JP6519675B2 - Ink jet ink, ink cartridge, ink jet recording apparatus, and method of producing ink recorded matter - Google Patents

Description

The present invention relates to an inkjet ink, an ink cartridge using the ink, an inkjet recording apparatus, and a method of producing an ink recorded matter.

The inkjet recording method is easy to process in full color compared to other recording methods, so full color is easy, and there is an advantage that a high-resolution image can be obtained even with a device having a simple configuration. Dye-based inks in which various water-soluble dyes are dissolved in water or a mixture of water and a water-soluble moisturizing agent are used as ink- jet inks.
In recent years, the need for speeding up has been increasing, but when aqueous ink is used for printing on plain paper, retransferability of the ink after printing has become a problem. The retransferability of ink means that when a large amount of ink remains on the surface of the recording medium after the ink is attached to the recording medium, the recording medium is conveyed and the printing surface is provided on the conveyance rollers and spurs. When contacted, the ink on the surface of the recording medium adheres to the roller, and the image and the apparatus are soiled.

Various methods can be considered to suppress retransfer of the ink, but it is possible to make the ink easy to evaporate and dry, to make it easy to penetrate the recording medium, and to improve the drying property and penetration drying of the recording medium itself. It is possible to consider a method of making the apparatus, and a method of providing a drying apparatus to the apparatus.
Aqueous face Ryoi link, in printing on plain paper, less bleeding, high image density, there is a merit such strike-through is small. However, when the evaporation drying property of the ink is improved, the ink viscosity is increased because the pigment is concentrated by evaporation when the ink jet head is at rest, and intermittent discharge stability (discharge reliability after head rest) is deteriorated. There is a problem of
In addition, although the ink containing 3-methoxy- 3-methyl butanol is disclosed by patent documents 1-2, the retransfer property is not made into the subject in any, and 3-methoxy- 1 used by this invention There is no mention or suggestion of the relationship between butanol and retranscription.

The present invention has been made in view of the above situation, to prevent the re-transfer of the ink, and to provide an ink jet ink which is excellent in reliability and storage stability of the ink jet head after cessation (intermittent ejection stability) To aim.

As a result of intensive studies, the present inventors have found that when 3-methoxy-1-butanol is contained in an inkjet ink, it is effective in suppressing retransfer of the ink and in intermittent discharge stability.
That is, the said subject is solved by invention of following 1).
1) An inkjet ink comprising at least water, a water-soluble organic substance, a colorant and a surfactant , wherein the water-soluble organic substance satisfies the following requirements.
(A) The water-soluble organic substance is contained in an amount of 30 to 50% by mass of the whole ink.
(B) As a water-soluble organic substance, 8% by mass or more of 3-methoxy-1-butanol is contained in the entire ink .
(C) As a water-soluble organic substance, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 3-methyl-3-hydroxymethyl oxetane, The ink contains at least one selected from 1,2-propanediol and 1,3-propanediol at 1% by mass or more of the entire ink.

According to the present invention, it is possible to provide an inkjet ink that prevents retransfer of the ink and is excellent in the reliability and storability (intermittent ejection stability) of the inkjet head after pausing.

FIG. 2 is a schematic view showing an example of an ink cartridge. FIG. 5 is a schematic view showing a modification of the ink cartridge of FIG. 1; FIG. 3 is a perspective view of the ink jet recording apparatus in a state in which the cover of the ink cartridge loading unit is opened. FIG. 4 is a cross-sectional view for explaining the overall configuration of the inkjet recording apparatus of FIG. 3. FIG. 2 is a schematic enlarged view showing an inkjet head of the inkjet recording apparatus.

Hereinafter, the present invention 1) will be described in detail, but the embodiments of the present invention 1) include the following 2) to 8), which will be described together.
2) The inkjet ink according to 1), which contains 15 to 40% by mass of the 3-methoxy-1-butanol based on the whole ink.
3) The ink for inkjet according to 1) or 2), wherein the content of the water-soluble organic substance in (c) is 5 to 40% by mass of the whole ink.
4) The inkjet ink according to any one of 1) to 3), which contains at least one of an acrylic silicone resin and a polyurethane resin.
5) The inkjet ink according to any one of 1) to 4), which contains at least one selected from a silicone surfactant and a fluorosurfactant.
6) An ink cartridge containing the ink for ink jet recording according to any one of 1) to 5) in a container.
7) An ink jet recording apparatus equipped with the ink cartridge described in 6).
8) A method for producing an ink recorded matter, wherein an image is formed on the recording medium with the ink for inkjet according to any one of 1) to 5).

( Ink jet ink)
The inkjet ink of the present invention contains at least water, a water-soluble organic substance, and a colorant, and further contains other components such as an antifoaming agent and a water-dispersible resin, as required.
The above water-soluble organic substance refers to an organic component which is soluble in water and dissolved in the ink at 15 ° C. to 35 ° C. Specifically, a water-soluble humectant, a water-soluble polymer, It refers to surfactants, penetrants, rust inhibitors, fungicides and dyes. Organic pigments, inorganic pigments, resin compounds and the like dispersed in the ink without being dissolved in the aqueous phase are not included in the water-soluble organic substance.
The content of the water-soluble organic substance in the ink is 30% to 50% by mass from the viewpoint of curling suppression and ejection reliability.

<Moisturizer>
In the present invention, a humectant is a highly hygroscopic organic substance that dissolves in water, and when added to an ink, refers to a water-soluble organic substance that remains on the surface of the ink or recording medium and has the effect of suppressing evaporation of water.
As a result of various investigations on the moisturizing agent, it was found that the ink containing 3-methoxy-1-butanol had a problem in storage stability (intermittent ejection stability). However, further studies as a result, in combination with 3-methoxy-1-butanol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,2-butanediol, 2, 3-butanediol An ink containing at least one selected from 3-methyl-3-hydroxymethyl oxetane, 1,2-propanediol, and 1,3-propanediol has inhibition of retransfer of the ink and storage stability (intermittent ejection stability ) Was found to be excellent.
The content of 3-methoxy-1-butanol is preferably 10% by mass or more, more preferably 15 to 48% by mass, and particularly preferably 15 to 40% by mass, based on the whole ink. It is further preferable because it is further excellent in the properties (intermittent discharge stability).
The content of the compound group used in combination with 3-methoxy-1-butanol is 1% by mass or more of the entire ink, and preferably 5 to 40% by mass.

  Examples of other humectants include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, Specific examples thereof include saccharides such as 1,2,3-butanetriol (bp 175 ° C./33 hPa), 1,2,4-butanetriol (bp 190-191 ° C./24 hPa), glycerin (bp 290 ° C.), Diglycerin (bp 270 ° C./20 hPa), triethylene glycol (bp 285 ° C.), tetraethylene glycol (bp 324-330 ° C.), diethylene glycol (bp 245 ° C.), β-methoxy-N, N-dimethylpropionamide (bp 216 ° C.), 2 -Pyrrolidone (bp 245 ° C), 1 3-dimethyl-2-imidazolidinone (bp225 ℃), and the like.

Besides the above, the following can be used.
Isobutyl diglycol (bp 220 ° C.), tripropylene glycol monomethyl ether (bp 242 ° C.), 2- (2-isopropyloxyethoxy) ethanol (bp 207 ° C.), isopropyl glycol (bp 142 ° C.), diethyl diglycol (bp 189 ° C.), propyl propylene Glycol (bp 150 ° C.), tributyl citrate (bp 234 ° C.), propyl propylene diglycol (bp 220 ° C.), butyl propylene glycol (bp 170 ° C.), butyl propylene diglycol (bp 212 ° C.), methyl propylene glycol acetate (bp 146 ° C.), tri Ethylene glycol dimethyl ether (bp 216 ° C.), N, N-dimethyl acrylamide (bp 171 ° C.), N, N-diethyl acrylamide (bp 56 ° C. / mmHg), dipropylene glycol (bp 232 ° C.), 1,5-pentanediol (bp 242 ° C.), propylene glycol (bp 187 ° C.), 2-methyl-2,4-pentanediol (bp 197 ° C.), ethylene glycol (bp 196-198) ° C), tripropylene glycol (bp 267 ° C), hexylene glycol (bp 197 ° C), polyethylene glycol (viscous liquid to solid), polypropylene glycol (bp 187 ° C), 1,6-hexanediol (bp 253-260 ° C), 1 , 2,6-hexanetriol (bp 178 ° C), and the like.

Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether (bp 135 ° C.), ethylene glycol monobutyl ether (bp 171 ° C.), diethylene glycol monomethyl ether (bp 194 ° C.), diethylene glycol monoethyl ether (bp 197 ° C.), diethylene glycol mono Examples include butyl ether (bp 231 ° C.), ethylene glycol mono-2-ethylhexyl ether (bp 229 ° C.), propylene glycol monoethyl ether (bp 132 ° C.) and the like.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether (bp 237 ° C.), ethylene glycol monobenzyl ether and the like.

As the nitrogen-containing heterocyclic compound, for example, N-methyl-2-pyrrolidone (bp 202 ° C.), 1,3-dimethyl-2-imidazolidinone (bp 226 ° C.), ε-caprolactam (bp 270 ° C.), γ-butyrolactone (Bp 204-205 ° C.) and the like.
Examples of the amides include formamide (bp 210 ° C.), N-methyl formamide (bp 199-201 ° C.), N, N-dimethylformamide (bp 153 ° C.), N, N-diethyl formamide (bp 176-177 ° C.), etc. It can be mentioned.
Examples of the amines include monoethanolamine (bp 170 ° C.), diethanolamine (bp 268 ° C.), triethanolamine (bp 360 ° C.), N, N-dimethylmonoethanolamine (bp 139 ° C.), N-methyldiethanolamine (bp 243 ° C.) And N-methyl ethanolamine (bp 159 ° C.), N-phenyl ethanolamine (bp 282-287 ° C.), 3-aminopropyldiethylamine (bp 169 ° C.) and the like.
Examples of the sulfur-containing compounds include dimethyl sulfoxide (bp 139 ° C.), sulfolane (bp 285 ° C.), thiodiglycol (bp 282 ° C.) and the like.

As another solid water-soluble organic substance, saccharides etc. are preferable.
Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides and the like. Specifically, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like can be mentioned. Here, polysaccharides mean sugars in a broad sense, and are used to mean substances including substances widely present in the natural world such as α-cyclodextrin and cellulose. Further, derivatives of these saccharides are represented by reducing saccharides of the aforementioned saccharides {eg, sugar alcohol [general formula: HOCH ₂ (CHOH) _n CH ₂ OH (wherein n represents an integer of 2 to 5)] . }, Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thioacids and the like. Among these, sugar alcohols are preferable, and specific examples include maltitol, sorbite and the like.

<Colorant>
Dyes and pigments are used as colorants.
Examples of the pigment include organic pigments such as azo type, phthalocyanine type, anthraquinone type, dioxazine type, indigo type, thioindigo type, thioindigo type, perylene type, isoindolinone type, aniline black, azomethine type, rhodamine B lake pigment, carbon black, oxidized Inorganic pigments such as iron, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chromium yellow, metal powder and the like can be mentioned.
Specific examples of black pigments include furnace black, lamp black, acetylene black, carbon black such as channel black (CI pigment black 7), copper oxide, iron oxide (CI pigment black 11) And metals such as titanium oxide, and organic pigments such as aniline black (C.I. 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, 12, 17 (brilliant first scarlet), 23, 31, 38, 48: 1 [permanent tread 2B (Ba)], 48: 2 [permanent tread 2B (Ca)], 48: 3 [Permanentred 2B (Sr)], 48: 4 [Permanentred 2B (Mn)], 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (rhodamine 6G lake), 83, 88, 92, 97, 101 (bengal), 104, 105, 106, 108 (cadmium red), 112, 112, 114, 122 (dimethyl quinacridone), 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.
Further, specific examples of the intermediate color pigment include C.I. 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.

Among the above pigments, carbon black is particularly preferable as the black pigment, and carbon black produced by the furnace method or the channel method has a primary particle diameter of 15 to 40 nm and a specific surface area of 50 to 300 m ² / g by BET adsorption method. A DBP oil absorption of 40 to 150 mL / 100 g, a volatile content of 0.5 to 10% by mass, and a pH of 2 to 9 are used, and in particular, acidic carbon black having a pH of 6 or less is preferable because of high concentration.
As the color pigments, especially pigment yellow 13, 17, 55, 74, 93, 97, 98, 110, 128, 139, 147, 150, 151, 154, 155, 180, 185, pigment red 122, 202, 209, Pigment Violet 19 and Pigment Blue 15: 3 and 15: 4 are preferable.

The volume average particle size of the pigment is not particularly limited, but is preferably 20 to 200 nm, more preferably 30 to 150 nm, and still more preferably 50 to 100 nm. The volume average particle diameter of the pigment in the present invention is particles using a sample diluted with pure water so that the pigment concentration in the measurement sample is 0.01 mass% using Microtrac UPA-150 manufactured by Nikkiso Co., Ltd. It is a 50% volume average particle diameter (D50) measured at 23 ° C., using a refractive index of 1.51, a particle density of 1.4 g / cm ³ , and a pure water parameter as a solvent parameter.
The pigment concentration in the ink is preferably 2 to 15% by mass, more preferably 3 to 12% by mass, and still more preferably 4 to 10% by mass.

In order to disperse the pigment in the ink, a method of introducing a hydrophilic functional group on the pigment surface to make it a self-dispersible pigment, a method of dispersing using a dispersing resin, a method of covering the pigment surface with a resin and dispersing A method, a method of dispersing using a surfactant, etc. may be mentioned.
Specifically, it is possible to use a self-dispersing pigment or the like in which a functional group such as a sulfone group or a carboxyl group is added to the surface of a pigment (for example, carbon) to be dispersed in water.
In addition, the pigment may be contained in microcapsules, and the pigment may be dispersed in water. This can be reworded as resin particles containing pigment particles. In this case, it is not necessary for all the pigments to be blended in the ink to be encapsulated or adsorbed in the resin particles, and the pigments may be dispersed in the ink as long as the effects of the present invention are not impaired.
In the case of a method of dispersing using a surfactant, a nonionic or anionic surfactant-based dispersant can be appropriately selected and used according to the pigment type or the ink formulation.
The addition amount of the surfactant is preferably about 10 to 50% by mass with respect to the pigment.

  As dyes, among dyes classified into acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes in color index, dyes having excellent water resistance and light resistance are used. These dyes may be used as a mixture of two or more kinds, and may be used as mixed with other colorants such as a pigment as required. However, it is necessary to add other coloring agents in the range which does not inhibit the effect of the present invention.

Specific examples of the dye include those shown in the following (a) to (d).
(A) Acid dyes and food dyes C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142
C. I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254 , 289
C. I. Acid Blue 9, 29, 45, 92, 249
C. I. Acid Black 1, 2, 7, 24, 26, 94
C. I. Food yellow 3, 4
C. I. Food red 7, 9, 14
C. I. Food black 1, 2

(B) Direct dye C.I. I. Direct Yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, 144
C. I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227
C. I. Direct Orange 26, 29, 62, 102
C. I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202
C. I. Direct Black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171

(C) Basic dye C.I. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65 , 67, 70, 73, 77, 87, 91
C. I. Basic red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70 , 73, 78, 82, 102, 104, 109, 112
C. I. Basic Blue 1, 3, 5, 7, 9, 21, 22, 22, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78, 89, 92, 93 , 105, 117, 120, 122, 124, 129, 137, 141, 147, 155
C. I. Basic Black 2, 8

(D) reactive dyes C.I. I. Reactive black 3, 4, 7, 11, 12, 17
C. I. Reactive yellow 1, 5, 11, 13, 14, 20, 21, 22, 25, 40, 47, 51, 55, 65, 67
C. I. Reactive red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97
C. I. Reactive Blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95

<Resin emulsion>
It is preferable to add a resin emulsion to the ink of the present invention mainly for the purpose of improving the image abrasion resistance and the storage stability when using a pigment as the colorant. The improvement in image rub resistance, an acrylic resin, a styrene - acrylic resin, acrylic silicon cone resins, emulsion preferably fluorine resin, storage stability polyurethane resin in improving, acrylic resin, styrene - emulsion of acrylic resin preferable. However, since there are few resin emulsions that can simultaneously achieve the improvement of the image abrasion resistance and the storage stability, two types of resin emulsions may be used in combination. As these resin emulsions, commercially available ones can be appropriately selected and used as needed.
Next, representative resin emulsions will be exemplified.

(1) Urethane Resin Emulsion The urethane resin of the urethane resin emulsion is obtained by polymerizing polyisocyanate and polyether polyol, polyester polyol, polylactone polyol, polycarbonate polyol or the like. As polyisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate Aliphatic diisocyanate compounds such as xylylene diisocyanate, aromatic aliphatic diisocyanate compounds such as tetramethylxylene diisocyanate, toluylene diisocyanate, aromatic diisocyanate compounds such as phenylmethane diisocyanate, modified products of these diisocyanates (carbodiimide, uretdione, uretimine) Contained metamorphic substances etc.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
Examples of polyester polyols include polyethylene adipate, polybutylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene / butylene adipate, polyneopentyl / hexyl adipate and the like.
Examples of polylactone polyols include polycaprolactone diol, polyomega hydroxy caproic acid polyol and the like.
Examples of polycarbonate polyols include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol such as diethylene glycol, triethylene glycol and tetraethylene glycol, phosgene and diaryl carbonate such as diphenyl carbonate Also, known products such as products obtained from the reaction with cyclic carbonates such as ethylene carbonate and propylene carbonate are included.

(2) Acrylic Resin Emulsion The acrylic resin of the acrylic resin emulsion is obtained by polymerizing acrylic monomers alone or by copolymerizing with other monomers.
As acrylic monomers, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-acrylate Pentyl, isopentyl acrylate, neopentyl acrylate, 3- (methyl) butyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate , Dodecyl acrylate, phenyl acrylate, methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, Isopentyl methacrylate, neopentyl methacrylate, 3- (methyl) butyl methacrylate, 2-ethylhexyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, acrylic Acids, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like can be mentioned.

  Other monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, p Vinyl aromatic hydrocarbons such as chlorostyrene and divinylbenzene, unsaturated carboxylic acids such as itaconic acid and maleic acid, N-substituted maleimides, maleic anhydride, vinyl ketone, vinyl acetate, vinylidene chloride and the like.

  The above-described resin emulsion exhibits further excellent water dispersibility by introducing an ionic group into the resin. As such an ionic group, a sulfonic acid group, a carboxylic acid group, a sulfuric acid group, a phosphoric acid group, a phosphonic acid group and a phosphinic acid group, or an alkali metal base thereof, an alkaline earth metal base, an ammonium base, And tertiary amine bases and the like. Among them, alkali metal carboxylate bases, ammonium carboxylate bases, alkali metal sulfonate bases and ammonium sulfonate bases are preferable, and alkali metal sulfonate bases and ammonium sulfonate bases are particularly preferable in view of water dispersion stability. The introduction of the ionic group is carried out by adding a monomer having an ionic group at the time of resin synthesis. Preferred as salts are Li, K or Na salts.

<Surfactant>
The ink of the present invention the addition of interfacial active agent.
As the surfactant, one having a low surface tension and a high permeability and a high leveling property is preferable, without impairing the dispersion stability depending on the kind of colorant and the combination of the humectant, and an anionic surfactant and a nonionic surfactant And at least one selected from silicone surfactants and fluoro surfactants. Among these, silicone surfactants and fluorine surfactants are particularly preferable.
These surfactants may be used alone or in combination of two or more.

The fluorinated surfactant preferably has 2 to 16 carbon atoms substituted with fluorine, and more preferably 4 to 16 carbon atoms. When the number of carbon atoms substituted by fluorine is 2 to 16, the ability to reduce the surface tension is high, and the storage stability is also good.
Examples of the fluorine-based surfactant include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkyl phosphoric acid ester compounds, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl ether groups as side chains. And polyoxyalkylene ether polymer compounds, and the like. Among these, polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in a side chain are particularly preferable because they have low foamability.
More preferable are fluorine-based surfactants represented by the following general formula.
_{CF 3 CF 2 (CF 2 CF} 2) m-CH 2 CH 2 O (CH 2 CH 2 O) nH
In said formula, m is an integer of 0-10, n represents the integer of 1-40.

Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonic acid salts.
Examples of the perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts.
Examples of the perfluoroalkyl phosphoric acid ester compounds include perfluoroalkyl phosphoric acid esters and salts of perfluoroalkyl phosphoric acid esters.
As the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain, a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, a polyoxyalkylene ether having a perfluoroalkyl ether group in the side chain A sulfuric acid ester salt of a polymer, a salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and the like can be mentioned.
As counter ions of salts in these fluorochemical surfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH ₃ ) and the like.

As the fluorine-based surfactant, one appropriately synthesized or a commercially available product may be used.
Examples of the commercially available product include Surfron S-111, S-112, S-113, S-121, S-131, S-132, S-141 and S-145 (all manufactured by Asahi Glass Co., Ltd.); -93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all are manufactured by Sumitomo 3M Limited); Megafuck F-470, F-1405, F -474, F-444 (all are manufactured by Dainippon Ink and Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all are DuPont) FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all from Neos), Polyfok PF-151N (manufactured by OMNOVA Solutions Inc.), and the like.
Among them, FS-300 manufactured by DuPont, FT-110 manufactured by Neos, FT-250, FT-251, and FT-- from the viewpoint that the excellent printing quality, particularly the color forming property and the leveling property to paper are remarkably improved. Particularly preferred are 400S, FT-150, FT-400SW, and Polyfox PF-151N manufactured by Omnova.

  As a preferable specific example of the said fluorine-type surfactant, the anionic fluorine-type surfactant represented by Structural formula shown below and a nonionic fluorine-type surfactant are mentioned. As these surfactants, those appropriately synthesized may be used, or commercially available products may be used. Such commercially available products can be easily obtained, for example, from Big Chemie, Shin-Etsu Silicone, Toray Dow Corning Silicone, etc.

上記式中、Ｒｆは、下記構造式〔化２〕で表されるフッ素含有疎水基の混合物を表す。Ａは、−ＳＯ_３Ｘ、−ＣＯＯＸ、又は−ＰＯ_３Ｘ〔ただし、Ｘは対アニオンであり、具体的には、水素原子、Ｌｉ、Ｎａ、Ｋ、ＮＨ_４、ＮＨ_３ＣＨ_２ＣＨ_２ＯＨ、ＮＨ_２（ＣＨ_２ＣＨ_２ＯＨ）_２、又はＮＨ（ＣＨ_２ＣＨ_２ＯＨ）_３が挙げられる〕を表す。

(1) Anionic fluorinated surfactant

In the above formula, R f represents a mixture of fluorine-containing hydrophobic groups represented by the following structural formula [Formula 2]. A _is, -SO 3 X, -COOX, or -PO ₃ X [However, X is a counter anion, specifically, a hydrogen _{atom, Li, Na, K, NH} 4, NH 3 CH 2 CH 2 OH , NH ₂ (CH ₂ CH ₂ OH) ₂ , or NH (CH ₂ CH ₂ OH) ₃ can be mentioned.

上記式中、Ｒｆ′は下記構造式〔化４〕で表されるフッ素含有基を表す。Ｘは、前記〔化１〕の場合と同じ意味を表す。ｎは１又は２の整数、ｍは２−ｎを表す。

上記式中、ｎは３〜１０の整数を表す。

In the above formula, Rf 'represents a fluorine-containing group represented by the following structural formula [Formula 4]. X represents the same meaning as in the case of the above [chemical formula 1]. n is an integer of 1 or 2 and m is 2-n.

In the above formula, n represents an integer of 3 to 10.

上記式中、Ｒｆ′及びＸは、前記〔化３〕の場合と同じ意味を表す。

In the above formulae, Rf ′ and X have the same meanings as in the above-mentioned [Chemical formula 3].

ただし、前記構造式中、Ｒｆ′及びＸは、前記〔化３〕の場合と同じ意味を表す。

However, in said structural formula, Rf 'and X represent the same meaning as the case of said [Chemical formula 3].

上記式中、Ｒｆは前記〔化１〕の場合と同じ意味を表す。ｎは５〜２０の整数を表す。 (2) Nonionic fluorinated surfactant

In the above formulae, R f has the same meaning as in the above-mentioned [Chemical formula 1]. n represents an integer of 5 to 20.

上記式中、Ｒｆ′は、前記〔化３〕の場合と同じ意味を表す。ｎは１〜４０の整数を表す。

In the above formulae, Rf 'represents the same meaning as in the above-mentioned [Chemical formula 3]. n represents an integer of 1 to 40.

ポリエーテル変性シリコーン系界面活性剤の市販品としては、例えば、ＫＦ−６１８、ＫＦ−６４２、ＫＦ−６４３（いずれも信越化学工業社製）などが挙げられる。 There is no restriction | limiting in particular as said polyether modified silicone type surfactant, According to the objective, it can select suitably, For example, Si of dimethylpolysiloxane represented by the following structural formula [Chemical formula 9] is a dimethylpolysiloxane The compound etc. which were introduce | transduced into the partial side chain etc. are mentioned.

As a commercial item of polyether modified silicone type surfactant, KF-618, KF-642, KF-643 (all are Shin-Etsu Chemical Co., Ltd. make) etc. are mentioned, for example.

Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate and salts of polyoxyethylene alkyl ether sulfate.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylamine, poly And oxyethylene alkylamides and the like.
0.01-3.0 mass% is preferable, and, as for content in the ink of the said surfactant, 0.5-2 mass% is more preferable.

<Penetration agent>
A penetrant may be added to the ink of the present invention. By adding the penetrant to the ink in an amount of 0.1 to 4.0% by mass, the permeability of the ink to the recording medium is improved and the filling of the dots is improved.
As the penetrant, it is preferable to include at least one of a C 8-11 polyol compound or a glycol ether compound. It is preferable that these have a solubility of between 0.2 and 5.0% by mass in water at 25 ° C., among which 2-ethyl-1,3-hexanediol [solubility: 4.2% (25 ° C.)] 2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0% (25 ° C.)] is preferable.

As other polyol compounds, for example, 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-Methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2-diol And aliphatic diols.
The other penetrants that can be used in combination are not particularly limited as long as they can be dissolved in the ink and adjusted to the desired physical properties, and can be appropriately selected according to the purpose. For example, diethylene glycol monophenyl ether, ethylene Alkyl and aryl ethers of polyhydric alcohols such as glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl ether, lower alcohols such as ethanol, etc. Can be mentioned.

<Other additives>
In addition to those described above, the ink of the present invention may contain conventionally known additives such as pH adjusters, antiseptic and fungicides, rust inhibitors, and chelating agents.
The pH adjuster is added for the purpose of stabilizing the dispersion state and stabilizing the discharge by keeping the ink alkaline. However, when the pH is 11 or more, the amount of melting of the ink jet head and the ink supply unit is large, and depending on the material of the head and the unit, problems such as deterioration of the ink, leakage, and ejection failure tend to occur when used for a long time . In the case of a pigment, it is more desirable to add a pH adjusting agent when kneading and dispersing the pigment in water together with the dispersing agent than kneading and dispersing it together with an additive such as a moisturizer or a penetrant. This is because, depending on the pH adjuster, the dispersion may be destroyed by the addition.

As the pH adjuster, those containing one or more kinds of 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 the like, and examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. As ammonium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, etc., as phosphonium hydroxide, quaternary phosphonium hydroxide, as alkali metal carbonate, lithium carbonate, sodium carbonate And potassium carbonate.

Examples of antiseptic and fungicides include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol and the like.
Examples of the rust inhibitor include acid sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite and the like.
As the chelating agent, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramildiacetate and the like can be mentioned.

  The ink of the present invention disperses or dissolves a colorant, a humectant, a surfactant, and water, and, optionally, a penetrant, a water dispersible resin, and other components in an aqueous medium, and further, if necessary, Stir and mix to produce. The dispersion can be carried out by, for example, a sand mill, homogenizer, ball mill, paint shaker, ultrasonic disperser, etc. Stirring mixing is carried out by a stirrer using a common stirring blade, magnetic stirrer, high speed disperser etc. Can.

The physical properties of the ink of the present invention are not particularly limited and may be appropriately selected according to the purpose. For example, the viscosity, surface tension and the like preferably fall within the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 to 15 mPa · s. By setting the ink viscosity to 5 mPa · s or more, the effect of improving the print density and the character quality can be obtained. On the other hand, by suppressing the ink viscosity to 15 mPa · s or less, the dischargeability can be secured.
Here, the ink viscosity can be measured at 25 ° C. using, for example, a viscometer (RL-500, manufactured by Toki Sangyo Co., Ltd.).
The surface tension of the ink at 25 ° C. is preferably 35 mN / m or less, more preferably 32 mN / m or less. If the surface tension is 35 mN / m or less, the leveling of the ink on the recording medium is improved.
There is no restriction | limiting in particular in the color of an ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set combining two or more of these colors, a multicolor image can be formed, and when recording is performed using an ink set combining all colors, a full-color image is formed be able to.

  In the ink according to the present invention, a piezoelectric element is used as pressure generating means for pressing the ink in the ink flow path, the diaphragm forming the wall surface of the ink flow path is deformed to change the volume inside the ink flow path. So-called piezo-type (see JP-A-2-51734) which discharges ink, or so-called thermal-type which generates bubbles by heating the ink in the ink flow path using a heating resistor (See, for example, Japanese Patent Application Laid-Open No. 59911/99), the diaphragm forming the wall surface of the ink channel and the electrode are disposed opposite to each other, and the diaphragm is deformed by the electrostatic force generated between the diaphragm and the electrode. The present invention can be favorably used for a printer equipped with any ink jet head such as an electrostatic type (refer to JP-A-6-71882) which discharges ink droplets by changing the product.

The ink of the present invention can be suitably used in an image forming apparatus (such as a printer) according to the inkjet recording method, for example, heating the recording medium and the ink at 50 ° C to 200 ° C before and after printing or printing and fixing It can also be used in a printer or the like having a function of promoting Further, the ink cartridge, the ink jet recording apparatus, and the method for producing an ink recording material of the present invention can be particularly suitably used.
As the recording medium, plain paper having no coating layer is suitably used, and plain paper having a size of 10 S or more and an air permeability of 5 to 50 S generally used as copy paper is preferable.

<Ink cartridge>
The ink cartridge of the present invention has a container containing the ink of the present invention, and other members appropriately selected as necessary.
The container is not particularly limited, and the shape, structure, size, material, and the like can be appropriately selected according to the purpose. For example, an ink bag made of an aluminum laminate film, a resin film, etc. Those having or the like are preferably mentioned.

Next, the ink cartridge will be described with reference to FIGS. 1 and 2. FIG. 1 is a schematic view showing an example of the ink cartridge, and FIG. 2 is a schematic view showing a modification of the ink cartridge of FIG.
As shown in FIG. 1, after the ink is filled in the ink bag 241 from the ink inlet 242 and exhausted, the ink inlet 242 is fused and closed. In use, the needle of the ink jet recording apparatus main body 101 shown in FIG. 3 is pierced through the ink discharge port 243 made of a rubber member to supply the ink to the apparatus main body 101. The ink bag 241 is formed of a packaging member such as an air-impermeable aluminum laminate film. As shown in FIG. 2, the ink bag 241 is usually housed in a plastic cartridge case 244, and is detachably mounted to various ink jet recording apparatuses.
It is particularly preferable that the ink cartridge 201 be detachable from various inkjet recording apparatuses. Further, the ink jet recording apparatus of the present invention can be manufactured by mounting the ink cartridge of the present invention.

<Ink jet recording method and ink jet recording apparatus>
The ink jet recording method includes at least an ink jetting step of applying a stimulus to the ink and causing the ink to fly to form an image on a recording medium, and further, other steps appropriately selected as necessary, for example, a stimulus generation step, a control step, etc. including.
The inkjet recording apparatus has at least an ink flying means for applying a stimulus to the ink and causing the ink to fly to form an image on a recording medium, and further, other means appropriately selected as necessary, for example, a stimulus generating means, a control means Etc.
The ink jet recording method can be suitably carried out by the ink jet recording apparatus, and the ink jetting step can be suitably carried out by the ink jetting unit. Further, the other steps can be suitably performed by the other means.
Further, in order to improve the image quality such as the image density, the penetration, and the bleeding, a process of applying the treatment liquid or a means of applying the treatment liquid may be provided on at least one of before and after attaching the ink to the recording medium.

-Ink flight process and ink flight means-
The ink flying step is a step of applying a stimulus (energy) to the ink to fly and form an image on a recording medium.
The ink flying means is a means for applying a stimulus (energy) to the ink and causing the ink to fly to form an image on the recording medium. There is no restriction | limiting in particular as said ink discharge means, For example, the various nozzles for ink discharge, etc. are mentioned.
In the present invention, it is preferable that at least a portion of the liquid chamber portion, the fluid resistance portion, the diaphragm and the nozzle member of the inkjet head be formed of a material containing silicon and / or nickel. Moreover, 30 micrometers or less are preferable and, as for the diameter of the said inkjet nozzle, 1-20 micrometers are more preferable.

The stimulation (energy) can be generated, for example, by the stimulation generating means, and the stimulation is not particularly limited and can be appropriately selected according to the purpose, and heat (temperature), pressure, vibration and Light etc. are mentioned. One of these may be used alone, or two or more may be used in combination. Among these, heat and pressure are preferable.
Examples of the stimulation generating means include, for example, a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, etc. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, A thermal actuator utilizing phase change due to film boiling of liquid using an electrothermal transducer such as a heating resistor, a shape memory alloy actuator using metal phase change due to temperature change, an electrostatic actuator using electrostatic force, etc. may be mentioned.

  There is no particular limitation on the mode of flight of the ink, and it differs depending on the type of the stimulus, etc. For example, when the stimulus is "heat", thermal energy corresponding to the recording signal for the ink in the inkjet head For example, there is a method of applying a thermal head or the like, generating a bubble in the ink by the thermal energy, and discharging the ink as droplets from the nozzle hole of the head by the pressure of the bubble. When the stimulus is "pressure", for example, the piezoelectric element is bent by applying a voltage to the piezoelectric element bonded to a position called a pressure chamber in the ink flow path in the head, and the volume of the pressure chamber And the ink is ejected as droplets from the nozzle holes of the recording head.

The size of the ink droplet to be ejected is preferably, for example, 3 × 10 ^-15 to 40 × 10 ^-15 m ³ ( ³ to 40 pL), and the ejection speed thereof is 5 to 20 m / s. The driving frequency is preferably 1 kHz or more, and the resolution is preferably 300 dpi or more.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

Here, an aspect of performing inkjet recording with a serial type inkjet recording apparatus will be described with reference to the drawings.
The inkjet recording apparatus shown in FIG. 3 includes an apparatus main body (101), a paper feed tray (102) for loading paper in the apparatus main body (101), and an image formed on the apparatus main body (101). It has a paper discharge tray (103) for stocking the processed paper, and an ink cartridge loading unit (104). An operation unit (105) such as an operation key or a display is disposed on the upper surface of the ink cartridge loading unit (104). The ink cartridge loading unit (104) has an openable front cover (115) for attaching and detaching the ink cartridge (201).

In the apparatus main body (101), as shown in FIG. 4 and FIG. 5, the carriage (the guide rod (131) and the stay (132)) are guide members which are guide members extended across the left and right side plates (not shown). 133) is slidably held in the main scanning direction, and moved and scanned in the arrow direction in FIG. 5 by a main scanning motor (not shown).
The carriage (133) has a recording head (134) consisting of four inkjet heads for ejecting ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk) into a plurality of inks. The ejection openings are arranged in a direction intersecting the main scanning direction, and the ink droplet ejection direction is directed downward.
As an inkjet head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator utilizing a phase change due to film boiling of liquid using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
Further, on the carriage (133), sub-tanks (135) of each color for supplying the ink of each color to the recording head (134) are mounted. The sub tank (135) is replenished with ink supplied from an ink cartridge (201) loaded in the ink cartridge loading unit (104) through an ink supply tube (not shown).

On the other hand, as a sheet feeding unit for feeding the sheets (142) stacked on the sheet stacking unit (pressure plate) (141) of the sheet feeding tray (102), the sheet (142) from the sheet stacking unit (141) is A separation pad 144 is disposed opposite to the sheet feeding roller (143) and the sheet feeding roller (143), and the separation pad 144 is made of a material having a large coefficient of friction. It is biased to the roller (143) side.
A transport belt (151) for electrostatically attracting and transporting the sheet (142) as a transport section for transporting the sheet (142) fed from the paper feed section below the recording head (134) And a counter roller (152) for conveying the sheet (142) fed from the sheet feeding section via the guide (145) between the sheet feeding section and the conveyance belt (151); 142) is rotated by approximately 90 ° and brought into contact with the conveyor belt (151), and a tip pressing roller biased toward the conveyor belt (151) by the pressing member (154) And (155) are provided. Further, a charging roller (156) is provided as charging means for charging the surface of the conveying belt (151).

  The transport belt (151) is an endless belt, and is stretched between a transport roller (157) and a tension roller (158), and can rotate in the belt transport direction. The transport belt (151) is, for example, a surface (surface) serving as a sheet adsorbing surface formed of a resin material having a thickness of about (40) μm, which is not controlled for resistance, such as a copolymer of tetrafluoroethylene and ethylene (ETFE). It has a back layer (a medium resistance layer, a ground layer) which is made of the same material as the surface layer and is subjected to resistance control by carbon. On the back side of the transport belt (151), a guide member (161) is disposed corresponding to the printing area by the recording head (134). Note that as a paper discharge unit for discharging the paper (142) recorded by the recording head (134), a separation claw (171) for separating the paper (142) from the conveyance belt (151), and paper discharge A roller (172) and a discharge roller (173) are provided, and the discharge tray (103) is disposed below the discharge roller (172).

A double-sided sheet feeding unit (181) is detachably mounted on the back of the apparatus body (101). The duplex feeding unit (181) takes in the sheet (142) returned by the reverse rotation of the conveying belt (151), reverses it, and feeds it again between the counter roller (152) and the conveying belt (151). . A manual paper feed unit (182) is provided on the upper surface of the double-sided paper feed unit (181).
In this inkjet recording apparatus, the sheets (142) are separated and fed one by one from the sheet feeding unit, and the sheets (142) fed substantially vertically upward are guided by the guide (145), and the conveying belt (151) ) And the counter roller (152). Further, the leading end is guided by the conveyance guide (153) and pressed against the conveyance belt (151) by the leading end pressure roller (155), and the conveyance direction is changed by about 90 °.
At this time, the conveyance belt (157) is charged by the charging roller (156), and the sheet (142) is electrostatically attracted to the conveyance belt (151) and conveyed. Therefore, by driving the recording head (134) according to the image signal while moving the carriage (133), ink droplets are ejected onto the stopped sheet (142) to record one line, After transporting the predetermined amount 142), the next line is recorded. The recording operation is ended by receiving the recording end signal or the signal that the rear end of the sheet (142) has reached the recording area, and the sheet (142) is discharged to the sheet discharge tray (103).
Then, when the ink residual amount near end in the sub tank (135) is detected, the required amount of ink is supplied from the ink cartridge (201) to the sub tank (135).

In this inkjet recording apparatus, when the ink in the ink cartridge (201) is used up, the housing of the ink cartridge (201) can be disassembled to replace only the ink bag (241) inside. In addition, the ink cartridge (201) can be stably supplied with ink even when the ink cartridge (201) is vertically mounted on the front side. Therefore, when the upper side of the device body (101) is closed and installed, for example, when the device is stored in a rack or when an object is placed on the upper surface of the device body (101), the ink The cartridge (201) can be easily replaced.
Although the example applied to the serial type (shuttle type) ink jet recording apparatus in which the carriage scans is described, the present invention can be similarly applied to a line type ink jet recording apparatus provided with a line type head.
The ink jet recording apparatus of the present invention can be applied to various recordings by the ink jet recording method, and is particularly suitably applied to, for example, a printer for ink jet recording, a facsimile machine, a copier, a printer / fax / copier complex machine, etc. can do.

<Ink recording material>
The ink recorded matter according to the present invention has an image formed using the ink of the present invention on a recording medium.
There is no restriction | limiting in particular as said to-be-recorded medium, According to the objective, it can select suitably, For example, a plain paper, glossy paper, a special paper, cloth, a film, an OHP sheet, general purpose printing paper etc. are mentioned. One of these may be used alone, or two or more may be used in combination.
The ink recorded matter has high image quality, no bleeding, and is excellent in stability over time, and can be suitably used as various printed matter or material on which an image is recorded or the like.

EXAMPLES The present invention will be more specifically described below with reference to examples , reference examples and comparative examples, but the present invention is not limited by these examples.

Each pigment dispersion was prepared as shown below.

Preparation Example 1 (surface-treated carbon black pigment dispersion)
90 g of carbon black with a CTAB specific surface area of 150 m ² / g and a DBP oil absorption of 100 mL / 100 g was added to 3000 mL of ^2.5 N sodium sulfate solution, stirred at a temperature of 60 ° C. at a speed of 300 rpm, and reacted for 10 hours for oxidation treatment . The reaction solution was filtered, and the filtered carbon black was neutralized with sodium hydroxide solution and subjected to ultrafiltration. The obtained carbon black was washed with water and dried, and then dispersed in deionized water so that the proportion of carbon black was 30% by mass, to obtain a surface-treated carbon black pigment dispersion.

Preparation Example 2 (Surface-treated yellow pigment dispersion)
Yellow pigments C.I. I. Pigment Yellow 128 was subjected to low temperature plasma treatment to prepare a pigment having a carboxylic acid group introduced. What disperse | distributed this in ion-exchange water is desalted and concentrated with an ultrafiltration membrane, and the surface-treated yellow pigment dispersion liquid of 30 mass% of pigment concentrations was obtained.

Preparation Example 3 (Surface-treated magenta pigment dispersion)
C. I. Pigment yellow 128, C.I. I. A surface-treated magenta pigment dispersion having a pigment concentration of 30% by mass was obtained in the same manner as in Preparation Example 2 except that pigment red 122 was used.

Preparation Example 4 (Surface-treated cyan pigment dispersion)
C. I. Pigment yellow 128, C.I. I. A surface-treated cyan pigment dispersion liquid having a pigment concentration of 30% by mass was obtained in the same manner as in Preparation Example 2 except that pigment blue 15: 3 was changed.

Synthesis Example 1 (Preparation of Polymer Solution)
After sufficiently displacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet 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 (trade name: AS-6, manufactured by Toago Synthetic Co., Ltd.) and 0.4 g of mercaptoethanol were charged, and the temperature was raised to 65 ° C. Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxyethyl methacrylate, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) 36. A mixed solution of 0 g, 3.6 g of mercaptoethanol, 2.4 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 2.5 hours. After completion of the dropwise addition, 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 aging was further 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% by mass.

Preparation Example 5 (Preparation of Pigment Dispersion Containing Phthalocyanine Pigment-Containing Polymer Particles)
28 g of the polymer solution of Synthesis Example 1, 26 g of phthalocyanine pigment (Dainichi Seika Kogyo Co., Ltd., Chromo fine blue A-220 JC), 13.6 g of 1 mol / L potassium hydroxide solution, 20 g of methyl ethyl ketone and 30 g of ion exchanged water Then, the mixture was kneaded using a three-roll mill. The obtained paste was put into 200 g of ion-exchanged water, and after sufficient stirring, methyl ethyl ketone and water were distilled off using an evaporator to obtain a cyan-colored fine polymer particle dispersion of a pigment concentration of 30% by mass.

Preparation Example 6 (Preparation of pigment dispersion containing dimethylquinacridone pigment-containing polymer particles)
A polymer fine particle dispersion of magenta color was obtained in the same manner as in Preparation Example 5, except that the phthalocyanine pigment was changed to pigment red 122.

Preparation Example 7 (Preparation of Pigment Dispersion Containing Monoazo Yellow Pigment-Containing Polymer Particles)
A yellow polymer fine particle dispersion was obtained in the same manner as in Preparation Example 5, except that the phthalocyanine pigment was changed to pigment yellow 74.

Preparation Example 8 (Preparation of pigment dispersion containing carbon black pigment-containing polymer particles)
A black polymer fine particle dispersion was obtained in the same manner as in Preparation Example 5 except that the phthalocyanine pigment was changed to carbon black (manufactured by Evonik Degussa Japan, NIPEX 150).

Examples 1 to 27 (where 6, 11, 14 and 22 are reference examples) , Comparative examples 1 to 19
<Preparation of ink >
The water-soluble organic substance, the surfactant and the ion-exchanged water were mixed at a ratio shown in each column of Examples , Reference Examples and Comparative Examples of Tables 1 to 4, and stirred for 1 hour to uniformly mix. Further, the mixture is further stirred for 1 hour by adding a resin dispersion was added the following Ide pigment dispersion was stirred for 1 hour. Subsequently, it adjusted so that pH might be set to 9 with lithium hydroxide 10 mass% aqueous solution, and stirred for 1 hour. The dispersion was filtered through a membrane filter having an average pore size of 0.8 μm to obtain an ink.
In addition, the numerical value of each column in Table 1-Table 4 is a "mass part."

The meanings of the abbreviations in Tables 1 to 4 are as follows.
Acrylic-silicone resin emulsion: Polysol ROY6312, manufactured by Showa Highpolymer Co., solid content 40% by mass, average particle diameter 171 nm, minimum film forming temperature (MFT) = 20 ° C.
Polyurethane resin emulsion: Hydran APX-101H manufactured by DIC, solid content 45%, average particle size 160 nm, minimum film forming temperature (MFT) = 20 ° C.
· DSN 403 N: Fluorinated surfactant (manufactured by Daikin Industries, 98% by mass or more of the active ingredient)
· Softanol EP-7025: polyoxyalkylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., component 100% by mass)
-NIKKOL ECTD-3 NEX: polyoxyethylene (3) tridecyl ether acetate sodium (manufactured by Nikko Chemical Co., component 98 mass% or more)

The characteristics of each ink of the example , the reference example and the comparative example were evaluated as follows.
As a recording medium, high-quality paper MyPaper (basis weight 69.6 g / m ² , size 23.2 seconds, air permeability 21 seconds) manufactured by NBS Ricoh Co., Ltd. was used.
The results are summarized and shown in Table 5.

-Preparation of printing evaluation-
Using an ink jet printer (IPSIO GXe 5500, manufactured by Ricoh Co., Ltd.) under an environment of a temperature of 23 ° C. and a humidity of 50% RH, the drive voltage of the piezo element is varied to equalize the discharge amount of ink, and the same adhesion to the recording medium The amount of ink was set to stick. The settings of each color “square solid” of the chart created by Microsoft Word 2000 are as follows.
[Color designation of "square solid" part of Word]
-RGB color model-Black: red (R) 0, green (G) 0, blue (B) 0
Yellow: Red (R) 255, green (G) 255, blue (B) 0
Magenta: red (R) 255, green (G) 0, blue (B) 255
・ Cyan: red (R) 0, green (G) 0, blue (B) 255

<Image density>
A chart with the description of 64 point characters "square solid" created by Microsoft Word 2000 was punched out on a recording medium, and the "square solid" portion of the printing surface was measured with X-Rite 938 (manufactured by X-Rite). The printing mode was "plain paper-standard quick" mode and color matching off from the user setting of plain paper with a driver attached to the printer.

<Ink retransferability (offset)>
The retransferability of the ink was used as a method of evaluating the dryness. Here, “re-transferability of ink” means that when a large amount of ink remains on the surface of the medium after the ink is attached to the medium to be recorded, the medium to be recorded is conveyed and the rollers, spurs, and printing for conveyance are printed. When the surface contacts, the ink on the surface of the media adheres to the roller and the image and the apparatus are stained.
A chart is punched out on a recording medium in the same manner as in the case of image density, and a 40 mm diameter polyethylene cylindrical roller is loaded within 5 seconds after printing on a 40 mm long "square solid" portion of the printing surface. It was rolled while being pressed at a strength of 5 N, and the portion where the ink was retransferred from the cylindrical roller to the recording medium was measured with X-Rite 938 and evaluated according to the following criteria. The printing mode was set to "plain paper-standard clear" mode and color matching off from the user setting of plain paper with a driver attached to the printer.

〔Evaluation criteria〕
A: less than 0.10 B: 0.10 or more, less than 0.25 C: 0.25 or more

<Curl evaluation>
Flatten the four corners of the recording media when the "square solid" chart set at the very limit of the printing range created with Microsoft Word 2000 is stamped out on the recording media and placed on the flat surface with the printing side back within 5 seconds after printing. The average of the height from the surface was measured.
The printing mode was "plain paper-standard is quick" mode and color matching off from the user setting of plain paper with the driver attached to the printer. The curling was measured 10 seconds after paper discharge, and evaluated according to the following criteria.

〔Evaluation criteria〕
A: less than 20 mm B: 20 mm or more, less than 40 mm C: 40 mm or more, or rounded

<Discharge stability>
A chart was continuously printed out on a recording medium with 200 sheets of a chart in which an area of 5% of A4 size paper per color created with Microsoft Word 2000 was filled with a solid image, and evaluation was made according to the following criteria from ejection disturbance of each nozzle after striking. The printing mode is a driver attached to the printer and changed the mode from "plain paper-standard is quick" to "no color correction" according to the user setting of plain paper. The evaluation was performed at a temperature of 23 ± 1 ° C. and a humidity of 50 ± 5% RH.

〔Evaluation criteria〕
A: There is no discharge disorder.
B: Discharge disordered a little.
C: There is a place which does not discharge.

<Intermittent discharge stability>
After leaving the head for 2 hours after head cleaning in an environment of 35 ± 1 ° C and 15 ± 5% RH, the chart is made by filling a 5% area of A4 size paper per color with a solid image created with Microsoft Word 2000 One sheet was punched out into MyPaper (manufactured by NBS Ricoh Co., Ltd.), and evaluated from the discharge disorder of each nozzle. The print mode was a driver attached to the printer and used a mode in which "plain paper-standard is quick" mode was changed to "no color correction" from the user setting of plain paper.

〔Evaluation criteria〕
A: There is no discharge disorder.
B: Discharge disordered a little.
C: There is a place which does not discharge.

<Storage stability>
Each ink was left to stand in a constant temperature bath at 65 ° C. for 4 weeks, and the viscosity change rate of the ink before and after being left in the constant temperature bath was measured and evaluated based on the following criteria.

〔Evaluation criteria〕
A: Viscosity change rate less than 5% B: Viscosity change rate 5% or more, less than 10% C: Viscosity change rate 10% or more

Reference Signs List 101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 111 top cover 112 front surface 115 front cover 131 guide rod 132 stay 133 carriage 134 recording head 135 subtank 141 paper stacking unit 142 paper 144 separation pad 151 transport belt 152 again Counter roller 156 Charge roller 157 Conveying roller 158 Tension roller 171 Separation claw 172 Ejection roller 173 Ejection roller 181 Double-sided feeding unit 201 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge case

JP, 2008-303380, A Unexamined-Japanese-Patent No. 2009-155662

Claims (8)

An inkjet ink comprising at least water, a water-soluble organic substance, a colorant and a surfactant , wherein the water-soluble organic substance satisfies the following requirements.
(A) The water-soluble organic substance is contained in an amount of 30 to 50% by mass of the whole ink.
(B) As a water-soluble organic substance, 8% by mass or more of 3-methoxy-1-butanol is contained in the entire ink .
(C) As a water-soluble organic substance, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 3-methyl-3-hydroxymethyl oxetane, The ink contains at least one selected from 1,2-propanediol and 1,3-propanediol at 1% by mass or more of the entire ink. The inkjet ink according to claim 1, wherein the 3-methoxy-1-butanol is contained in an amount of 15 to 40% by mass of the entire ink. The inkjet ink according to claim 1 or 2 content of the water-soluble organic substances, characterized in that from 5 to 40% by weight of the total ink of said (c). The ink for ink jet recording according to any one of claims 1 to 3, which contains at least one of an acrylic silicone resin and a polyurethane resin. The inkjet ink according to any one of claims 1 to 4, which contains at least one selected from a silicone surfactant and a fluorosurfactant. An ink cartridge containing the ink for ink jet recording according to any one of claims 1 to 5 in a container.   An ink jet recording apparatus comprising the ink cartridge according to claim 6. A method of producing an ink recorded matter, comprising forming an image on the recording medium with the ink for inkjet according to any one of claims 1 to 5.

Images