Polyethylene glycol lauryl ether [Ethylene oxide addition mole number = 20, manufactured by Kao Corporation, trade name: Emulgen 120]

Next, as the performance of the water-based ink compositions obtained in Examples and Comparative Examples, the printing density, printability (ejection stability), water resistance, and marker resistance were evaluated based on the following methods. Examined. The results are shown in Table 1.

[Printing Density] An ink jet printer [made by Hewlett-Packard, trade name: Desk Jet720C] was filled with a water-based ink composition, and then plain paper [Xerox, trade name: 4024 DP 20 lb.Paper] was printed, the printed matter was dried at 25 ° C. for 3 hours, and then the print density was measured using a Macbeth densitometer (manufactured by Macbeth, trade name: RD918).

[Printability (ejection stability)] Using the printer and plain paper used for examining the above [print density], 10 A4 solid prints were produced by continuous printing, and then the text, solid pattern and ruled lines A test document containing the was printed and the printability (ejection stability) was evaluated. The evaluation criteria are as follows.

(Evaluation Criteria) ⊚: Sharp and clear characters, uniform solid printing,
And when all three items of ruled line printing with no wrinkle are satisfied ○: Sharp and clear characters, uniform solid printing,
And if all three items of ruled line printing with no wrinkle are almost satisfied △: Sharp and clear characters, uniform solid printing,
And if one item is not satisfied in the ruled line printing without wobbling ×: Sharp and clear characters, uniform solid printing,
And if two or more items are not satisfied in the ruled line printing without wobbling

[Water Resistance] Solid printing was performed using the printer and plain paper used for examining the above [print density], and the print density at a specific print portion of the sample dried at 25 ° C. for 1 hour was measured. It was immersed in still water for 10 seconds and then pulled up. After air-drying at 25 ° C for 24 hours, the print density at the same place as before the immersion was measured, and the residual ratio of the print density after immersion to the print density before immersion was calculated by the formula: [Residual ratio] = [Print after immersion] Density] / [Print density before immersion] × 100, and water resistance was evaluated based on the following evaluation criteria.

(Evaluation criteria) ◎: Residual rate 95% or more ○: Residual rate 90% or more and less than 95% △: Residual rate 70% or more and less than 90% X: residual rate less than 70%

[Marker Resistance] Text was printed using the printer and plain paper used for examining the above [print density], and after 6 hours at 25 ° C., a commercially available water-based highlighter pen (PILOT, Spotliter) was used. The degree of smearing of the printed sample when traced was visually observed and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: There is no stain such as tailing even when tracing with a highlighter pen. ○: Traces with a highlighter pen, but there is no problem in practical use. ×: When traced with a highlighter pen, tailing occurs and the stain is severe.

[0133]

[Table 1]

From the results shown in Table 1, the aqueous ink compositions obtained in Examples 1 to 10 showed excellent print density and printability in comparison with those obtained in Comparative Examples 1 and 2. Further, it can be seen that the use of polymer particles containing a dye or pigment in a water-insoluble polymer rather than the self-dispersion type pigment makes it possible to satisfy both water resistance and marker resistance.

[0135]

The water-based ink composition of the present invention exhibits good water resistance, marker resistance, and high print density, and has excellent printing characteristics (ejection stability) when used in a water-based ink for ink jet recording. Has the effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-157955 (JP, A) JP-A-9-241565 (JP, A) JP-A-10-279873 (JP, A) JP-A-11- 152424 (JP, A) JP 10-298294 (JP, A) JP 10-265710 (JP, A) International publication 96/028518 (WO, A1) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C09D 11/00 B41J 2/01

Claims (11)

(57) [Claims] 1. An aqueous medium, polymer particles in which a dye or pigment is contained in a water-insoluble polymer as a colorant, and / or a self-dispersible pigment, and a compound of formula (I): [In the formula, R ¹ , R ² , R ⁴ , R ^6, and R ⁷ are each independently a hydrogen atom, —C _n H _{2n + 1} (n is an integer of 1 to 6) or —C _n H _2n O ( CH ₂ CHYO) _m H (Y is a hydrogen atom or a methyl group, m is a number from 0 to 20, n is the same as above); R
³ and R ⁵ are each independently a hetero atom, —C _n H _2n
-(N is the same as above) or a divalent hydrocarbon group which may contain a hetero atom; a, e and i are each independently 0 or 1; b, f and j are each independently 0- Number of 30; c, g and k are each independently an integer of 1 to 5; d
And h each independently represent 0 or 1. However, the compound represented by the total number of -CH ₂ CHYO- units is 6-80] in the molecule,及 beauty formula (III): ## STR2 ## [In the formula, R ⁹ is a hydrogen atom or —C _q H _{2q + 1} (q is 0 to 4)
Y is the same as above; r, s, t, and u each independently represent a number from 0 to 30. However, the total number of —CH ₂ CHYO— units in one molecule is 6 to 80 ], and one or more compounds A selected from the group consisting of compounds represented by
An aqueous ink composition containing: 2. The aqueous ink composition according to claim 1, wherein the colorant is polymer particles in which a dye or pigment is contained in a water-insoluble polymer. 3. The aqueous ink composition according to claim 1, wherein the surface tension of the compound A is 40 to 70 mN / m. 4. The aqueous ink composition according to claim 1 , wherein the content of the compound A is 1 to 8 % by weight. 5. An aqueous medium, which is insoluble in water as a colorant
Polymer particles containing a dye or pigment in the polymer, and
And / or a self-dispersion pigment and a compound of formula (I): [Wherein R ¹ , R ² , R ⁴ , R ⁶ and R ⁷ are each independently
Standing a hydrogen _{atom, -C n H 2n + 1 (} n is an integer from 1 to 6) The
Is —C _n H _2n O (CH ₂ CHYO) _m H (Y is a hydrogen atom
Or a methyl group, m is a number from 0 to 20, and n is the same as the above); R
³ and R ⁵ are each independently a hetero atom, —C _n H _2n
-(N is the same as above) or may contain a hetero atom
A divalent hydrocarbon group; a, e and i are each independently
0 or 1; b, f and j are each independently 0 to 30
Number; c, g and k are each independently an integer of 1 to 5; d
And h each independently represent 0 or 1. However, 1 minute
Is the total number of -CH ₂ CHYO- units in the child from 1 to 100
A compound represented by the formula (II): [In the formula, R ⁸ is — (CH ₂ CHYO) _k — (Y is the same as above ).
Same; k is a number from 0 to 25); X is hydrogen atom, hydroxyl group, -C
H ₂ O (CH ₂ CHYO) _k H (Y and k are the same as above )
_{Flip), - O (CH 2 CHYO} ) k H (Y and k are said
Same) or -OM (M is an alkali metal); p is 2 to 7
Indicates an integer. However, -CH ₂ CHYO in one molecule
-The total number of units is from 1 to 100], and
Formula (III): [In the formula, R ⁹ is a hydrogen atom or —C _q H _{2q + 1} (q is 0 to 4
Y is the same as above; r, s, t and u are each
Independently, a number of 0 to 30 is shown. However, definitive in one molecule
The total number of --CH ₂ CHYO-- units is 1 to 100]
One or more compounds selected from the group consisting of
And A, formula ^{(IV): R 10 O- (} CH 2 CHYO) v -H (IV) wherein, Y is as defined above. R ¹⁰ represents a hydrogen atom, or a saturated or unsaturated monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms, and v represents a number of 1 to 100], a compound represented by the formula: _{(V): H (OCHYCH 2} ) W -O-R 11 O- (CH 2 cHYO) in _X -H (V) [wherein, Y is as defined above. R ¹¹ is C _y H _{2y +} 1 _(y is 3
(Integer of 10) or a saturated or unsaturated divalent hydrocarbon group optionally containing a hetero atom, w and x each independently represent a number of 1 to 99. However, CH in one molecule
Compounds represented by ₂ total number of chyo units is 2 to 100], and formula ^{(VI): R 12 - (} OCHYCH 2) W -O-R 11 O- (CH 2 CHYO) X -H (VI) [In the formula, R ¹¹ , Y, w and x are the same as defined above. R ¹² represents a saturated or unsaturated monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms. However, CH ₂ chyo units of the total number to that water soluble ink composition comprising one or more compounds B selected from the group consisting of compounds represented by a 1-100] in the molecule. 6. A total of —CH ₂ CHYO— units of compound A.
The aqueous ink composition according to claim 5, wherein the number is 6 to 80. 7. The content of compound A is 0.1 to 50% by weight.
7. The aqueous ink composition according to claim 5 or 6. 8. A compound aqueous ink composition according to any one of claims 5-7 has a surface tension of 40~70mN / m of B. 9. The compound aqueous ink composition according to any one claims 5-8 content is 0.1 to 50 wt% of B. 10. The water-insoluble polymer comprises a monomer mixture containing (a) a salt-forming group-containing monomer, (b) a macromer, and (c) a salt-forming group-containing monomer and a monomer copolymerizable with the macromer. claim 1-9 the aqueous ink composition according to any one containing a water dispersion of vinyl polymer particles in the vinyl polymer by polymerizing was a pigment. 11. The monomer mixture comprises (d) a hydroxyl group-containing monomer and (e) formula (VII): CH ₂ C═C (R ¹³ ) COO (R ¹⁴ O) _{P 1} R ¹⁵ (VII) (wherein R is ¹³ is a hydrogen atom or a methyl group; R ¹⁴ is a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom; R ¹⁵ is a hydrogen atom or a carbon which may have a hetero atom 11. The aqueous ink composition according to claim 10 , containing one or more selected from the group consisting of monomers represented by a monovalent hydrocarbon group of the number 1 to 30; p ₁ represents an integer of ₁ to 60). .