JP2010163533A - Ink for inkjet recording, ink cartridge, recording method, and recorded matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ink for inkjet recording having high ejection reliability, significantly minimizing color bleeding, and having excellent color development even on plain paper. <P>SOLUTION: The ink for inkjet recording includes a colorant, surfactants A, B, and C, a water-soluble organic solvent, and water; wherein an example of the surfactant A is a fluorine-based compound of formula (1), the surfactant B is a polyether-based compound, and the surfactant C is a polyether-modified silicone compound. In the formula, R<SP>1</SP>is hydrogen, alkyl, or acyl; Rf is -CF<SB>3</SB>or -CF<SB>2</SB>CF<SB>3</SB>; and m, n, and p are natural numbers. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ink for ink jet recording capable of achieving both improvement in image quality on plain paper and ejection stability in an ink jet printer, and further suppressing color bleeding, an ink cartridge using the ink, an ink jet recording method, and a recorded matter. Is.

In ink jet recording, attempts have been made to improve ink permeability in order to improve the saturation (color development) of plain paper. In order to improve the permeability, it is effective to reduce the surface tension, and a fluorine-based surfactant, a silicone-based surfactant and the like are blended. However, silicone surfactants are easily decomposed by heat and have a problem in storage stability when used as an ink. On the other hand, fluorosurfactants are highly stable against heat, but they are not compatible with water-soluble organic solvents and resin components blended in the ink. Is likely to occur and causes problems such as ejection failure.
For example, Patent Document 1 describes that a fluorosurfactant corresponding to the surfactant A [Structural Formula (1)] used in the present invention is used. In this case, a fluorosurfactant is used. Although there was little foaming, there was a problem that the ink storage stability was poor and the ink jet head was easily fixed to the nozzle surface.
Therefore, the present inventors have invented and filed a solution using a combination of surfactant A and surfactant B (Japanese Patent Application No. 2008-280327). However, it has been found that the prior invention has a problem that color bleeding easily occurs.

  The present invention provides an inkjet recording ink that has high ejection reliability, does not cause color bleeding, and can provide excellent color development even on plain paper, and further an ink repellent layer containing a fluorine-based silane coupling agent, or An object of the present invention is to provide an ink for ink jet recording that can be applied to an ink jet head having an ink repellent layer containing a silicone resin without any problem, an ink cartridge using the ink, an ink jet recording method, and a recorded matter.

（上記式中、Ｒ^１は、水素、アルキル基、又はアシル基であり、Ｒｆは、−ＣＦ_３、又は−ＣＦ_２ＣＦ_３であり、ｍ、ｎ、ｐは自然数である。）

（上記式中、Ｍはアルカリ金属、アンモニウム、ホスホニウム、又はアルカノールアミンであり、Ｒｆは、−ＣＦ_３、又は−ＣＦ_２ＣＦ_３であり、ｑは自然数である。）

（上記式中、Ｒ^３、Ｒ^４は、それぞれ水素又はアルキル基であり、ｒ、ｓ、ｔ、ｕは自然数である。）
２） 前記着色剤として、有機顔料又はカーボンブラックを下記構造式（４）で表されるノニオン系分散剤により分散したものを用いたことを特徴とする１）記載のインクジェット記録用インク。

（上記式中、Ｒ^２は炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、又はアリル基であり、ｌは０〜７の整数であり、ｋは２０〜８０の整数である。）
３） 前記着色剤として、有機顔料又はカーボンブラックの表面に親水基を反応させた自己分散型顔料を用いたことを特徴とする１）記載のインクジェット記録用インク。
４） 更に樹脂エマルジョンを含有することを特徴とする１）〜３）の何れかに記載のインクジェット記録用インク。
５） １）〜４）の何れかに記載のインクジェット記録用インクを収容したインクカートリッジ。
６） フッ素系シランカップリング剤を含む撥インク層、又はシリコーン樹脂を含む撥インク層を有するインクジェットヘッドを備えたインクジェット記録装置を用い、１）〜４）の何れかに記載のインクジェット記録用インクを吐出させることを特徴とするインクジェット記録方法。
７） １）〜４）の何れかに記載のインクジェット記録用インクを用いて記録が行われた記録物。 The above problems are solved by the following inventions 1) to 7).
1) At least a coloring agent, surfactant A, surfactant B, surfactant C, water-soluble organic solvent and water are contained, and the surfactant A is represented by the following structural formula (1) or structural formula (2). An ink for inkjet recording, wherein the surfactant B is represented by the following structural formula (3), and the surfactant C is a polyether-modified silicone compound.

(In the above formula, R ¹ is hydrogen, an alkyl group, or an acyl group, Rf is —CF ₃ or —CF ₂ CF ₃ , and m, n, and p are natural numbers.)

(In the above formula, M is an alkali metal, ammonium, phosphonium, or alkanolamine, Rf is —CF ₃ or —CF ₂ CF ₃ , and q is a natural number.)

(In the above formula, R ³ and R ⁴ are each hydrogen or an alkyl group, and r, s, t, and u are natural numbers.)
2) The ink for ink jet recording according to 1), wherein an organic pigment or carbon black dispersed with a nonionic dispersant represented by the following structural formula (4) is used as the colorant.

(In the above formula, R ² is an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, or an allyl group, l is an integer of 0 to 7, and k is an integer of 20 to 80. is there.)
3) The ink for ink jet recording according to 1), wherein a self-dispersing pigment obtained by reacting a hydrophilic group on the surface of an organic pigment or carbon black is used as the colorant.
4) The ink for inkjet recording according to any one of 1) to 3), further comprising a resin emulsion.
5) An ink cartridge containing the inkjet recording ink according to any one of 1) to 4).
6) Ink jet recording ink according to any one of 1) to 4) using an ink jet recording apparatus including an ink repellent layer containing a fluorine-based silane coupling agent or an ink repellent layer containing a silicone resin. An ink jet recording method characterized by discharging the ink.
7) A recorded matter recorded by using the ink for ink jet recording according to any one of 1) to 4).

Hereinafter, the present invention will be described in detail.
<Penetration agent>
When a penetrating agent is added to the ink, the surface tension is reduced, and the penetration into the recording medium after the ink droplets have landed on the recording medium such as paper is accelerated. Therefore, feathering and color bleeding can be reduced. In the present invention, as the penetrant, the fluorine-based surfactant A represented by the structural formula (1) or the structural formula (2), the nonionic surfactant B represented by the structural formula (3), and the polyether Surfactant C made of a modified silicone compound is used.
Fluorosurfactants are excellent in penetrability and foaming prevention, but have problems with ink storage stability and head adhesion. In particular, it tends to adhere to an ink jet head having an ink repellent layer containing a fluorine-based silane coupling agent or an ink repellent layer containing a silicone resin.
On the other hand, nonionic surfactants are excellent in ink storability, but have problems in penetrability, foaming prevention, and head fixation.
However, as disclosed in the invention of the prior application, when the surfactant A and the surfactant B are combined, surprisingly, the respective advantages are utilized to improve the permeability, the prevention of foaming, and the ink storage stability. Not only is the head sticking, which is a problem of both, improved.
However, since subsequent investigations revealed that color bleed is likely to occur in the invention of the prior application, further investigation revealed that the difference in surface tension between surfactant A and surfactant B was too large and the balance was poor. It was speculated that. Therefore, when surfactant C having a surface tension between them was added, the effect of the invention of the prior application was maintained while maintaining the effect of the combination of surfactant A and surfactant B (comparative example) 1), it was confirmed that color bleeding could be suppressed, and the present invention was achieved.

Surfactant A has less foaming among the fluorosurfactants, and is effective in improving reliability and color development. Examples of commercially available products include Polyfox PF-151N as structural formula (1) and Polyfox PF-136A and PF-156A (both manufactured by Omninova) as structural formula (2).
R ^{1 in the} structural formula (1) is hydrogen in the above-mentioned commercially available product, and hydrogen is preferable from the viewpoint of storage stability, but it may be an alkyl group or an acyl group. Rf is —CF ₂ CF ₃ in the above-mentioned commercially available product, but RCF is equivalent to —CF _{3 in} view of the fact that Rf of the above-mentioned commercially available product of the structural formula (2) described later is —CF ₃ or —CF ₂ CF _3. It is thought that there is an effect of. m, n, and p are m = 21, n = ˜4, and p = ˜4 in the above-mentioned commercially available products, but m is the number of blocks that bear hydrophilicity, and n and p are the blocks that bear lipophilicity. Since it is a number, it can be considered that it can be used in a range where the balance between hydrophilicity and lipophilicity is maintained, for example, in the range of m = 10 to 30, n + p = 4 to 10.
Further, M in the structural formula (2) is ammonium in the above-mentioned commercially available product, but any compound capable of forming a sulfonate salt may be used. For example, alkali metal, phosphonium, alkanolamine, and the like may be used. q is 6 in the above-mentioned commercially available product, but q is the number of blocks responsible for lipophilicity, so that it is used in a range where the balance between hydrophilicity and lipophilicity is maintained, for example, in the range of about q = 4-10. It is considered possible.
A preferable surface tension range of the surfactant A is 20 to 35 mN / m. The amount added to the ink is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight.

Surfactant B has particularly good storage stability among nonionic surfactants. Examples of commercially available products include Softanol EP5035, Softanol EP9050, Softanol EP7025, Softanol EP7045 (manufactured by Nippon Shokubai Co., Ltd.), EMALEXDAPE-0205, EMALEXDAPE-0207, EMALEXDAPE-0210, and EMALEXDAPE-0212 (manufactured by Nippon Emulsion).
R ³ and R ^{4 in} the structural formula (3) are hydrogen and an alkyl group having 9 carbon atoms, or an alkyl group having a carbon number of R ³ and R ⁴ of 11 to 13 in the above-mentioned commercial product. It is considered that hydrogen or an alkyl group having about 10 or less carbon atoms can be used without greatly affecting the properties of the compound. Moreover, r, s, t, and u are r = 5-9, s = 2.5-5, t = 2, u = 7-12 in the said commercial item, but r and u are ethylene oxide. The number of blocks, s, and t are the number of propylene oxide blocks, and propylene oxide is less hydrophilic than ethylene oxide. It is thought that it is possible to select and use a range that maintains a lipophilic balance.
The amount of the surfactant B added to the ink is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight.

Surfactant C tends to deteriorate the storage stability of the ink, but is effective in suppressing the occurrence of color bleeding and can provide an extremely high-quality image.
Commercially available products include Shin-Etsu Silicone: KF-6004, KF-353, Toray Dow Corning Silicone: L-7604, SF-3771 and the like.
The polyether-modified silicone compound is widely used as a release agent and has releasability. Therefore, when it is added to ink, it also has an effect of suppressing head sticking.
Furthermore, in the ink of the present invention, other than anionic surfactants, acetylene glycol surfactants, etc., as long as the effects of the combination of surfactant A, surfactant B, and surfactant C are not impaired. These surfactants may be used in combination.
In order to improve the permeability, a polyol having 8 to 11 carbon atoms such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol may be used in combination.

<Colorant>
As the colorant, a dye or a pigment is used.
Examples of pigments include organic pigments such as azo, phthalocyanine, anthraquinone, dioxazine, indigo, thioindigo, perylene, isoindolenone, aniline black, azomethine, rhodamine B lake pigment, carbon black, oxidation Examples thereof include inorganic pigments such as iron, 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.

Among the above pigments, carbon black is particularly preferable as the black pigment, carbon black produced by the furnace method or the channel method, the primary particles are 15 to 40 nm, the specific surface area by the BET adsorption method is 50 to 300 m ² / g, A DBP oil absorption of 40 to 150 ml / 100 g, a volatile content of 0.5 to 10% and a pH of 2 to 9 is used, and acidic carbon black having a pH of 6 or less is particularly preferred at a high concentration.
Examples of color pigments include 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, 15: 4 are preferable.

The average particle diameter 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. When the average particle diameter of the pigment exceeds 200 nm, not only the saturation of the printed image is lowered, but also thickening aggregation during ink storage and clogging of the nozzle during printing are likely to occur. If it is less than 20 nm, not only the light resistance is lowered but also the storage stability tends to be deteriorated.
In addition, the average particle diameter of the pigment in the present invention is a particle refraction 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. It is a 50% average particle diameter (D50) measured at 23 ° C. with a rate 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 weight, more preferably 3 to 12% by weight, and still more preferably 4 to 10% by weight. If the pigment concentration is less than 2% by weight, the image strength tends to be inferior due to insufficient coloring power, and if it exceeds 15% by weight, not only the storage stability of the ink is lowered but also the image tends to be dull. .

In pigment ink, a dispersant is generally used. Usually, a nonionic or anionic surfactant-based dispersant is appropriately selected according to the pigment type or ink formulation.
Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether. Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene-α-naphthyl ether, polyoxyethylene-β-naphthyl ether, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether, Polyoxyethylene alkyl naphthyl ether, polyoxyethylene monostyryl naphthyl ether, polyoxyethylene Examples include distyryl naphthyl ether and polyoxyethylene polyoxypropylene block copolymer. Also used are surfactants in which a part of polyoxyethylene in these surfactants is replaced with polyoxypropylene, and surfactants condensed with a compound having an aromatic ring such as polyoxyethylene alkylphenyl ether with formalin. it can.
The nonionic surfactant has an HLB of preferably 12 to 19.5, more preferably 13 to 19. If the HLB is less than 12, there is a tendency for the dispersion stability to deteriorate due to poor conformity of the surfactant to the dispersion medium. If the HLB exceeds 19.5, the surfactant becomes difficult to adsorb to the pigment, so that the dispersion stability is also reduced. There is a tendency to deteriorate.

  Anionic surfactants include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene monostyryl phenyl ether sulfate, polyoxyethylene distyryl phenyl ether sulfate, polyoxyethylene alkyl ether phosphorus Acid salt, polyoxyethylene alkyl phenyl ether phosphate, polyoxyethylene monostyryl phenyl ether phosphate, polyoxyethylene distyryl phenyl ether phosphate, polyoxyethylene alkyl ether carboxylate, polyoxyethylene alkyl phenyl ether Carboxylate, polyoxyethylene monostyryl phenyl ether carboxylate, polyoxyethylene distyryl phenyl ether carboxylate, naphthalene Phosphonate formalin condensate, melanin sulfonate formalin condensate, dialkyl sulfosuccinic acid ester salt, sulfosuccinic acid alkyl disalt, polyoxyethylene alkyl sulfosuccinic acid disalt, alkyl sulfoacetate, α-olefin sulphonate, alkylbenzene sulfone Examples thereof include acid salts, alkylnaphthalene sulfonates, alkyl sulfonates, N-acyl amino acid salts, acylated peptides, soaps and the like. Of these, sulfates or phosphates of polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene distyryl phenyl ether are particularly preferable.

In order to improve the storage stability of the pigment ink, the nonionic dispersant represented by the structural formula (4) is particularly preferable. In the examples, R ² , l, and k in the structural formula (4) are R ² = C ₁₂ H ₂₅ , l = 1, k = 42, and R ² is alkyl having 1 to 20 carbon atoms. It may be a group, an aralkyl group having 1 to 20 carbon atoms, or an allyl group, l is an integer of 0 to 7, and k is considered to be usable if it is in the range of about 20 to 80.
The addition amount of the surfactant-based dispersant is preferably about 10 to 50% by weight of the pigment. If the added amount is less than 10% by weight of the pigment, the storage stability of the pigment dispersion and the ink is lowered, or the dispersion takes an extremely long time. If the added amount exceeds 50% by weight, the viscosity of the ink becomes too high. Therefore, the discharge stability tends to decrease.

As the dye, those having excellent water resistance and light resistance among dyes classified in the color index into acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes are used. These dyes may be used as a mixture of plural kinds, or may be used as a mixture with other colorants such as pigments as necessary. However, it is necessary to add other colorants as long as the effects of the present invention are not inhibited.
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 1,3,5,7,9,21,22,26,35,
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

<Water-soluble organic solvent (wetting agent)>
The ink of the present invention uses water as a liquid medium, but contains a water-soluble organic solvent for the purpose of preventing the ink from drying (as a wetting agent) 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, glycerin, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, dipropylene glycol, trimethylolpropane, tetramethylolpropane When 3-methyl-1,3-butanediol, D-sorbitol, or xylitol is used, an ink excellent in storage stability and ejection stability can be produced.
In the case of pigment ink, the ratio of pigment to wetting agent has a great influence on the ejection stability of ink from the head. If the pigment solid content ratio is high, but the amount of the wetting agent is small, water evaporation near the ink meniscus of the nozzle advances, resulting in ejection failure.
The amount of the wetting agent is about 10 to 50% by weight of the whole ink. The ratio of the total weight of the colorant and the resin emulsion to the total weight of the wetting agent in the ink is preferably 0.5 to 12.5, more preferably 1.0 to 6.0, and most preferably 2.0 to 5.0. Range. Ink within this range has very good drying, storage and reliability tests.

It is preferable to add a resin emulsion to the ink of the present invention mainly for the purpose of improving image rubbing resistance and improving storage stability when a pigment is used as a colorant. An acrylic resin, a styrene-acrylic resin, an acrylic silicon resin, or a fluororesin emulsion is preferable for improving image abrasion resistance, and a polyurethane resin, an acrylic resin, or a styrene-acrylic resin emulsion is preferable for improving storage stability. . However, since there are few resin emulsions that can simultaneously improve image rubbing resistance and storage stability, two types of resin emulsions may be used in combination. These resin emulsions can be appropriately selected from commercially available ones as required.
Next, typical resin emulsions will be exemplified.

(1) Urethane resin emulsion The urethane resin of the urethane resin emulsion is obtained by polymerizing polyisocyanate, polyether polyol, polyester polyol, polylactone polyol, polycarbonate polyol and the like.
Examples of polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. Cycloaliphatic diisocyanate compounds such as xylylene diisocyanate and tetramethylxylene diisocyanate, aromatic diisocyanate compounds such as toluylene diisocyanate and phenylmethane diisocyanate, and modified products of these diisocyanates (including carbodiimide, uretdione and uretoimine) Metamorphic materials, etc.).

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

(2) Acrylic resin emulsion The acrylic resin of the acrylic resin emulsion is obtained by polymerizing an acrylic monomer alone or copolymerizing it with another monomer.
As acrylic monomers, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-t-butyl, acrylic acid-n- 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, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid isobutyl, methacrylic acid-t-butyl, methacrylic acid-n-pentyl, Isopentyl acrylate, neopentyl methacrylate, -3- (methyl) butyl methacrylate, 2-ethylhexyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, acrylic Examples include acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like.
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, and vinylidene chloride.

  Said resin emulsion expresses the further outstanding water dispersibility by introduce | transducing an ionic group into resin. Examples of such ionic groups include sulfonic acid groups, carboxylic acid groups, sulfuric acid groups, phosphoric acid groups, phosphonic acid groups and phosphinic acid groups, or alkali metal bases, alkaline earth metal bases, ammonium bases, Examples include a primary to tertiary amine group. Among them, carboxylic acid alkali metal bases, carboxylic acid ammonium bases, sulfonic acid alkali metal bases and sulfonic acid ammonium bases are preferable, and sulfonic acid alkali metal bases and sulfonic acid ammonium bases are particularly preferable in terms of water dispersion stability. The introduction of the ionic group is performed by adding a monomer having an ionic group during the resin synthesis. Preferred as the salt are Li, K or Na salts.

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 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. In addition, it has an excellent characteristic that the head does not adhere to a recording apparatus including an ink jet head having an ink repellent layer containing a fluorine-based silane coupling agent or an ink repellent layer containing a silicone resin.

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 that eject ink droplets onto a recording paper 142, and a carriage on which the four ink jet heads 134 are movably mounted in the carriage scanning direction (main scanning direction). 133, an endless transport belt 141 that transports the recording paper 142 in the belt (paper) transport direction (sub-operation direction), and a driving roller 157 and a driven roller 158 over which the transport belt is stretched.
Further, although not shown, each ink-jet head 134 is provided with an ink cartridge and carriage 133 for introducing inks of different colors (for example, yellow, cyan, magenta, black) ink-jet ink (hereinafter also simply referred to as “ink”). A carriage driving unit that moves in the carriage scanning direction, a belt driving unit that rotates the driving roller 157 to run the transport belt 151, a head driver that drives and discharges each inkjet head 134, and is provided at one end of the scanning region of the carriage 133. And a maintenance device for performing 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 via the carriage 133 in the carriage scanning direction, and conveys the recording paper 142 in the belt conveyance direction. As a result, 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, a fluid resistance portion 2a, and a carved formation. The pressurized liquid chamber 2b, the flow path plate 20 in which the communication port 2c communicating with the nozzle 3a is formed, the nozzle plate 30 in which a large number of nozzles 3a are formed, and the base 40 are fixed to the head driver. The laminated piezoelectric element 50 to which the driving waveform is applied, the vibration plate 60 having the convex portion 6a, the diaphragm portion 6b, and the ink inlet 6c joined to the laminated piezoelectric element 50, and the laminated piezoelectric element 50 and the vibration plate 60 are bonded. And an adhesive layer 70. 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 30 is formed of a metal material, for example, a Ni plating film by an electroforming method. An ink repellent layer 3 b (liquid repellent layer) according to the present invention is formed on the ink discharge surface side surface (droplet discharge surface side surface) of the nozzle plate 30.

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 fluorine-based silane coupling agent has high mechanical durability because it forms a chemical bond with the underlying layer, but it is resistant to chemical hazards where the bond breaks like ink contact. 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 housed in a container and used as an ink cartridge, and other members appropriately selected as necessary may be provided.
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 diagram illustrating an example of the ink bag 241 of the ink cartridge of the present invention, and FIG. 4 is a schematic diagram illustrating the ink cartridge 200 in which the ink bag 241 of FIG. 3 is accommodated in the cartridge case 244. is there.
As shown in FIG. 3, ink is filled into the ink bag 241 from the ink inlet 242 and air remaining in the ink bag is exhausted, and then the ink inlet 242 is closed by fusion. 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 mounted on various ink jet recording apparatuses.
The ink cartridge of the present invention is particularly preferably used by being detachably mounted on the ink jet recording apparatus of the present invention described later.

  According to the present invention, an ink for ink-jet recording having high ejection reliability, extremely little color bleeding, and excellent color developability even on plain paper, and further an ink repellent containing a fluorinated silane coupling agent An ink for ink jet recording, an ink cartridge using the ink, an ink jet recording method, and a recorded matter that can be applied without problems to an ink jet head having a layer or an ink repellent layer containing a silicone resin can be provided.

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.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. The “parts” in the blending amounts are all “parts by weight”.

・イオン交換水 ８０．０部
上記分散剤を水に加えて溶解し、続いて顔料を混合・攪拌して充分に湿潤したところで、φ０．５ｍｍジルコニアビーズを充填した混練装置：ダイノーミルＫＤＬ Ａ型（ＷＡＢ社製）を用いて、２０００ｒｐｍで６０分間混練を行なった。次いで、ミルベースを取り出し、１μｍのフィルターで濾過して、イエロー顔料分散体ｙ２を得た。 Each pigment dispersion was prepared as shown below.
<Pigment dispersion y2>
・ C. I. Pigment Yellow 155 15.0 parts (manufactured by Clariant Japan: TONER YELLOW 3GP)
-5.0 parts of a dispersant represented by the following structural formula (5)

・ Ion-exchanged water 80.0 parts The above dispersant was dissolved in water, and then the mixture was mixed and stirred to sufficiently wet the kneading apparatus filled with φ0.5 mm zirconia beads: Dino mill KDL A type ( Kneading for 60 minutes at 2000 rpm. Subsequently, the mill base was taken out and filtered through a 1 μm filter to obtain a yellow pigment dispersion y2.

<Pigment dispersion m2>
The pigment is C.I. I. A magenta pigment dispersion m2 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y2, except that it was changed to CI Pigment Red 122 (manufactured by Ciba Specialty Chemicals: Jet Magenta DMQ).

<Pigment dispersion c2>
The pigment is C.I. I. A cyan pigment dispersion c2 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y2, except that the pigment blue was changed to Pigment Blue 15: 3 (manufactured by BASF Japan: HELIOGEN Blue D7079).

<Pigment dispersion k2>
Except that the pigment was changed to carbon black (Degussa: NiPex150) and the dispersant was changed to sodium alkyl naphthalene sulfonate (Kao: Perex NB-L), the same method as for the pigment dispersion y2, A black pigment dispersion k2 having a pigment concentration of 15% was obtained.

<Pigment dispersion y3>
-Polymer synthesis-
(Polymer raw material 1)
-Styrene ... 11.2 parts-Acrylic acid ... 2.8 parts-Lauryl methacrylate ... 12.0 parts-Polyethylene glycol methacrylate ... 4.0 parts-Styrene macromer (manufactured by Toa Gosei Co., Ltd .: AS-6) ... 4.0 parts -Mercaptoethanol: 0.4 parts After fully replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube and dropping funnel with nitrogen gas, the above raw material 1 was charged to 65 ° C The temperature rose.
(Polymer raw material 2)
-Styrene ... 100.8 parts-Acrylic acid ... 25.2 parts-Lauryl methacrylate ... 108.0 parts-Polyethylene glycol methacrylate ... 36.0 parts-Hydroxyethyl methacrylate ... 60.0 parts-Styrene macromer (manufactured by Toa Gosei Co., Ltd .: AS-6) 36.0 parts Mercaptoethanol 3.6 parts Azobisdimethylvaleronitrile 2.4 parts Methyl ethyl ketone 18.0 parts Subsequently, the mixed solution of the raw material 2 was added over 2.5 hours. It was dripped in the heated flask.
After completion of the dropwise addition, a mixed solution of 0.8 parts of azobisdimethylvaleronitrile and 18.0 parts of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 part of azobisdimethylvaleronitrile was added, and further aging was performed for 1 hour.
After completion of the reaction, 364.0 parts of methyl ethyl ketone was added to the flask to obtain 800 parts of a polymer solution having a concentration of 50%.
A dispersion was prepared using the following materials containing this polymer solution. That is, after sufficiently stirring the pigment and the polymer solution, they were kneaded 20 times using a three-roll mill (manufactured by Noritake Company: NR-84A). The obtained paste was put into 200 parts of ion-exchanged water and sufficiently stirred, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain a yellow dispersion y3 having a pigment concentration of 15%.
(Dispersion material)
・ C. I. Pigment Yellow 74 (manufactured by Clariant Japan:
HANSA Yellow 5GX01) 26.0 parts Polymer solution 28.0 parts 1 mol / L aqueous potassium hydroxide solution 13.6 parts Methyl ethyl ketone 20.0 parts Ion-exchanged water 30.0 parts

<Pigment dispersion m3>
The pigment is C.I. I. A magenta pigment dispersion m3 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y3, except that it was changed to CI Pigment Red 122 (manufactured by Ciba Specialty Chemicals: Jet Magenta DMQ).

<Pigment dispersion c3>
The pigment is C.I. I. A cyan pigment dispersion c3 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y3, except that the pigment was changed to CI Pigment Blue 15: 3 (manufactured by BASF Japan: HELIOGENBlue D7079).

<Pigment dispersion k3>
A black pigment dispersion k3 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y3 except that the pigment was changed to carbon black (NiPex 150, manufactured by Degussa).

<Pigment dispersion y4>
C. I. 300 parts of Pigment Yellow 74 (manufactured by Clariant Japan: HANSA Yellow 5GX01) was mixed well with 1000 parts of water, and 450 parts of sodium hypochlorite (effective chlorine concentration: 12 mol%) was added dropwise to 100 to 105 ° C. For 8 hours.
Next, 100 parts of sodium hypochlorite (effective chlorine concentration: 12 mol%) was further added to this solution, and dispersed for 2 hours at 2000 rpm using a Dinomill KDL A type (manufactured by WAB) filled with φ0.5 mm zirconia beads. did.
Next, the obtained slurry was diluted 10-fold with water, the pH was adjusted with lithium hydroxide, and then desalted and concentrated with an ultrafiltration membrane to a conductivity of 0.2 mS / cm.
Further, coarse particles were removed by centrifugation, and filtered through a 1 μm nylon filter to obtain a yellow pigment dispersion y4 having a pigment concentration of 15%.

<Pigment dispersion m4>
The pigment is C.I. I. A magenta pigment dispersion m4 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y4, except that it was changed to CI Pigment Violet 19 (manufactured by Ciba Specialty Chemicals: CINQUASIA PACIFIC Red2020).

<Pigment dispersion c4>
The pigment is C.I. I. A cyan pigment dispersion c4 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y4, except that the pigment was changed to CI Pigment Blue 15: 3 (manufactured by BASF Japan: HELIOGENBlue D7079).

<Pigment dispersion k4>
A black pigment dispersion k4 having a pigment concentration of 15% was obtained in the same manner as the pigment dispersion y4 except that the pigment was changed to acidic carbon black (manufactured by Cabot: Monarch 1300).

Example 1
<Ink Y1>
・ C. I. Direct yellow 142 ... 3.0 parts (Daiwa Kasei Co., Ltd .: DaiwaIJ Yellow 307HLR)
Surfactant A: Structural formula (2) Rf: —CF ₃ , M: ammonium, q = 6,
Solid content 30% (Omnova Co., Ltd .: Polyfox PF-136A) 0.1 part Surfactant B: Structural formula (3) R ³ : Carbon number 9, R ⁴ : Hydrogen, t = 2, u = 7 ,
(Nippon Emulsion Co., Ltd .: EMALEXDAPE-0207) ... 1.0 part Surfactant C: Polyether-modified silicone oil ... 0.01 part (Shin-Etsu Silicone Co., Ltd .: KF-6004)
-Glycerin ... 8.0 parts-Propylene glycol ... 16.0 parts-Acrylic silicone resin emulsion (manufactured by Showa Polymer Co., Ltd .: AP4710) ... 1.0 part-2,2,4-trimethyl-1,3-pentanediol ... 2.0 parts-Lithium hydroxide ... 0.1 part-Antiseptic / antifungal agent (manufactured by Avecia: Proxel LV) ... 0.1 part-Ion exchange water ... 68.69 parts The above materials are dissolved in ion exchange water. And 0.2 μm filter to obtain ink Y1 for ink jet recording.
<Ink M1>
The dye of ink Y1 is C.I. I. Ink jet recording ink M1 was obtained by the same prescription and method except that it was changed to Acid Red 52 (manufactured by Daiwa Kasei Co., Ltd .: Daiwa IJ Red 207H).
<Ink C1>
Ink C1 for inkjet recording was obtained by the same formulation and method except that the dye of ink Y1 was changed to Direct Blue 199 (manufactured by Ciba Specialty Chemicals: IRGASPPERSE JET CYANL).
<Ink K1>
For ink jet recording, the same formulation and method except that the dye of ink Y1 was changed to 20 parts direct black 168 (manufactured by Clariant Japan: Direct Black HEF Liquid) and the ion exchange water was changed to 51.69 parts. Ink K1 was obtained.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Example 2
<Ink Y2>
· Pigment dispersion y2 ... 30.0 parts Surfactant A: Structural Formula _{^{(1) R 1: H,}} Rf: -CF 2 CF 3, m = 20,
n + p = 4-8, solid content 50% (Omnova: Polyfox PF-151N)
... 0.2 parts Surfactant B: Structural formula (3) Sum of carbon numbers of R ³ and R ⁴ = 11 to 13, r = 5,
s = 3.5 (Nippon Shokubai Co., Ltd .: Softanol EP5035) ... 0.9 part Surfactant C: Polyether-modified silicone oil ... 0.75 part (Shin-Etsu Silicone Co., Ltd .: KF-353)
-Glycerin ... 12.0 parts-1,3-butanediol 18.0 parts-Urethane resin emulsion (solid content 35%, manufactured by Mitsui Takeda Chemical Co., Ltd .: W-5661)
... 6.0 parts-Styrene-acrylic resin emulsion (solid content 48%, manufactured by BASF Japan Ltd .:
Jonkrill 7100) ... 2.0 parts-2-ethyl-1,3-hexanediol ... 2.0 parts-2-amino-2-ethyl-1,3-propanediol ... 0.2 parts-Antiseptic / antifungal agent (Avecia Co., Ltd .: Proxel LV) 0.1 part ・ Ion-exchanged water 27.85 parts The above materials other than the pigment dispersion y2 were dissolved in ion-exchanged water, a vehicle was prepared and sufficiently stirred, and then the pigment The ink was mixed with the dispersion y2 and filtered through a 1 μm filter to obtain an ink Y2 for inkjet recording.
<Ink M2>
The same formulation and method except that the pigment dispersion y2 (30.0 parts) of the ink Y2 was changed to the pigment dispersion m2 (50.0 parts) and the ion exchange water was changed to 7.85 parts. Ink jet recording ink M2 was obtained.
<Ink C2>
An inkjet recording ink C2 was obtained by the same formulation and method except that the pigment dispersion y2 of the ink Y2 was changed to the pigment dispersion c2.
<Ink K2>
The same formulation and method except that the pigment dispersion y2 (30.0 parts) of the ink Y2 was changed to the pigment dispersion k2 (50.0 parts) and the ion-exchanged water was changed to 7.85 parts. Ink jet recording ink K2 was obtained.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Example 3
<Ink Y3>
· Pigment dispersion y3 ... 30.0 parts Surfactant A: Structural Formula _{(2) Rf: -CF 2 CF} 3, M: ammonium, q = 6,
Solid content 30% (Omnova Co., Ltd .: Polyfox PF-156A) ... 0.6 part Surfactant B: Structural formula (3) Sum of carbon number of R ³ and R ⁴ = 11 to 13, r = 7,
s = 2.5 (Nippon Shokubai Co., Ltd .: Softanol EP7025) ... 0.3 part Surfactant C: Polyether-modified silicone oil ... 0.6 part (Toray Dow Corning Silicone Co., Ltd .: L-7604)
-Glycerin ... 16.0 parts-3-methyl-1,3-butanediol ... 16.0 parts-2-ethyl-1,3-hexanediol ... 2.0 parts-Fluorine resin emulsion (solid content 50%, Asahi Glass Co., Ltd .: Lumiflon FE4500)
... 5.0 parts-2-amino-2-ethyl-1,3-propanediol ... 0.2 parts-Antiseptic / antifungal agent (manufactured by Avecia: Proxel LV) ... 0.1 parts-Ion-exchanged water ... 29. 2 parts The above materials other than the pigment dispersion y3 are dissolved in ion-exchanged water, a vehicle is prepared and sufficiently stirred, mixed with the pigment dispersion y3, filtered through a 1 μm filter, and ink jet recording ink Y3 Got.
<Ink M3>
The same formulation and method except that the pigment dispersion y3 (30.0 parts) of the ink Y3 was changed to the pigment dispersion m3 (50.0 parts) and the ion exchange water was changed to 9.2 parts. Ink jet recording ink M3 was obtained.
<Ink C3>
An inkjet recording ink C3 was obtained by the same formulation and method except that the pigment dispersion y3 of the ink Y3 was changed to the pigment dispersion c3.
<Ink K3>
The same formulation and method except that the pigment dispersion y3 (30.0 parts) of the ink Y3 was changed to the pigment dispersion k3 (50.0 parts) and the ion exchange water was changed to 9.2 parts. Ink jet recording ink K3 was obtained.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Example 4
<Ink Y4>
Pigment dispersion y4 30.0 parts Surfactant A: Structural formula (1) R ¹ : H, Rf: —CF ₂ CF ₃ , m = 20
n + p = 4-8, solid content 50% (Omnova: Polyfox PF-151N)
0.12 part Surfactant B: Structural formula (3) Sum of carbon number of R ³ and R ⁴ = 11 to 13, r = 9,
s = 5 (Nippon Shokubai Co., Ltd .: Softanol EP9050) ... 0.90 parts Surfactant C: Polyether-modified silicone oil ... 1.2 parts (Toray Dow Corning Silicone Co., Ltd .: SF-3771)
-Glycerin ... 10.0 parts-1,6 hexanediol ... 20.0 parts-Styrene-acrylic resin emulsion (solid content 48%, manufactured by BASF Japan Ltd .:
Jonkrill 7100) ... 2.0 parts-2-ethyl-1,3-hexanediol ... 2.0 parts-Triethanolamine 0.2 parts-Antiseptic / antifungal agent (manufactured by Avecia: Proxel LV) ... 0.1 Part ・ Ion-exchanged water ... 33.48 parts The above materials other than the pigment dispersion y4 were dissolved in ion-exchanged water, a vehicle was prepared and sufficiently stirred, then mixed with the pigment dispersion y4, and filtered through a 1 μm filter. Thus, an inkjet recording ink Y4 was obtained.
<Ink M4>
The same formulation and method except that the pigment dispersion y4 (30.0 parts) of the ink Y4 was changed to the pigment dispersion m4 (50.0 parts) and the ion exchange water was changed to 13.48 parts. Ink jet recording ink M4 was obtained.
<Ink C4>
Ink jet recording ink C4 was obtained by the same formulation and method except that the dispersion of ink Y4 was changed to pigment dispersion c4.
<Ink K4>
The same formulation and method except that the pigment dispersion y4 (30.0 parts) of the ink Y4 was changed to the pigment dispersion k4 (50.0 parts) and the ion exchange water was changed to 13.48 parts. Ink jet recording ink K4 was obtained.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Example 5
An ink cartridge for a printer (Ricoh Co., Ltd .: IPSiO G707) was filled with a set of four color inks (Y2, M3, C2, K4) having different types and composition ratios of surfactants. .

Comparative Example 1
Ink Y5, M5 for inkjet recording was prepared in the same formulation and method as Example 2 except that surfactant C (SF-3771) was not added to inks Y4, M4, C4, K4 of Example 4. , C5 and K5 were obtained.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Comparative Example 2
Ink Y2 for inkjet recording was prepared in the same manner as in Example 2 except that surfactant A (Polyfox PF-151N) was not added to inks Y2, M2, C2, and K2 of Example 2. , M6, C6 and K6 were obtained, respectively.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Comparative Example 3
The implementation ink Y2 of Example 2, M2, C2, interface in K2 active agent A (POLYFOX _{PF-151N), C 12 H} 4 F 11 NaO 4 S ( Neos Co., Ltd.: FT-110) except for changing the Ink jet recording inks Y7, M7, C7, and K7 were obtained by the same formulation and method as in Example 2, respectively.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Comparative Example 4
Ink Y8, M8, inkjet recording ink Y8, M8, Ink Y3, M3, C3, K3 of Example 3 was the same formulation and method as Example 3 except that surfactant B (Softanol EP7025) was not added. C8 and K8 were obtained, respectively.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Comparative Example 5
Except that the ink Y3 in Example 3, M3, C3, surface in K3 active agent B (SOFTANOL _EP7025), was changed to the surfactant represented by _{C 13 H 27 (OCH 2 CH} 2) 8 -OH, Ink jet recording inks Y9, M9, C9, and K9 were obtained by the same formulation and method as in Example 3.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

Comparative Example 6
The surfactant C (SF-3771) in the inks Y4, M4, C4, and K4 of Example 4 was changed to polyoxyethylene acetylenic glycol [manufactured by Kawaken Fine Chemicals Co., Ltd .: acetylenol E100, solid content 100%, the following structural formula (6 Except for the point changed to]), inkjet recording inks Y10, M10, C10, and K10 were obtained by the same formulation and method as in Example 2, respectively.
The obtained four-color ink set was filled in an ink cartridge for a printer (manufactured by Ricoh: IPSiO G707).

The viscosity, foaming property, and defoaming property of each ink of the above Examples and Comparative Examples were measured as follows. The results are shown in Tables 1 and 2.
(1) Viscosity Viscosity was measured at 25 ° C. using RC-500 manufactured by Toki Sangyo Co., Ltd. immediately after the preparation of each ink for ink jet recording (initial stage) and after standing for 1 month at 50 ° C. (aging).
The change rate (%) of the viscosity with time with respect to the initial viscosity is also shown. If the rate of change is within ± 10%, the storage stability is good, and if it changes more than that, it is judged that the storage stability is poor.

(2) Foam test 10 ml of each ink stored at 50 ° C. for 1 month after preparation is put into a 100 ml graduated cylinder in an environment of 25 ° C., then air of constant pressure is injected, and the total volume of ink and bubbles is added. When 100 ml was reached, the air injection was stopped.
Measure the time from the start of air injection to the stop of injection (foaming time) and the time from when the air injection stops until the total volume of ink and bubbles is reduced to 20 ml (foaming time). The foaming property and antifoaming property were evaluated on the basis. Only A is acceptable for both foaming and antifoaming properties.
[Foamability evaluation criteria]
A: Foaming time is 30 seconds or more B: Foaming time is 10 seconds or more and less than 30 seconds C: Foaming time is less than 10 seconds [defoaming evaluation criteria]
A: Defoaming time is less than 30 seconds B: Defoaming time is more than 30 seconds and less than 300 seconds C: Defoaming time is more than 300 seconds

The nozzle plate of the printer head was produced as follows (α) (β).
(Α) A SiO ₂ layer having a thickness of about 10 mm was formed by a sputtering method on a polyimide film (manufactured by DuPont: no Kapton particles added), and then a modified perfluoropolyoxetane (Daikin) having a thickness of about 50 mm by a vacuum deposition method. An ink repellent layer (manufactured by Kogyo Co., Ltd .: OPTOOL DSX) was formed, and nozzle holes were processed with an excimer laser from the polyimide film side to produce a nozzle plate.
(Β) On the surface of the Ni electroforming nozzle, a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd .: SR2411) was applied with a dispenser to form a silicone layer having a thickness of 1.2 μm. At this time, the nozzle holes and the back surface of the nozzle plate were masked with a water-soluble resin, and were peeled off after the silicone layer was formed. Then, it was left to stand at room temperature for 2 days to be cured, and a nozzle plate having an ink repellent layer was formed.
Each nozzle recording produced by the Example and the comparative example which set the nozzle plate produced by the method of said ((alpha)) ((beta)) to the printer (the Ricoh company make: IPSiO G707) of the structure of FIGS. 1-2 mentioned above. The ink was filled in the ink cartridge and set, and the saturation, color bleed, ejection stability, and nozzle surface adhesion evaluation on plain paper were performed by the following methods.
The results are summarized in Tables 3 and 4. The (α) column shows the case where the (α) nozzle plate is used, and the (β) column shows the case where the (β) nozzle plate is used.

(1) Saturation Using the following recording evaluation paper (plain paper), using only magenta, cyan and yellow color inks (black ink is not subject to evaluation), printing a solid image in one pass, and after drying, The value of L * a * b * was measured using a reflection type color spectrophotometric densitometer (manufactured by X-Rite).
Saturation values (average values of three types of test papers) for the saturation values (yellow: 91.34, magenta: 74.55, cyan: 62.82) of the standard color (Japan color ver. 2) The ratio was calculated and evaluated according to the following evaluation criteria.
<Recording evaluation form>
・ My paper (manufactured by NBS Ricoh)
・ Multiace (Fuji Xerox Office Supply)
・ PB paper (manufactured by Canon Inc.)
<Evaluation criteria>
A: 0.9 or more B: 0.8 or more and less than 0.9 C: Less than 0.8

(2) Color bleed My paper (printing pattern using black ink characters printed in magenta, cyan and yellow color ink solid image portions, and using the printer set with the nozzle plates (α) and (β)) (Printed by NBS Ricoh). The printing conditions were 100% duty, the recording density was 300 dpi, and one-pass printing.
The color bleed (smear) between the color ink and the black ink was visually observed and evaluated according to the following criteria. Only rank A is acceptable.
〔Evaluation criteria〕
A: No color bleeding occurs and black characters can be clearly recognized.
B: Some color bleeding occurs and black characters blur slightly.
C: Color bleeding occurs and black characters are difficult to recognize.

(3) Ejection stability Using the printer with the nozzle plate set, continuous printing was performed for 10 minutes, and a moisturizing cap was applied with the ink adhering to the head surface. The printer was kept at 50 ° C and 60% RH for 1 month. After leaving, cleaning was performed to restore the same level as before. Then, an intermittent printing test was performed under the following conditions to evaluate the discharge stability.
That is, after printing the following print pattern charts continuously for 20 sheets, it was put into a pause state in which printing was not performed for 20 minutes, this was repeated 50 times, and a total of 1000 sheets were printed, and then the same chart was printed. The presence or absence of streaks, white spots, and jet disturbance in the 5% chart solid portion at the time was visually evaluated. In addition, the printing pattern printed each ink at 100% duty in a chart in which each color printing area is 5% in the entire area of the paper. The printing conditions were a recording density of 360 dpi and one-pass printing. The evaluation criteria are shown below, but only rank A is an allowable range.
〔Evaluation criteria〕
A: There are no streaks, white spots, or jet disturbance in the solid part.
B: Streaks, white spots, and jet disturbance are slightly observed in the solid portion.
C: Streaks, white spots, and jet turbulence are observed throughout the solid portion.

(4) Nozzle surface adhering Place the printer in a constant temperature and humidity chamber, set the environment in the bath to a temperature of 32 ° C and a humidity of 30%, and print 20 sheets of the following print pattern charts continuously, then print for 20 minutes. In a resting state, this was repeated 50 times, and after a total of 1,000 copies were printed, the nozzle plate was observed with a microscope to determine the presence or absence of sticking.
In addition, the printing pattern printed each ink at 100% duty in a chart in which each color printing area is 5% in the entire area of the paper. The printing conditions were a recording density of 300 dpi and one-pass printing. Evaluation criteria are shown below, but rank A is the allowable range.
〔Evaluation criteria〕
A: No sticking in the vicinity of the nozzle.
B: There is sticking in the vicinity of the nozzle.
C: There is sticking on the entire surface of the nozzle plate.

As can be seen from Tables 1 and 2 above, in the examples, the rate of change in viscosity after storage, foaming properties, and defoaming properties are all ranked A. On the other hand, in Comparative Example 2 that does not contain surfactant A and Comparative Example 3 in which another surfactant is used instead of surfactant A, the foaming properties and defoaming properties are B and C ranks. In Comparative Example 4 that does not contain Surfactant B, and in Comparative Example 5 that uses another surfactant instead of Surfactant B, the rate of change in viscosity after storage exceeds 10%, and storage Stability will deteriorate.
Further, as can be seen from Tables 3 and 4 above, in the examples, the saturation, color bleed, ejection stability, and adhesion evaluation are all A ranks. On the other hand, in the comparative example 1 which does not contain the surfactant C, the color bleed becomes C rank, and in the comparative examples 2 to 4, the discharge stability becomes C rank. Further, in Comparative Examples 1 to 6 including Comparative Example 6 using another surfactant instead of the surfactant C, B rank is included in most items, and it is clearly inferior to the examples. It is.

1b Common liquid chamber 2a Fluid resistance part 2b Pressurized liquid chamber 2c Communication port 3a Nozzle 5f Drive part 5g Support part (non-drive part)
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 Conveying roller 158 Tension roller 200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge case

JP 2007-084807 A

Claims (7)

It contains at least a colorant, surfactant A, surfactant B, surfactant C, water-soluble organic solvent and water, and the surfactant A is represented by the following structural formula (1) or structural formula (2). The inkjet recording ink, wherein the surfactant B is represented by the following structural formula (3), and the surfactant C is a polyether-modified silicone compound.

(In the above formula, R ¹ is hydrogen, an alkyl group, or an acyl group, Rf is —CF ₃ or —CF ₂ CF ₃ , and m, n, and p are natural numbers.)

(In the above formula, M is an alkali metal, ammonium, phosphonium, or alkanolamine, Rf is —CF ₃ or —CF ₂ CF ₃ , and q is a natural number.)

(In the above formula, R ³ and R ⁴ are each hydrogen or an alkyl group, and r, s, t, and u are natural numbers.) 2. The ink for ink jet recording according to claim 1, wherein an organic pigment or carbon black dispersed with a nonionic dispersant represented by the following structural formula (4) is used as the colorant.

(In the above formula, R ² is an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, or an allyl group, l is an integer of 0 to 7, and k is an integer of 20 to 80. is there.)   2. The ink for ink jet recording according to claim 1, wherein a self-dispersing pigment obtained by reacting a hydrophilic group on the surface of an organic pigment or carbon black is used as the colorant.   The ink for inkjet recording according to any one of claims 1 to 3, further comprising a resin emulsion.   An ink cartridge containing the ink for ink jet recording according to claim 1.   An ink jet recording apparatus comprising an ink jet head having an ink repellent layer containing a fluorine-based silane coupling agent or an ink repellent layer containing a silicone resin is used to eject the ink for ink jet recording according to any one of claims 1 to 4. An ink jet recording method characterized by comprising:   A recorded matter recorded by using the ink for ink jet recording according to claim 1.

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