JP5919854B2 - Ink for inkjet recording - Google Patents

Description

  The present invention relates to an inkjet recording ink.

  The ink jet recording method is a recording method in which ink droplets are ejected from very fine nozzles and deposited on a recording member to form characters and images. This method has been widely used in recent years because it is easier to achieve full color than other recording methods and has an advantage that a high-resolution image can be obtained even with an apparatus having a simple configuration.

  As inks used in ink jet printers, there are pigment-based inks and dye-based inks, and pigments are superior in terms of water resistance and weather resistance compared to dyes. Ink is increasingly used.

  However, pigment-based inks have the problem that the uniformity of the solid image portion during printing, color color development, wettability, and the like are inferior to dye-based inks.

  To improve the above problems in pigment-based inks, it is effective to reduce the surface tension of the ink and improve the permeability of the ink. However, the hydrocarbon surfactant sufficiently improves the permeability of the ink. In addition, silicone surfactants are prone to thermal decomposition and have problems with storage stability. Fluorosurfactants have low compatibility with water-soluble organic solvents and resins, and air bubbles. This is likely to cause the discharge to become unstable.

Japanese Patent Application Laid-Open No. 2010-163533 of Patent Document 1 uses a fluorosurfactant having a specific structure, so that even plain paper has color developability close to that of dye-based ink, prevents occurrence of color bleed, and discharge reliability. An ink with improved properties is disclosed.
However, when the amount of the fluorosurfactant added is increased, the ink tends to generate air bubbles, which may make the ejection unstable. Has not been achieved at a high level.

The present invention improves the pigment ink containing the fluorosurfactant described in Patent Document 1 and increases the wettability of the ink, thereby providing color development, uniformity of the solid image portion, low bleeding. An object of the present invention is to provide an ink that improves image quality such as property and has low foaming properties and excellent ejection stability.

As a result of intensive studies by the present inventors to solve the above problems, it is difficult to generate bubbles due to the addition of the fluorosurfactant by combining the fluorosurfactant having the specific structure and the amide compound having the specific structure, and it is sufficient. We have found that it is possible to ensure good wettability and to achieve both image quality and ejection stability. The present invention has been completed based on such knowledge.
That is, the said subject is solved by following (1)-(8) of this invention.
(1) “Ink for ink jet recording containing at least water, a water-soluble organic solvent, and a colorant, the fluorine-based surfactant represented by the following structural formula (I), and the following structural formula (II)” An ink for inkjet recording, comprising the amide compound.

(In Structural Formula (I), A represents H or —CO—R ₁ , R ₁ represents H or CF ₃ (CF ₂ ) m, and m represents an integer of 0 to 3.
B represents an alkylene group having 1 to 3 carbon atoms which may have a substituent.
Rf _represents a _{CF 3 (CF 2) n,} n is an integer of 0 to 3.
X and Y represent an integer of 1 to 4, and Z represents an integer of 1 to 25. )

(In the structural formula (II), R represents CH ₃ (CH ₂ ) m, and m represents an integer of 0 to 3). ”
(2) “Ink for inkjet recording according to the above (1), wherein the fluorosurfactant represented by the structural formula (I) is contained in an amount of 0.01 wt% to 10.0 wt%”;
(3) “Ink for inkjet recording according to (1) or (2) above, which contains 10.0 wt% or more and 45.0 wt% or less of the amide compound represented by the structural formula (II)”,
(4) “The ink for inkjet recording according to any one of (1) to (3) above, wherein the colorant is polymer fine particles containing a colorant”;
(5) “Inkjet recording ink set including black ink and color ink, wherein the black ink and color ink are inks according to any one of (1) to (4)” Ink set for recording ",
(6) "Ink cartridge in which the ink according to any one of (1) to (4) is accommodated in a container",
(7) “Ink jet recording apparatus having ink flying means for applying energy to ink to cause ink to fly and forming an image on a recording member, wherein the ink is any one of (1) to (3)” An ink jet recording apparatus according to any one of (1) to (4) above,
(8) “Recorded matter having an image formed by flying the ink according to any one of (1) to (4) above onto a recording member”.

As will be understood from the following detailed and specific description, according to the present invention, even if the amount of the specific fluorosurfactant added is increased, bubbles are not easily generated, and the ink wettability is increased. Thus, it is possible to achieve both the improvement of image quality such as the color developing property and the uniformity of the solid image portion and the improvement of the ejection stability.
Furthermore, aggregation of pigments in the ink can be prevented, nozzle clogging can be prevented, and ejection stability can be improved.

It is a plane schematic diagram of the principal part of the mechanism part of an ink jet recording device. It is a principal part enlarged view of an inkjet head. It is the schematic which shows an example of the ink bag of the ink cartridge of this invention. FIG. 2 is a schematic diagram illustrating an ink cartridge in which the ink bag of FIG. 1 is accommodated in a cartridge case.

The ink for inkjet recording of the present invention will be described in detail.
The ink for ink jet recording of the present invention is an ink for ink jet recording containing at least water, a water-soluble organic solvent, and a colorant, and contains a specific fluorosurfactant and a specific amide compound in the ink. To do.

<Fluorosurfactant>
The fluorosurfactant of the present invention is a polyether copolymer having a pendant trifluoroethoxy group and is represented by the following structural formula (I).

(In Structural Formula (I), A represents H or —CO—R ₁ , R ₁ represents H or CF ₃ (CF ₂ ) m, and m represents an integer of 0 to 3.
B represents an alkylene group having 1 to 3 carbon atoms which may have a substituent, and the substituent is an alkyl group having 1 or 2 carbon atoms.
Rf _represents a _{CF 3 (CF 2) n,} n is an integer of 0 to 3.
X and Y represent an integer of 1 to 4, and Z represents an integer of 1 to 25. )

The fluorosurfactant reduces the surface tension of the pigment-based ink, improves the wettability, improves the filling between dots during printing, and improves the color developability of the color.
A commercial item can be used as said fluorosurfactant, for example, polyfox (Omnova company make) PF-7002 etc. can be used.

The addition amount of the fluorosurfactant is preferably 0.01% by mass or more and less than 15.0% by mass, and more preferably 0.01% by mass or more and 10.0% by mass or less.
If it is less than 0.1% by mass, sufficient wettability may not be ensured, and color developability may deteriorate. On the other hand, when the content is 15.0% by mass or more, bubbles are likely to be generated, which may affect the ejection stability.

<Amide compound>
The amide compound of the present invention is an amphiphilic solvent having a high solubility having an amide group, an alkyl group and an ether bond, and is represented by the following structural formula (II).

(R in the structural formula (II) represents CH ₃ (CH ₂ ) m, and m represents an integer of 0 to _3. )

By adding the amide compound, the compatibility between the water-soluble organic solvent and the polymer fine particles, which will be described later, is improved, the dispersibility is improved, and even if the amount of the fluorosurfactant is increased, the foam of the ink is increased. And a sufficient amount of a fluorosurfactant can be added, thereby ensuring sufficient wettability to the recording member. In addition, water-soluble solvents having a high equilibrium water content such as glycerin and 1,3-butanediol, and relatively hydrophobic organic materials such as 2-ethylhexanediol and 2,2,4-trimethyl-1,3-pentanediol. The solvent can be mixed evenly to improve the dispersion force capable of maintaining the dispersion state of the pigment in the ink, the uniformity of the solid image portion after printing can be increased, and aggregation of the colorant in the ink can be prevented. .
Furthermore, since the amide compound has a high boiling point and a high equilibrium water content, it has a high moisturizing power, is difficult to dry, improves storage properties, and has good discharge stability.

A commercial item can be used as said amide compound, for example, ecamide: M100 (made by Idemitsu Kosan Co., Ltd.), ecamide: B100 (made by Idemitsu Kosan Co., Ltd.), etc. can be used.
The addition amount of the amide compound is preferably 5% by mass or more and 55% by mass or less, and more preferably 10.0% by mass or more and 45.0% by mass or less.
If the amount is less than 5.0% by mass, the effect of uniformly mixing may not be sufficiently secured. If the amount exceeds 55.0% by mass, members such as the ink discharge means may be eroded and the discharge may be adversely affected. .

<Water-soluble organic solvent>
The ink of the present invention also contains a water-soluble organic solvent for preventing the ink from drying and improving the dispersion stability.
Examples of the water-soluble organic solvent include the following. A mixture of a plurality of these water-soluble organic solvents may be used.
Glycerin, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, trimethylolethane, ethylene glycol, diethylene glycol, dipropylene glycol, Tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4-butane Polyhydric alcohols such as triol, 1,2,3-butanetriol, petriol;
Polyhydric alcohol alkyl ethers 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, propylene glycol monoethyl ether;
Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether;
Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone;
Amides such as formamide, N-methylformamide, N, N-dimethylformamide;
Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine;
Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol;
Propylene carbonate, ethylene carbonate, etc.

In addition to the water-soluble organic solvent, other wetting agents may be used. As such wetting agents, those containing urea compounds and sugars are preferable. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, Examples include lactose, sucrose, trehalose, and maltotriose. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose.
Examples of derivatives of these saccharides include reducing sugars of the saccharides described above (for example, sugar alcohol [general formula HOCH ₂ (CHOH) nCH ₂ OH (n = 2 to 5)), oxidized sugar (for example, aldonic acid). , Uronic acids, etc.), amino acids, thioic acids, etc. Sugar alcohols are particularly preferred, and specific examples include D-sorbitol, sorbitan, maltitol, erythritol, lactitol, xylitol and the like.

In particular, in the present invention, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, dipropylene glycol, trimethylolpropane, tetramethylolpropane, 3 When methyl-1,3-butanediol, D-sorbitol, or xylitol is used, an ink having excellent storage stability and ejection stability can be produced.

In the case of pigment ink, the ratio of the pigment to the water-soluble organic solvent has a great influence on the ejection stability of the ink from the head. If the pigment solid content ratio is high but the blending amount of the water-soluble organic solvent is small, water evaporation near the ink meniscus of the nozzle proceeds, resulting in ejection failure.
The blending amount of the water-soluble organic solvent is preferably about 10 to 50% by weight of the whole ink.

<Colorant>
As the colorant of the present invention, polymer fine particles containing a pigment or a colorant can be used.
Examples of the pigment include organic pigments such as azo, phthalocyanine, anthraquinone, dioxazine, indigo, thioindigo, perylene, isoindolenone, aniline black, azomethine, rhodamine B lake pigment, carbon black, Examples include inorganic pigments such as iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chrome yellow, and metal powder.

Specific examples of black pigments include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper oxide, iron oxide (CI pigment black 11). And organic pigments such as metals such as titanium oxide and aniline black (CI Pigment Black 1).

  Specific examples of yellow pigments include C.I. I. Pigment Yellow 1 (Fast Yellow G), 2, 3, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 20, 23, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55 73, 74, 75, 81, 83 (disazo yellow HR), 86, 93, 95, 97, 98, 100, 101, 104, 108, 109, 110, 114, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185 and the like.

  Specific examples of the magenta pigment include C.I. I. Pigment violet 19, C.I. I. Pigment Red 1, 2, 3, 5, 7, 9, 12, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 1 [Permanent Red 2B (Ba)], 48: 2 [Permanent Red 2B (Ca)], 48: 3 [permanent red 2B (Sr)], 48: 4 [permanent red 2B (Mn)], 49: 1, 52: 2, 53: 1, 57: 1 (brilliant carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 92, 97, 101 (Bengara), 104, 105, 106, 108 (Cadmium red), 112, 114, 122 (dimethylquinacridone), 123, 146, 149, 166, 168, 170, 172, 175, 176, 178, 179, 180 184,185,190,192,193,202,209,215,216,217,219,220,223,226,227,228,238,240,254,255,272, and the like.

Specific examples of cyan pigments include C.I. I. Pigment Blue 1, 2, 3, 15 (copper phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 22, 56, 60, 63, 64, Bat Blue 4, Bat Blue 60, and the like.
Specific examples of the intermediate color pigment include C.I. for red, green and blue. I. Pigment red 177, 194, 224, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, 71, C.I. I. Pigment violet 3, 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment green 7, 36, and the like.

In the ink of the present invention, polymer fine particles containing a colorant can be used to improve printing density and printing durability.
As the dispersion of polymer fine particles containing a coloring agent, a dispersion of polymer fine particles containing a hydrophobic dye and a polymer fine particle containing a pigment can be used, but a polymer fine particle containing a pigment, particularly an organic pigment or carbon black, can be used. A dispersion is more preferred.

Examples of the polymer used for the dispersion of the polymer fine particles containing the pigment include a vinyl polymer, a polyester polymer, and a polyurethane polymer. Among the polymers, vinyl polymers are preferable.

The vinyl polymer includes (a) one or more vinyl monomers selected from the group consisting of acrylic acid esters, methacrylic acid esters, and styrene monomers, and (b) a polymerizable unsaturated monomer having a salt-forming group. (C) A polymer obtained by copolymerizing a monomer composition containing a vinyl monomer and a polymerizable unsaturated monomer having a salt-forming group and a copolymerizable component is preferred.

Examples of the vinyl monomer (a) include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-amyl acrylate, n-hexyl acrylate, Acrylic acid esters such as n-octyl acrylate and dodecyl acrylate; methyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, 2-ethylhexyl methacrylate And methacrylic acid esters such as lauryl methacrylate; and styrene monomers such as styrene, vinyltoluene and 2-methylstyrene.

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

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

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

Components capable of copolymerization with the vinyl monomer and the polymerizable unsaturated monomer having a salt-forming group (c) include acrylamide monomers, methacrylamide monomers, hydroxyl group-containing monomers, and macromers having a polymerizable functional group at one end. For example, silicone macromer, styrenic macromer, polyester macromer, polyurethane macromer, polyalkyl ether macromer, especially CH ₂ ═C (R ⁵ ) COO (R ⁶ O) _p R ⁷ (wherein R ⁵ is hydrogen) An atom or a lower alkyl group; R ⁶ is a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom; and R ⁷ is a carbon number 1 to optionally having a hydrogen atom or a hetero atom. 30 monovalent hydrocarbon groups, p represents a number of 1 to 60), and the like. It may be mixed up. In addition, those monomers are illustrations and the present invention is not limited only to such illustrations.

As the hydroxyl group-containing monomer, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable.

As the macromer of CH ₂ ═C (R ⁵ ) COO (R ⁶ O) _p R ⁷ , polyethylene glycol (2-30) (meth) acrylate and methoxypolyethylene glycol (1-30) (meth) acrylate are preferable. In addition, "(meth) acrylate" in this specification shows an acrylate or a methacrylate.

Among the copolymerizable components, macromers are preferable, and silicone macromers, styrenic macromers, and polyalkyl ether macromers are more preferable.

The content of the vinyl monomer in the monomer composition is from 1 to 75% by weight, preferably from 5 to 60% by weight, more preferably from the viewpoint of improving the dispersion stability of the polymer emulsion and avoiding scorching of the ink jet printer head. Desirably, it is ˜50% by weight.

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

The content of the monomer that can be copolymerized with the vinyl monomer and the polymerizable unsaturated monomer having a salt-forming group in the monomer composition is 5 from the viewpoint of improving the dispersion stability of the polymer emulsion and avoiding scorching of the ink jet printer head. It is desirable to be -90 wt%, preferably 10-85 wt%, more preferably 20-60 wt%.

Further, the average particle diameter of the polymer fine particles is preferably 20 to 200 nm from the viewpoint of dispersion stability, and the content of the polymer fine particles in the ink is preferably 10% by weight to 40% by weight.

The average particle diameter in the present invention is a particle refractive index of 1 using a sample diluted with pure water so that the pigment concentration in the measurement sample becomes 0.01% by weight using Microtrac UPA-150 manufactured by Nikkiso Co., Ltd. .51, a particle density of 1.4 g / cm ³ , and a 50% average particle diameter (D50) measured at 23 ° C. using a pure water parameter as a solvent parameter.

In addition to those described above, conventionally known additives such as a pH adjuster, an antiseptic / antifungal agent, a rust preventive agent, and a chelating reagent can be added to the ink of the present invention.

The pH adjuster is added for the purpose of stabilizing the dispersion state by keeping the ink alkaline and stabilizing ejection. However, when the pH is 11 or more, the amount of the ink jet head and the ink supply unit that melts out is large, and depending on the material of the head and unit, problems such as ink deterioration, leakage, and defective discharge are likely to occur when used for a long time. . In the case of a pigment, it is more desirable to add a pH adjuster when kneading and dispersing the pigment in water together with the dispersant than to add with additives such as a wetting agent and a penetrating agent after kneading and dispersing. This is because the dispersion may be destroyed by addition depending on the pH adjusting agent.

As the pH adjuster, those containing one or more alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates are preferable.
Examples of alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide. As ammonium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, etc., phosphonium hydroxide as quaternary phosphonium hydroxide, and alkali metal carbonate as lithium carbonate, sodium carbonate And potassium carbonate.

Examples of antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol and the like.
Examples of the antirust agent include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like.

The viscosity, surface tension, and pH of the recording ink of the present invention can be appropriately selected according to the purpose of use, but the viscosity is preferably 25 to 20 mPa · sec and 5 to 10 mPa · sec. It is preferable. If the viscosity exceeds this range, it may be difficult to ensure ejection stability.
Further, the surface tension is preferably 20 to 55 mN / m at 20 ° C. If the surface tension is less than this, bleeding on the paper becomes noticeable and stable jetting may not be obtained, and if it exceeds this, ink penetration into the paper does not occur sufficiently, and the drying time May cause longer time.
Moreover, it is preferable that pH is 7-10.

  The recording ink of the present invention can form a multicolor image when recording is performed using an ink set that is used in combination of two or more. When recording is performed using an ink set that is used in combination with all colors, the full color is recorded. An image can be formed.

The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording system, such as an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like.

Next, an example of the ink jet recording apparatus will be described with reference to FIGS.
The ink jet recording apparatus shown in FIG. 1 includes four ink jet heads (134) for ejecting ink droplets onto a recording paper (142), and four ink jet heads (134) in the carriage scanning direction (main scanning direction). A carriage (133) that is movably mounted, an endless conveyance belt (141) that conveys the recording paper (142) in the belt (paper) conveyance direction (sub operation direction), and a driving roller on which the conveyance belt is stretched (157) and a driven roller (158).
Further, although not shown, an ink cartridge and a carriage for introducing inkjet inks (hereinafter, also simply referred to as “inks”) having different colors (for example, yellow, cyan, magenta, black) into each inkjet head (134). (133) is a carriage drive unit that moves in the carriage scanning direction, a belt drive unit that drives the transport belt by rotating the drive roller (157), a head driver that discharges and drives each inkjet head (134), and a carriage (133). A maintenance device or the like is provided at one end of the scanning region and performs maintenance on each inkjet head (134). The maintenance device includes a cap, a wiper blade, an empty discharge receiver, a wiper cleaner, and the like.
The ink jet recording apparatus ejects ink of each color onto the recording paper (142) while moving the four ink jet heads (134) in the carriage scanning direction via the carriage (133). ) In the belt conveyance direction, an image is formed (printed) on the recording paper (142).

  As shown in FIG. 2, each inkjet head is of a piezo type, and includes an ink supply port (not shown), a frame (10) formed with a carving to be a common liquid chamber (1b), and a fluid resistance portion ( 2a), an engraved pressurizing liquid chamber (2b), a flow passage plate (20) having a communication port (2c) communicating with the nozzle (3a), and a number of nozzles (3a) were formed. The laminated piezoelectric element (50) fixed to the nozzle plate and the base (40) and applied with the driving waveform from the head driver, the convex part (6a) joined to the laminated piezoelectric element (50), and the diaphragm part (6b) ) And an ink inlet (6c), and an adhesive layer (70) for bonding the laminated piezoelectric element (50) and the diaphragm (60). Each inkjet head is not limited to a piezo type, but may be a thermal type, an electrostatic type, or the like.

The nozzle plate is formed of a metal material, for example, an Ni plating film by an electroforming method. An ink repellent layer (liquid repellent layer) is formed on the ink discharge surface side surface (droplet discharge surface side surface) of the nozzle plate.

On the nozzle plate surface of the ink jet head, PTFE (polytetrafluoroethylene) / Ni eutectoid plating, electrodeposition coating of fluororesin, vapor deposition of evaporable fluororesin (for example, fluoride pitch), silicone resin, fluorine An ink repellent layer is provided by application of a resin. In order to maintain sufficient ink repellency even with a low surface tension highly permeable ink, it is preferable to provide an ink repellent layer containing a fluorine-based silane coupling agent or an ink repellent layer containing a silicone resin.
When an ink repellent layer containing a fluorine-based silane coupling agent is provided, a large amount of hydroxyl groups serving as bonding points with the fluorine-based silane coupling agent are present to improve adhesion. In some cases, an inorganic oxide layer is provided. Examples of the material for the inorganic oxide layer include SiO ₂ and TiO _{2. The} film thickness is preferably 10 to 2000 mm, more preferably 100 to 1000 mm.

Although the fluorine-based silane coupling agent is not particularly limited, JP-B-3-43065, JP-A-6-210857, JP-A-10-32984, JP-A-2000-94567, JP-A-2002-145645 JP-A 2003-341070, JP-A 2007-106024, JP-A 2007-125849, and the like. As a particularly preferred example, modified perfluoropolyoxetane (manufactured by Daikin Industries, Ltd .: OPTOOL DSX) can be mentioned. In this case, the film thickness is preferably 1 to 200 mm, more preferably 10 to 100 mm.
Examples of the method for forming an ink repellent layer using a fluorine-based silane coupling agent include coating methods such as spin coating, roll coating, and dipping, printing methods, and vacuum deposition methods.
The ink-repellent layer made of a fluorinated silane coupling agent has high mechanical durability because it forms a chemical bond with the underlying layer. Is not durable enough. However, when the ink of the present invention is used, the ink wettability is greatly improved.

Silicone resin is a resin having a siloxane bond made of Si and O as a basic skeleton, and is commercially available in various forms such as oil, resin, and elastomer. In addition to the ink repellency important in the present invention, it has various properties such as heat resistance, releasability, defoaming property, and adhesiveness. Silicone resins include a room temperature curing type, a heat curing type, an ultraviolet curing type, and the like, which can be selected according to the production method and usage.
Examples of methods for forming an ink repellent layer containing a silicone resin on the nozzle surface include a method of vacuum-depositing a liquid silicone resin material, a method of forming a silicone oil by plasma polymerization, spin coating, dipping, spray coating, etc. Examples thereof include a method of forming by coating and an electrodeposition method. When forming the ink repellent layer, except for the electrodeposition method, the nozzle hole and the back surface of the nozzle plate are masked with photoresist, water-soluble resin, etc. Only an ink-repellent layer containing a silicone resin can be formed. In this case, care should be taken because use of a strong alkaline stripping solution will damage the ink-repellent layer.
The thickness of the ink repellent layer containing a silicone resin is preferably 0.1 to 5.0 μm, and more preferably 0.1 to 1.0 μm. If the film thickness is less than 0.1 μm, the durability against wiping deteriorates, and the ink repellency may deteriorate when used for a long period of time. This will result in useless manufacturing costs.

Each ink constituting the ink set of the present invention can be accommodated in a container and used as an ink cartridge, and other members appropriately selected as necessary may be attached.
The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. For example, the container has an ink bag formed of an aluminum laminate film, a resin film, etc. Etc. are preferable.

The ink cartridge will be described with reference to FIGS. Here, FIG. 3 is a schematic view showing an example of the ink bag (241) of the ink cartridge of the present invention, and FIG. 4 is an ink cartridge in which the ink bag (241) of FIG. 3 is accommodated in the cartridge case (244). It is the schematic which shows (200).

As shown in FIG. 3, after filling the ink bag (241) with ink from the ink inlet (242) and exhausting the air remaining in the ink bag, the ink inlet (242) is fused. close up. In use, the needle of the apparatus main body is pierced into the ink discharge port (243) made of a rubber member and supplied to the apparatus. The ink bag (241) is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 4, it is usually housed in a plastic cartridge case (244) and used as an ink cartridge (200) detachably attached to various ink jet recording apparatuses.
The ink cartridge of the present invention is particularly preferably used by being detachably mounted on the above-described ink jet recording apparatus of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. In addition, unless otherwise indicated,% represents mass%.

<Preparation of pigment dispersion>
(Cyan dispersion)
After sufficiently replacing the inside of the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube and dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) and 0.4 g of mercaptoethanol were charged, and the temperature was raised to 65 ° C. Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyethyl methacrylate 60.0 g, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) A mixed solution of 36.0 g, mercaptoethanol 3.6 g, azobisdimethylvaleronitrile 2.4 g and methyl ethyl ketone 18 g was dropped into the flask over 2.5 hours.
After completion of dropping, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobisdimethylvaleronitrile was added, and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50%.
Next, a part of the polymer solution was dried and measured by gel permeation chromatography (standard: polystyrene, solvent: tetrahydrofuran). The weight average molecular weight was 15000.

28 g of the polymer solution, 26 g of copper phthalocyanine pigment, 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone and 30 g of ion-exchanged water were sufficiently stirred.
Thereafter, the mixture was kneaded 20 times using a three-roll mill (manufactured by Noritake Co., Ltd., trade name: NR-84A). The obtained paste was put into 200 g of ion-exchanged water and stirred sufficiently, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain 160 g of a blue polymer fine particle dispersion having a solid content of 20.0 wt%.
The average particle diameter (D50%) of the fine polymer particles measured by Microtrac UPA was 98 nm.

(Magenta dispersion)
A red-purple polymer fine particle dispersion was obtained in the same manner as the preparation of the cyan dispersion except that the copper phthalocyanine pigment of the cyan dispersion was changed to Pigment Pigment Red 122. The average particle size (D50%) of the polymer fine particles measured by Microtrac UPA was 124 nm.

(Yellow dispersion)
A yellow polymer fine particle dispersion was obtained in the same manner as the preparation of the cyan dispersion except that the copper phthalocyanine pigment of the cyan dispersion was changed to Pigment Pigment Yellow 74. The average particle diameter (D50%) of the polymer fine particles measured by Microtrac UPA was 78 nm.

(Black dispersion)
A black polymer fine particle dispersion was obtained in the same manner as the preparation of the cyan dispersion except that the copper phthalocyanine pigment of the cyan dispersion was changed to carbon black (Degussa FW100). The average particle diameter (D50%) of the polymer fine particles measured by Microtrac UPA was 110 nm.

Example 1
(Adjustment of ink 1-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 13.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 1-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 12.5%
Glycerin 9.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 1-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 10.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 1-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,5-pentanediol 10.0%
Glycerin 7.5%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
_{C 12 H 24 - (OCH 2} CH 2) 9 OH 1.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Example 2)
(Adjustment of ink 2-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 10.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Hexylene glycol 4.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 2-M)
Magenta dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 10.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
3-methyl-1,3-butanediol 11.5%
Ethylene glycol 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 2-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 10.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 8.5%
Glycerin 7.5%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 2-K)
Black dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 10.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
2-methyl-2,4-pentanediol 11.5%
2-pyrrolidone 2.0%
2,2,4-Trimethyl 1,3-pentanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Example 3)
(Adjustment of ink 3-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 8.0%
2,2,4-Trimethyl 1,3-pentanediol 2.0%
3-methyl-1,5-pentanediol 7.5%
Proxel LV 0.2%
1N-NaOH 0.3%
Ion exchange water

(Adjustment of ink 3-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 10.0%
2,2,4-Trimethyl 1,3-pentanediol 2.0%
3-methyl-1,5-pentanediol 5.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 3-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ (CH ₂ ) ₃ )
3-methyl-1,5-pentanediol 8.0%
Glycerol 7.0%
2,2,4-Trimethyl 1,3-pentanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.3%
Ion exchange water

(Adjustment of ink 3-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ (CH ₂ ) ₃ )
3-methyl-1,3-butanediol 5.0%
Glycerin 10.0%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Comparative Example 1)
(Adjustment of ink 4-C)
Cyan dispersion 20.0%
1,3-butanediol 23.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
ECTD-3NEX (Nikko Chemicals) 1.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 4-M)
Magenta dispersion 30.0%
1,3-butanediol 22.5%
Glycerin 9.0%
2-ethyl 1,3-hexanediol 2.0%
ECTD-3NEX (Nikko Chemicals) 1.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 4-Y)
Yellow dispersion 20.0%
1,6-hexanediol 24.5%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Unisafe A-LY (Nippon Yushi Co., Ltd.) 0.5%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 4-K)
Black dispersion 30.0%
1,5-pentanediol 2.0%
Glycerin 9.0%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
_{C 12 H 24 - (OCH 2} CH 2) 9 OH 1.0%
NISSAN ANON BL-SF (made by NOF Corporation) 0.1%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Comparative Example 2)
(Adjustment of ink 5-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
3-methyl-1,3-butanediol 10.0%
Hexylene glycol 4.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Adjustment of ink 5-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
3-methyl-1,3-butanediol 11.5%
Ethylene glycol 5.0%
Glycerin 5.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 5-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
3-methyl-1,5-pentanediol 12.0%
3-methyl-1,3-butanediol 15.0%
Glycerol 7.0%
2,2,4-Trimethyl 1,3-pentanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Adjustment of ink 5-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
3-methyl-1,3-butanediol 22.5%
Glycerin 7.5%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Comparative Example 3)
(Adjustment of ink 6-C)
Cyan dispersion 20.0%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 13.0%
Glycerin 6.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
ECTD-3NEX (Nikko Chemicals) 0.4%
Ion exchange water

(Adjustment of ink 6-M)
Magenta dispersion 30.0%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 12.5%
Glycerol 7.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
ECTD-3NEX (Nikko Chemicals) 0.8%
Ion exchange water

(Adjustment of ink 6-Y)
Yellow dispersion 20.0%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,6-hexanediol 16.5%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Unisafe A-LY (Nippon Yushi Co., Ltd.) 0.5%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 6-K)
Black dispersion 30.0%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,5-pentanediol 12.5%
Glycerin 5.5%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
Nissan Anon BL-SF (Nippon Yushi) 0.3%
_{C 12 H 24 - (OCH 2} CH 2) 9 OH 1.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

Example 4
(Adjustment of ink 7-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₃ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,3-butanediol 13.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 7-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₃ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,3-butanediol 12.5%
Glycerin 9.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 7-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₃ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,6-hexanediol 10.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 7-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = (CF ₂ ) ₃ CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,5-pentanediol 10.0%
Glycerin 7.5%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
_{C 12 H 24 - (OCH 2} CH 2) 9 OH 1.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Example 5)
(Adjustment of ink 8-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 8.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,3-butanediol 15.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.3%
Ion exchange water

(Adjustment of ink 8-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 8.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,3-butanediol 15.0%
Glycerin 9.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 8-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 8.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,6-hexanediol 15.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.3%
Ion exchange water

(Adjustment of ink 8-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 3, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 8.0%
(R = CH ₃ (CH ₂ ) ₃ )
1,5-pentanediol 10.0%
Glycerin 7.5%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
_{C 12 H 24 - (OCH 2} CH 2) 9 OH 1.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Example 6)
(Adjustment of ink 9-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (Polyfox manufactured by OMNOVA) 13.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 10.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 9-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (Polyfox manufactured by OMNOVA) 13.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 10.0%
Glycerin 9.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 9-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (Polyfox manufactured by OMNOVA) 13.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,6-hexanediol 10.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 9-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (Polyfox manufactured by OMNOVA) 13.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,5-pentanediol 10.0%
Glycerin 7.5%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
_{C 12 H 24 - (OCH 2} CH 2) 9 OH 1.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Example 7)
(Adjustment of ink 10-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 48.0%
(R = CH ₃ )
1,3-butanediol 5.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 10-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 48.0%
(R = CH ₃ )
1,3-butanediol 5.0%
Glycerin 6.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 10-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 48.0%
(R = CH ₃ )
1,6-hexanediol 5.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 10-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 2.0%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₃ )
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 48.0%
(R = CH ₃ )
1,5-pentanediol 5.0%
Glycerol 7.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Comparative Example 4)
(Adjustment of ink 11-C)
Cyan dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Oleamide 15.0%
1,3-butanediol 13.5%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 11-M)
Magenta dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Oleamide 15.0%
1,3-butanediol 12.5%
Glycerin 9.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 11-Y)
Yellow dispersion 20.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Oleamide 15.0%
1,6-hexanediol 10.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 11-K)
Black dispersion 30.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = H, B = CH ₂ C (CH ₃ ) ₂ CH ₂ , X = 2, Y = 2, Z = 1, Rf = CF ₂ CF ₃ )
Oleamide 15.0%
1,5-pentanediol 10.0%
Glycerin 7.5%
2-pyrrolidone 2.0%
2-ethyl 1,3-hexanediol 2.0%
_{C 12 H 24 - (OCH 2} CH 2) 9 OH 1.0%
Proxel LV 0.2%
1N-NaOH 0.6%
Ion exchange water

(Comparative Example 5)
(Adjustment of ink 12-C)
Cyan dispersion 20.0%
Fluorine-containing surfactant (Surflon S-141; manufactured by Asahi Glass) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Hexylene glycol 4.0%
Glycerin 8.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 12-M)
Magenta dispersion 30.0%
Fluorine-containing surfactant (Surflon S-141; manufactured by Asahi Glass) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
3-methyl-1,3-butanediol 11.5%
Ethylene glycol 5.0%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 12-Y)
Yellow dispersion 20.0%
Fluorine-containing surfactant (Surflon S-141; manufactured by Asahi Glass) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
1,3-butanediol 8.5%
Glycerin 7.5%
2-ethyl 1,3-hexanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 12-K)
Black dispersion 30.0%
Fluorine-containing surfactant (Surflon S-141; manufactured by Asahi Glass) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
2-methyl-2,4-pentanediol 11.5%
2-pyrrolidone 2.0%
2,2,4-Trimethyl 1,3-pentanediol 2.0%
Proxel LV 0.2%
1N-NaOH 0.5%
Ion exchange water

(Example 8)
(Adjustment of ink 12-C)
Cyan dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COH, B = (CH ₂ ) ₂ , Rf = CF ₃ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 8.0%
1,3-butanediol 13.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 12-M)
Magenta dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COH, B = (CH ₂ ) ₂ , Rf = CF ₃ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 7.5%
1,6-hexanediol 15.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 12-Y)
Yellow dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 8.0%
1,3-butanediol 13.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 12-K)
Black dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 7.5%
1,6-hexanediol 15.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

Example 9
(Adjustment of ink 13-C)
Cyan dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 5.0%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 30.0%
(R = CH ₃ )
Glycerol 7.0%
1,6-hexanediol 2.0%
1,5-pentanediol 5.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 13-M)
Magenta dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 5.0%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 30.0%
(R = CH ₃ )
Glycerin 8.0%
1,3-butanediol 7.5%
2-pyrrolidone 2.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 13-Y)
Yellow dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 5.0%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 30.0%
(R = CH ₃ )
Glycerol 7.0%
1,3-butanediol 7.5%
2-pyrrolidone 2.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 13-K)
Black dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 5.0%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 30.0%
(R = CH ₃ )
Glycerin 8.0%
1,6-hexanediol 2.0%
1,5-pentanediol 5.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Example 10)
(Adjustment of ink 14-C)
Cyan dispersion 15.0%
Fluorosurfactant with structural formula (I) (OMNOVA Polyfox) 1.5%
(A = COH, B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ )
Glycerin 18.0%
Ethylene glycol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 14-M)
Magenta dispersion 15.0%
Fluorosurfactant with structural formula (I) (OMNOVA Polyfox) 1.5%
(A = COH, B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ )
Glycerin 18.0%
Ethylene glycol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 14-Y)
Yellow dispersion 15.0%
Fluorosurfactant with structural formula (I) (OMNOVA Polyfox) 1.5%
(A = COH, B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ )
Glycerin 15.0%
Ethylene glycol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 14-K)
Black dispersion 15.0%
Fluorosurfactant with structural formula (I) (OMNOVA Polyfox) 1.5%
(A = COH, B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 45.0%
(R = CH ₃ )
Glycerin 15.0%
Ethylene glycol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Example 11)
(Adjustment of ink 15-C)
Cyan dispersion 15.0%
Fluorosurfactant of structural formula (I) (Polyfox manufactured by OMNOVA) 1.0%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = CF ₃ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 10.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 15.0%
3-methyl-1,3-butanediol 20.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 15-M)
Magenta dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = CF ₃ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 15.0%
Ethylene glycol 20.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 15-Y)
Yellow dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = CF ₃ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 20.0%
3-methyl-1,3-butanediol 20.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 15-K)
Black dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = CF ₃ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 20.0%
2-pyrrolidone 1.0%
Ethylene glycol 20.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Comparative Example 6)
(Adjustment of ink 16-C)
Cyan dispersion 15.0%
Surfactant (ECTD-6NEX manufactured by Nikko Chemicals) 1.0%
Glycerin 8.0%
3-methyl-1,3-butanediol 14.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 16-M)
Magenta dispersion 15.0%
Surfactant (ECTD-6NEX manufactured by Nikko Chemicals) 1.0%
Glycerin 7.5%
3-methyl-1,3-butanediol 14.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 16-Y)
Yellow dispersion 15.0%
Surfactant (ECTD-6NEX manufactured by Nikko Chemicals) 1.0%
Glycerin 8.0%
3-methyl-1,3-butanediol 14.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 16-K)
Black dispersion 15.0%
Surfactant (ECTD-6NEX manufactured by Nikko Chemicals) 1.0%
Glycerin 7.5%
3-methyl-1,3-butanediol 14.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Comparative Example 7)
(Adjustment of ink 17-C)
Cyan dispersion 15.0%
Surfactant (Nippon Yushi Co., Ltd. Unisafe A-LY) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 13.0%
1,5-pentanediol 8.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 17-M)
Magenta dispersion 15.0%
Cyan dispersion 15.0%
Surfactant (Nippon Yushi Co., Ltd. Unisafe A-LY) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 13.0%
1,6-hexanediol 15.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 17-Y)
Yellow dispersion 15.0%
Surfactant (Nissan Anon BL-SF, manufactured by NOF Corporation) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 12.0%
1,6-hexanediol 8.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 17-K)
Black dispersion 15.0%
Surfactant (Nissan Anon BL-SF, manufactured by NOF Corporation) 0.5%
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 15.0%
(R = CH ₃ )
Glycerin 13.0%
1,6-hexanediol 8.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Comparative Example 8)
(Adjustment of ink 18-C)
Cyan dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Glycerin 10.0%
Ethylene glycol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 18-M)
Magenta dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Glycerin 10.0%
Ethylene glycol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 18-Y)
Yellow dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Glycerin 10.0%
1,5-pentanediol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 18-K)
Black dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Glycerin 10.0%
1,5-pentanediol 10.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Example 12)
(Adjustment of ink 19-C)
Cyan dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 5.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 8.0%
3-methyl-1,3-butanediol 14.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 19-M)
Magenta dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 5.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 7.5%
3-methyl-1,3-butanediol 14.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 19-Y)
Yellow dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 5.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 8.0%
1,5-pentanediol 15.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 19-K)
Black dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 0.005%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 2, Y = 2, Z = 10)
Amide compound of structural formula (II) (Examide: B100 manufactured by Idemitsu Kosan Co., Ltd.) 5.0%
(R = CH ₃ (CH ₂ ) ₃ )
Glycerin 7.5%
1,5-pentanediol 15.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Example 13)
(Adjustment of ink 20-C)
Cyan dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 13.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 20.0%
(R = CH ₃ )
Glycerol 7.0%
3-methyl-1,3-butanediol 10.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 20-M)
Magenta dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 13.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 20.0%
(R = CH ₃ )
Glycerol 7.0%
3-methyl-1,3-butanediol 10.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 20-Y)
Yellow dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox)) 13.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 20.0%
(R = CH ₃ )
Glycerol 7.0%
3-methyl-1,3-butanediol 10.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

(Adjustment of ink 20-K)
Black dispersion 15.0%
Fluorosurfactant of structural formula (I) (OMNOVA Polyfox) 13.5%
(A = COCF ₃ , B = (CH ₂ ) ₂ , Rf = C ₂ F ₅ , X = 4, Y = 4, Z = 20)
Amide compound of structural formula (II) (Examide: M100 manufactured by Idemitsu Kosan Co., Ltd.) 20.0%
(R = CH ₃ )
Glycerol 7.0%
3-methyl-1,3-butanediol 10.0%
2-pyrrolidone 1.0%
Proxel LV 0.25%
2-ethyl 1,3-hexanediol 2.0%
1N-NaOH 0.5%
Ion exchange water

For each color of the inks of Examples 1 to 13 and Comparative Examples 1 to 8, the saturation, foaming property, ejection stability, solid portion uniformity, and bleed were evaluated by the following methods.
About Examples 8-13 and Comparative Examples 6-8, the surface tension and the viscosity were also evaluated.
The evaluation results are shown in Tables 1 and 2.

<Evaluation of color development (saturation)>
Using a printer (Ricoh Gxe 3300), printing was performed on My Paper (manufactured by NBS Ricoh Co., Ltd.), and the printing pattern was printed with 100% duty for each of the yellow, magenta, and cyan color inks of the present invention.
The printing conditions were 600 dpi and one-pass printing.
After printing and drying, in the above ink set, each single-color solid image portion of yellow, magenta, and cyan is measured with a reflective color spectrometric densitometer (manufactured by X-Rite), and the color difference display method defined by CIE is used. The coordinates of the L ^* a ^* b ^* color system were determined, and the saturation C ^* for each color was determined. The higher the saturation, the better the color.
The saturation C ^* is defined by the following mathematical formula (1).
C ^* = [(a ^* ) ² + (b ^* ) ² ] ^1/2 Formula (1)

<Foamability evaluation test>
In an environment of 25 ° C., 10 ml of the prepared recording ink is put into a 100 ml graduated cylinder, and air of a constant pressure is injected until the volume of the recording ink and bubbles reaches 100 ml. The volume of the recording ink and bubbles is increased. When 100 ml was reached, the air injection was stopped. The time from the start of air injection to the stop of air injection was defined as the foaming time, and the following criteria were used for evaluation.

A: Foaming time 15 seconds or more B: Foaming time 10 seconds or more and less than 15 seconds C: Foaming time 5 seconds or more and less than 10 seconds D: Foaming time less than 5 seconds The above is the allowable range.

<Discharge stability evaluation>
Using a printer (IPSIO GXe3300 manufactured by Ricoh), print on My Paper (manufactured by NBS Ricoh Co., Ltd.). The inks of yellow, magenta, cyan, and black according to the present invention were printed at 100% duty.
The printing conditions were one-pass printing with a recording density of 600 dpi.
In addition, after the color development evaluation was performed with the ink sets in the above examples and comparative examples, the ejection stability was evaluated. As intermittent printing, when the above chart is printed continuously for 20 sheets, it is put into a resting state in which no discharge is performed for 20 minutes, this is repeated 50 times, and after a total of 1000 sheets are printed, the same chart is printed again. The presence or absence of streaks, white spots and jet disturbance in the 5% chart solid part was visually evaluated.

AA: There are no streaks, white spots, or jet disturbance in the solid part.
A: On the 1st scan, streaks, white spots, and jet disturbances of 1ch or more are observed.
B: On the first scan, some streaks, white spots, and jet disturbance are observed in the solid portion.
C: On the first scan, streaks, white spots, and jet disturbance are observed.
D: Streaks, white spots, and jet turbulence are observed throughout the solid portion.
In these standards, A or more is set as an allowable range.

<Uniformity of solid printing part (solid uniformity)>
Using a printer (IPSio GXe3300 manufactured by Ricoh), printing was performed on My Paper (manufactured by NBS Ricoh Co., Ltd.), and the printing pattern was printed with 100% duty for each of the yellow, magenta, cyan and black inks of the present invention. .
The uniformity of the obtained solid image was visually observed and evaluated.

AA: A solid image excellent in uniformity.
A: Almost no spots are observed on the solid part.
B: Some spots are observed in the solid part.
C: Spots are observed throughout the solid portion.
In these standards, A or more is set as an allowable range.

<Bleed evaluation between black and color>
Printing was performed on My Paper (manufactured by NBS Ricoh Co., Ltd.) using a printer (IPSio GXe3300 manufactured by Ricoh). As a printing pattern, each color ink was printed at 100% duty.
By printing black ink characters in each color ink solid image portion obtained, the bleed between the color ink and the black ink was visually evaluated according to the following criteria.
Further, the color ink and the black ink were evaluated in combination as shown in Table 3 for the bleed between black and color.

The recording density of printing conditions was 600 dpi, and one-pass printing was used.
AAA: There is no occurrence of bleeding, black characters can be clearly recognized, and no blur is observed visually.
AA: Bleed does not occur, black characters can be clearly recognized, and no blur is observed visually.
A: There is no bleed and black characters can be clearly recognized.
B: Slight bleeding occurs and black characters blur slightly.
C: Bleed occurs and it is difficult to recognize black characters.
In these standards, A or more is set as an allowable range.

<Surface tension>
The surface tension (mN / m) was measured using a fully automatic surface tension meter (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.).

<Viscosity>
The viscosity (mPa · s) was measured using an R-type viscometer (RC-500, manufactured by Toki Sangyo Co., Ltd.).

(1) Evaluation of saturation: From the comparison between the inks of Examples 1 to 7 and the inks of Comparative Examples 1, 3, and 5, the fluorine-based surfactant represented by the structural formula (I) is added. It can be seen that the saturation increases.

(2) Evaluation of saturation: From the comparison between the inks of Examples 1 to 7 and the inks of Comparative Examples 2 and 4, even if the fluorine-based surfactant represented by the structural formula (I) was added, It can be seen that when the amide compound is not included and when the amide compound represented by the structural formula (II) is not included, the saturation increasing effect is low.

(3) Evaluation of foaming property: From the comparison between the ink adjustment examples of Examples 1 to 7 and the ink adjustment examples of Comparative Examples 1 to 5, the fluorine-based surfactant represented by the structural formula (I) It can be seen that by adding the amide compound represented by the structural formula (II), the foaming property is suppressed, the ink does not easily foam, and the ejection stability can be secured.

(5) Evaluation of solid uniformity: From the comparison between the inks of Examples 1 to 7 and the inks of Comparative Examples 1 to 5, the fluorine-based surfactant represented by the structural formula (I) and the structural formula It can be seen that the uniformity of the solid print portion is increased by using the amide compound represented by (II) together.

(6) From the comparison between the ink of Example 1 and the ink of Example 6, in order to suppress foaming and improve ejection stability, the fluorine-based surface activity represented by the structural formula (I) It can be seen that the addition amount of the agent is preferably 10 wt% or less.
Further, it can be seen from the comparison between the ink of Example 1 and the ink of Example 4 that the addition amount of the fluorosurfactant represented by the structural formula (I) is preferably 0.01 wt% or more.
From a comparison between the ink of Example 1 and the ink of Example 5, it can be seen that the addition amount of the amide compound represented by the structural formula (II) is preferably 10 wt% or more.
From comparison between Example 3 and Example 7, it can be seen that the addition amount of the amide compound represented by the structural formula (II) is preferably 45.0 wt% or less.

(7) Bleed evaluation: According to a comparison between Examples 1 to 7 and Comparative Examples 1 to 5, the fluorine-based surfactant represented by the structural formula (I) was added to the color ink and the black ink. By doing so, the vehicle penetrates quickly, and the color material remains uniformly on the paper surface, so that bleeding can be suppressed. Further, from Reference Examples 1 and 2, the ink containing the fluorinated surfactant represented by the structural formula (I) and the amide compound represented by the structural formula (II) is only a color ink or a black ink only. In this case, it can be seen that bleeding occurs.

(8) Evaluation of chroma: According to the comparison between Examples 8 to 11 and the ink adjustment examples of Comparative Examples 6 and 7, the specific fluorine-based surfactant of the structural formula (I) is added. This shows that the saturation increases.

(9) Evaluation of saturation: According to the comparison between Examples 8 to 11 and Example 12, even if the specific fluorine-based surfactant of the structural formula (I) is added, it does not reach the required amount. In this case, the saturation increasing effect is low.

(10) Confirmation of foaming property: According to the comparison between the ink adjustment examples of Examples 8 to 11 and the ink adjustment examples of Comparative Examples 6 to 8, the fluorine-based surfactant of the structural formula (I) was added. By doing so, it can be seen that the foaming property is suppressed and the ink is less likely to foam.

(11) Confirmation of foaming property: According to a comparison between the ink adjustment example of Example 8 and the ink adjustment example of Example 13, the amount of addition of the fluorosurfactant of the structural formula (I) is too large. It turns out that foaming property will become large.

(12) Evaluation of ejection stability: According to a comparison between Examples 8 to 11 and Comparative Examples 6 and 7, the foaming of the ink was achieved by adding the fluorine-based surfactant of the structural formula (I). Therefore, it is understood that the foaming property in the head is suppressed and bubbles are hardly generated, and the ejection stability is ensured.

(13) Evaluation of ejection stability: According to a comparison between the ink adjustment example of Example 8 and the ink adjustment example of Example 13, the addition amount of the fluorine-based surfactant of the structural formula (I) is large. If the amount is too large, the foaming property becomes large, and it is understood that the discharge stability cannot be secured.

(14) Evaluation of color bleed: According to the comparison between Examples 8 to 11 and Comparative Examples 6 to 8, the fluorine-based surfactant of the structural formula (I) is added to the color ink and the black ink. Thus, it can be seen that bleed can be suppressed because the vehicle penetrates quickly and the colorant remains uniformly on the paper surface.

(15) Evaluation of color bleed: According to a comparison between Example 8 and Reference Examples 3 and 4, the color ink or black ink can be obtained even if the fluorine-based surfactant of the structural formula (I) is added. It can be seen that the effect is small when added only to the color ink, and the bleed is deteriorated unless added to both the color ink and the black ink.

(16) Evaluation of solid uniformity: According to the comparison between Examples 8 to 11 and Examples 12 and 13 and Comparative Examples 6 to 8, the fluorine-based surfactant of the structural formula (I) and the structure It can be seen that by using the amide compound of the formula (II) in combination, the uniformity of the solid print portion is increased.

1b Common liquid chamber 2a Fluid resistance section 2b Pressurized liquid chamber 2c Communication port 3a Nozzle 5f Drive section 5g Support section (non-drive section)
6a Convex portion 6b Diaphragm portion 6c Ink inlet 10 Frame 20 Flow path plate 30 Nozzle plate 40 Base 50 Multilayer piezoelectric element 60 Vibration plate 70 Adhesive layer 131 Guide rod 133 Carriage 134 Recording head 141 Paper stacking portion (pressure plate)
142 Paper 157 Transport roller 158 Tension roller 200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge case

JP 2010-163533 A

Claims (8)

An inkjet recording ink containing at least water, a water-soluble organic solvent, and a colorant, comprising: a fluorine-based surfactant represented by the following structural formula (I); and an amide compound represented by the following structural formula (II): An ink for ink-jet recording, comprising:
(In Structural Formula (I), A represents H or —CO—R ₁ , R ₁ represents H or CF ₃ (CF ₂ ) m, and m represents an integer of 0 to 3.
B is table an alkylene group having 1 to 3 carbon atoms which may have a substituent, the substituent is an alkyl group having 1 or 2 carbon atoms.
Rf _represents a _{CF 3 (CF 2) n,} n is an integer of 0 to 3.
X and Y represent an integer of 1 to 4, and Z represents an integer of 1 to 25. )
(In Structural Formula (II), R represents CH ₃ (CH ₂ ) m, and m represents an integer of 0 to 3).   2. The ink for ink jet recording according to claim 1, further comprising 0.01 wt% or more and 10.0 wt% or less of the fluorine-based surfactant represented by the structural formula (I).   3. The ink for ink jet recording according to claim 1, wherein the amide compound represented by the structural formula (II) is contained in an amount of 10.0 wt% to 45.0 wt%.   The ink for inkjet recording according to any one of claims 1 to 3, wherein the colorant is polymer fine particles containing a colorant.   An ink set for ink jet recording comprising a black ink and a color ink, wherein the black ink and the color ink are inks according to any one of claims 1 to 4.   An ink cartridge comprising the ink according to claim 1 contained in a container. An ink jet recording apparatus having ink flying means for forming an image on a recording member by applying energy to the ink and causing the ink to fly, wherein the ink is the ink according to any one of claims 1 to 4. Louis to the ink jet recording apparatus.   A recorded matter comprising an image formed by flying the ink according to claim 1 onto a recording member.