JP4264969B2 - Aqueous pigment ink composition, and recording method, recording system and recorded matter using the same - Google Patents

Aqueous pigment ink composition, and recording method, recording system and recorded matter using the same Download PDF

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JP4264969B2
JP4264969B2 JP2003019724A JP2003019724A JP4264969B2 JP 4264969 B2 JP4264969 B2 JP 4264969B2 JP 2003019724 A JP2003019724 A JP 2003019724A JP 2003019724 A JP2003019724 A JP 2003019724A JP 4264969 B2 JP4264969 B2 JP 4264969B2
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ink composition
pigment ink
pigment
aqueous pigment
polymer
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JP2004231711A (en
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崇 小柳
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セイコーエプソン株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous pigment ink composition containing a pigment having a hydrophobic surface, and in particular, it has excellent printing stability even when it has a high pigment concentration and suppresses blurring of images such as characters obtained. In addition, the present invention relates to an aqueous pigment ink composition capable of obtaining an image having a high OD (Optical Density) value and excellent fixability, and a recording method, a recording system, and a recorded matter using the same.
[0002]
[Prior art]
Conventionally, many pigments have been used as colorants (coloring materials) such as ink for ink jet recording and ink for writing instruments because of their excellent fastness such as water resistance and light resistance. Since the pigment is not soluble in water, it is important to stably disperse the pigment in water when used in an aqueous pigment ink composition. For this reason, various aqueous pigment ink compositions in which pigments are stably dispersed with a dispersion resin or the like have been developed.
[0003]
In addition, an ink composition using a surface-treated pigment that does not use a dispersion resin in order to disperse the pigment has been developed, and it is generally possible to obtain a recorded image having a high OD value by using this ink composition. Known. However, the ink composition using the surface-treated pigment lacks fixability to the recording medium, and since the applicable recording medium is limited, improvement is desired.
[0004]
On the other hand, an aqueous pigment ink composition in which a pigment is dispersed with a dispersion resin can be designed to have excellent fixability to a recording medium by selecting an appropriate dispersion resin. However, when the amount of the dispersion resin added to the ink composition increases, the OD value tends to decrease, the viscosity of the ink composition increases, and the viscosity is relatively low (10 mPa · s or less). It is not preferable when used as a required ink composition for ink jet recording.
[0005]
As an aqueous pigment ink composition in which a pigment is dispersed with a dispersion resin, those using an acrylic acid-styrene copolymer as a dispersion resin have been conventionally used. In order to obtain an image having a high OD value when using a conventional acrylic acid-styrene copolymer for a dispersion resin, it is necessary to reduce the amount of addition of the dispersion resin. Fixability is lowered and storage stability of the ink composition in which the pigment is dispersed is lowered. On the other hand, when the amount of the dispersion resin added is increased for the purpose of improving the fixability, the fixability is improved but the OD value is lowered. In addition, if the dispersion resin is excessively added, the free resin that is not adsorbed on the pigment surface or detached from the pigment surface deteriorates the printing stability (for example, when used as an ink composition for ink jet recording, It has been found that this is undesirable because of the occurrence of scattering and flight bends. In addition, conventionally used dispersion resins made of an acrylic acid-styrene copolymer have a random structure because it is difficult to control the molecular structure, and it is difficult to achieve high functionality.
For this reason, in order to satisfy both high OD value and fixability, pigment dispersion ability is excellent, and even with a small amount of addition, good fixability and dispersion stability can be obtained, and the development of highly functional dispersion resins has been made. It was desired.
[0006]
Japanese Patent Application Laid-Open No. 6-100810 provides an aqueous pigment ink for ink-jet recording that is excellent in fastness of printed matter, has no problem of scratching, can always perform stable ejection, and has excellent long-term storage stability. A water-based pigment ink for ink-jet recording containing a specific water-soluble resin, which is a graft copolymer composed of a hydrophilic polymer chain part and a hydrophobic polymer chain part, proposed as an object is disclosed (Patent Document 1).
[0007]
Japanese Laid-Open Patent Publication No. 6-122846 has been proposed for the purpose of providing an ink jet recording liquid that is excellent in long-term storage stability and capable of always performing stable ejection and eliminates the solidification of ink at the head tip. A specific water-soluble resin containing a cationic group-containing component (cationic component) or a sulfone group-containing acrylic component (anionic component) together with at least one monomer selected from styrenes and alkyl (meth) acrylates, Alternatively, an aqueous pigment ink containing a specific water-soluble resin containing a carboxyl group-containing component (anionic component) is disclosed (Patent Document 2).
[0008]
However, the ink composition using the water-soluble resin described in these publications as a pigment-dispersed resin has not yet achieved a satisfactory effect.
[0009]
By the way, among the pigments, carbon black is usefully used as a black pigment in an aqueous pigment ink composition in that a particularly excellent black image can be formed. The surface of carbon black is inherently hydrophobic. Therefore, in an aqueous pigment ink composition containing a pigment having a hydrophobic surface such as carbon black, the hydrophobic component is preferentially adsorbed on the pigment, while the hydrophilic component is in water as an aqueous medium. Will be oriented. However, in a conventional aqueous pigment ink composition including a pigment having a hydrophobic surface and a dispersion resin thereof, it can be said that the hydrophilic-hydrophobic balance between the pigment and the dispersion resin is not always achieved. Absent. Actually, in the conventional aqueous pigment ink composition using carbon black, when the concentration (content) of carbon black increases, the pigment cannot be stably dispersed, and the viscosity of the ink composition increases. In some cases, it becomes a gel and cannot function as an ink composition such as printing stability. On the other hand, when the concentration of carbon black is low, the problem of increase in the viscosity of the ink composition does not occur, but it may be insufficient to achieve formation of a recorded image having a high OD value.
[0010]
[Patent Document 1]
JP-A-6-100810
[Patent Document 2]
Japanese Patent Laid-Open No. 6-122846
[0011]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to obtain an image having excellent printing stability, suppressing blurring of images such as characters, and having a high OD value and excellent fixability even when having a high pigment concentration. It is an object of the present invention to provide an aqueous pigment ink composition that can be used.
[0012]
[Means for Solving the Problems]
As a result of diligent research, the present inventor has used a hydrophobic component and a specific hydrophilic component at a specific ratio in the trunk portion as a pigment having a hydrophobic surface and a dispersion resin thereof, while at the branch portion, The present inventors have found that an aqueous pigment ink composition containing a function-separated comb-type graft polymer using a specific hydrophilic component can achieve the above object.
[0013]
  The present invention was made based on the above knowledge, and is an aqueous pigment ink composition comprising at least a pigment having a hydrophobic surface, and at least a comb-type graft polymer composed of a trunk polymer and a branch polymer as a dispersion resin,
The trunk polymer includes a structural unit composed of a hydrophobic component and a structural unit having an anionic functional group as a hydrophilic component, and the weight ratio of the structural units (the former / the latter) is 30/70 to 80/20. Within the range ofThe structural unit comprising the hydrophobic component has at least styrene, the structural unit having the anionic functional group has at least acrylic acid and / or methacrylic acid,
The branched polymer includes a structural unit having a cationic component as a hydrophilic component, and the structural unit having the cationic component is contained in the dispersion resin at 30% by weight or less.A polymerizable compound having at least an amide groupThe above object is achieved by providing an aqueous pigment ink composition characterized by the above.
[0014]
That is, according to the aqueous pigment ink composition of the present invention having such a configuration, even when having a high pigment concentration, it has excellent printing stability, suppresses fading of images such as characters, and has a high OD. An image having a good value and excellent fixability can be obtained.
[0015]
The present invention also provides a recording method for forming an image using the aqueous pigment ink composition.
[0016]
The present invention also provides a recording system for forming an image using the aqueous pigment ink composition.
[0017]
The present invention also provides a recorded matter in which an image is formed using the aqueous pigment ink composition.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
As described above, the aqueous pigment ink composition of the present invention comprises at least a pigment having a hydrophobic surface and a comb-type graft polymer comprising a trunk polymer and a branch polymer as a dispersion resin.
[0019]
As the pigment having a hydrophobic surface used in the present invention, carbon black is preferable because it is particularly useful for forming an excellent black image. Examples of the carbon black include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black.
[0020]
Examples of preferred carbon black include No.2300, No.900, MCF88, No.33, No.40, No.52, MA7, MA8, MA100, No.2200B made by Mitsubishi Chemical, Raven5750 made by Colombia, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex U, Printex V, Printex 140U, Specil Black 6, Specil Black5, Specil Black 4A, Specil Black 4 etc. are mentioned.
[0021]
The content of the pigment having a hydrophobic surface (pigment concentration) is preferably from 0.5 to 5 in that an image having good dispersion stability and a high OD value can be stably obtained in the ink composition. 25% by weight, more preferably 2 to 15% by weight.
In the present invention, as described above, even when a high concentration of pigment is contained, the pigment is stably dispersed without increasing the viscosity.
[0022]
The pigment having a hydrophobic surface according to the present invention is not limited to carbon black. As long as the surface is at least hydrophobic, any pigment other than carbon black or any color other than black pigment can be used. It may be a pigment.
[0023]
The comb-type graft polymer as a dispersion resin (a resin for dispersing a pigment) used in the present invention uses a polymer chain that is a linear main chain as a backbone polymer, and the linear polymer as a branch polymer. It has a structure in which linear side chains are regularly arranged (grafted) with respect to a polymer chain which is a main chain.
[0024]
The trunk polymer in the comb-shaped graft polymer includes a structural unit composed of a hydrophobic component and a structural unit having an anionic functional group as a hydrophilic component. As described above, when the backbone polymer in the dispersion resin contains a structural unit composed of a hydrophobic component, the hydrophobic component and the hydrophobic surface of the pigment interact, and the trunk polymer is oriented on the surface of the pigment. become. In addition, as described above, the backbone polymer in the dispersion resin contains a structural unit having an anionic functional group as a hydrophilic component, so that the hydrophilic component and water as a solvent in the aqueous pigment ink composition of the present invention can be used. The interaction works to prevent the pigment from agglomerating and stably disperse the pigment in the ink composition.
[0025]
In the trunk polymer, the weight ratio (former / latter) of the structural unit composed of the hydrophobic component and the structural unit having an anionic functional group is 30/70 to 75/25. When the weight ratio is less than 30/70 and exceeds 75/25, the orientation of the hydrophobic component in the trunk polymer to the pigment surface and the interaction between the hydrophilic component in the trunk polymer and water are weakened. In the water-based pigment ink composition, the pigment aggregates and it is difficult to disperse the pigment. As a result, the resulting aqueous pigment ink composition becomes gelled and impractical.
[0026]
The weight ratio (the former / the latter) is preferably 40/60 to 70/30, more preferably 50/50, from the viewpoint of improving the anti-aggregation property and dispersion stability of the pigment in the ink composition. Within the range of ~ 70/30.
[0027]
Examples of the structural unit composed of a hydrophobic component in the trunk polymer include polymerizable aromatic compounds such as styrene, vinyl naphthalene and divinylbenzene, polymerizable ester compounds such as acrylic ester and methacrylic ester, and polymerizable nitriles such as acrylonitrile. Examples thereof include polymers and monomers having one or more selected from the group consisting of compounds and derivatives thereof as monomers. Among them, a polymerizable aromatic compound and its derivative, particularly a polymer containing styrene as a monomer is preferable from the viewpoint of adsorptivity to a pigment having a hydrophobic surface, particularly carbon black.
[0028]
Examples of the structural unit having an anionic functional group in the trunk polymer include a polymer having a polymerizable compound having an anionic functional group such as a carboxyl group, a sulfone group, a phosphoric acid group and a derivative thereof as a monomer. Among these, from the viewpoint of dispersion stability in an aqueous solvent, a polymerizable compound having a carboxyl group, particularly a polymer containing acrylic acid and methacrylic acid, particularly acrylic acid as a monomer, is preferable.
[0029]
Moreover, as the structural unit having an anionic functional group, it is only necessary to have an anionic functional group in the molecule, such as an amino acid having both an anionic functional group and a cationic functional group. The polymer which uses an amphoteric substance as a monomer may be sufficient.
[0030]
On the other hand, the branch polymer in the comb-shaped graft polymer includes a structural unit having a cationic component as a hydrophilic component. Thus, by including the structural unit having a cationic component in the branch polymer, the two components of the cationic component and the anionic component (structural unit having an anionic functional group) contained in the above-described trunk polymer can be obtained. Therefore, the dispersion resin (comb-shaped graft polymer) as a whole exhibits neutral properties in terms of charge. Thus, according to the aqueous pigment ink composition of the present invention, since the dispersion resin contains both a cationic component and an anionic component, it is affected by the surface condition (acidity etc.) of the recording medium such as printing paper. Therefore, an image having a high OD value can be obtained, and after fixing, sufficient fixability can be obtained by electrostatic interaction between the cation and the anion.
[0031]
And the structural unit which has this cationic component is contained at 30 weight% or less in the whole dispersion resin (comb type graft polymer). When the content of the structural unit having a cationic component exceeds 30% by weight, the resulting aqueous pigment ink composition becomes a gel and becomes impractical.
[0032]
The content of the structural unit having such a cationic component in the dispersion resin is preferably 10 to 30% by weight, more preferably 15 to 25% by weight, from the viewpoint of storage stability of the ink composition.
[0033]
Further, the content of the structural unit having a cationic component in the branch polymer is not particularly limited as long as the content in the entire dispersion resin is 30% by weight or less as described above. It is preferably 10% by weight or more.
[0034]
Examples of the structural unit having a cationic component in the branched polymer include polymerizable compounds having an amide group such as acrylamide, methacrylamide, and dimethylacrylamide, polymerizable compounds having an imino group such as ethyleneimine, and amino such as allylamine. Preferable examples include one or more polymers selected from the group consisting of a polymerizable compound having a group, and a polymer containing a polymerizable compound containing —NH— in the molecule as a monomer. Among these, from the viewpoint of the viscosity and storage stability of the ink composition, a polymerizable amide compound, particularly a polymer containing acrylamide and dimethylacrylamide as a monomer is preferable.
[0035]
In addition, as the structural unit having the cationic component, it is only necessary to have a cationic component in the molecule, and in the same manner as the structural unit having an anionic functional group in the above-described trunk polymer, together with the cationic component A polymer having both anionic components and an amphoteric substance represented by an amino acid as a monomer may be used.
[0036]
In the present invention, a styrene-acrylic acid copolymer and a styrene-methacrylic acid copolymer are particularly preferable as the comb-type graft polymer composed of a trunk polymer and a branch polymer, and in particular, a styrene-acrylic acid copolymer is preferable. preferable.
[0037]
The average molecular weight of the comb-shaped graft polymer (meaning the weight average molecular weight; the same applies hereinafter) is such that the average molecular weight of the trunk polymer is 5,000 to 50,000, and the average molecular weight of the branched polymer is 1,000 to It is preferable to set it to be 50,000.
[0038]
Comb-shaped graft polymers are, for example, a method in which a main chain (trunk polymer) is synthesized by a polymerization reaction and then a side chain (branched polymer) is polymerized (grafted) continuously, or each polymer synthesized separately It can be obtained by a method of grafting a chain (trunk polymer and branch polymer) by a polymer reaction.
[0039]
The content of the comb-shaped graft polymer as a dispersion resin (solid content conversion amount) is 3 to 15 in the ink composition in that it increases the OD value of the obtained image and appropriately maintains the viscosity of the ink composition. It is preferable that it is weight%, especially 4 to 10 weight%. In the present invention, even if the amount of the dispersion resin is relatively small, it is effectively adsorbed on the surface of the pigment, excellent dispersion stability is obtained, and free resin is hardly generated.
[0040]
The aqueous pigment ink composition of the present invention has a viscosity of usually 10 mPa · s or less, and is particularly useful when used as an ink for ink jet recording excellent in printing stability. Further, the viscosity of the ink composition of the present invention is 1.0 to 10 mPa · s, particularly 3.0 to 5.0 mPa · s, which is useful in terms of printing stability and ink droplet flying characteristics. As described above, the water-based pigment ink composition of the present invention retains the viscosity within the above range without increasing the viscosity even when it contains a high concentration of pigment, and has been stored especially for a long period of time. Even in this case, the viscosity change is extremely small.
[0041]
In addition, the aqueous pigment ink composition of the present invention preferably contains a wet solvent from the viewpoint of preventing ink from drying and preventing clogging at the head of an ink jet printer when used for ink jet recording. As the wetting solvent, polyhydric alcohols are particularly preferable from the viewpoint of improving the prevention of clogging. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1 2.6-hexanetriol, thiodiglycol, hexylene glycol, glycerin, trimethylolethane, trimethylolpropane and the like. In addition, as a wet solvent, saccharides such as urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1.3-dimethyl-2-imidazolidinone, triethanolamine, and sugar alcohol can be used. One or more of these wet solvents are used.
[0042]
The wet solvent is preferably contained in the ink composition in an amount of 0.1 to 30% by weight, more preferably 0.5 to 20% by weight.
[0043]
In addition, the aqueous pigment ink composition of the present invention preferably contains a surfactant from the viewpoint of increasing the wettability to the recording medium and increasing the permeability. As the surfactant, acetylene glycols and / or polysiloxanes are particularly preferably used from the viewpoint of improving permeability.
Preferred examples of acetylene glycols include acetylene glycol compounds represented by the following general formula (1).
[0044]
[Chemical 1]
[0045]
(Where 0 ≦ m + n ≦ 50, R1~ RFourEach independently represents an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms. )
[0046]
As the acetylene glycol compound represented by the general formula (1), commercially available compounds can be used. For example, Olphine Y, Surfynol 82, 440, 465, STG, E1010 (all trade names, Air Products and Chemicals Co., Ltd.), and Surfynol 465 is particularly preferable.
[0047]
Preferred examples of polysiloxanes include polysiloxane compounds represented by the following general formula (2).
[0048]
[Chemical formula 2]
[0049]
What is marketed can be used as a polysiloxane type compound represented by the said General formula (2), For example, BYK347, the same 348 (made by Big Chemie Japan), etc. can be used conveniently.
[0050]
Various surfactants such as a cationic surfactant, an anionic surfactant, and a nonionic surfactant can also be used as the surfactant.
One or more surfactants are used.
[0051]
The surfactant is preferably contained in the ink composition in an amount of 0.1 to 5% by weight, more preferably 0.5 to 2% by weight.
[0052]
In addition, the aqueous pigment ink composition of the present invention preferably contains a penetrating solvent from the viewpoint of improving wettability to a recording medium and improving penetrability. As the osmotic solvent, alkanediols and / or glycol ethers are preferably used particularly from the viewpoint of improving permeability.
[0053]
Examples of alkanediols include 1,2-pentanediol and 1.2-hexanediol.
Examples of glycol ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether. Etc.
These penetrating solvents are used alone or in combination of two or more thereof.
[0054]
The penetrating solvent is preferably contained in the ink composition in an amount of 1 to 20% by weight, more preferably 1 to 10% by weight.
[0055]
In the aqueous pigment ink composition of the present invention, water is used as an aqueous medium. As water, it is preferable to use pure or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water. In particular, water obtained by sterilizing these waters by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bacteria is prevented over a long period of time. In general, water is added to the ink composition in consideration of the balance of properties after blending each component such as a pigment, a dispersion resin, a penetrating solvent, a wetting solvent, and a surfactant.
[0056]
In addition, the aqueous pigment ink composition of the present invention further includes a fixing agent such as a water-soluble rosin, an antifungal agent such as sodium benzoate, an antiseptic agent, an antioxidant such as an allophanate, and an ultraviolet ray absorbing agent, if necessary. An additive such as an agent, a chelating agent, and a pH adjusting agent can be contained, and one or more of these can be used.
[0057]
The aqueous pigment ink composition of the present invention can be prepared in the same manner as a conventional ink composition used conventionally. For example, carbon black as a pigment and comb-shaped graft polymer as a dispersion resin are premixed together with water, and a pigment dispersion is obtained in advance through an appropriate dispersion process. Separately, components other than the pigment and the dispersion resin are added to water. A method of preparing an ink composition by adding an ink solvent prepared by dissolution to the above-mentioned pigment dispersion, or an ink composition by mixing each component in respective compounding amounts without preparing a pigment dispersion A method of preparing a product is employed. In the preparation, it is preferable to remove coarse particles using a membrane fighter, a mesh filter or the like.
[0058]
The use of the aqueous pigment ink composition of the present invention is not limited, and can be used as various ink compositions such as ink for ink jet printers and ink for writing instruments such as pens. It is preferably used for an ink jet recording method which is a recording method for forming an image such as a character or a figure by discharging and attaching the droplets to a recording medium, and in particular, it is used for an on-demand type ink jet recording method. preferable. As an on-demand type ink jet recording method, for example, a piezoelectric element recording method in which recording is performed using a piezoelectric element disposed in a printer head, or heat energy generated by a heater of a heating resistance element disposed in the printer head is used. And a thermal jet recording method for recording, and can be suitably used for any ink jet recording method.
[0059]
Further, according to the present invention, it is possible to provide a recording method for forming an image using the above-described aqueous pigment ink composition. According to the recording method of the present invention having such a configuration, since the aqueous pigment ink composition described above is used, even when the ink composition has a high pigment concentration, the printing stability is excellent, and Therefore, it is possible to obtain an image having a high OD value and excellent fixability.
[0060]
In addition, according to the present invention, it is possible to provide a recording apparatus such as an inkjet printer that forms an image using the above-described aqueous pigment ink composition, and other recording systems. According to the recording system of the present invention having such a configuration, since the aqueous pigment ink composition described above is used, even when the ink composition has a high pigment concentration, the printing stability is excellent, and Therefore, it is possible to obtain an image having a high OD value and excellent fixability.
[0061]
Moreover, according to the present invention, it is possible to provide a recorded matter in which an image is formed using the above-described aqueous pigment ink composition. According to the recorded matter of the present invention having such a structure, since it has an image such as a character formed using the above-mentioned aqueous pigment ink composition, blurring is suppressed, the OD value is high, and the fixing property is improved. An excellent image can be obtained.
[0062]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples and test examples of the present invention. However, the present invention is not limited to the examples.
[0063]
[Example 1]
(Preparation of ink composition)
12.5 g of carbon black, 9.0 g of dispersion resin, and 78.5 g of ion-exchanged water are premixed to obtain a mixed solution, and then a sand grinder mill is used as a disperser and zirconia beads having a diameter of 1.0 mm as a dispersion medium Was used to disperse the mixed solution for 2 hours. After completion of the dispersion step, zirconia beads were separated to obtain a pigment dispersion.
Subsequently, components other than the pigment and the dispersion resin in the following blending components are dissolved in 30 g of ion exchange water to form an ink solvent, and while stirring the above pigment dispersion 56.0 g, 46 g of the ink solvent is added to the pigment dispersion. Was added. After completion of the addition, the mixture was stirred for 20 minutes and then filtered using a 5 μm membrane filter to obtain an aqueous pigment black ink composition for inkjet recording.
[0064]
[0065]
Further, by the same operation as in Example 1, black pigment ink compositions (Examples 2 and 3 and Comparative Examples 1 to 5) having the following respective compositions were prepared.
[0066]
[Example 2] Compounding amount
・ Carbon black FW-18 (manufactured by Degussa) (pigment) 7.0wt%
・ Comb type graft polymer (dispersion resin) 5.0wt%
Stem polymer; styrene-acrylic acid copolymer (copolymerization ratio 67:33,
Average molecular weight 10,000), branched polymer; polyacrylamide
(Average molecular weight 3,000) 20wt% grafted type
・ Glycerin 8.0wt%
・ BYK-348 0.5wt%
(Surfactant, BYK Chemie)
・ 1,2-hexanediol 5.0wt%
・ Remaining amount of ion-exchanged water
[0067]
[Example 3] Compounding amount
・ Carbon black FW-18 (manufactured by Degussa) (pigment) 7.0wt%
・ Comb type graft polymer (dispersion resin) 5.0wt%
Stem polymer; styrene-acrylic acid copolymer (copolymerization ratio 67:33,
Average molecular weight 10,000), branched polymer; polydimethylacrylamide
(Average molecular weight 3,000) 20wt% grafted type
・ Glycerin 8.0wt%
・ BYK-348 0.5wt%
(Surfactant, BYK Chemie)
・ 1,2-hexanediol 5.0wt%
・ Remaining amount of ion-exchanged water
[0068]
[Comparative Example 1] Compounding amount
・ Carbon black FW-18 (manufactured by Degussa) (pigment) 7.0wt%
・ Styrene-acrylic acid copolymer ・ Ammonium salt 5.0wt%
(Copolymerization ratio 67:33, average molecular weight 10,000) (dispersed resin)
・ Glycerin 8.0wt%
・ Surfinol 465 1.0wt%
(Surfactant, manufactured by Air Product and Chemical, Inc)
・ Triethylene glycol monomethyl ether 5.0wt%
・ Remaining amount of ion-exchanged water
[0069]
[Comparative Example 2] Compounding amount
・ Carbon black FW-18 (manufactured by Degussa) (pigment) 7.0wt%
・ Styrene-acrylic acid copolymer 5.0wt%
(Copolymerization ratio 67:33, average molecular weight 10,000) (dispersed resin)
・ Glycerin 8.0wt%
・ Surfinol 465 1.0wt%
(Surfactant, manufactured by Air Product and Chemical, Inc)
・ Triethylene glycol monomethyl ether 5.0wt%
・ Remaining amount of ion-exchanged water
[0070]
[Comparative Example 3] Blending amount
・ Carbon black FW-18 (manufactured by Degussa) (pigment) 7.0wt%
・ Comb type graft polymer (dispersion resin) 5.0wt%
Stem polymer; styrene-acrylic acid copolymer (copolymerization ratio 80:20,
Average molecular weight 10,000), branched polymer; polyacrylamide
(Average molecular weight 3,000) 20wt% grafted type
・ Glycerin 8.0wt%
・ Surfinol 465 1.0wt%
(Surfactant, manufactured by Air Product and Chemical, Inc)
・ Triethylene glycol monomethyl ether 5.0wt%
・ Remaining amount of ion-exchanged water
[0071]
[Comparative Example 4] Blending amount
・ Carbon black FW-18 (manufactured by Degussa) (pigment) 7.0wt%
・ Comb type graft polymer (dispersion resin) 5.0wt%
Stem polymer; styrene-acrylic acid copolymer (copolymerization ratio 20:80,
Average molecular weight 10,000), branched polymer; polyacrylamide
(Average molecular weight 3,000) 20wt% grafted type
・ Glycerin 8.0wt%
・ Surfinol 465 1.0wt%
(Surfactant, manufactured by Air Product and Chemical, Inc)
・ Triethylene glycol monomethyl ether 5.0wt%
・ Remaining amount of ion-exchanged water
[0072]
[Comparative Example 5] Blending amount
・ Carbon black FW-18 (manufactured by Degussa) (pigment) 7.0wt%
・ Comb type graft polymer (dispersion resin) 5.0wt%
Stem polymer; styrene-acrylic acid copolymer (copolymerization ratio 67:33,
Average molecular weight 10,000), branched polymer; polyacrylamide
(Average molecular weight 3,000) 40wt% grafted type
・ Glycerin 8.0wt%
・ Surfinol 465 1.0wt%
(Surfactant, manufactured by Air Product and Chemical, Inc)
・ Triethylene glycol monomethyl ether 5.0wt%
・ Remaining amount of ion-exchanged water
[0073]
[Ink viscosity measurement]
The viscosity of the ink composition immediately after the preparation of each black pigment ink composition of Examples and Comparative Examples (initial ink viscosity) and the viscosity of the ink composition one month after the preparation were determined by “MCR” manufactured by Physica Messtechnik GmbH. -300 ", and the results are shown in Table 1. The black pigment ink compositions of Comparative Examples 3 to 5 were gel-like at the time immediately after the preparation and at the time one month later, and thus the viscosity could not be measured. For this reason, Comparative Examples 3-5 did not perform a printing stability test and an optical density test.
[0074]
[Printing stability test]
Each black pigment ink composition of Examples and Comparative Examples was set in an ink jet printer (EM-930C manufactured by Seiko Epson Corporation), and using this printer, A4 size PPC paper (Xerox P; manufactured by Xerox Corporation) was used. ), Solid black printing was continuously performed, and the number of sheets of paper until a printing failure such as nozzle clogging, flying bending, and blurring of printing occurred was examined. At this time, the printing stability was evaluated according to the following criteria. The results are shown in Table 1.
X: The number of papers until printing failure occurred was less than 10.
Δ: The number of papers until printing failure occurred was 10 or more and less than 50.
○: No printing defect occurred even when printing 50 sheets or more.
[0075]
[Optical density test]
Each black pigment ink composition of Examples and Comparative Examples was set in an ink jet printer (EM-930C manufactured by Seiko Epson Corporation), and using this printer, “plain paper” and “clean” mode were set, Black solid printing was performed on A4 size double-sided plain plain paper (model number KA4250NPD manufactured by Seiko Epson Corporation), and OD (Optical Density) value measurement was performed using SPM-50 manufactured by Gretag-Macbeth. went. The results are shown in Table 1.
[0076]
[Table 1]

Claims (8)

  1. An aqueous pigment ink composition comprising at least a pigment having a hydrophobic surface, and at least a comb-type graft polymer comprising a trunk polymer and a branch polymer as a dispersion resin,
    The trunk polymer includes a structural unit composed of a hydrophobic component and a structural unit having an anionic functional group as a hydrophilic component, and the weight ratio of the structural units (the former / the latter) is 30/70 to 75/25. And the structural unit comprising the hydrophobic component has at least styrene, the structural unit having the anionic functional group has at least acrylic acid and / or methacrylic acid,
    The branched polymer includes a structural unit having a cationic component as a hydrophilic component, and the structural unit having the cationic component is contained in the dispersion resin in an amount of 30% by weight or less and has at least an amide group. having compound, water-based pigment ink composition characterized by.
  2. The concentration of the pigment having a hydrophobic surface is 0.5 to 25 wt%, claim 1 aqueous pigment ink composition.
  3. The aqueous pigment ink composition according to claim 1 or 2 , wherein the pigment having a hydrophobic surface is carbon black.
  4. The aqueous pigment ink composition according to any one of claims 1 to 3 , wherein the content of the dispersion resin is 3 to 15% by weight in terms of solid content.
  5. The water-based pigment ink composition according to any one of claims 1 to 4 , wherein the viscosity is 1.0 to 10 mPa · s.
  6. Recording method for forming an image using aqueous pigment ink composition according to any one of claims 1-5.
  7. Recording system for forming an image using aqueous pigment ink composition according to any one of claims 1-5.
  8. A recorded matter in which an image is formed using the water-based pigment ink composition according to any one of claims 1 to 5 .
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