JP2003260347A - Dispersant, method for manufacturing the same, dispersion prepared by using the dispersant, and water- based ink prepared by using the dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersant with which an ink having high color developing property with little oozing on a plain paper and having not only sufficient color developing property but gloss and fixing property on a single-purpose paper can be produced, to provide a method for manufacturing the dispersant, and to provide a dispersion prepared by using the dispersant, a water-based ink prepared by using the dispersion, and a printed material recorded by using the water-based ink. <P>SOLUTION: The dispersant is produced by polymerizing one or more kinds selected from reactive monomers, oligomers and macromers in a solvent by using a radical polymerization initiator having a carboxyl group, or further by extending the obtained polymer by using one or more kinds selected from reactive monomers, oligomers and macromers. The dispersion is prepared by using the above dispersant, and the water-based ink is prepared by using the dispersion. The recorded material is obtained by using the water-based ink. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersant for obtaining a dispersion suitable for a water-based ink which has high printing quality on plain paper, recycled paper or coated paper and is excellent in storage stability, and a dispersant for the same. The present invention relates to a dispersion used, a water-based ink using the dispersion, and a recording material using the ink.

[0002]

2. Description of the Related Art A conventional dispersion has a method in which a surfactant is used as a means for dispersing in water, as disclosed in JP-A No. 01-301760, or a hydrophobic portion and a hydrophilic portion as disclosed in JP-B-5-064724. Was dispersed using a dispersion polymer having Further, as a method for coating the surface of the colorant with a polymer, as for ink for inkjet printers, a method of using microcapsules encapsulating a dye ink as described in JP-A-62-95366, JP-A-1-170672. As disclosed in JP-A-5-39447, a method of dissolving or dispersing a dye in a water-insoluble solvent, emulsifying the dye in water with a surfactant, and using a microencapsulated dye. like,
A method of using a microcapsule as an encapsulant in which a sublimable disperse dye is dissolved or dispersed in at least one of water, a water-soluble solvent, and polyester as a recording liquid, and JP-A-6-313.
No. 141 discloses an ink composition comprising colored emulsion-polymerized particles and an aqueous material, and JP-A-10-140065 discusses a phase inversion emulsification reaction or a method using an acid precipitation method.

[0003]

However, conventional dispersions are unstable, and when a substance having a hydrophilic portion and a hydrophobic portion such as a surfactant or 1,2-alkylene glycol or glycol ether is present, adsorption / desorption is not possible. Is likely to occur. In order to reduce bleeding on paper, ordinary water-based ink requires a substance having a hydrophilic part and a hydrophobic part, such as a surfactant or glycol ether.
Conventional inks that do not use these substances have insufficient penetrability into paper, and there is a problem that the type of paper is limited in order to perform uniform printing, and the print image tends to deteriorate. In addition, additives such as those used in the present invention, particularly in conventional dispersions (acetylene alcohol surfactants, acetylene glycol surfactants and silicone surfactants, 1,2-alkylene glycols and alkylene glycol monoalkyl ethers). Long-term storage stability cannot be obtained if one or more selected from
There is a problem that the re-dissolvability of the ink is poor and the ink is easily dried and clogged. Further, with respect to the pigment dispersed by such a dispersant, the residue of the dispersant remains in the ink, or the dispersant does not sufficiently contribute to the pigment dispersion and is detached from the pigment, resulting in high viscosity. There were challenges. When the viscosity is high, the amount of the coloring material such as pigment added is limited, and sufficient image quality cannot be obtained especially on plain paper.

Therefore, the present invention is intended to solve such a problem, and its purpose is to produce a high degree of color development with little bleeding on plain paper, and to provide sufficient color development on special paper.
A dispersion capable of producing an ink having glossiness and fixability and capable of producing an ink having excellent ejection stability in ink jet recording, a water-based ink using the dispersion, and a recording material using the same. It is in the place of providing.

[0005]

The first dispersant of the present invention uses a radical polymerization initiator having a carboxyl group,
One or more selected from reactive monomers, oligomers, and macromers is polymerized in a solvent, and the second is the use of a radical polymerization initiator having a carboxyl group to prepare reactive monomers, oligomers, and macromers. Characterized in that the first polymer obtained by polymerizing at least one selected from the group above in a solvent is further extended with at least one selected from a monomer, oligomer and macromer having reactivity. And

The first method for producing the dispersant of the present invention uses a radical polymerization initiator having a carboxyl group,
It is characterized in that it is prepared by polymerizing at least one selected from a reactive monomer, oligomer and macromer in a solvent. The second one is a monomer having a radical polymerization initiator having a carboxyl group and having reactivity. , One or more selected from an oligomer and a macromer are polymerized in a solvent to form a first polymer, and then the reaction is temporarily lowered, and one or more selected from a monomer, an oligomer and a macromer having reactivity. Is used to polymerize the first polymer to extend the polymer.

Furthermore, the dispersion of the present invention is characterized in that a molecular color material is dispersed by using the above dispersant. The aqueous ink of the present invention is characterized by containing the above dispersion as one component. The recording material of the present invention is characterized by being printed using the above water-based ink.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The dispersion using the dispersant according to the present invention itself has excellent storage stability, and the aqueous ink using the dispersion has little bleeding on plain paper and high color development, and on special paper. In view of the fact that it is possible to create an ink that has sufficient glossiness and fixability in addition to sufficient color development, and that ink jet recording requires characteristics such as excellent ink ejection stability from the ink jet head. This is due to the result of diligent examination.

A first dispersant according to the present invention is characterized in that a radical polymerization initiator having a carboxyl group is used and at least one selected from a reactive monomer, oligomer and macromer is polymerized in a solvent, Secondly, a radical polymerization initiator having a carboxyl group is used, and the first polymer obtained by polymerizing at least one selected from a reactive monomer, oligomer and macromer in a solvent is further added to the monomer and oligomer having further reactivity. And the first polymer is extended by using one or more kinds selected from macromers.

The first method of producing the dispersant of the present invention uses a radical polymerization initiator having a carboxyl group,
It is characterized in that it is prepared by polymerizing at least one selected from reactive monomers, oligomers and macromers in a solvent. The second is to use a radical polymerization initiator having a carboxyl group and polymerize one or more kinds selected from reactive monomers, oligomers and macromers in a solvent to prepare a first polymer, and then once. It is characterized in that it is prepared by polymerizing the first polymer by using one or more kinds of monomers, oligomers and macromers having a lower reaction rate and having reactivity, and extending the polymer. Further, the dispersion of the present invention is characterized in that it is dispersed by the above dispersion method using the above dispersant. The aqueous ink of the present invention is characterized by containing the above dispersion as one component. Furthermore, the printed matter of the present invention is characterized by being printed using the above-mentioned water-based ink.

In any of the above cases, since the radical polymerization initiator having a carboxyl group is used, a polymer having the carboxyl group as a hydrophilic portion is formed, but the selectivity of the molecule added near the hydrophilic portion is improved. However, the selectivity of the hydrophobic portion of the dispersant to be adsorbed on the surface hydrophobic portion of the pigment or the like is also improved. Therefore, the adsorption to the pigment or the like can be stabilized, and therefore, the dispersion having excellent dispersion stability can be formed. As a result, it is possible to use one or more selected from surfactants, 1,2-alkylene glycols and alkylene glycol monoalkyl ethers, which are good additives in the present invention, and reduce bleeding and color development. It is possible to improve the sex. The above-mentioned carboxyl group is a carboxylic acid, which is preferably neutralized with an inorganic and / or organic alkali. As the inorganic and / or organic alkali, ammonia, alkylammonium, sodium hydroxide, lithium hydroxide, potassium hydroxide or the like is preferable.

It is preferable that at least one selected from the above-mentioned reactive monomers, oligomers and macromers has at least a vinyl group.

The above-mentioned monomers, oligomers and macromers are composed of acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, alkylstyrene, ester, amide, imide, silicon-containing body, sulfur-containing body and derivatives thereof. It is preferably one or more selected from the group. The hydrophilic group of the above-mentioned polymer is preferably at least a carboxyl group, a sulfonic acid group, a hydroxyl group, an amino group, an amide group and their bases. They are copolymerized with monomers and oligomers having an acryloyl group having a double bond, a methacryloyl group, a vinyl group or an allyl group.

At least one selected from the acetylene alcohol surfactants, acetylene glycol surfactants and silicon surfactants used in the present invention, di (tri).
The substance consisting of one or more selected from ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol undergoes adsorption-desorption reaction with the dispersant used for the usual dispersant dispersion, and is therefore desorbed. The dispersant floats in the ink, which tends to disturb the printing.

However, by carrying out suitable dispersion using the above-mentioned polymer, since the polymer stably contains the colorant, adsorption and desorption do not easily occur.

Specific examples of the component forming the dispersant include styrene, tetrahydrofurfuryl acrylate,
Butyl methacrylate, (α, 2,3 or 4) -alkylstyrene, (α, 2,3 or 4) -alkoxystyrene, 3,4-dimethylstyrene, α-phenylstyrene, divinylbenzene, vinylnaphthalene, dimethylamino ( (Meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropylacrylamide, N, N-dimethylaminoethyl acrylate, acryloylmorpholine, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N
-Diethyl acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ethylhexyl (meth) acrylate, other alkyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxy group, propoxy group, butoxy group Diethylene glycol or polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyalkyl (meth) acrylate, other fluorine-containing, chlorine-containing, Introduce a crosslinked structure in addition to monofunctional such as silicon-containing (meth) acrylate, (meth) acrylamide, maleic acid amide, (meth) acrylic acid. If the (mono-, di-, tri-, tetra,
Poly) ethylene glycol di (meth) acrylate, 1,
3-propanediol, 1,4-butanediol, 1,
5-pentanediol, 1,6-hexanediol,
(Meth) acrylates such as 1,8-octanediol and 1,10-decanediol, trimethylolpropane tri (meth) acrylate, glycerin (di, tri)
(Meth) acrylate, ethylene oxide adduct of bisphenol A or F, di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Acrylic group and methacryl The compound which has a group is mentioned.

In the polymerization of the present invention, a chain transfer agent may or may not be used. When used, for example, in addition to t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, xanthogens such as dimethylxanthogen disulfide, diisobutylxanthogen disulfide, or dipentene, indene, 1,4-cyclohexadiene, dihydrofuran, xanthene. And so on.

The number average molecular weight of the above-mentioned dispersant is preferably 10,000 or more and 1,000,000 or less in terms of styrene in gel permeation chromatography (GPC). If it is less than 10,000, adsorption and desorption tends to occur, and if it exceeds 1,000,000, dispersion tends to be unstable. It is more preferably 15,000 or more and 100,000 or less.

It is preferable that the weight average molecular weight (Mw) / number average molecular weight (Mn), which is a measure of dispersion of the above-mentioned dispersant molecular weight, is 5 or less. If it exceeds 5, dispersion tends to be unstable. It is more preferably 4 or less.

It is preferable that the molecular color former is dispersed using the dispersant prepared by the method according to claim 2 and / or 4. Here, the molecular chromophore is
It refers to a substance having a so-called colored molecule, and includes a colorant, a coloring material, a pigment, and a dye. And as a molecular color body, an organic pigment or an inorganic pigment can be used conveniently. For example, for black ink, carbon black such as furnace black, lamp black, acetylene black, and channel black (C.I.
I. Pigment Black 7), metals such as copper oxide, iron oxide (C.I. Pigment Black 11) and titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1). For inkjet use, carbon black having a relatively low specific gravity and hard to settle in water is preferable.

For color, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 24, 3
4, 35, 37, 42 (yellow iron oxide), 53, 55, 7
4, 81, 83 (Disazo Yellow HR), 95, 9
7, 98, 100, 101, 104, 108, 109,
110, 117, 120, 138, 153, 180,
C. I. Pigment Red 1, 2, 3, 5, 17, 22
(Brilliant First Scarlet), 23, 3
1, 38, 48: 2 (Permanent Red 2B (B
a)), 48: 2 (Permanent Red 2B (C
a)), 48: 3 (Permanent Red 2B (S
r)), 48: 4 (Permanent Red 2B (M
n)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2,
64: 1, 81 (Rhodamine 6G rake), 83, 8
8, 101 (Bengara), 104, 105, 106, 1
08 (Cadmium red), 112, 114, 122
(Quinacridone magenta), 123, 146, 149,
166, 168, 170, 172, 177, 178, 1
79, 185, 190, 193, 209, 219, C.I.
I. Pigment violet 19, 23, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 56 , 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18,
36, etc. can be used.

When a water-based ink is used in an ink jet, the amount of these pigments added is 0.5 to 30% by weight.
(Hereinafter, it may be referred to as “%”.), But 1.0 to 12% is more preferable. If the addition amount is less than this, the printing density cannot be secured, and if the addition amount is more than this, the ink viscosity increases or structural viscosity occurs in the viscosity characteristics, and the ejection stability of the ink from the inkjet head tends to deteriorate. . The particle size of the pigment is preferably 25 μm or less, more preferably 1 μm or less, more preferably 0.01 to 0.15 μm.

As the dispersion method, ultrasonic dispersion, a bead mill, a sand mill, a roll mill, a jet mill or the like may be used.

The surface tension of the above water-based ink at 25 ° C. is preferably 40 mN / m or less. 40 mN / m
If it exceeds the range, it takes time to dry the print, bleeding between different colors increases, and bleeding on plain paper such as PPC paper also increases, and more preferably 20 mN / m or more and 35 mN
/ M or less. If it is less than 20 mN / m, the ejection stability becomes poor.

The contact angle of the above-mentioned aqueous ink with polytetrafluoroethylene at 25 ° C. is preferably 40 ° or more. If the angle is less than 40 °, the nozzle surface will get wet easily,
Discharge stability cannot be obtained.

It is preferable that the concentration of the molecular color former of the above-mentioned aqueous ink is 0.5% or more and 20% or less. 0.5
If it is less than%, it is difficult to obtain the color developability, and if it exceeds 20%, the viscosity becomes high and the ejection stability deteriorates.

A surfactant, 1,2-
It is preferable to add one or more selected from alkylene glycol and alkylene glycol monoalkyl ether.

The above-mentioned surfactant is preferably one or more selected from acetylene alcohol-based surfactants, acetylene glycol-based surfactants and silicon-based surfactants.

As the acetylene glycol-based surfactant, commercially available Surfynol 104, 82, 465, 4
85, or TG (both Air Products
and Chemicals. Inc. (Available from Nisshin Chemical Industry Co., Ltd.), orufin STG, orufin E1010 (all are trade names of Nisshin Chemical Co., Ltd.). As the acetylene alcohol-based surfactant, commercially available Surfynol 61 (Air Products a
nd Chemicals. Inc. More available).

Examples of the silicone-based surfactants include BYK-345, 346, 348 and BYK-347, which are silicone-based surfactants, from Big Chemie Japan Co., Ltd.
Can be suitably used.

The above-mentioned 1,2-alkylene glycol is preferably 1,2-pentanediol which may be branched or 1,2-hexanediol which may be branched.

The above-mentioned alkylene glycol monoalkyl ether is preferably an alkylene glycol having 10 or less repeating units and having 4 to 10 carbon atoms. In the alkylene glycol having 10 or less repeating units, the alkyl ether having 4 to 10 carbon atoms is preferably di (tri) ethylene glycol monobutyl ether and / or (di) propylene glycol monobutyl ether. Furthermore, it is preferable that the above-mentioned 1,2-alkylene glycol is 1,2-hexanediol and / or 1,2-pentanediol.

The amount of the above-mentioned substance consisting of one or more selected from the group consisting of di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol is 0.5. % Or more and 30% or less is preferable. 0.
If it is less than 5%, the penetrating effect is low and the printing quality is not improved. If it exceeds 30%, it becomes difficult to use due to the increase in viscosity.
Adding more than that does not have the effect of improving print quality. It is more preferably 1% or more and 15% or less.

One or more selected from the group consisting of the above-mentioned acetylene glycol-based surfactant, acetylene alcohol-based surfactant and silicon-based surfactant is 0.1.
% Or more and 5% or less is preferable. If it exceeds 5%, the effect of the print quality reaches a ceiling, and even if added, the viscosity rises, making it difficult to use, and the ink tends to adhere to the tip of the head, and the print tends to be disturbed. If it is less than 0.1%, the effect of improving the printing quality becomes low. A more preferable addition amount is 0.
It is 15 to 2%.

At least one selected from the above-mentioned acetylene glycol-based surfactants, acetylene alcohol-based surfactants and silicon-based surfactants,
Di (tri) ethylene glycol monobutyl ether,
It is preferable to simultaneously add (di) a substance consisting of one or more kinds selected from propylene glycol monobutyl ether and 1,2-alkylene glycol. One or more selected from acetylene glycol-based surfactants, acetylene alcohol-based surfactants and silicon-based surfactants, and di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene. Printing quality is improved by using at least one selected from glycols at the same time.

The addition amount of at least one selected from the group consisting of the above-mentioned acetylene glycol-based surfactant, acetylene alcohol-based surfactant and silicon-based surfactant is 0.01 to 0.5%. It is preferable that the amount of one or more selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol be 1% or more. One or more selected from acetylene glycol-based surfactants, acetylene alcohol-based surfactants and silicon-based surfactants have the effect of improving the permeability even in a small amount. Therefore, the addition amount is 0.5% or less, and the addition amount of one or more selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol is 1% or more. Therefore, the print quality is further improved.

The above-mentioned 1,2-alkylene glycol is a 1,2-alkylene glycol having 4 to 10 carbon atoms and which may be branched, and the addition amount thereof is preferably 10% or less. If it exceeds 10%, it becomes difficult to use for inkjet due to an increase in viscosity, and addition of more than that does not have the effect of improving print quality. It is more preferably 1% or more and 8% or less.

Specifically, the above-mentioned 1,2-alkylene glycol is preferably 1,2-pentanediol or 1,2-hexanediol. The addition amount of 1,2-pentanediol is preferably 3 to 15%. If it is less than 3%, the effect of improving the permeability is low, and therefore bleeding often occurs. If the carbon number exceeds 15%, the water solubility is low, and thus it is difficult to use in a water-soluble ink such as the present invention. 1,
2-hexanediol is preferably 0.5 to 10%.
If it is less than 0.5%, the effect of improving the permeability is low, and if it has more than 10 carbon atoms, the water solubility is lowered and it is difficult to use it in the water-soluble ink of the present invention. 1 selected from the group consisting of the above-mentioned acetylene alcohol-based surfactant, acetylene glycol-based surfactant and silicon-based surfactant
When the addition amount of the seeds or more is 0.5% or more, the ratio with the 1,2-alkylene glycol is preferably 1: 0.01 to 1:50 from the viewpoint of printing quality, and the 1,2-alkylene glycol is preferable. When the amount exceeds 50 times that of the acetylene glycol and / or acetylene alcohol-based surfactant, the effect of improving the printing quality reaches the ceiling, and the effect is low even if it is added more and the adverse effect of increasing the viscosity occurs.

0.5% of one or more selected from the above-mentioned acetylene alcohol-based surfactant, acetylene glycol-based surfactant and silicon-based surfactant is added.
It is above, and it is preferable that the ratio of the addition amount with the 1,2-alkylene glycol is 1: 0.01 to 1:50. And, it is preferable to contain 10% or less of the above-mentioned (di) propylene glycol monobutyl ether. 10%
If the value exceeds the limit, the effect of improving the print quality reaches a ceiling, and conversely, it becomes necessary to add a dissolution aid due to the adverse effect of increased viscosity and low water solubility. It is more preferably 0.5 to 5%.

At least one selected from the group consisting of the above-mentioned acetylene alcohol-based surfactant, acetylene glycol-based surfactant and silicon-based surfactant, and (di)
Propylene glycol monobutyl ether ratio is 1: 0
It is preferably ˜1: 50. (Di) Propylene glycol monobutyl ether exceeds 50 times more than one selected from the group consisting of acetylene glycol-based surfactants, acetylene alcohol-based surfactants, and silicon-based surfactants, and the improvement effect of print quality reaches a peak. However, the effect is low even if it is added more, and the adverse effect of increasing the viscosity occurs.

It is preferable that the di (tri) ethylene glycol monobutyl ether is contained in an amount of 20% or less. What is di (tri) ethylene glycol monobutyl ether? Diethylene glycol monobutyl ether (DEGmB
E) and / or triethylene glycol monobutyl ether (TEGmBE) are shown, but addition of 20% or less is preferable as a necessary level of penetrability for improving print quality. If it exceeds 20%, the effect of improving the printing quality reaches a ceiling and, conversely, the adverse effect of increasing the viscosity occurs. It is more preferably 0.5 to 10%.

The amount of one or more selected from the group consisting of the above-mentioned acetylene alcohol surfactant, acetylene glycol surfactant and silicon surfactant is 0.5% or more, and di (tri) The ratio with ethylene glycol monobutyl ether is preferably 1: 0.01 to 1:50. From the viewpoint of print quality, it is preferable to add up to 50 times the amount of at least one selected from the group consisting of acetylene glycol-based surfactants, acetylene alcohol-based surfactants, and silicon-based surfactants. Di (tri) ethylene glycol monobutyl ether improves the solubility and print quality of at least one selected from the group consisting of acetylene glycol surfactants, acetylene alcohol surfactants and silicone surfactants. However, if the amount of addition exceeds 50 times, the effects will reach the limit, and it will be difficult to use for inkjet.

A humectant is preferably added to the above-mentioned water-based ink. In the case of inkjet ink, a moisturizing agent is added to prevent drying and clogging, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and a molecular weight of 2000 or less. Polyethylene glycol,
1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, alkyleneoxy adduct of glycerin , Mesoerythritol, pentaerythritol and the like.

It is also possible to use many types of sugars. There are monosaccharides and polysaccharides, glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, etc., as well as alginic acid and its salts, cyclo. Dextrins and celluloses can be used. And the addition amount is 0.05% or more and 3
0% or less is preferable. If it is less than 0.05%, the effect of recovering the clogging phenomenon in which the ink is dried and clogged at the tip of the head is small, and if it exceeds 30%, the viscosity of the ink increases and proper printing cannot be performed. More preferable addition amount of glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, etc. Is 3 to 20%. Alginic acid and its salt, cyclodextrins, and celluloses must be added in amounts such that the viscosity of the ink does not become too high.

It is preferable to add polymer fine particles to the above-mentioned aqueous ink. The particle size of the polymer fine particles is 50 to 500 nm, and the addition amount is 0.1 to 20%.
Is preferred. Particle size of polymer particles is 50 nm
If it is less than the above, it becomes difficult to obtain dispersion stability, and it becomes difficult to obtain ejection stability as an inkjet ink. However, if the addition amount is 3% or less, the effect is reduced.
It can also be used at less than nm. Even if it exceeds 500 nm, ejection stability as an inkjet ink cannot be obtained. It is preferably 70 to 300 nm. If the addition amount is less than 0.1%, the effect of improving the fixing property becomes low. However, the occurrence of unevenness due to ink aggregation on the special paper is effective even if it is less than 0.1%. If it exceeds 20%, the viscosity increases, and discharge stability cannot be obtained. In order to improve the fixability, it is preferably 1 to 10%.

As substances for forming an emulsion in which the polymer fine particles are dispersed in water, in addition to styrene, tetrahydrofurfuryl acrylate and butyl methacrylate, (α, 2,3 or 4) -alkylstyrene, (α,
2, 3 or 4) -alkoxystyrene, 3,4-dimethylstyrene, α-phenylstyrene, divinylbenzene, vinylnaphthalene, dimethylamino (meth) acrylate, dimethylaminoethyl (meth) acrylate,
Dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylate, acryloylmorpholine, N, N-dimethyl acrylamide, N-isopropyl acrylamide, N, N-diethyl acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, ethylhexyl (meth) acrylate, other alkyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxy group, propoxy group, butoxy group diethylene glycol or polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobonyl (meth) acrylate, hydroxy Alkyl (meth) acrylate, other fluorine-containing, chlorine-containing, silicon-containing (meth) acrylate,
(Meth) acrylamide, maleic acid amide, (meth)
When a crosslinked structure is introduced in addition to monofunctional such as acrylic acid (mono, di, tri, tetra, poly) ethylene glycol di (meth) acrylate, 1,4-butanediol,
(Meth) acrylates such as 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol, trimethylolpropane tri (meth) acrylate, glycerin (di, tri) ( (Meth) acrylate, bisphenol A or F
An ethylene oxide adduct of di (meth) acrylate,
A compound having an acryl group or a methacryl group such as neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate can be used.

It is also possible to use an emulsifier used for forming such polymer fine particles. Examples thereof include sodium lauryl sulphate and potassium lauryl sulphate, and stearyl groups, nonyl groups, alkyl groups having branched groups such as octyl groups and branched alkyl groups, or phosphates in addition to activators that are sulfates such as alkylphenyl groups. A borate active agent, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, or the like can be used.

Polymerization initiators include potassium persulfate and ammonium persulfate, hydrogen persulfate, azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide, peracetic acid, cumene hydroperoxide, t-butyl hydroxyperoxide. Although a general initiator used for radical polymerization such as oxide and paramenthane hydroxyperoxide can be used, the polymerization reaction is carried out in water, so that it is preferably water-soluble. Examples of the chain transfer agent for polymerization include t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, xanthogens such as dimethylxanthogen disulfide, diisobutylxanthogen disulfide, or dipentene, indene, 1,4-cyclohexadiene. , A general chain transfer agent such as dihydrofuran or xanthene can be used.

Further, in addition to the multiple phase using the core-shell type polymer fine particles in which the core and the shell have different structures, a single phase may be used. The film forming temperature (MFT) of these polymer particles is preferably designed to be room temperature or lower, or is preferably set to room temperature or lower by using an MFT lowering agent (film forming aid). Further, the above-mentioned additives may not be used depending on reaction conditions and the like. For example, when the micelle-forming monomer is used, the micelle-forming agent is not necessary, and depending on the reaction conditions, the chain transfer agent may not be used, so that it can be appropriately selected.

A recording material printed using the water-based ink according to any one of claims 12 to 20 has high color development and is excellent in water resistance, light resistance and abrasion resistance. The ink for inkjet recording according to the present invention is used as a permeation control agent, a pH adjusting agent, a dissolution aid, an antioxidant, a viscosity adjusting agent, and a dispersion for the purpose of ensuring the stability of leaving the ink and achieving stable ejection from the ink ejection head. In some cases, various additives such as a chelating agent, a fungicide, and a corrosion inhibitor for capturing the affecting metal ions are added. These are illustrated below.

In addition, it has compatibility with water and improves solubility of glycol ethers and ink components having low solubility in water contained in the ink, and further as a penetration control agent for a recording medium such as paper, or Ethanol, methanol, butanol, to prevent nozzle clogging
1 to 4 carbon atoms such as propanol and isopropanol
Alkyl alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n -Butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propyi Glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Glycol ethers such as propylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, sulfolane, etc. Can be used, and these are appropriately selected and used.

Further, it is possible to add another surfactant to the ink according to the present invention as a permeation control agent for a medium such as paper or special paper. Examples thereof include amphoteric surfactants and nonionic surfactants. Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ether type such as ethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearate ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesqui Esters such as oleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. Alkyl esters, and the like fluorine-containing surfactants such as perfluoroalkyl carboxylates.

Further, amines such as diethanolamine, triethanolamine, propanolamine and morpholine as pH adjusters, solubilizers or antioxidants and their modified products, potassium hydroxide, sodium hydroxide, lithium hydroxide and the like. Inorganic salts, ammonium hydroxide, quaternary ammonium hydroxide (such as tetramethylammonium), potassium carbonate (hydrogen), sodium carbonate (hydrogen), carbonates such as lithium carbonate (hydrogen carbonate) and other phosphates, or N-methyl 2-Pyrrolidone, urea, thiourea, tetramethylurea and other ureas, alohanates, methylallohanates and other alohanates, biuret, dimethylbiuret, tetramethylbiuret and other biurets, L-ascorbic acid and its salts, etc. There is. Further, commercially available antioxidants, ultraviolet absorbers and the like can also be used. Examples include Ciba Geigy's Tinuvin 328, 900, 1130, 3
84, 292, 123, 144, 622, 770, 29
2, Irgacor252, 153, Irganox1
010, 1076, 1035, MD1024, or oxides of lanthanide.

Further, as the viscosity modifier, rosins,
Examples include alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylate, polyvinyl pyrrolidone, and gum arabic starch.

Preservatives include alkylisothiazolone, chloroalkylisothiazolone, benzisothiazolone, bromonitroalcohol, oxazolidine compound and / or
Alternatively, chlorxylenol or the like can be used, and the metal ion trapping agent can be ethylenediamine acetate, and the antirust agent can be dicyclohexyl ammonium nitrate, benzotriazole, or the like.

Among the preservatives, those containing octylisothiazolone as an active ingredient among alkylisothiazolones (for example, NS-800H, NS800G, NS-800).
P: Above Nagase Kasei Co., Ltd.) is commercially available. As the chloroalkylisothiazolone, one containing chloroisomethylthiazolone as an active ingredient (for example, NS-50
0W, NS-80D, NS-CG, NS-TM, NS-
RS: Above Nagase Chemical Industry Co., Ltd.) is commercially available.
Those containing benzisothiazolone as an active ingredient (for example, Proxel BDN, Proxel BD20, Proxel G
XL, Proxel LV, Proxel TN: above Geneca (UK), Denide BIT, Denide NIPA: Above Nagase Kasei Co., Ltd.) are commercially available. Those containing bromonitro alcohol as an active ingredient are commercially available (for example, Bronopol, Miaside BT, Miaside AS: Nagase Kasei Kogyo Co., Ltd.). Those containing chlorxylenol as an active ingredient are commercially available (for example, PCMX: Nagase Kasei Co., Ltd.). In addition, an oxazolidine compound or a mixture or modified product of these components as an active ingredient is used depending on the application (for example, NS-BP,
Denise BIT-20N, Denise SPB, Sanisette HP, Microstat S520, Sanisette SK
2, Denise side NS-100, Denise side BF-1, Denise side C3H, Sanisetto 161, Denise side CS
A, Denise CST, Denise C3, Denise O
MP, Denide XR-6, Denide NM, Moldenize N760, Denisat P4, Denisat P-8, Denisat CHR: Nagase Kasei Kogyo Co., Ltd.). Among them, in aqueous inks, those containing an oxazolidine compound as an active ingredient, those containing chloroisomethylthiazolone as an active ingredient, and those containing benzisothiazolone as an active ingredient are highly effective. Further, these preservatives are not a single component, but a composite component containing two or more kinds of structures which are not so similar in structure is preferable because the resistant bacteria can be suppressed.

Examples of ethylenediamine acetic acid salts include ethylenediaminediacetic acid free acid, ethylenediaminetetraacetic acid free acid, disodium salt, trisodium salt and tetrasodium salt, and disodium salt, trisodium salt and tetrasodium salt are preferred. In the aqueous ink, in addition to ethylenediaminediacetic acid free acid, lithium salts, potassium salts, ammonium salts, triethanolamine salts and the like are effective as ethylenediaminetetraacetic acid salts. This ethylenediamineacetate salt has the effect of preventing metal ions from existing in the ink path in the ink cartridge or head, and thereby preventing the dispersion of the molecular color former and the fine polymer particles from aggregating or deteriorating.

Dicyclohexyl ammonium nitrate and benzotriazole are effective as the rust preventive. This rust preventive agent is a rust preventive agent when the head material is made of metal, and is especially effective when the front surface of the nozzle rusts and the ink does not fly easily.

[0059]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to such embodiments.

The case where an organic or inorganic pigment is used as the molecular color former will be described. In Examples and Comparative Examples, pigment 1 is an inorganic pigment, carbon black pigment, pigment 2 is an organic pigment, phthalocyanine pigment, pigment 3 is an organic pigment, dimethylquinacridone pigment, and pigment 4 is an organic pigment, diketopyrrolol. A pyrrole pigment is shown. But,
Not limited to these, many organic and inorganic pigments can be used. Also, the average particle size of each is in <>
Indicated in (nanometer) units.

(Production of Dispersant 1) 200 parts of methyl ethyl ketone, 1 part of azobiscyanovaleric acid and 50 parts of butylmethacrylate were placed in a reaction vessel having a stirrer, a reflux tube, a thermometer and a dropping funnel, and after nitrogen substitution, the mixture was heated to 70 ° C. And stir. 50 parts of butyl methacrylate, 10 parts of methacrylic acid, 30 parts of styrene, 15 parts of polypropylene glycol methacrylate and 20 parts of methyl ethyl ketone, which have been placed in a dropping funnel, are gradually added to a reaction vessel and reacted for 3 hours. Then, 1 part of t-dodecyl mercaptan is gradually added to reduce the reaction. Methyl ethyl ketone is further added to the reaction vessel to obtain a 35% dispersant A.

A part of the prepared dispersant was taken and the solvent was adjusted to TH by using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd.
3000 in styrene-equivalent molecular weight when measured as F
It is 0. In addition, Mw / Mn, which is a measure of dispersion, is 2.3.
Is.

(Production of Dispersion 1) Dispersant A Solution 40
Part and carbon black Raven C (made by Colombian Carbon) are used. A mixture of 50 parts of Raven C, 1 part of Olfine E1010 (manufactured by Nisshin Chemical Co., Ltd.) and 50 parts of water was kneaded with a three-roll mill, and 100 parts of the kneaded product and 40 parts of the polymer aqueous solution were mixed in 150 parts of ion-exchanged water. In addition, the dispersion treatment is carried out for 2 hours with Nanomizer YSNM-1500-5 (manufactured by Yoshida Kikou Co., Ltd.) to obtain an aqueous dispersion of carbon black. Then, using a rotary evaporator, the entire amount of methyl ethyl ketone and a part of water were distilled off, the mixture was neutralized with 0.1 mol / L sodium hydroxide to adjust to pH 9, and then filtered with a 0.3 μm membrane filter. To obtain Dispersion 1 having a solid content (dispersion polymer and carbon black) of 20%.

(Production of Dispersion 2) Dispersion 2 is prepared in the same manner as Dispersion 1 except that Pigment Blue 15: 4 (copper phthalocyanine pigment: manufactured by Clariant) is used.

(Production of Dispersion 3) Dispersion 3 is prepared in the same manner as Dispersion 1 except that Pigment Red 122 (dimethylquinacridone pigment: manufactured by Clariant) is used.

(Production of Dispersion 4) Dispersion 4 is prepared in the same manner as Dispersion 1 except that Pigment Yellow 180 (diketopyrrolopyrrole pigment: manufactured by Clariant) is used.

(Production of Dispersant 2) 200 parts of methyl ethyl ketone, 1 part of azobiscyanovaleric acid and 50 parts of butylmethacrylate were placed in a reaction vessel having a stirrer, a reflux tube, a thermometer and a dropping funnel, and after nitrogen substitution, the mixture was heated to 70.degree. And stir. 50 parts of butyl methacrylate, 10 parts of methacrylic acid, 10 parts of styrene, 15 parts of polypropylene glycol methacrylate, and 20 parts of methyl ethyl ketone, which have been placed in a dropping funnel, are gradually added to a reaction vessel and reacted for 4 hours. Then, 1 part of t-dodecyl mercaptan is gradually added to reduce the reaction. After that, 1 part of azobisisobutyronitrile, 150 parts of styrene, 80 parts of butyl methacrylate, and 20 parts of methyl ethyl ketone, which were placed in another dropping funnel, were gradually added to the reaction container and allowed to react for 3 hours, and further methyl ethyl ketone was added to the reaction container. In addition 35
% Dispersant B is obtained.

A part of the prepared dispersant was taken and the solvent was changed to TH using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd.
3500 in styrene equivalent molecular weight when measured as F
It is 0. In addition, Mw / Mn, which is a measure of dispersion, is 2.8.
Is.

(Production of Dispersion 5) Dispersant B Solution 40
Part and carbon black MA100 (manufactured by Mitsubishi Chemical)
To use. 50 parts of MA100 and Olfin E1010
(Manufactured by Nisshin Chemical Co., Ltd.) and a mixture of 1 part and 50 parts of water are kneaded by a three-roll mill, and 100 parts of the kneaded material and 40 parts of the polymer aqueous solution are added to 150 parts of ion-exchanged water, and Nanomizer (YSNM- 1500-5: Yoshida Kikai Kogyo Co., Ltd.) for 2 hours to obtain an aqueous dispersion of carbon black. Then, using a rotary evaporator, the entire amount of methyl ethyl ketone and a part of water were distilled off, and the mixture was neutralized with 0.1 mol / L sodium hydroxide to obtain p
Solid content (dispersion polymer and carbon black) after being adjusted to H9 and then filtered through a 0.3 μm membrane filter
Is 20% of Dispersion 5.

(Production of Dispersion 6) Dispersion 6 is prepared in the same manner as Dispersion 5 except that Pigment Blue 15: 4 (copper phthalocyanine pigment: manufactured by Clariant) is used.

(Production of Dispersion 7) Dispersion 7 is prepared in the same manner as Dispersion 5, except that Pigment Red 122 (dimethylquinacridone pigment: manufactured by Clariant) is used.

(Production of Dispersion 8) Dispersion 8 is prepared in the same manner as Dispersion 8 except that Pigment Yellow 180 (diketopyrrolopyrrole pigment: manufactured by Clariant) is used.

(Production 3 of Dispersant) Ion-exchanged water 200 was placed in a reaction vessel having a stirrer, a reflux tube, a thermometer, and a dropping funnel.
Parts, 1 part of azobiscyanovaleric acid and 50 parts of butylmethacrylate were added and the atmosphere was replaced with nitrogen, and then the mixture was heated to 70 ° C. and stirred. Butyl methacrylate 50 in a dropping funnel
Parts, 10 parts of methacrylic acid, 30 parts of styrene, 15 parts of polypropylene glycol methacrylate, and 1.5 parts of sodium lauryl sulfate are gradually added to the reaction vessel and reacted for 3 hours. Then, 1 part of t-dodecyl mercaptan is gradually added to reduce the reaction. Methyl ethyl ketone is further added to the reaction vessel to obtain a dispersant C having a concentration of 35%.

A part of the prepared dispersant was taken, and the solvent was adjusted to TH using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd.
3000 in styrene-equivalent molecular weight when measured as F
It is 0. In addition, Mw / Mn, which is a measure of dispersion, is 2.3.
Is.

(Production of Dispersion 9) Dispersant C Solution 40
Part and carbon black Raven C (made by Colombian Carbon) are used. A mixture of 50 parts of Raven C, 1 part of Olfine E1010 (manufactured by Nisshin Chemical Co., Ltd.) and 50 parts of water was kneaded with a three-roll mill, and 100 parts of the kneaded product and 40 parts of the polymer aqueous solution were mixed in 150 parts of ion-exchanged water. In addition, the dispersion treatment is carried out for 2 hours with Nanomizer YSNM-1500-5 (manufactured by Yoshida Kikou Co., Ltd.) to obtain an aqueous dispersion of carbon black. And 0.1 mol /
It is neutralized with L sodium hydroxide and adjusted to pH 9, and then filtered through a 0.3 μm membrane filter to obtain a dispersion 9 having a solid content (dispersion polymer and carbon black) of 20%.

(Production of Dispersion 10) Dispersion 10 is prepared in the same manner as Dispersion 1 except that Pigment Blue 15: 4 (copper phthalocyanine pigment: manufactured by Clariant) is used.

(Production of Dispersion 11) Dispersion 11 is produced in the same manner as Dispersion 1 except that Pigment Red 122 (dimethylquinacridone pigment: manufactured by Clariant) is used.

(Production of Dispersion 12) Dispersion 12 is prepared in the same manner as Dispersion 1 except that Pigment Yellow 180 (diketopyrrolopyrrole pigment: manufactured by Clariant) is used.

(Production of Dispersant 4) Ion-exchanged water 200 was placed in a reaction vessel having a stirrer, a reflux tube, a thermometer and a dropping funnel.
Parts, 1 part of azobiscyanovaleric acid and 50 parts of butylmethacrylate were added and the atmosphere was replaced with nitrogen, and then the mixture was heated to 70 ° C. and stirred. Butyl methacrylate 50 in a dropping funnel
Parts, 10 parts of methacrylic acid, 10 parts of styrene, 15 parts of polypropylene glycol methacrylate, and 2.1 parts of sodium lauryl sulfate are gradually added to the reaction vessel and reacted for 4 hours. Then, 1 part of t-dodecyl mercaptan is gradually added to reduce the reaction. After that, 1 part of azobisisobutyronitrile, 150 parts of styrene, 80 parts of butyl methacrylate, and 20 parts of methyl ethyl ketone, which were placed in another dropping funnel, were gradually added to the reaction container and allowed to react for 3 hours, and further ion-exchanged into the reaction container. Water is added to obtain Dispersant D with a concentration of 35%.

A part of the prepared dispersant was taken, and the solvent was changed to TH using gel permeation chromatography (GPC) of Hitachi Ltd. L7100 system.
3500 in styrene equivalent molecular weight when measured as F
It is 0. In addition, Mw / Mn, which is a measure of dispersion, is 2.8.
Is.

(Production of Dispersion 13) Dispersant D Solution 4
MA100 (manufactured by Mitsubishi Chemical) which is 0 part and carbon black is used. 50 parts of MA100 and Olfin E10
A mixture of 1 part of 10 (manufactured by Nisshin Chemical Co., Ltd.) and 50 parts of water was kneaded with a three-roll mill, and 100 parts of the kneaded product and 40 parts of the polymer aqueous solution were added to 150 parts of ion-exchanged water to prepare a nanomizer (YSNM). -1500-5: Yoshida Kikko Co., Ltd.) for 2 hours to obtain an aqueous dispersion of carbon black. Then, after neutralizing with 0.1 mol / L sodium hydroxide to adjust to pH 9, 0.3 μm
The solid content (dispersion polymer and carbon black) is 20% to obtain a dispersion 13 by filtering with a membrane filter of m.

(Production of Dispersion 14) Dispersion 14 is prepared in the same manner as Dispersion 5 except that Pigment Blue 15: 4 (copper phthalocyanine pigment: manufactured by Clariant) is used.

(Production of Dispersion 15) Dispersion 15 is prepared in the same manner as Dispersion 5 except that Pigment Red 122 (dimethylquinacridone pigment: manufactured by Clariant) is used.

(Production of Dispersion 16) Dispersion 16 is prepared in the same manner as Dispersion 8 except that Pigment Yellow 180 (diketopyrrolopyrrole pigment: manufactured by Clariant) is used.

(Preparation Example of Inkjet Ink) Specific examples of compositions suitable for the inkjet recording ink according to the present invention will be shown below. The amount of the dispersion added is shown as the amount (solid content concentration: the total amount of the pigment and the dispersion polymer surrounding the pigment) converted into weight. () Is the pigment used, <
> Indicates the particle size of the pigment in nm. In the examples, the remaining amount of water indicates 0.05% of Proxel XL-2 to prevent ink corrosion, 0.02% of benzotriazole to prevent ink jet head member corrosion, and ink system. In order to reduce the influence of metal ions in the solution, 0.04% of EDTA was added to ion-exchanged water.

[0086]   Example 1 Addition amount (%)     Dispersion 1 <105> 7.5     TEGmBE 5.0     Olfin E1010 1.0     Glycerin 9.0     1,5-pentanediol 5.0     Triethanolamine 0.8     Water level TEGmBE: triethylene glycol monobutyl ether Olfine E1010 (acetylene glycol surfactant: Nissin Chemical Industry Co., Ltd. Made by company)

Example 2 Addition Amount (%) Dispersion 2 <85> 4.5 1,2-Hexanediol 4.0 DEGmBE 1.0 Glycerin 10.0 Dipropylene Glycol 5.0 Surfynol 465 1.2 Triethanolamine 0.9 water residual amount DEGmBE: diethylene glycol monobutyl ether surfynol 465 (acetylene glycol surfactant: manufactured by Air Products (USA))

Example 3 Addition Amount (%) Dispersion 3 <90> 8.5 1,2-Hexanediol 5.0 Olfine STG 0.5 Triethylene glycol 15.0 Thiodiglycol 3.5 1,6- Hexanediol 3.0 Triethanolamine 1.0 Potassium hydroxide 0.1 Water Remainder Olfine STG (acetylene glycol surfactant: Nisshin Chemical Industry Co., Ltd.)

Example 4 Addition amount (%) Dispersion 4 <80> 10.0 TEGmBE 5.0 1,2-pentanediol 5.0 Surfynol 61 0.5 Glycerin 10.0 Tetraethylene glycol 9.0 1 , 5-Pentanediol 2.0 Dimethyl-2-imidazolidinone 2.0 Sodium benzoate 0.1 Triethanolamine 0.7 Water Remainder Surfynol 61 (acetylene alcohol surfactant: Air Products (USA) )

Example 5 Addition Amount (%) Dispersion 5 8.0 DPGmBE 2.0 DEGmBE 7.0 Glycerin 14.0 Triethanolamine 0.9 Water Remaining DPGmBE: Dipropylene Glycol Monobutyl Ether

[0091] Example 6 Addition amount (%) Agent dispersion 6 10.0 Olfin E1010 1.0 TEGmBE 6.0 Glycerin 15.0 Thiodiglycol 2.0 1,5-pentanediol 1.0 Triethanolamine 0.9 Water level

[0092] Example 7 Addition amount (%) Dispersion 7 12.0 Surfynol 61 0.5 DEGmBE 8.0 Glycerin 15.0 Trimethylolpropane 1.0 Trimethylolethane 1.0 Surfynol 465 1.0 Triethanolamine 0.5 KOH 0.05 Water level

[0093] Example 8 Addition amount (%) Dispersion 8 10.5 Olfin STG 1.0 PGmBE 2.0 DEGmBE 10.0 Glycerin 7.0 Diethylene glycol 5.0 Tetrapropylene glycol 5.0 Triethanolamine 0.9 KOH 0.1 Water level

[0094] Example 9 Addition amount (%) Dispersion 9 <105> 7.5 TEGmBE 5.0 Olfin E1010 1.0 Glycerin 9.0 1,5-pentanediol 5.0 Triethanolamine 0.8 Water level

[0095] Example 10 Addition amount (%) Dispersion 10 <85> 4.5 1,2-hexanediol 4.0 DEGmBE 1.0 Glycerin 10.0 Dipropylene glycol 5.0 Surfynol 465 1.2 Triethanolamine 0.9 Water level

[0096] Example 11 Addition amount (%) Dispersion 11 <90> 8.5 1,2-Hexanediol 5.0 Olfin STG 0.5 Triethylene glycol 15.0 Thiodiglycol 3.5 1,6-hexanediol 3.0 Triethanolamine 1.0 Potassium hydroxide 0.1 Water level

[0097] Example 12 Addition amount (%) Dispersion 12 <80> 10.0 TEGmBE 5.0 1,2-Pentanediol 5.0 Surfynol 61 0.5 Glycerin 10.0 Tetraethylene glycol 9.0 1,5-pentanediol 2.0 Dimethyl-2-imidazolidinone 2.0 Sodium benzoate 0.1 Triethanolamine 0.7 Water level

[0098] Example 13 Addition amount (%) Dispersion 13 8.0 DPGmBE 2.0 DEGmBE 7.0 Glycerin 14.0 Triethanolamine 0.9 Water level

[0099] Example 14 Addition amount (%) Agent dispersion 14 10.0 Olfin E1010 1.0 TEGmBE 6.0 Glycerin 15.0 Thiodiglycol 2.0 1,5-pentanediol 1.0 Triethanolamine 0.9 Water level

[0100] Example 15 Addition amount (%) Dispersion 15 12.0 Surfynol 61 0.5 DEGmBE 8.0 Glycerin 15.0 Trimethylolpropane 1.0 Trimethylolethane 1.0 Surfynol 465 1.0 Triethanolamine 0.5 KOH 0.05 Water level

[0101] Example 16 Addition amount (%) Dispersion 16 10.5 Olfin STG 1.0 PGmBE 2.0 DEGmBE 10.0 Glycerin 7.0 Diethylene glycol 5.0 Tetrapropylene glycol 5.0 Triethanolamine 0.9 KOH 0.1 Water level The composition of the ink used in the comparative example is shown below.

Comparative Example 1 Pigment 1 <105> 7.0 Glycerin 10.0 Dispersant 3.0 Nonionic surfactant 1.0 Ion-exchanged water Remaining amount nonionic surfactant: Neugen EA160 (Daiichi Kogyo) (Pharmaceutical Co., Ltd.) The dispersant was prepared by performing a dispersion treatment for 2 hours by using a beads mill mini-zeta (manufactured by Ajisawa Co., Ltd.) using Sols Perth 27000 (manufactured by Avicia).

Comparative Example 2 Acid Blue 9 6.5 DEGmME 7.0 Diethylene glycol 10.0 2-Pyrrolidone 5.0 Ion-exchanged water Remaining DEGmME: Diethylene glycol monomethyl ether

Comparative Example 3 Direct Black 154 2.5 Diethylene glycol 10.0 Nonionic surfactant 1.0 Ion-exchanged water Remaining amount Nonionic surfactant: Epan 450 (Daiichi Kogyo Seiyaku Co., Ltd.)

(Storage Stability Test) The inks of Examples 1 to 16 and the ink using the pigment of Comparative Example 1 in place of the pigment of Example 1 in Example 1 (Comparative Example 4) were placed in a glass sample bottle. After capping and sealing, each was left at 60 ° C. for one week, and foreign matter generated in ink and physical properties (viscosity, surface tension) before and after standing were examined. The results are shown in Table 1. In the foreign matter test, 5 g of the ink of Examples 1 to 8 had a diameter of 1 mm and a hole diameter of 1
Count the amount remaining on the 0 μm metal filter and count 10
A method of quantification is used as the number in which μm holes are filled. The foreign matter generation test shows the number of foreign matters after the heating test / the value of the initial amount of foreign matters. The viscosity was an average value of values measured four times at 60 ° using a rolling ball viscometer (manufactured by Anton Paar) AMVn. The surface tension was measured using an automatic surface tensiometer (Kyowa Interface Science Co., Ltd.) CBVP-A3. The viscosity is the value of viscosity after heating test / initial viscosity, and the surface tension is the value of surface tension after heating / initial surface tension.

[0106]

[Table 1]

From the results shown in Table 1, the inks of Examples 1 to 16 according to the present invention showed good storage stability with almost no generation of foreign matters and almost no change in physical properties. However, in Comparative Example 4, the change in the surface tension was small, but foreign matter was generated, the filterability was lowered, a thickening phenomenon occurred, and discharge stability was not obtained.

(Print Evaluation Test) Table 2 shows the evaluation result of bleeding when a character is printed as a print evaluation result. In Table 2, A indicates that it is extremely good, B is good, C is bad, and D is extremely bad.

[0109]

[Table 2]

As is clear from the results of Table 2, the inks used in the comparative examples have poor print quality, and the ink jet recording ink used in the present invention has good print quality.

Incidentally, these printing evaluations were measured by an ink jet printer PM-9 manufactured by Seiko Epson Corporation.
This was done by using 00C. The papers used in these evaluations are ordinary commercial papers in Europe, America and Japan, Conqueror Paper, Favorite paper.
it paper, Modo Copy paper, Rapid Copy
Paper, EPSON EPP paper, Xerox 4024 paper,
Xerox 10 paper, Neenha Bond paper, Ri
These are copy 6200 paper, Yamayuri paper, and Xerox R paper.

As described above, according to the present invention, it is possible to provide a high quality and highly practical ink jet recording ink in which the bleeding of a printed image on a recording medium such as paper is reduced.

(Storage stability test by changing penetrant) In the composition of Example 1, instead of DEGmBE and E1010, other additives (acetylene glycol-based surfactant, acetylene alcohol-based surfactant) which are acceptable in the present invention, An ink prepared by using a silicone-based surfactant, one or more kinds selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol) and Comparative Example 1 Additives (acetylene glycol-based surfactants, acetylene alcohol-based surfactants, silicon-based surfactants, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-
About the case of adding one or more substances selected from alkylene glycol) (Examples 17 to 2 in Table 2)
6) Similarly, after leaving at 60 ° C. for 1 week, foreign matter generated in the ink after leaving, physical properties (viscosity, surface tension) and ejection stability were examined, and the results are shown in Table 3. The amount of foreign matter generated is 60
The amount of foreign matter after leaving at ℃ / initial amount of foreign matter, the viscosity is the viscosity after leaving at 60 ° C / the initial viscosity, and the surface tension is the value of surface tension after leaving at 60 ° C / initial surface tension. The discharge stability is Seiko Epson Inkjet printer EM-9 manufactured by Co., Ltd.
00C to print 100 pages continuously on A4 size Xerox P paper without any print disturbance.
Less than 0 places B with printing disorder, 10 places or more 10
Less than 0 spots with print disturbance are designated as C, and 100 spots with print disturbance are designated as D.

[0114]

[Table 3]

As can be seen from the results of Tables 2 and 3, the step of dispersing the molecular colorant of the present invention in a solution using a reactive dispersant, and the step of extending the molecule mainly with a substance having hydrophobicity In addition, the inkjet recording ink using the dispersion, which is characterized by being formed by a step of extending with a substance group containing a substance having at least one or more hydrophilic functional groups, has good printing quality and stable ejection. It can be seen that it becomes an ink for ink jet recording excellent in stability and storage stability. Further, when the tests were conducted by changing the additives in Examples 2 to 16 as well, substantially the same result was obtained.

That is, the additives which are suitable for the present invention when they are dispersed by a general dispersant as in the prior art (acetylene glycol surfactant, acetylene alcohol surfactant, silicon surfactant, di ( It is difficult to use (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and / or a substance consisting of one or more kinds selected from 1,2-alkylene glycol), and therefore sufficient printing quality cannot be obtained. However, the use of the dispersion according to the present invention provides a water-based ink that has sufficient color developability and storage stability and ejection stability.

The present invention should not be considered to be limited to these examples, and various modifications can be made without departing from the gist of the present invention.

[0118]

INDUSTRIAL APPLICABILITY As described above, the present invention is stable, has little bleeding on plain paper, and has high color development. In addition to sufficient color development on special paper, it is even more ejection stable for ink jet recording inks. It has the effect of providing a polymer that enables the production of an excellent ink, a dispersion using the same, and an aqueous ink using the same.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 17/00 B41J 3/04 101Y 4J039 F term (reference) 2C056 EA04 EA05 FC01 2H086 BA01 BA53 BA59 BA60 4D077 AB05 AC05 BA02 DD03Y DD14Y DD17Y DD18Y DE09Y DE10Y DE24Y DE28Y DE37Y 4J015 AA06 4J037 AA02 AA08 AA15 AA22 AA30 CC13 CC16 CC18 CC21 CC24 CC27 CC28 DD24 EE28 FF03 4J039 AD03 AD09 AD20 AE06 AE08 AE09 AE11 AE13 BA04 BC07 BC09 BC13 BE01 BE02 BE22 BE28 BE33 CA06 EA33 EA43 EA47 EA48

Claims (20)

[Claims] 1. A dispersant obtained by polymerizing at least one selected from a reactive monomer, an oligomer and a macromer in a solvent using a radical polymerization initiator having a carboxyl group. 2. A first polymer obtained by polymerizing at least one selected from a reactive monomer, an oligomer and a macromer in a solvent by using a radical polymerization initiator having a carboxyl group, and further improving the reactivity. A dispersant obtained by polymerizing at least one selected from the monomers, oligomers and macromers, and extending the first polymer. 3. The carboxyl group is a carboxylic acid, and the dispersant is neutralized with an inorganic and / or organic alkali.
The dispersant according to. 4. The dispersant according to claim 1, wherein at least one selected from the reactive monomer, oligomer and macromer has at least a vinyl group. 5. The monomer, oligomer and macromer are selected from acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, alkylstyrene, ester, amide, imide, silicon-containing body, sulfur-containing body and derivatives thereof. The dispersant according to any one of claims 1 to 4, which is one or more selected from the group consisting of: 6. The dispersant according to claim 1, wherein the number average molecular weight of the dispersant is 10,000 or more and 1,000,000 or less in terms of styrene in gel permeation chromatography (GPC). 7. The weight average molecular weight (Mw) / of the dispersant
A number average molecular weight (Mn) is 5 or less, The dispersant in any one of Claims 1-6 characterized by the above-mentioned. 8. A method for producing a dispersant, which is prepared by polymerizing at least one selected from a reactive monomer, an oligomer and a macromer in a solvent using a radical polymerization initiator having a carboxyl group. Method. 9. A radical polymerization initiator having a carboxyl group is used to polymerize at least one selected from a reactive monomer, an oligomer and a macromer in a solvent to prepare a first polymer, which is then reacted once. Lowers
A method for producing a dispersant, further comprising polymerizing the first polymer by using at least one selected from a reactive monomer, an oligomer and a macromer to extend the polymer. 10. A dispersion comprising a molecular color body dispersed by using the dispersant according to any one of claims 1 to 7. 11. An aqueous ink containing the dispersion according to claim 10 as one component. 12. The water-based ink according to claim 11, wherein the surface tension of the water-based ink at 25 ° C. is 40 mN / m or less. 13. The water-based ink according to claim 11, wherein the contact angle of the water-based ink with respect to polytetrafluoroethylene at 25 ° C. is 40 ° or more. 14. The concentration of the molecular color former of the water-based ink is 0.5% by weight or more and 20% by weight or less.
4. The water-based ink according to any one of 3 above. 15. The aqueous ink comprises a surfactant, 1,
The water-based ink according to any one of claims 11 to 14, comprising at least one selected from 2-alkylene glycol and alkylene glycol monoalkyl ether. 16. The surfactant according to claim 15, wherein the surfactant is one or more selected from acetylene alcohol-based surfactants, acetylene glycol-based surfactants and silicon-based surfactants. Water-based ink. 17. The aqueous solution according to claim 15, wherein the 1,2-alkylene glycol is 1,2-pentanediol which may be branched or 1,2-hexanediol which may be branched. ink. 18. The aqueous ink according to claim 11, further comprising a moisturizer. 19. The aqueous ink according to claim 11, further comprising polymer fine particles. 20. An object to be recorded recorded using the water-based ink according to claim 11.