JP7266781B2 - Liquid composition, ink, ink set, printing method, printing apparatus - Google Patents

Description

The present invention relates to liquid compositions, inks, ink sets, printing methods, and printing apparatuses.

2. Description of the Related Art In recent years, the applications of printed recording media (hereinafter also referred to as recorded matter) have been diversified, and recorded matter is used in a wide range of applications such as office use and commercial use. With the diversification of applications, the target color gamut may be insufficient with only the conventional four color materials such as cyan, magenta, yellow, and black. It is being studied to expand the color gamut and obtain a wide color gamut by using inks having color tones such as green and violet.
For example, Patent Document 1 discloses an inkjet recording ink set comprising a cyan ink composition, a magenta ink composition, a yellow ink composition, a green ink composition, and an orange ink composition, which contain specific pigments. It is

Zeta potential is also used as an indicator of the dispersion stability of pigment particles.
In Patent Document 2, water-insoluble fine particles having both a cationic group and an anionic group have a zeta potential of −90 to 0 mV at pH=8 and a zeta potential of 0 to 90 mV at pH=4. Certain ink compositions are described.
Patent Document 3 describes an ink in which the zeta potential of the self-dispersing pigment is -10 to -35 mV and the neutralization titer of the self-dispersing pigment is 0.1 to 0.6 mmol/g.
Patent Document 4 describes an ink containing a hydrophobic dye, an aqueous organic substance, and water encapsulated in a hydrophilic resin and having an absolute value of zeta potential of 30 mV or more.
Patent Document 5 describes a water-insoluble colorant dispersion containing fine particles of a water-insoluble colorant containing at least two colorants and a polymer compound having a specific repeating unit. The pH dependence of the zeta potential of the ink is shown.

By adding orange, green, and violet inks as complementary inks, it is possible to obtain a wide color gamut that could not be achieved with conventional four colors (CMYK inks). However, these complementary color inks have the problem of deterioration in storage stability and beading properties.
An object of the present invention is to provide a liquid composition that can achieve both beadability and storage stability.

The liquid composition of the present invention is as follows.
(1) In a liquid composition containing a coloring material, a polymer compound, and water,
The coloring material is Pigment Orange 43, Pigment Green 36, or Pigment Violet 23,
The liquid composition was diluted with ion-exchanged water so that the colorant concentration was 0.01% by mass, and the liquid was stored at 70 ° C. for 72 hours. A liquid composition having a zeta potential of −30.0 mV or more and a zeta potential of −45.0 mV or less at pH 9.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid composition that achieves both beadability and storage stability.

1 is a diagram showing an example of an ink ejection device using the ink of the present invention; FIG. FIG. 2 is a perspective view of a main tank containing ink of the ink set of the present invention; 1 is an external perspective explanatory view of an ink ejection head according to an embodiment of the present invention; FIG. It is a cross-sectional explanatory drawing of the direction orthogonal to the nozzle arrangement direction of the same head. It is a partial cross-sectional explanatory drawing of the direction parallel to the nozzle arrangement direction of the same head. FIG. 4 is an explanatory plan view of a nozzle plate of the same head; FIG. 4 is an explanatory plan view of each member constituting a channel member of the same head; FIG. 4 is an explanatory plan view of each member constituting a common liquid chamber member of the same head; 1 is a block diagram showing an example of an ink circulation system according to the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory plan view of essential parts of an example of an ink ejection device according to the present invention; It is an explanatory side view of the main part of the device. FIG. 4 is a model diagram of an image sample printed in Examples.

The present invention (1) will be described in detail below. Since the embodiment of the present invention (1) includes the following (2) to (12), these will also be described.
(2) The liquid composition according to (1) above, containing either sodium hydroxide or triethanolamine.
(3) The liquid composition according to (1) or (2) above, wherein the coloring material is Pigment Orange 43, and the concentration of Pigment Orange 43 is 1.0% by mass or more and 5.0% by mass or less.
(4) The liquid composition according to (1) or (2), wherein the coloring material is Pigment Green 36, and the concentration of Pigment Green 36 is 3.0% by mass or more and 5.0% by mass or less.
(5) The liquid composition according to (1) or (2), wherein the coloring material is Pigment Violet 23 and the concentration of Pigment Violet 23 is 0.5% by mass or more and 3.0% by mass or less.
(6) The liquid composition according to any one of (1) to (5) above, wherein the polymer compound contains either or both of a styrene-acrylic resin and a urethane resin.
(7) The liquid composition according to any one of (1) to (6) above, wherein the polymer compound comprises a plurality of resins, and the plurality of resins comprises a styrene-acrylic resin and a urethane resin.
(8) An ink containing the liquid composition according to any one of (1) to (7) above.
(9) An ink set containing the ink described in (8) above, a black ink, a cyan ink, a magenta ink, and a yellow ink.
(10) In a printing method comprising a step of applying a treatment liquid containing a component that agglomerates a coloring material in the ink, and a step of applying ink, the ink is the ink described in (8) above, or the above ( A printing method using the ink set described in 9).
(11) The printing method according to (10) above, including the step of applying a clear ink containing no colorant and containing a resin.
(12) In a printing apparatus having a liquid ejection head for ejecting ink and ink, the ink is the ink described in (8) above or the ink constituting the ink set described in (9) above, and The liquid ejection head includes a plurality of nozzles for ejecting liquid, individual liquid chambers communicating with the nozzles, a common liquid chamber supplying liquid to the individual liquid chambers, a circulating flow path communicating with the individual liquid chambers, and the circulating flow. A printing apparatus, which is a liquid discharge head, comprising a circulation common liquid chamber communicating with a channel, and pressure generating means for applying pressure to the liquid in the individual liquid chambers.

The liquid composition of the present invention contains a coloring material, a polymer compound, and water, wherein the coloring material is Pigment Orange 43, Pigment Green 36, or Pigment Violet 23, and the liquid composition has a coloring material concentration of The pH of the sample obtained by storing a liquid diluted with ion-exchanged water to 0.01% by mass at 70 ° C. for 72 hours was adjusted, and the zeta potential at pH 5 was -30.0 mV or more. and the zeta potential at pH 9 is -45.0 mV or less.

In the present invention, the zeta potential is defined as an index of the dispersion stability of the liquid composition.
The zeta potential is known as one of the indicators of the dispersion stability of particles, and when the potential of an electrically neutral region sufficiently distant from the particles is defined as zero, the zeta potential is defined as this zero point. It is defined as the potential of the slip surface when measured as a reference. In the case of fine particles, if the absolute value of the zeta potential increases, the repulsive force between the particles becomes stronger and the stability of the particles increases. On the other hand, particles tend to aggregate when the zeta potential is close to zero.
In the present invention, the pH of a sample obtained by storing a liquid diluted with ion-exchanged water so that the colorant concentration in the liquid composition is 0.01% by mass at 70° C. for 72 hours is adjusted to a pH of 5. The zeta potential is -30.0 mV or more at . In addition, the zeta potential at pH 9 is −45.0 mV or less, and the repulsive force between the particles is strong, increasing the stability of the particles, so that a liquid composition with excellent storage stability can be obtained. . The zeta potential was measured at a measurement temperature of 25°C.
The pH of the sample can be adjusted by adding an acid or alkali aqueous solution such as hydrochloric acid or sodium hydroxide.
The pH of the liquid composition is preferably weakly alkaline (more than pH 7 and less than or equal to pH 12). When combined with a low pretreatment liquid or the like, the dispersibility becomes unstable when the pH of the liquid composition becomes low, and the coloring material aggregates to improve the beading property. When the zeta potential at pH 9 is -45.0 mV or less, the storage stability of the liquid composition is improved.

<Liquid composition>
The liquid composition of the present invention contains a coloring material, a polymer compound, and water, and may further contain organic solvents, lubricants, additives, and the like.
Colorants, polymer compounds, water, organic solvents, lubricants, additives, and the like used in the liquid composition are described below.

<Color material>
Pigment Orange 43 (Structural Formula 1) and Pigment Green 36 (Structural Formula 2) are used as colorants for the orange, green, and violet regions where a mixture of black, cyan, magenta, and yellow cannot produce a clear color gamut. , Pigment Violet 23 (structure 3). From the viewpoint of hue angle, the above colorants are excellent.
An orange liquid composition containing Pigment Orange 43 as a coloring material is called an orange ink, a green liquid composition containing Pigment Green 36 is called a green ink, and a violet liquid composition containing Pigment Violet 23 is called a violet ink, and at least one of these inks is used. , black ink, cyan ink, magenta ink, and yellow ink, the color gamut can be expanded and a wide color gamut can be obtained.

The liquid composition of the present invention can be used as ink, and an ink set containing this ink, black ink, cyan ink, magenta ink, and yellow ink can be formed. When producing an ink set, the following coloring materials can be used as coloring materials contained in black ink, cyan ink, magenta ink, and yellow ink.
The coloring material is not particularly limited, and pigments and dyes can be used.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used individually by 1 type, and may use 2 or more types together. Mixed crystals may also be used.
Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, and metallic pigments.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by known methods such as contact method, furnace method, thermal method, etc. can be used.
Organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. Among these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of pigments for black include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (C.I. Pigment Black 11). , metals such as titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1).
Further, for color, C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52: 2, 53:1, 57:1 (brilliant carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 (red iron oxide), 104, 105, 106, 108 ( cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (rhodamine lake), 3, 5:1, 16, 19, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15:1, 15:2, 15:3, 15:4 (phthalocyanine blue), 16, 17:1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, etc.
Dyes are not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and may be used singly or in combination of two or more.
Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9,45,249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. Direct Red 1, 4, 9, 80, 81, 225, 227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. and Reactive Black 3,4,35.

The content of the colorant in the liquid composition is preferably 1.0% by mass or more and 5.0% by mass or less, more preferably 1.0% by mass or more and 5.0% by mass or less for Pigment Orange 43, from the viewpoints of improving the color gamut, good fixability, and ejection stability. is 1.0% by mass or more and 3.0% by mass or less. In Pigment Green 36, the content is preferably 3.0% by mass or more and 5.0% by mass or less, more preferably 3.0% by mass or more and 4.0% by mass or less. Pigment Violet 23 is preferably 0.5% by mass or more and 3.0% by mass or less, more preferably 1.0% by mass or more and 2.0% by mass or less.

In order to disperse the pigment and obtain a liquid composition, a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin to disperse it, and a method of using a dispersant method of dispersing, and the like.
As a method of making a self-dispersing pigment by introducing a hydrophilic functional group into a pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) to make it dispersible in water. is mentioned.
As a method of coating the surface of a pigment with a resin and dispersing it, there is a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary for all of the pigments to be incorporated into the liquid composition to be coated with a resin. may be dispersed throughout.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants.
As the dispersant, it is possible to use, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant.
As the pigment dispersion, a dispersion obtained by using a polymer-type dispersant can be particularly suitably used.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

<Pigment dispersion>
A liquid composition can be obtained by mixing a pigment with a material such as water or an organic solvent. It is also possible to produce a liquid composition by mixing a pigment, water, a dispersant, and the like to form a pigment dispersion, and then mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion should be carried out using a disperser.
The particle diameter of the pigment in the pigment dispersion is not particularly limited, but the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is improved. 500 nm or less is preferable, and 20 nm or more and 150 nm or less is more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected according to the purpose. % or more and 50 mass % or less is preferable, and 0.1 mass % or more and 30 mass % or less is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator, or the like, if necessary.

It is preferable to add a neutralizing agent to the pigment dispersion for the purpose of dispersion stability of the pigment dispersion and storage stability of the liquid composition. A neutralizing agent is an agent for neutralizing a substance biased towards acidity or alkalinity. It is a compound for causing a neutralization reaction, and from the viewpoint of the dispersion stability of the pigment and the storage stability of the liquid composition, it is preferable to use sodium hydroxide or triethanolamine.
When sodium hydroxide is used, it is preferably contained in the pigment dispersion in an amount of 0.1 to 0.5% by mass, and when triethanolamine is used, it is preferably contained in the pigment dispersion in an amount of 1 to 5% by mass.

<Polymer compound>
The type of polymer compound contained in the liquid composition is not particularly limited and can be appropriately selected depending on the purpose. resins, butadiene-based resins, styrene-butadiene-based resins, vinyl chloride-based resins, styrene-acrylic-based resins, acrylic silicone-based resins, and the like. It preferably contains a plurality of resins as the polymer compound, and more preferably the plurality of resins include a styrene-acrylic resin and a urethane resin.
By including a plurality of styrene-acrylic resins and urethane resins, it is possible to achieve both cohesiveness and fixability of the colorant. As preferable contents of both, the resin concentration is preferably 1 or more and 15 or less, more preferably 1 or more and 5 or less with respect to 1 colorant. Further, as a preferable ratio of the two, it is preferable that the styrene-acrylic resin is 1 and the urethane resin is 0.2 to 1, and the styrene-acrylic resin is 1 and the urethane resin is 0.5 to 1. More preferably: When the ratio of the urethane resin is less than the ratio of the styrene-acrylic resin, the zeta potential at pH 5 is large and the zeta potential at pH 9 is small, resulting in excellent cohesiveness, storage stability, and ejection stability. .

Resin particles made of these resins may be used as the polymer compound. It is possible to obtain a liquid composition by mixing resin particles in a state of a resin emulsion in which water is dispersed as a dispersion medium with materials such as a coloring material and an organic solvent. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. 200 nm or less is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and can be appropriately selected depending on the intended purpose. 30 mass % or less is preferable, and 5 mass % or more and 20 mass % or less is more preferable.

The particle size of the solid content in the liquid composition is not particularly limited and can be appropriately selected according to the purpose. The maximum frequency is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

<Water>
The content of water in the liquid composition is not particularly limited and can be appropriately selected according to the intended purpose. Preferably, 20% by mass to 60% by mass is more preferable.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and any water-soluble organic solvent can be used. Examples thereof include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of water-soluble organic solvents include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone , 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, nitrogen-containing heterocyclic compounds such as γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N- Amides such as dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine, and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane, and thiodiethanol, propylene carbonate, and ethylene carbonate. etc.
It is preferable to use an organic solvent having a boiling point of 250° C. or less because it not only functions as a wetting agent but also provides good drying properties.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and the like.

A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve the permeability of the liquid composition when paper is used as a recording medium.

The content of the organic solvent in the liquid composition is not particularly limited and can be appropriately selected according to the purpose. The following is preferable, and 20% by mass or more and 60% by mass or less is more preferable.

<Lubricant>
The liquid composition used in the present invention preferably contains a wax or a siloxane compound for the purpose of imparting lubricity to the image area.
Among the above waxes, polyethylene wax or carnauba wax is particularly preferable from the viewpoint of film-forming properties and slipperiness when the liquid composition is applied to the image area.
The melting point of the wax is preferably 80° C. or higher and 140° C. or lower, more preferably 100° C. or higher and 140° C. or lower. By setting the melting point to 80° C. or higher, excessive melting or solidification of the wax is reduced even in a room temperature environment, and the storage stability of the liquid composition can be maintained. On the other hand, by setting the melting point to 140° C. or lower, the wax can be sufficiently melted even in a room temperature environment, and the liquid composition can be given lubricity.
The particle size of the wax is preferably 0.01 μm or more, more preferably 0.01 μm or more and 0.1 μm or less. By setting the particle size to 0.01 μm or more, the wax particles are easily oriented on the surface of the liquid composition, and it becomes possible to impart lubricity to the liquid composition.
Examples of the polyethylene wax include commercially available products such as Hitech series manufactured by Toho Chemical Industry Co., Ltd. and AQUACER series manufactured by BYK.
Examples of the carnauba wax include commercially available products such as Cellosol 524 and Trasol CN manufactured by Chukyo Yushi Co., Ltd.
The content of the wax is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less.
Examples of the siloxane compound include commercial products such as BYK307, BYK333, and BYK378 manufactured by BYK.
The content of the siloxane compound is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 1% by mass or less.

<Additive>
Surfactants, antifoaming agents, antiseptic and antifungal agents, antirust agents, pH adjusters and the like may be added to the liquid composition, if necessary.

<Surfactant>
Any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used as surfactants.
The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those that do not decompose even at high pH are preferable. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as water-based surfactants. As the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Polyoxyalkylene ether polymer compounds are particularly preferred due to their low foaming properties. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonate. Examples of the perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. As the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain, a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and a perfluoroalkyl ether group in a side chain Examples thereof include salts of polyoxyalkylene ether polymers. Counter ions _of salts _in these fluorosurfactants include Li, Na, _K , _NH4 , _NH3CH2CH2OH , _NH2 ( _CH2CH2OH ) _{2 ,} and NH( _CH2CH2OH ). ₃ , etc.
Examples of amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates.
These may be used individually by 1 type, or may use 2 or more types together.

（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include polydimethylsiloxane modified at both chain ends, and polyether-modified silicone-based surfactants having polyoxyethylene groups or polyoxyethylene-polyoxypropylene groups as modifying groups exhibit excellent properties as water-based surfactants. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products are available from, for example, BYK Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nihon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.
The above polyether-modified silicone-based surfactant is not particularly limited and can be appropriately selected according to the purpose. Examples include those introduced into the side chain of the Si portion of siloxane.

(However, in general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)
Commercially available products can be used as the above polyether-modified silicone-based surfactants. 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Dow Corning Toray Silicone Co., Ltd.), BYK-33, BYK-387 (BYK-Chemie Corporation), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like.

上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。
一般式（Ｆ－２）
Ｃ_nＦ_2n+1－ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂－Ｏ－(ＣＨ₂ＣＨ₂Ｏ)_a－Ｙ
上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣ_mＦ_2m+1でｍは１～６の整数、又はＣＨ₂ＣＨ(ＯＨ)ＣＨ₂－Ｃ_mＦ_2m+1でｍは４～６の整数、又はＣ_pＨ_2p+1でｐは１～１９の整数である。ｎは１～６の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。 この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ－１３６Ａ、ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ－３１００、ＦＳ－３４、ＦＳ－３００、株式会社ネオス製のＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ、オムノバ社製のポリフォックスＰＦ－１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ－４０３Ｎが特に好ましい。 As the fluorosurfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of fluorine-based surfactants include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain is preferable because of its low foamability, and in particular, fluorine-based compounds represented by general formulas (F-1) and (F-2) Surfactants are preferred.

In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
_{CnF2n +1- CH2CH} (OH)CH2 _- O-( _CH2CH2O ) _{a -} Y
In the compound represented by the general formula (F-2), Y is H, or C _m F _2m+1 and m is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ —C _m F _{2m+ 1} and m is an integer of 4 to 6, or C _p H _2p+1 and p is an integer of 1 to 19; n is an integer of 1-6. a is an integer from 4 to 14;
Commercially available products may be used as the fluorosurfactant. Examples of commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Fleurard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (both manufactured by Sumitomo 3M); Megafac F-470, F -1405, F-474 (both manufactured by Dainippon Ink and Chemicals); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omnova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) Among these, Chemours FS-3100, FS-34, FS- 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omnova Co., Ltd. and Unidyne DSN- manufactured by Daikin Industries, Ltd. 403N is particularly preferred.

The content of the surfactant in the liquid composition is not particularly limited and can be appropriately selected according to the intended purpose. 001% by mass or more and 5% by mass or less is preferable, and 0.05% by mass or more and 5% by mass or less is more preferable.

<Antifoaming agent>
The antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These may be used individually by 1 type, or may use 2 or more types together. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

<Preservative and antifungal agent>
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<Antirust agent>
The rust inhibitor is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

<pH adjuster>
The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or higher, and examples thereof include amines such as diethanolamine and triethanolamine.

The physical properties of the liquid composition are not particularly limited and can be appropriately selected according to the intended purpose. For example, viscosity, surface tension, pH and the like are preferably within the following ranges.
The viscosity of the liquid composition at 25° C. is preferably 5 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 25 mPa·s, in order to improve print density and character quality and to obtain good ejection properties. The following are more preferred. Here, the viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25° C., standard cone rotor (1°34′×R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, 3 minutes.
The surface tension of the liquid composition is preferably 35 mN/m or less, more preferably 32 mN/m or less at 25° C., since the liquid composition is suitably leveled on the recording medium and the drying time of the liquid composition is shortened. is more preferred.
The pH of the liquid composition is preferably from 7 to 12, more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members in contact with the liquid.

The liquid composition of the invention can be used as an ink.
A printing method using the ink of the present invention preferably includes a step of applying a treatment liquid containing a component that agglomerates the coloring material in the ink, and a step of applying the ink.
Further, it is more preferable to include a step of applying a clear ink that does not contain a coloring material but contains a resin.
The treatment liquid containing a component for aggregating the coloring material in the ink (hereinafter also referred to as an aggregating agent) is preferably applied before the step of applying the ink, and is also referred to as a pretreatment liquid hereinafter.
The clear ink containing no colorant and containing resin is preferably applied after the step of applying ink, and is hereinafter also referred to as post-treatment liquid.

<Pretreatment liquid>
The pretreatment liquid contains a flocculant, an organic solvent, and water, and may optionally contain a surfactant, an antifoaming agent, a pH adjuster, an antiseptic agent, an antirust agent, and the like.
Organic solvents, surfactants, antifoaming agents, pH adjusters, antiseptic antifungal agents, and antirust agents can be the same materials as those used in the liquid composition, and other materials used in known treatment liquids. Available.
The type of flocculant is not particularly limited, and examples thereof include water-soluble cationic polymers, acids, polyvalent metal salts, and the like.

<Post-treatment liquid>
The post-treatment liquid is not particularly limited as long as it can form a transparent layer. The post-treatment liquid is obtained by selecting and mixing organic solvents, water, resins, surfactants, antifoaming agents, pH adjusters, antiseptic antifungal agents, anticorrosive agents, etc., as necessary. The post-treatment liquid may be applied to the entire recording area formed on the recording medium, or may be applied only to the area where the liquid composition image is formed.

<Recording medium>
The recording medium used for recording is not particularly limited, but includes plain paper, glossy paper, special paper, cloth, film, OHP sheet, general-purpose printing paper, and the like.

The recording medium is not limited to those used as general recording media, and wallpaper, floor materials, building materials such as tiles, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate. Ceramics, glass, metal, etc. can also be used by adjusting the configuration of the path for conveying the recording medium.

<Records>
The liquid composition recorded matter of the present invention has an image formed on a recording medium using the liquid composition of the present invention.
A recorded matter can be obtained by recording with an inkjet recording apparatus and an inkjet recording method.

A recording apparatus and recording method using black (K), cyan (C), magenta (M), and yellow (Y) inks will be described below. The inks of the present invention (orange ink, green ink, violet ink) are used. A pre-treatment liquid and a post-treatment liquid may also be used.

<Recording device, recording method>
The ink of the present invention can be suitably used for various inkjet recording apparatuses, such as printers, facsimile machines, copiers, printer/facsimile/copier complex machines, stereolithography machines, and the like.
In the present invention, a recording apparatus and a recording method refer to an apparatus capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of performing recording using the apparatus. A recording medium means a medium to which ink or various processing liquids can adhere even temporarily.
This recording apparatus can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and recording method may have heating means used in the heating process and drying means used in the drying process. The heating means and drying means include, for example, means for heating and drying the printing surface and the back surface of the recording medium. The heating means and drying means are not particularly limited, but for example, hot air heaters and infrared heaters can be used. Heating and drying can be performed before, during, or after printing.
Also, the recording apparatus and recording method are not limited to those that visualize significant images such as characters and graphics with ink. For example, it includes those that form patterns such as geometric patterns, and those that form three-dimensional images.
In addition, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Furthermore, this recording device can be used not only as a desktop type, but also as a wide recording device that can print on A0 size recording media, and for example, can use continuous paper wound into a roll as a recording medium. A continuous feed printer is also included.
An example of a recording apparatus will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial image forming apparatus. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminated film. It is made up of members. The ink containing portion 411 is housed, for example, in a container case 414 made of plastic. Thus, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the far side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404 . As a result, each ink discharge port 413 of the main tank 410 communicates with the ejection head 434 for each color via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 onto the printing medium.

This recording apparatus can include not only a portion that ejects ink, but also devices called pre-processing devices and post-processing devices.
As an aspect of the pre-treatment device and the post-treatment device, it has a pre-treatment liquid and a post-treatment liquid in the same manner as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is a mode in which a liquid container and a liquid ejection head are added, and the pretreatment liquid and the posttreatment liquid are ejected by an inkjet recording method.
As another aspect of the pre-treatment device and the post-treatment device, there is an aspect in which a pre-treatment device and a post-treatment device using a method other than the inkjet recording method, such as a blade coating method, a roll coating method, and a spray coating method, are provided.

The printing apparatus of the present invention is a printing apparatus having a liquid ejection head for ejecting ink and ink, wherein the ink is the ink of the present invention or ink constituting an ink set, and the liquid ejection head ejects liquid. a plurality of nozzles, individual liquid chambers communicating with the nozzles, a common liquid chamber supplying liquid to the individual liquid chambers, a circulating flow path communicating with the individual liquid chambers, and a common circulating liquid chamber communicating with the circulating flow paths. and pressure generating means for applying pressure to the liquid in the individual liquid chambers.

<Printing Apparatus Having Recirculating Ejection Head, Printing Method>
An example of the circulation type ejection head will be described below with reference to FIGS. 3 to 8. FIG. 3 is an explanatory perspective view of the appearance of the ink discharge head, FIG. 4 is an explanatory cross-sectional view of the head in a direction orthogonal to the nozzle array direction, and FIG. 5 is a cross-sectional view of the head in a direction parallel to the nozzle array direction. 6 is an explanatory plan view of a nozzle plate of the same head, FIG. 7 is an explanatory plan view of each member constituting a flow path member of the same head, and FIG. 8 is an explanatory plan view of each member constituting a common liquid chamber member of the same head. is.

This ink discharge head has a nozzle plate 1, a channel plate 2, and a vibration plate member 3 as a wall member which are laminated and joined together. A piezoelectric actuator 11 for displacing the vibration plate member 3, a common liquid chamber member 20, and a cover 29 are provided.
The nozzle plate 1 has a plurality of nozzles 4 for ejecting ink.
The channel plate 2 forms an individual liquid chamber 6 communicating with the nozzle 4 , a fluid resistance section 7 communicating with the individual liquid chamber 6 , and a liquid introducing section 8 communicating with the fluid resistance section 7 . Further, the channel plate 2 is formed by laminating and joining a plurality of plate-like members 41 to 45 from the nozzle plate 1 side, and laminating and joining these plate-like members 41 to 45 and the diaphragm member 3 to form the channel. A member 40 is constructed.
The diaphragm member 3 has a filter portion 9 as an opening that communicates with the liquid introducing portion 8 and the common liquid chamber 10 formed by the common liquid chamber member 20 .
The inflow channel may be a channel connected to the individual liquid chamber 6 and "before" the inflow into the individual liquid chamber. do.
The vibration plate member 3 is a wall member that forms the walls of the individual liquid chambers 6 of the channel plate 2 . The vibration plate member 3 has a two-layer structure (not limited to this), and is formed of a first layer forming a thin portion from the flow path plate 2 side and a second layer forming a thick portion. A deformable vibration region 30 is formed in a portion corresponding to the chamber 6 .

Here, as shown in FIG. 6, the nozzle plate 1 has a plurality of nozzles 4 arranged in a zigzag pattern.
As shown in FIG. 7A, the plate-like member 41 constituting the flow path plate 2 includes a through groove portion (meaning a groove-shaped through hole) 6a constituting the individual liquid chamber 6, a fluid resistance portion 51, Through grooves 51a and 52a forming the circulation flow path 52 are formed.
Similarly, as shown in FIG. 7B, the plate member 42 is formed with a through groove portion 6b forming the individual liquid chamber 6 and a through groove portion 52b forming the circulation flow path 52. As shown in FIG.
Similarly, as shown in FIG. 7(c), the plate member 43 is formed with a through groove portion 6c forming the individual liquid chamber 6 and a through groove portion 53a having a nozzle array direction forming the circulation flow path 53 as a longitudinal direction. It is
Similarly, the plate-like member 44 includes, as shown in FIG. , and a through groove portion 53b whose longitudinal direction is the direction in which the nozzles constituting the circulation flow path 53 are arranged is formed.
Similarly, as shown in FIG. 7(e), the plate-like member 45 includes through grooves 6e forming the individual liquid chambers 6, and through grooves 8b (filters) forming the liquid introduction section 8 and having the nozzle arrangement direction as a longitudinal direction. and a through groove portion 53c having a longitudinal direction in the direction of arrangement of the nozzles forming the circulation flow path 53 is formed.

As shown in FIG. 7( f ), the vibration plate member 3 is formed with a vibration region 30 , a filter portion 9 , and a through groove portion 53 d whose longitudinal direction is the nozzle arrangement direction that constitutes the circulation flow path 53 . .
In this way, by forming the channel member by laminating and joining a plurality of plate-like members, it is possible to form a complicated channel with a simple configuration.
With the above configuration, the flow path member 40 composed of the flow path plate 2 and the vibration plate member 3 includes the fluid resistance portion 51 along the surface direction of the flow path plate 2 communicating with the individual liquid chambers 6 , the circulation flow path 52 and the circulation flow path 52 . A circulation flow path 53 is formed in the thickness direction of the flow path member 40 to communicate with the flow path 52 . The circulation flow path 53 communicates with a circulation common liquid chamber 50, which will be described later.
The outflow channel may be a channel connected to the individual liquid chamber 6 and "after" the inflow into the individual liquid chamber. It corresponds to the road.

On the other hand, in the common liquid chamber member 20, a common liquid chamber 10 to which ink is supplied from the supply/circulation mechanism 494 and a common circulation liquid chamber 50 are formed.
As shown in FIG. 8(a), the first common liquid chamber member 21 constituting the common liquid chamber member 20 has a through hole 25a for piezoelectric actuator, a through groove portion 10a that becomes the downstream common liquid chamber 10A, a circulation A bottomed groove portion 50a serving as a common liquid chamber 50 is formed.
Similarly, as shown in FIG. 8B, the second common liquid chamber member 22 is formed with a piezoelectric actuator through-hole 25b and a groove portion 10b that serves as the upstream common liquid chamber 10B.
Also referring to FIG. 3 , the second common liquid chamber member 22 is formed with a through hole 71 a serving as a supply port that communicates with one end of the common liquid chamber 10 in the nozzle arrangement direction and the supply port 71 .
Similarly, in the first common liquid chamber member 21 and the second common liquid chamber member 22, the other end of the circulation common liquid chamber 50 in the nozzle arrangement direction (the end opposite to the through hole 71a) and the circulation port 81 are provided. Communicating through holes 81a and 81b are formed.
In FIG. 8, grooves with bottoms are shown with surface coating applied (the same applies to the following figures).
Thus, the common liquid chamber member 20 is composed of the first common liquid chamber member 21 and the second common liquid chamber member 22, and the first common liquid chamber member 21 is joined to the diaphragm member 3 side of the channel member 40. Then, the second common liquid chamber member 22 is layered and joined to the first common liquid chamber member 21 .

Here, the first common liquid chamber member 21 forms a downstream common liquid chamber 10A, which is a part of the common liquid chamber 10 communicating with the liquid introducing portion 8, and a circulation common liquid chamber 50 communicating with the circulation flow path 53. ing. Further, the second common liquid chamber member 22 forms an upstream common liquid chamber 10B, which is the remainder of the common liquid chamber 10. As shown in FIG.
At this time, the downstream common liquid chamber 10A, which is a part of the common liquid chamber 10, and the circulation common liquid chamber 50 are arranged side by side in a direction orthogonal to the nozzle arrangement direction, and the circulation common liquid chamber 50 placed at a position that is projected into the
As a result, the dimensions of the circulation common liquid chamber 50 are not restricted by the dimensions necessary for the flow path including the individual liquid chambers 6 formed by the flow path member 40, the fluid resistance section 7, and the liquid introduction section 8. FIG.
The circulating common liquid chamber 50 and a part of the common liquid chamber 10 are arranged side by side, and the circulating common liquid chamber 50 is arranged at a position projected into the common liquid chamber 10, so that it is perpendicular to the nozzle arrangement direction. The width of the head in the direction can be suppressed, and the enlargement of the head can be suppressed. The common liquid chamber member 20 forms a common liquid chamber 10 to which ink is supplied from a head tank or an ink cartridge and a circulating common liquid chamber 50 .

On the other hand, on the opposite side of the diaphragm member 3 to the individual liquid chambers 6, a piezoelectric actuator 11 including an electromechanical conversion element is arranged as driving means for deforming the vibration region 30 of the diaphragm member 3. As shown in FIG.
As shown in FIG. 5, this piezoelectric actuator 11 has a piezoelectric member 12 bonded onto a base member 13. The piezoelectric member 12 is grooved by half-cut dicing to form a required number of piezoelectric members 12 per piezoelectric member 12, as shown in FIG. columnar piezoelectric elements 12A and 12B are formed in a comb shape at predetermined intervals.
Here, the piezoelectric element 12A of the piezoelectric member 12 is used as a piezoelectric element to be driven by applying a driving waveform, and the piezoelectric element 12B is used as a mere post without applying a driving waveform. It can also be used as a piezoelectric element that allows
The piezoelectric element 12A is joined to a convex portion 30a, which is an island-shaped thick portion formed in the vibration region 30 of the diaphragm member 3. As shown in FIG. Also, the piezoelectric element 12B is joined to the convex portion 30b, which is the thick portion of the diaphragm member 3. As shown in FIG.

The piezoelectric member 12 is formed by alternately laminating piezoelectric layers and internal electrodes. The internal electrodes are drawn out to the end faces to provide external electrodes, and flexible wiring members 15 are connected to the external electrodes.
In the circulation type ejection head constructed as described above, for example, by lowering the voltage applied to the piezoelectric element 12A from the reference potential, the piezoelectric element 12A contracts, the vibration region 30 of the diaphragm member 3 descends, and the individual liquid chamber 6 is closed. Ink flows into the individual liquid chamber 6 due to the volume expansion.
After that, the voltage applied to the piezoelectric element 12A is increased to extend the piezoelectric element 12A in the stacking direction, deform the vibration region 30 of the diaphragm member 3 in the direction toward the nozzle 4, and contract the volume of the individual liquid chamber 6. As a result, the ink in the individual liquid chamber 6 is pressurized, and the ink is ejected from the nozzle 4 .
By returning the voltage applied to the piezoelectric element 12A to the reference potential, the vibrating region 30 of the diaphragm member 3 is restored to the initial position, and the individual liquid chamber 6 expands to generate a negative pressure. Ink is filled from the chamber 10 into the individual liquid chamber 6 . Therefore, after the vibration of the meniscus surface of the nozzle 4 is attenuated and stabilized, the operation for the next ejection is started.

The method of driving the head is not limited to the above example (pull-push-hit), and pull-hit or push-hit can also be performed depending on which drive waveform is applied. Further, in the above-described embodiment, the laminated piezoelectric element is used as the pressure generating means for applying pressure fluctuations to the individual liquid chambers 6, but the present invention is not limited to this, and it is also possible to use a thin-film piezoelectric element. . Furthermore, a heating resistor may be arranged in the individual liquid chamber 6 to generate air bubbles by generating heat from the heating resistor to generate pressure fluctuations, or a pressure fluctuation may be generated by using electrostatic force. .

Next, an example of an ink circulation system using a circulation type ejection head will be described with reference to FIG.
FIG. 9 is a block diagram showing an ink circulation system.
As shown in FIG. 9, the ink circulation system includes a main tank, an ink discharge head, a supply tank, a circulation tank, a compressor, a vacuum pump, a first liquid-sending pump, a second liquid-sending pump, a regulator (R), and a supply side pressure. It consists of a sensor, circulation side pressure sensor, etc. The vacuum pump corresponds to means for generating negative pressure. The supply-side pressure sensor is connected between the supply tank and the ink discharge head and on the side of the supply channel connected to the supply port 71 (see FIG. 3) of the ink discharge head. The circulation-side pressure sensor is connected between the ink ejection head and the circulation tank and on the side of the circulation channel connected to the circulation port 81 (see FIG. 3) of the ink ejection head.

One of the circulation tanks is connected to the supply tank via the first liquid-sending pump, and the other of the circulation tanks is connected to the main tank via the second liquid-sending pump. As a result, ink flows from the supply tank through the supply port 71 into the ink ejection head, is discharged from the circulation port, is discharged to the circulation tank, and is further sent from the circulation tank to the supply tank by the first liquid sending pump. The ink circulates by being
A compressor is connected to the supply tank, and is controlled so that a predetermined positive pressure is detected by the supply side pressure sensor. On the other hand, a vacuum pump is connected to the circulation tank and controlled so that a predetermined negative pressure is detected by the circulation side pressure sensor. As a result, the negative pressure of the meniscus can be kept constant while the ink is circulated through the ink ejection head.
In addition, when droplets are ejected from the nozzles of the circulation type ejection head, the amount of ink in the supply tank and the circulation tank decreases. It is desirable to replenish the ink. The timing of ink replenishment from the main tank to the circulation tank depends on the detection result of the liquid level sensor installed in the circulation tank, such as when the ink level in the circulation tank drops below a predetermined level. can be controlled.

Next, the circulation of ink in the circulation type ejection head will be described. As shown in FIG. 3, at the end of the common liquid chamber member 20, a supply port 71 communicating with the common liquid chamber and a circulation port 81 communicating with the circulation common liquid chamber 50 are formed. The supply port 71 and the circulation port 81 are connected to supply tanks and circulation tanks (see FIG. 9) that store ink through tubes, respectively. Ink stored in the supply tank is supplied to the individual liquid chamber 6 via the supply port 71 , common liquid chamber 10 , liquid introduction portion 8 , and fluid resistance portion 7 .
Further, while the ink in the individual liquid chamber 6 is ejected from the nozzle 4 by driving the piezoelectric member 12, some or all of the ink remaining in the individual liquid chamber 6 without being ejected is transferred to the fluid resistance portion 51, the circulation It is circulated to the circulation tank via the flow paths 52 and 53, the circulation common liquid chamber 50, and the circulation port 81.

In addition, the circulation of ink can be performed not only during operation of the circulation type ejection head, but also during non-operation. By circulating when the operation is paused, the ink in the individual liquid chambers is always refreshed, and aggregation and sedimentation of the components contained in the ink can be suppressed, which is preferable. Since sedimentation can be suppressed, even when the apparatus is stopped for a long period of time, images with excellent ejection stability can be obtained immediately after restarting.

Next, an example of an apparatus for ejecting ink using a circulation type ejection head will be described with reference to FIGS. 10 and 11. FIG. FIG. 10 is an explanatory plan view of the essential parts of the device, and FIG. 11 is an explanatory side view of the essential parts of the same device.
This apparatus is a serial type apparatus, and a main scanning movement mechanism 493 reciprocates the carriage 403 in the main scanning direction. The main scanning movement mechanism 493 includes a guide member 401, a main scanning motor 405, a timing belt 408, and the like. The guide member 401 is bridged between the left and right side plates 491A and 491B to movably hold the carriage 403 . A main scanning motor 405 reciprocates the carriage 403 in the main scanning direction via a timing belt 408 stretched between a drive pulley 406 and a driven pulley 407 .
The carriage 403 is equipped with an ink ejection unit 440 having an ink ejection head 404 mounted thereon. The ink ejection head 404 of the ink ejection unit 440 ejects each color of ink, for example, yellow (Y), cyan (C), magenta (M), black (K), and the ink of the present invention (orange, green, violet). Dispense. The ink ejection head 404 is mounted with a nozzle row having a plurality of nozzles arranged in a sub-scanning direction perpendicular to the main scanning direction, with the ejection direction directed downward.

Ink is supplied and circulated inside the ink ejection head 404 by a supply/circulation mechanism 494 for supplying the ink stored outside the ink ejection head 404 to the ink ejection head 404 . In this example, the supply/circulation mechanism 494 is composed of a supply tank, a circulation tank, a compressor, a vacuum pump, a liquid transfer pump, a regulator (R), and the like. Further, the supply-side pressure sensor is connected between the supply tank and the ink ejection head and on the side of the supply channel connected to the supply port 71 of the ink ejection head. The circulation-side pressure sensor is connected between the ink ejection head and the circulation tank and on the circulation channel side connected to the circulation port 81 of the ink ejection head.

This device has a transport mechanism 495 for transporting the paper 410 . The transport mechanism 495 includes a transport belt 412 as transport means and a sub-scanning motor 416 for driving the transport belt 412 .
The transport belt 412 attracts the paper 410 and transports it at a position facing the ink ejection head 404 . The conveying belt 412 is an endless belt and stretched between a conveying roller 413 and a tension roller 414 . Adsorption can be performed by electrostatic adsorption, air suction, or the like.
The conveying belt 412 rotates in the sub-scanning direction when the conveying roller 413 is rotationally driven by the sub-scanning motor 416 via the timing belt 417 and the timing pulley 418 .

Further, on one side of the carriage 403 in the main scanning direction, a maintenance/recovery mechanism 420 for maintaining/recovering the ink ejection head 404 is arranged on the side of the transport belt 412 .
The maintenance/recovery mechanism 420 is composed of, for example, a cap member 421 that caps the nozzle surface (surface on which the nozzles are formed) of the ink ejection head 404, a wiper member 422 that wipes the nozzle surface, and the like.
The main scanning movement mechanism 493, supply/circulation mechanism 494, maintenance/recovery mechanism 420, and transport mechanism 495 are attached to a housing including side plates 491A and 491B and a back plate 491C.
In this apparatus configured as described above, the paper 410 is fed onto the conveying belt 412 and attracted thereto, and the conveying belt 412 is rotated to convey the paper 410 in the sub-scanning direction.
Therefore, by moving the carriage 403 in the main scanning direction and driving the ink ejection head 404 in accordance with the image signal, ink is ejected onto the stationary paper 410 to form an image.
As described above, since this apparatus is equipped with a circulating ejection head, it is possible to stably form a high-quality image.

It should be noted that the method of using the ink is not limited to the ink jet recording method, and can be widely used. In addition to the inkjet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method and a spray coating method can be used.

Applications of the liquid composition of the present invention are not particularly limited, and can be appropriately selected according to the intended purpose. Furthermore, it can be used not only as a liquid composition to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming three-dimensional images (three-dimensional objects).
A known three-dimensional modeling apparatus for modeling three-dimensional objects can be used, and is not particularly limited. can be used. The three-dimensional object includes a three-dimensional object obtained by coating the liquid composition repeatedly. It also includes a molded product obtained by processing a structure obtained by applying a liquid composition onto a base material such as a recording medium. The molded product is, for example, a sheet-shaped or film-shaped recorded matter or structure that has been subjected to molding such as heat stretching or punching.・Suitably used for applications where molding is performed after the surface is decorated, such as electronic equipment, meters for cameras, and operation panels.

In the present invention, the terms image formation, recording, printing, and printing are all synonymous.

The terms recording medium, medium, and printed material are all synonymous.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. "Parts" and "%" in the examples are "mass parts" and "mass%" unless otherwise specified.

<Synthesis of copolymer>
"Synthesis of Monomers"
After dissolving 62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Kasei Co., Ltd.) in 700 ml of methylene chloride, 20.7 g (262 mmol) of pyridine was added. Next, a solution of 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 ml of methylene chloride was added dropwise with stirring over 2 hours, and then stirred at room temperature for 6 hours. After further washing with water, the organic phase was isolated. After drying with magnesium sulfate, the solvent was distilled off. Further purification was performed by silica gel column chromatography using a mixed solvent of methylene chloride/methanol (volume ratio 98/2) as an eluent to obtain 52.5 g of 2-naphthoic acid-2-hydroxyhexyl ester.
42.1 g (155 mmol) of 2-naphthoic acid-2-hydroxyhexyl ester was dissolved in 80 ml of dry methyl ethyl ketone and heated to 60°C. Next, a solution of 24.0 g (155 mmol) of Karenz MOI (2-methacryloyloxyethyl isocyanate) (manufactured by Showa Denko) dissolved in 20 ml of dry methyl ethyl ketone was added dropwise with stirring over 1 hour, and the temperature was kept at 70°C. and stirred for 12 hours. After further cooling to room temperature, the solvent was distilled off. Next, using a mixed solvent of methylene chloride/methanol (volume ratio 99/1) as an eluent, purification was performed by silica gel column chromatography, and 57.0 g of the following chemical formula (I-1) represented by the following "monomer M- 1” was obtained.

"Synthesis of Copolymer R-1"
A monomer solution was prepared by dissolving 3.80 g (52.7 mmol) of acrylic acid (manufactured by Aldrich) and 11.26 g (26.3 mmol) of "Monomer M-1" in 75 ml of dry methyl ethyl ketone. After heating 10% of the monomer solution to 75° C. under an argon stream, 0.59 g (3.61 mmol) of 2,2′-azoiso(butyronitrile) (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in the remaining monomer solution. was added dropwise over 1.5 hours, and the mixture was stirred at 75°C for 4 hours. After that, it was cooled to room temperature, and the obtained reaction solution was dropped into hexane. The precipitated copolymer was filtered and dried under reduced pressure to obtain 14.55 g of "Copolymer R-1" (weight average molecular weight (Mw): 30000).
5.00 g (carboxyl group amount 17.5 mmol) of the obtained “copolymer R-1” was weighed, and 7.36 g (tetraethylammonium ion content of 17.5 mmol) and 37.64 g of ion-exchanged water were added and mixed and stirred to prepare a 10% by mass aqueous solution of "Copolymer R-1".

<Preparation of pigment dispersion>
(Preparation Example 1)
"Preparation of Black Pigment Dispersion"
16.0 parts of carbon black (NIPEX160 manufactured by degussa) and 44.0 parts of deionized water were added to 40.0 parts of a 10% by mass aqueous solution of copolymer R-1, and the mixture was stirred for 12 hours. Next, using a disc-type bead mill KDL type (manufactured by Shinmaru Enterprises), the mixture was circulated and dispersed for 1 hour at a peripheral speed of 10 m/s. At this time, zirconia balls with a diameter of 0.3 mm were used as media. Further, after filtration through a membrane filter with a pore size of 1.2 μm, ion-exchanged water was added so that the concentration of the pigment was 16% by mass to obtain a black pigment dispersion.

(Preparation Example 2)
"Preparation of Cyan Pigment Dispersion"
A cyan pigment dispersion having a pigment concentration of 16% by mass was obtained in the same manner as for the black pigment dispersion, except that Pigment Blue 15:3 (chromofine blue manufactured by Dainichiseika Co., Ltd.) was used instead of carbon black.

(Preparation Example 3)
"Preparation of Magenta Pigment Dispersion"
A magenta pigment dispersion having a pigment concentration of 16% by mass was obtained in the same manner as the black pigment dispersion, except that Pigment Red 122 (Toner Magenta EO02 manufactured by Clariant) was used instead of carbon black.

(Preparation Example 4)
"Preparation of Yellow Pigment Dispersion"
A yellow pigment dispersion having a pigment concentration of 16% by mass was obtained in the same manner as the black pigment dispersion, except that Pigment Yellow 74 (manufactured by Dainichiseika Co., Ltd., Fast Yellow 531) was used instead of carbon black.

この顔料溶解液に超音波処理をした後、スターラーで攪拌している２０００質量部のイオン交換水中に送液ポンプを用いて１００ｍｌ／分の条件で速やかに注入し、透明で赤みがかった顔料分散液が得られた。この顔料分散液中の顔料微粒子の動的光散乱法により求めた平均粒径は２７．２ｎｍであり、凝集状態の進行を抑え、微細な高濃度分散液を得ることができた。
次いでこの分散液を３Ｌフラスコに入れ、５０℃に加熱し６時間攪拌した。次に室温まで冷却後、塩酸１１ｍｌを滴下してｐＨを３程度に調整し、顔料の分散体から顔料粒子を凝集させた。その後、更に酢酸エチル２００ｍｌを加えて２時間攪拌した後、平均孔径０．２μｍのメンブレンフィルターを用いて減圧濾過し、水不溶性色材と特定の高分子化合物を含む色材のケーキを得た。その後、前記色材ケーキをアセトンにより洗浄し、その後、イオン交換水で２回水洗し、脱塩及び脱溶剤されたＣ．Ｉ．ピグメントレッド１２２及びＣ．Ｉ．ピグメントバイオレット１９、及び高分子化合物Ｄ－１の凝集体を得た。
次に、この凝集体１質量部に１規定の水酸化ナトリウム水溶液を加え、顔料分１０％になるようにイオン交換水を加えた後、超音波処理による再分散処理を行い、ｐＨ９．０に調整した顔料分散液Ａを得た。この顔料分散液Ａ中の顔料微粒子の動的光散乱法による平均粒子径は２９．０ｎｍであり、高濃度にもかかわらず微細な顔料微粒子を含有する顔料分散液Ａが得られた。 <Preparation of Pigment Dispersion Liquid A Used in Comparative Example>
C. I. Pigment Red 122, 6.6 parts by mass, C.I. I. 6.6 parts by mass of Pigment Violet 19, 6.6 parts by mass of polymer compound D-1 having the following structure (acid value: 200 mgKOH/g, Mw = 18000), 140 parts by mass of dimethyl sulfoxide, tetramethylammonium hydroxide ( Alfa Aesar, 25% methanol solution) is mixed with 40.7 parts by mass, heated to 60° C., and stirred for 2 hours to completely dissolve the pigment and the specific compound, resulting in a dark blue-purple color. A pigment solution was obtained.

After subjecting this pigment solution to ultrasonic treatment, it was rapidly injected into 2000 parts by mass of ion-exchanged water stirred with a stirrer at a rate of 100 ml/min using a liquid feed pump to obtain a transparent and reddish pigment dispersion. was gotten. The average particle diameter of the fine pigment particles in this pigment dispersion was 27.2 nm as determined by the dynamic light scattering method.
This dispersion was then placed in a 3 L flask, heated to 50° C. and stirred for 6 hours. After cooling to room temperature, 11 ml of hydrochloric acid was added dropwise to adjust the pH to about 3, and the pigment particles were aggregated from the pigment dispersion. After that, 200 ml of ethyl acetate was further added and stirred for 2 hours, followed by filtration under reduced pressure using a membrane filter with an average pore size of 0.2 μm to obtain a colorant cake containing a water-insoluble colorant and a specific polymer compound. After that, the colorant cake was washed with acetone and then washed with deionized water twice to obtain desalted and solvent-removed C.I. I. Pigment Red 122 and C.I. I. Pigment Violet 19 and aggregates of polymer compound D-1 were obtained.
Next, 1 part by mass of this aggregate is added with a 1 N sodium hydroxide aqueous solution, ion-exchanged water is added so that the pigment content becomes 10%, and then redispersion treatment is performed by ultrasonic treatment to adjust the pH to 9.0. An adjusted pigment dispersion liquid A was obtained. The average particle diameter of the pigment fine particles in this pigment dispersion A was 29.0 nm as determined by the dynamic light scattering method, and a pigment dispersion A containing fine pigment fine particles was obtained despite the high concentration.

<Preparation of black ink, cyan ink, magenta ink, yellow ink, pre-treatment liquid, and post-treatment liquid>
The organic solvent, surfactant, antifoaming agent, pH adjuster, antiseptic/antifungal agent, pigment flocculating agent, and ion-exchanged water shown in Table 1 were stirred for 1 hour to mix uniformly. Next, resin particles were added and the mixture was stirred for an additional hour to mix uniformly. After that, the pigment dispersion liquid was added, and the mixture was further stirred for 1 hour to be uniformly mixed. This mixture is pressure-filtered through a polyvinylidene fluoride membrane filter with an average pore size of 0.8 μm to remove coarse particles and dust, and black ink K-01, cyan ink C-01, magenta ink M-01, yellow ink. Y-01, a pre-treatment liquid (treatment liquid-01), and a post-treatment liquid (Clear-01) were obtained. In Table 1, the numerical values described in the column of concentration of the pigment dispersion do not represent the concentration of the pigment dispersion in the ink, but the concentration of the pigment in the ink.

(Examples 1 to 15, Comparative Examples 1 to 4)
<Preparation of liquid composition>
First, an organic solvent, a surfactant, an antifoaming agent, a pH adjuster, an antiseptic and an antifungal agent, and ion-exchanged water shown in Table 2 were uniformly mixed by stirring for 1 hour. Next, the resin particles were added and stirred for an additional hour to mix uniformly. After that, the pigment dispersion liquid was added, and the mixture was further stirred for 1 hour to be uniformly mixed. This mixture was subjected to pressure filtration through a polyvinylidene fluoride membrane filter having an average pore size of 0.8 μm to remove coarse particles and dust, thereby obtaining liquid compositions of Examples 1-15 and Comparative Examples 1-4. In Table 2, the numerical value described in the column of the concentration of the pigment dispersion does not represent the concentration of the pigment dispersion in the liquid composition, but the concentration of the pigment in the liquid composition.
The liquid compositions of Examples 7-2, 7-3 and 7-4 have the same composition as the liquid composition of Example 7.

Details of the pigment dispersion liquid, organic solvent, resin particles, pigment flocculant, surfactant, antifoaming agent, pH adjuster, and antiseptic/antifungal agent in Tables 1 and 2 are as follows.
<Pigment dispersion>
Black pigment dispersion (prepared by the above preparation method)
Cyan pigment dispersion (prepared by the above preparation method)
Magenta pigment dispersion (prepared by the above preparation method)
Yellow pigment dispersion liquid (prepared by the above preparation method)
Pigment Dispersion A (prepared by the above preparation method: Pigment Red 122/Pigment Violet 19, neutralizer: sodium hydroxide (content = 0.5%))
Pigment dispersion B (642 manufactured by Fuji Pigment Co., Ltd.: Pigment Orange 34, neutralizer: none)
Pigment dispersion liquid C (523 manufactured by Fuji Pigment Co., Ltd.: Pigment Green 36, neutralizer: none)
Pigment dispersion D (495 manufactured by Fuji Pigment Co., Ltd.: Pigment Violet 23, neutralizer: none)
Pigment dispersion E (AH2088F manufactured by Sanyo Pigment Co., Ltd.: Pigment Orange 43,
Neutralizing agent: triethanolamine (content = 2.5%))
Pigment Dispersion F (AH2123F manufactured by Sanyo Pigment Co., Ltd.: Pigment Green 36,
Neutralizing agent: triethanolamine (content = 2.5%))
Pigment dispersion G (AF2011F manufactured by Sanyo Pigment Co., Ltd.: Pigment Violet 23,
Neutralizing agent: sodium hydroxide (content = 0.5%))

<Organic solvent>
Organic solvent A (3-methyl-1,3-butanediol manufactured by Tokyo Chemical Industry Co., Ltd.)
Organic solvent B (1,2-butanediol manufactured by Tokyo Chemical Industry Co., Ltd.)
Organic solvent C (Glycerol manufactured by Tokyo Chemical Industry Co., Ltd.)

<Resin particles>
Resin particles A (VONCOAT CG-8520 manufactured by DIC,
styrene-acrylic resin)
Resin particles B (superflex 420 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin)

<Pigment flocculant>
Magnesium sulfate heptahydrate (manufactured by Hayashi Pure Chemical Industries, Ltd. Magnesium sulfate heptahydrate)
<Surfactant>
KF-640 manufactured by Shin-Etsu Silicone Co., Ltd.
<Antifoaming agent>
KM-72F manufactured by Shin-Etsu Silicone Co., Ltd.
<pH adjuster>
Tokyo Chemical Industry Co., Ltd. 2-amino-2-ethyl-1,3-propanediol <antiseptic antifungal agent>
Avecia LV (S)

<Print method>
First, in Table 2, when the column for the presence or absence of treatment liquid-01 is "Yes", treatment liquid-01 shown in Table 1 is applied to a recording medium (manufactured by Oji Paper Co., Ltd.) using a liquid coating device (liquid coating device manufactured by Ricoh Co., Ltd.). OK Topcoat + 104.7 g/m ² ) at a coating weight of 0.06 mg/cm ² . Thereafter, the liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 4, black ink K-01, cyan ink C-01, magenta ink M-01, and yellow ink Y-01 were used in the following combinations, and the image forming apparatus (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), printing resolution 1200 × 1200 dpi, liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 4, black ink K-01, cyan ink C-01, magenta ink M-01, yellow After printing with ink Y-01 in an adhesion amount of 0.9 mg/cm ² , drying was performed for 60 seconds in a constant temperature bath (PR-3J manufactured by ESPEC) set at 100°C. In Table 2, when the column for presence/absence of treatment liquid-01 was "absent", printing was performed in the same manner as in the case of "presence" without application of the treatment liquid, followed by drying.
In addition, when the column for the presence or absence of Clear-01 is "Yes", the liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 4 are printed, dried, and printed using the same image forming apparatus. 1 was printed with a printing resolution of 1200×1200 dpi and an adhesion amount of 0.9 mg/cm ² , and then dried for 60 seconds in a constant temperature bath (PR-3J manufactured by ESPEC) set at 100° C. A print sample.
The liquid compositions shown in Table 2 are orange ink for Examples 1 to 4 and Comparative Example 2, green ink for Examples 5 to 11 and Comparative Example 3, and violet ink for Examples 12 to 15 and Comparative Example 4. Ink. The liquid composition of Comparative Example 1 was printed as an orange ink.
Note that printing was performed using the following color combinations due to the number of heads of the image forming apparatus.
・Black ink/magenta ink/orange ink/yellow ink ・Black ink/cyan ink/green ink/yellow ink ・Black ink/cyan ink/violet ink/magenta ink A model diagram of a printed image sample is shown in FIG. FIG. 12 shows an image in the case of a combination of "black ink/magenta ink/orange ink/yellow ink".

<Beading evaluation method>
The solid image portions of the liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 4 of the print samples were evaluated according to the following ranks. △ or more is the level at which practical use is possible.
Note that beading is a phenomenon such as density unevenness due to the coalescence of adjacent dots.
○: No beading △: Slight beading ×: Significant beading

<Chroma measurement method>
The chromaticities a* and b* of the printed portions of the printed samples of Examples 1 to 15 and the liquid compositions of Comparative Examples 1 to 4 were measured with a densitometer (939 manufactured by X-Rite). Chroma (C*) was calculated from the a* and b* data. A larger value of chroma is more preferable.

<Zeta potential measurement method>
The liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were diluted with ion-exchanged water so that the colorant concentration was 0.01% by mass. ) for 72 hours was used as a measurement sample.
A measurement sample is set in a zeta potential measuring device (ELSZ-2000 manufactured by Otsuka Electronics Co., Ltd.), and the pH of the sample is adjusted with 0.1 mol/l aqueous hydrochloric acid and 0.5 mol/l aqueous sodium hydroxide solution to pH 5. and the zeta potential at pH 9 were measured.

<Storage stability evaluation method>
The liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were placed in a sealed container (Iboy manufactured by AS ONE) and stored in a constant temperature bath (PR-3J manufactured by ESPEC) at 70°C for 14 days. The viscosity before and after storage was measured with a viscometer (RE-85L manufactured by Toki Sangyo Co., Ltd.) to determine the rate of change in viscosity. If the rate of change in viscosity is within ±5% of the initial viscosity, it is at a practically usable level.

<Ejection stability measuring method 1>
Liquid compositions other than those of Examples 7 and 11 were subjected to an image forming apparatus (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.) having an ink discharge head without a circulation mechanism under an environment of temperature: 35°C and humidity: 30% Rh. After printing 100 sheets of a 10 cm square solid image with a printing resolution of 1200×1200 dpi and a liquid composition adhesion amount of 0.9 mg/cm ² , the number of missing nozzles for all 385 nozzles was visually measured, Judgment was made according to the following evaluation criteria. It should be noted that if the number of nozzles in which nozzle missing occurs is 5 or less, it is at a practicable level.
◎: Number of nozzles with missing nozzles: 0 ○: Number of nozzles with missing nozzles: 2 or less △: Number of nozzles with missing nozzles: 3 to 5 ×: Number of nozzles with missing nozzles : 6 or more

<Ejection stability measurement method 2>
The liquid compositions of Examples 7 and 11 (the same formulation) were applied to an image forming apparatus (Ricoh IPSiO GXe5500 modified machine) as an ink ejection head having a circulation mechanism shown in FIGS. 3 to 11. was installed and evaluated. The ink containing portion was filled with ink and left for 24 hours under an environment of temperature: 35° C. and humidity: 30% Rh. During the standing, circulation was operated for 2 minutes once every hour.
After leaving, the circulation mechanism was operated for 1 minute before printing. Temperature: 35 ° C., humidity: 30% Rh, print resolution 1200 × 1200 dpi on recording medium (Oji Paper Co., Ltd. OK top coat + 104.7 g / m ² ), adhesion amount of liquid composition 0 A nozzle check pattern was printed at .9 mg/cm ² to confirm the number of nozzle missing nozzles among all 385 nozzles, and evaluation was performed according to the following criteria. It is desirable for practical use that the above evaluation is Δ or higher. An apparatus with a circulation device was used, but when the liquid composition of Example 7 was used, the liquid composition was not circulated.
◎: Number of nozzles with missing nozzles: 0 ○: Number of nozzles with missing nozzles: 2 or less △: Number of nozzles with missing nozzles: 3 to 5 ×: Number of nozzles with missing nozzles : 6 or more

(About Figures 1 and 2))
400 Image forming apparatus 401 Exterior of image forming apparatus 401c Cover of apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For black (K), cyan (C), magenta (M), and yellow (Y) main tank 411 ink storage unit 413 ink discharge port 414 storage container case 420 mechanism unit 434 ejection head 436 supply tube

(About Figures 3 to 8)
REFERENCE SIGNS LIST 1 nozzle plate 2 channel plate 3 diaphragm member 4 nozzle 6 individual liquid chambers 6a, 6b, 6c, 6d, and 6e through grooves forming individual liquid chambers 7 fluid resistance portion 7a through groove portion serving as fluid resistance portion 8 liquid introducing portion 8a , 8b through-groove portion constituting a liquid introduction portion 9 filter portion 10 common liquid chamber 10A downstream side common liquid chamber 10a through-groove portion 10B upstream side common liquid chamber 10b groove portion 11 piezoelectric actuator 12 piezoelectric member 12A, 12B piezoelectric element 13 base member 15 flexible Wiring member 20 Common liquid chamber member 21 First common liquid chamber member 22 Second common liquid chamber member 25a, 25b Piezoelectric actuator through hole 30 Vibration region 30a, 30b Convex portion 40 Channel member 41 to 45 Plate member 50 Common circulation Liquid chamber 50a Groove 51 Fluid resistance 51a Through grooves 52, 53 forming the fluid resistance Circulation channels 52a, 52b Through grooves forming the circulation flow channel 53a, 53b, 53c, 53d Through grooves 71 forming the circulation flow channel Supply port 71a Through hole 81 Circulation port 81a, 81b Through hole

(Regarding Figures 10 and 11)
401 guide member 403 carriage 404 ink ejection head 405 main scanning motor 406 driving pulley 407 driven pulley 408 timing belt 410 paper 412 transport belt 413 transport roller 414 tension roller 416 sub-scanning motor 417 timing belt 418 timing pulley 420 maintenance recovery mechanism 421 cap member 422 wiper member 440 ink discharge unit 491A, 491B side plate 491C rear plate 493 main scanning movement mechanism 494 supply/circulation mechanism 495 transport mechanism

JP 2009-173853 A JP 2009-013394 A JP-A-2000-256593 JP-A-2002-241649 JP 2010-235741 A

Claims (10)

In a liquid composition containing a coloring material, a polymer compound, and water,
the polymer compound comprises a plurality of resins, the plurality of resins comprising a styrene-acrylic resin and a urethane resin;
The coloring material is Pigment Orange 43, Pigment Green 36, or Pigment Violet 23,
The liquid composition was diluted with ion-exchanged water so that the colorant concentration was 0.01% by mass, and the liquid was stored at 70 ° C. for 72 hours. A liquid composition having a zeta potential of −30.0 mV or more and a zeta potential of −45.0 mV or less at pH 9. A liquid composition according to claim 1, containing either sodium hydroxide or triethanolamine. 3. The liquid composition according to claim 1, wherein the coloring material is Pigment Orange 43, and the concentration of Pigment Orange 43 is 1.0% by mass or more and 5.0% by mass or less. 3. The liquid composition according to claim 1, wherein the coloring material is Pigment Green 36, and the concentration of Pigment Green 36 is 3.0% by mass or more and 5.0% by mass or less. 3. The liquid composition according to claim 1, wherein the coloring material is Pigment Violet 23, and the concentration of Pigment Violet 23 is 0.5% by mass or more and 3.0% by mass or less. An ink containing the liquid composition according to any one of claims 1 to 5. An ink set comprising the ink according to claim 6, a black ink, a cyan ink, a magenta ink and a yellow ink. In a printing method comprising a step of applying a treatment liquid containing a component that agglomerates a coloring material in the ink, and a step of applying an ink, the ink according to claim 6 or the ink according to claim 7 . A printing method using an ink set. 9. The printing method according to claim 8, comprising the step of applying a clear ink containing no coloring material and containing a resin. In a printing apparatus having a liquid ejection head for ejecting ink and ink, the ink is the ink according to claim 6 or the ink constituting the ink set according to claim 7 , and the liquid ejection head is a liquid. an individual liquid chamber communicating with the nozzles; a common liquid chamber supplying liquid to the individual liquid chambers; a circulation channel communicating with the individual liquid chambers; and a common circulation channel communicating with the circulation channel. A printing apparatus, which is a liquid discharge head, comprising a liquid chamber and pressure generating means for applying pressure to the liquid in the individual liquid chamber.

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