JP5703602B2 - Ink set for ink jet recording, ink jet recording method, recorded matter - Google Patents

Description

  The present invention relates to an ink set for ink jet recording, an ink jet recording method using the ink set, and a recorded matter.

Inkjet printers have been remarkably popular due to the advantages of low noise and low running cost, and color printers that can print on plain paper have come to the market.
However, image color reproducibility, abrasion resistance, durability, light resistance, image drying, character bleeding (feathering), color boundary bleeding (color bleeding), double-sided printability, ejection stability, etc. are required. It is very difficult to satisfy all the characteristics, and the ink to be used is selected according to the characteristics that are prioritized according to the application.
Ink used for ink jet recording generally contains water as a main component and contains a colorant and a wetting agent such as glycerin for the purpose of preventing clogging. As colorants, dyes and pigments are mainly used. Dyes are excellent in color developability and stability, but inferior in light resistance, gas resistance, water resistance and the like of images. On the other hand, pigments are excellent in light resistance, gas resistance and water resistance, but have a problem of poor color development.
Dye inks have a problem that they tend to bleed on plain paper or the like, and in particular, there is a problem of eliminating bleed (color bleeding) at the boundary between black ink and color ink. As a method for solving color bleeding, there is a method of preventing the black ink from penetrating into the color ink region on the image by increasing the penetrability of the color ink over the penetrability of the black ink to paper. We are trying to respond by adding the agent and adjusting the amount, but we have not reached the same level as the pigment ink. In addition, there is a method of suppressing the permeability by increasing the ink viscosity, but there is an upper limit to the viscosity for stably ejecting ink by inkjet, so that a sufficient effect is not obtained at present. .

There is a method of adding a surfactant to improve the penetrability, but the surfactant lowers the surface tension of the ink, so bubbles are likely to be generated. Especially in the case of ink jet, when ink is filled into the ink jet head, etc. In the case where bubbles are generated, blocking the ink flow path in the head leads to problems such as ejection failure. In order to reduce bubbles, a method of adding an antifoaming agent such as silicon oil, silica fine particles, and lower alcohol to the ink is generally used. However, silicon oil and silica fine particles are not soluble in water and often cause problems such as aggregation when dyes are used as colorants. Even when pigments are used, the dispersion stability of pigment particles is reduced. Often damaging. In addition, since the lower alcohol is highly volatile, there is a problem that the effect of reducing bubbles is not sustained, and color unevenness occurs when printed on paper. At present, the effect of reducing bubbles is not sufficiently obtained.
As a publicly known document, Patent Document 1 describes an inkjet ink in which a fluorine-based surfactant is applied to a dye ink. Further, Patent Document 2, although the inkjet ink according to the full Tsu Motokei surfactant dye ink is described, used in the present invention, the structural formula having defoaming properties to fluorine-containing surfactant Since the material represented by (1) is not used, the generated bubbles are difficult to disappear, and bubbles are generated when ink is filled into the ink jet head and the ink flow path is blocked, causing problems such as ejection failure. End up.

  The present invention solves the bleed, which is a problem of water-based ink using a water-soluble dye as a coloring material, and uses an ink set for ink jet recording that has high ejection reliability and excellent image quality because it does not foam. An object is to provide an ink jet recording method and a recorded matter.

［構造式（６）］

ただし、上記式中、Ａ、Ｂはアルコキシ基、Ｔはアルカノールアミノ基、Ｄは−ＳＯ_３Ｍ（Ｍはアルカリ金属）であり、ｔは１である。
４） 前記マゼンタインクに用いられる水溶性染料が下記構造式（７）で表されることを特徴とする１）又は２）に記載のインクジェット記録用インクセット。
［構造式（７）］

ただし、上記式中、Ｘは水素又はアリール基、Ｚは水素又はハロゲン、Ｍはアルカリ金属である。
５） 前記シアンインクに用いられる水溶性染料が下記構造式（８）で表されることを特徴とする１）又は２）に記載のインクジェット記録用インクセット。
［構造式（８）］

ただし、上記式中、Ｍはアルカリ金属又は第４級アンモニウムであり、ｔは０〜３の整数、ｕは１〜２の整数である。
６） １）〜５）のいずれかに記載のインクジェット記録用インクセットを用い、各インクに刺激を印加して飛翔させ画像を記録することを特徴とするインクジェット記録方法。
７） １）〜５）のいずれかに記載のインクジェット記録用インクセットを用いて記録された記録物。 The above problems are solved by the following inventions 1) to 7).
1) In an inkjet recording ink set comprising at least black, cyan, magenta, and yellow inks, each ink is represented by at least a water-soluble dye, a water-soluble solvent, a fluorosurfactant, and the following structural formula (1). An ink set for ink-jet recording , comprising: a compound having water and water, wherein the fluorosurfactant is a compound represented by the following structural formula (2 ):
[Structural formula (1)]
^{_{HOR 1 R 3 C- (CH 2}} ) j -CR 2 R 4 OH
In the above formula, R ¹ and R ² are each independently an alkyl group having 3 to 6 carbon atoms, R ³ and R ⁴ are each independently an alkyl group having 1 to 2 carbon atoms, and j is It is a natural number of 1-6.
[Structural formula (2)]
^{_{Rf 1 -CH 2 CH (OH)}} CH 2 O- (CH 2 CH 2 O) k -Q
However, in the above formula, Rf ¹ is _-C 3 _{F 7} or _-C 4 _F 9, Q is _-C b _{H 2b +} 1 (b is a natural number of _{11~19), - CH 2 CH (} OH) CH 2 - C ₃ F _7, or represents _{-CH 2 CH (OH) CH 2} -C 4 F 9, k is 20 to 35.
2) The ratio between the content S of the water-soluble solvent and the content W of water is in the range of 0.7 ≦ S / W ≦ 1.6, and each ink has no flash point. The ink set for inkjet recording as described in 1).
3) The ink set for inkjet recording according to 1) or 2), wherein the water-soluble dye used in the yellow ink is represented by the following structural formula (5) or structural formula (6).
[Structural formula (5)]

[Structural formula (6)]

In the above formula, A and B are alkoxy groups, T is an alkanolamino group, D is —SO ₃ M (M is an alkali metal), and t is 1.
4) The ink set for inkjet recording according to 1) or 2), wherein the water-soluble dye used in the magenta ink is represented by the following structural formula (7).
[Structural formula (7)]

However, in said formula, X is hydrogen or an aryl group, Z is hydrogen or a halogen, M is an alkali metal.
5) The ink set for inkjet recording according to 1) or 2), wherein the water-soluble dye used in the cyan ink is represented by the following structural formula (8).
[Structural formula (8)]

However, in said formula, M is an alkali metal or quaternary ammonium, t is an integer of 0-3, u is an integer of 1-2.
6) An ink jet recording method comprising recording an image using the ink set for ink jet recording according to any one of 1) to 5) by applying a stimulus to each ink to fly.
7) A recorded matter recorded using the ink set for ink jet recording according to any one of 1) to 5).

  According to the present invention, a bleed that is a problem of water-based ink using a water-soluble dye as a coloring material is solved, and since there is no foaming, the ejection reliability is high and the ink set for ink jet recording excellent in image quality is provided. The ink jet recording method and recorded matter used can be provided.

FIG. 4 is a perspective explanatory view showing a state where an ink cartridge loading unit cover of the ink jet recording apparatus is opened. It is a schematic block diagram explaining the whole structure of an inkjet recording device. FIG. 3 is a partially enlarged explanatory view of the ink jet recording apparatus shown in FIG. 2.

Hereinafter, the present invention will be described in detail.
The present inventors have at least a water-soluble dye, a water-soluble solvent, a fluorosurfactant, and a structural formula (1) as each ink of an ink set for ink jet recording composed of at least black, cyan, magenta, and yellow inks. compounds represented, and with those containing water, as the fluorine-containing surfactant, the use of compounds represented by the structural formula (2), a compound represented by the structural formula (1) is, penetration It has been found that it not only functions as an agent but also exhibits antifoaming properties, and has reached the present invention.
In order to reliably fill the ink flow path leading to the nozzle hole of the inkjet head, it is necessary to reduce the surface tension of the ink and improve the wettability to the flow path. By adding the fluorosurfactant represented by the structural formula (2 ) , the surface tension can be reduced to 30 mN / m or less and the wettability to the flow path can be ensured, but it is once generated easily with foaming. Since the bubbles do not disappear, the bubbles generated in the ink flow path impede ink filling into the nozzles, and when ink droplets are ejected, defects such as non-ejection and bending occur. On the other hand, the compound represented by the structural formula (1) has an antifoaming property, and when used in combination with the fluorosurfactant represented by the structural formula (2 ), it is possible to effectively suppress foaming. it can. Furthermore, since the surface tension can be suppressed to 30 mN / m or less, the nozzle can be reliably filled, and ink droplets can be discharged well. In addition to this, by adding a surfactant, the permeability on the recording medium is improved, and even on plain paper, there is no white spot in the solid portion, and the permeability balance between the inks is maintained. High quality images with reduced bleeding can be obtained.

In order for the surfactant to exhibit high penetrability, the balance between the hydrophilic part and the non-hydrophilic part in the surfactant molecule is important, and the ratio of the hydrophilic part to the whole surfactant is expressed numerically by the HLB value. Things have been done. In the case of a nonionic surfactant, the surfactant expressed by “HLB = molecular weight of hydrophilic group / molecular weight of surfactant × 20” and having an HLB value in the range of about 7 to 15 generally has high permeability. A surfactant having an HLB value in the range of about 0 to 4 is generally considered to have antifoaming properties. In the present application, the compounds represented by the structural formulas (1) and (2 ) correspond to the nonionic surfactant, and the compound represented by the structural formula (1) has a high defoaming property, and the structural formula The compound represented by (2) is characterized by having both antifoaming properties and permeability.

-Penetration agent-
When a penetrant is added to the ink, the surface tension is reduced, the ink filling property to the nozzle is improved, the ejection stability is improved, and the ink penetrates into the recording medium after the ink droplet has landed. Since it becomes faster, feathering and color bleeding can be reduced. As the penetrant, a solvent represented by the structural formula (1), a surfactant, or a water-soluble solvent can be used. The range of the appropriate surface tension in the ink of the present invention is 20 to 30 mN / m at 25 ° C.
Since the penetrant represented by the structural formula (1) has a very low solubility in water of less than 0.1% by weight, the blending amount is less than 1% by weight even in an ink containing a water-soluble solvent and water. It is preferable to use in the range of 0.01 to 0.5% by weight.
In the case of the compound represented by the structural formula (1), HLB is maximized because the carbon number of R ¹ and R ² is “3”, the carbon number of R ³ and R ⁴ is “1”, and j is “ 1 ”, and HLB = OH molecular weight × 2 / surfactant molecular weight × 20 = 34/188 × 20 = 3.6. On the contrary, the HLB is minimized in the structure in which the carbon number of R ¹ and R ² is “6”, the carbon number of R ³ and R ⁴ is “2”, and j is “6”, and HLB = 34 /370×20=1.8. However, if the non-hydrophilic portion becomes larger than this, it hardly dissolves in water, so that it is separated from the ink in the ink cartridge or the ink path, and sufficient defoaming properties cannot be exhibited. Therefore, if it is in the range of the structural formula (1), sufficient antifoaming properties can be exhibited even if it is added to the inkjet ink, and therefore it can be suitably used.

［構造式（１）−２］（Ｒ^１、Ｒ^２：−Ｃ_４Ｈ_９、Ｒ^３、Ｒ^４：−ＣＨ_３、ｊ＝２）
２，４，７，９−テトラメチルデカン−４，７−ジオール

Particularly effective structures are shown below.
[Structural Formula (1) -1] (R ¹ , R ² : —C ₅ H ₁₁ , R ³ , R ⁴ : —CH ₃ , j = 2)
2,5,8,11-tetramethyldodecane-5,8-diol

[Structural Formula (1) -2] (R ¹ , R ² : —C ₄ H ₉ , R ³ , R ⁴ : —CH ₃ , j = 2)
2,4,7,9-tetramethyldecane-4,7-diol

-Surfactant-
Surfactants have the function of imparting penetrability, and are roughly classified into nonionic surfactants, anionic surfactants and amphoteric surfactants by hydrophilic groups, and silicone surfactants and fluorine surfactants by hydrophobic groups. An agent or the like is usefully used. Further, two or more kinds of surfactants can be mixed and used.
Fluorosurfactants include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide, perfluoro. Although alkyl ether compounds, and the like, in the ink of the present invention have use a fluorine-based surfactant represented by the structural formula (2).

In the case of the compound represented by the structural formula (2), the maximum HLB is that “Rf ¹ ” is “—C ₃ F ₇ ”, “k = 35”, and “Q” is “—C ₁₁ H _23. HLB = (molecular weight of polyethylene glycol × 35 + OH molecular weight) / molecular weight of surfactant × 20 = 1557/1938 × 20 = 16.1. Conversely, HLB is minimized because “Rf ¹ ” is “—C ₄ F ₉ ”, “k = 20”, and “Q” is “—CH ₂ CH (OH) CH ₂ —C ₄ F ₉ ”. HLB = (molecular weight of polyethylene glycol × 20 + molecular weight of OH × 2) / molecular weight of surfactant × 20 = 914/1466 × 20 = 12.5. Therefore, if it is a compound represented by Structural formula (2), although HLB is a little high as a osmotic agent, it can exhibit sufficient permeability | transmittance and can be used suitably for the ink for inkjet.

［構造式（２）−２］
（Ｒｆ^１：−Ｃ_４Ｆ_９、ｋ＝３５、Ｑ：−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_４Ｆ_９）

［構造式（２）−３］
（Ｒｆ^１：−Ｃ_４Ｆ_９、ｋ＝２３、Ｑ：−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_４Ｆ_９）

In particular, the structure shown below is effective.
[Structural Formula (2) -1]
^{_{(Rf 1: -C 3 F 7}} , k = 21, Q: -C 12 H 25)

[Structural Formula (2) -2]
(Rf ¹ : —C ₄ F ₉ , k = 35, Q: —CH ₂ CH (OH) CH ₂ —C ₄ F ₉ )

[Structural Formula (2) -3]
(Rf ¹ : —C ₄ F ₉ , k = 23, Q: —CH ₂ CH (OH) CH ₂ —C ₄ F ₉ )

-Water-soluble solvent-
Each ink according to the present invention uses water as a liquid medium, and a water-soluble solvent is used as a wetting agent for preventing the ink from drying and as a penetrating agent for imparting permeability to the ink. A plurality of water-soluble solvents may be used in combination.
Each ink according to the present invention preferably has a ratio of the water-soluble solvent content S to the water content W in the range of 0.7 ≦ S / W ≦ 1.6. When S / W> 1.6, the amount of the water-soluble solvent is increased, so that a water-soluble dye is precipitated and the adverse effect of crystallization in the ink tends to occur. Even if a water-soluble solvent having a high boiling point is used, if the amount is large, the ink itself may have a flash point. In order to ensure the safety of the product, it is preferable that the ink does not have a flash point. On the other hand, when S / W <0.7, the amount of the water-soluble solvent decreases and the amount of the material represented by the structural formula (1) dissolved in the ink decreases. It can no longer be obtained.

  As the water-soluble solvent used as the penetrant, a polyol having 8 to 11 carbon atoms such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol is preferable. The amount of the water-soluble solvent used as the penetrating agent is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. When the blending amount is less than 0.1% by weight, the permeability is insufficient, so that the solid image portion cannot be covered with ink, causing problems such as a decrease in image density. However, a water-soluble solvent used as a penetrating agent has low solubility in water and does not dissolve when the blending amount exceeds 5% by weight, which causes problems such as poor ink storage stability.

Examples of the water-soluble solvent used as the wetting agent include the following.
Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, hexylene glycol, 1,3-butanediol, 3-methyl-1,3-butane Diol, 1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,6- Polyhydric alcohols such as hexanetriol and 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.

As other wetting agents, those containing sugar are preferable. Sugars include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, Examples include sucrose, trehalose, 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.
The derivatives of these saccharides are represented by the reducing sugars of the saccharides described above {for example, sugar alcohol [general formula HOCH ₂ (CHOH) _n CH ₂ OH (where n represents an integer of 2 to 5)]. The ], Oxidized sugars (eg, aldonic acid, uronic acid, etc.). Sugar alcohol is particularly preferable, and specific examples include maltitol and sorbit.

In each ink according to the present invention, by using the water-soluble solvent as a wetting agent, it is possible to create an ink excellent in storage stability and ejection stability.
The blending amount of the wetting agent in the ink is preferably 15 to 75% by weight, more preferably 35 to 65% by weight. In the range of 35 to 65% by weight, the drying property, the storage property and the reliability are very good. If the blending amount of the wetting agent is less than 15% by weight, water is evaporated from the nozzle holes of the ejection head and the viscosity increases, so that it becomes difficult to eject ink normally. On the other hand, when the amount exceeds 75% by weight, the dye is difficult to dissolve, which causes problems such as crystallization and precipitation of the dye and clogging of the nozzle holes.

-Water-soluble dye-
Examples of the water-soluble dye used in each ink according to the present invention include direct dyes, acid dyes, basic dyes, and reactive dyes. In particular, the dyes represented by the structural formulas (5), (6), (7), and (8) have excellent color developability and can be used favorably. Specific examples of water-soluble dyes include, but are not limited to, the following.
(Direct dye)
C. I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, etc .;
C. I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, etc .;
C. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163, etc .;
C. I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291 etc .;
C. I. Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132, 146, 154, 166, 168, 173, 195, 199, etc.

(Acid dyes)
C. I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397, etc .;
C. I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126 etc .;
C. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, etc .;
C. I. Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 205, 207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, etc .;
C. I. Acid Black 7, 24, 29, 48, 52: 1, 172, etc.

(Basic dye)
C. 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, 465, 67, 70, 73, 77, 87, 91 etc .;
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, etc .;
C. I. Basic violet 1, 3, 7, 10, 11, 27, etc .;
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, etc .;
C. I. Basic black 2, 8, etc.

(Reactive dye)
C. I. Reactive Yellow 1, 2, 3, 5, 11, 13, 14, 15, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 29, 35, 37, 40, 41, 42 47, 51, 55, 65, 67 etc .;
C. I. Reactive Red 1, 3, 13, 14, 17, 19, 21, 22, 23, 24, 25, 26, 29, 31, 32, 35, 37, 40, 41, 43, 44, 45, 46, 49 55, 60, 66, 74, 79, 96, 97, 180, etc .;
C. I. Reactive violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, etc .;
C. I. Reactive Blue 1, 2, 3, 5, 7, 8, 10, 13, 14, 15, 17, 18, 19, 21, 23, 25, 26, 27, 28, 29, 32, 35, 38, 41 63, 80, 95 etc .;
C. I. Reactive black 3, 4, 5, 7, 8, 11, 12, 14, 17, 21, 23, 26, 31, 32, 34, etc.

-PH adjuster-
Each ink according to the present invention can stabilize a dispersion state by adding a pH adjusting agent to keep it alkaline, and can stabilize ejection. When the pH is 11 or more, the amount of the ink jet head and the ink supply unit that dissolves increases, and problems such as ink deterioration, leakage, and ejection failure occur.
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 the like. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, and quaternary phosphonium hydroxide. Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

For each ink according to the present invention, conventionally known antiseptic / antifungal agents, chelating agents, rust inhibitors, antioxidants, ultraviolet absorbers, oxygen absorbers, light stabilizers, anti-kogation agents, etc. Additives can be appropriately selected and added.
-Antiseptic and fungicide-
Examples of antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol and the like.
-Chelating reagent-
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

-Antirust agent-
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
-Antioxidant-
Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
-UV absorber-
Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.

-Kogation inhibitor-
An anti-kogation agent can be added to each ink according to the present invention.
Kogation is a malfunction in a thermal head that heats ink instantaneously by passing a current through a heater and ejects ink using the force of ink foaming. It changes to an ink component when the ink is heated. This is a phenomenon in which altered substances adhere to the heater. When kogation occurs, heating by the heater is not normally performed, and the ejection force becomes weak, or in the worst case, ink cannot be ejected. Therefore, it is preferable to add an anti-kogation agent to the ink in order to prevent kogation.
Examples of the anti-kogation agent include polyphosphoric acid, polyaminocarboxylic acid, aldonic acid, hydroxycarboxylic acid, polyol phosphoric acid ester, and salts thereof, or an acid having an amino group and / or a salt thereof, or a methyl group. Or the ammonium salt of the acid which has a methylene group and a carboxyl group, etc. are mentioned.

-Recording device-
The ink set of the present invention can be suitably used for various recording apparatuses based on the ink jet recording system, for example, 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.
The outline of the ink jet recording apparatus used in the examples will be described below.
The ink jet recording apparatus shown in FIG. 1 has an apparatus main body (101), a paper feed tray (102) for loading paper mounted on the apparatus main body (101), and an image mounted on the apparatus main body (101). A paper discharge tray (103) for stocking the formed paper and an ink cartridge loading section (104) are provided. On the upper surface of the ink cartridge loading section (104), an operation section (105) such as operation keys and a display is arranged. The ink cartridge loading unit (104) has an openable / closable front cover (115) for attaching and detaching the ink cartridge (200). (111) is the upper cover, and (112) is the front surface of the front cover.

In the apparatus main body (101), as shown in FIGS. 2 and 3, a guide rod (131), which is a guide member horizontally mounted on left and right side plates (not shown), and a stay (132), a carriage (133) ) Is slidably held in the main scanning direction, and is moved and scanned in the direction indicated by the arrow in FIG. 3 by a main scanning motor (not shown).
The carriage (133) includes a plurality of recording heads (134) including four inkjet recording heads that discharge ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.
As an inkjet recording head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator that utilizes a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a temperature change A shape memory alloy actuator using a metal phase change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
The carriage (133) is equipped with a sub tank (135) for each color for supplying ink of each color to the recording head (134). The sub tank (135) is supplied with ink according to the ink set of the present invention from the ink cartridge (200) of the present invention loaded in the ink cartridge loading section (104) via an ink supply tube (not shown). To be replenished.

On the other hand, as a paper feeding unit for feeding the paper (142) stacked on the paper stacking unit (pressure plate) (141) of the paper feed tray (103), 1 sheet (142) is fed from the paper stacking unit (141). Opposite to the half-moon roller [sheet feeding roller (143)] for separating and feeding one sheet at a time, and the sheet feeding roller (143), a separation pad (144) made of a material having a large friction coefficient is provided, and this separation pad (144) is It is biased toward the paper feed roller (143).
A conveying belt (151) for electrostatically adsorbing and conveying the paper (142) as a conveying unit for conveying the paper (142) fed from the paper feeding unit below the recording head (134). A counter roller (152) for conveying the paper (142) sent from the paper supply unit via the guide (145) between the conveying belt (151) and a paper (substantially vertically upward) ( 142) and a leading guide roller 153 urged toward the conveying belt (151) by the holding member (154). (155) and a charging roller (156) which is a charging means for charging the surface of the conveyor belt (151).

The conveyance belt (151) is an endless belt, is stretched between the conveyance roller (157) and the tension roller (158), and can circulate in the belt conveyance direction. The transport belt (151) includes, for example, a surface layer serving as a sheet adsorbing surface formed of a resin material (for example, a copolymer of tetrafluoroethylene and ethylene (ETFE)) having a thickness of about 40 μm that is not subjected to resistance control. This surface layer has a back layer (medium resistance layer, ground layer) which is made of the same material and subjected to resistance control by carbon. On the back side of the conveyance belt (151), a guide member (161) is arranged corresponding to the printing area by the recording head (134). 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 transport belt (151), and paper discharge A roller (172) and a paper discharge roller (173) are provided, and a paper discharge tray (103) is arranged below the paper discharge roller (172).
A double-sided paper feeding unit (181) is detachably attached to the back surface of the apparatus main body (101). The double-sided paper feeding unit (181) takes in the paper (142) returned by the reverse rotation of the transport belt (151), reverses it, and feeds the paper again between the counter roller (152) and the transport belt (151). To do. A manual paper feed unit (182) is provided on the upper surface of the double-sided paper feed unit (181).

In this ink jet recording apparatus, the sheet (142) is separated and fed one by one from the sheet feeding unit, and the sheet (142) fed substantially vertically upward is guided by the guide (145) and the transport belt (151). ) And the counter roller (152). Further, the leading end is guided by the conveying guide (153) and pressed against the conveying belt (151) by the leading end pressure roller (155), and the conveying direction is changed by about 90 °.
At this time, the conveyance belt (157) is charged by the charging roller (156), and the paper (142) is electrostatically adsorbed 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, and the sheet ( 142), the next line is recorded after a predetermined amount is conveyed. Upon receiving a recording end signal or a signal that the rear end of the paper (142) has reached the recording area, the recording operation is finished and the paper (142) is discharged to the paper discharge tray (103).

When a near-end ink remaining amount in the sub tank (135) is detected, a required amount of ink is supplied from the ink cartridge (200) to the sub tank (135).
In this ink jet recording apparatus, when the ink in the ink cartridge (200) is used up, the casing of the ink cartridge (200) can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge (200) can supply ink stably even when the ink cartridge (200) is vertically placed and has a front loading configuration. Therefore, even when the upper part of the apparatus main body (101) is closed and installed, for example, even when it is stored in a rack or an object is placed on the upper surface of the apparatus main body (101), the ink The cartridge (200) can be easily replaced.
Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.

  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.

[Example 1 ]
< 1- K> Ink The material having the following formulation was dissolved in ion-exchanged water and filtered through a 0.2 μm filter to obtain a black ink for ink jet recording.

-Dye represented by said structural formula (9) 9.0 weight part-0.1 weight part of material represented by said structural formula (1) -1-Fluorine represented by said structural formula (2) -1 Surfactant 0.1 parts by weight-Glycerin 8.0 parts by weight-3-methyl-1,3-butanediol 24.0 parts by weight-2-ethyl-1,3-hexanediol 2.0 parts by weight-2 -Amino-2-ethyl-1,3-propanediol 0.3 part by weight-Proxel LV (Avecia, antiseptic / antifungal agent) 0.1 part by weight-Remaining amount of ion-exchanged water
100 parts by weight

The dye <1 -C> Ink the <1 -K> ink, instead of the dye 4.5 parts by weight represented by the Symbol structural formula (8) -1, 10.0 parts by weight of glycerin, 3- A cyan ink for inkjet recording was obtained using the same formulation and method except that methyl-1,3-butanediol was changed to 30.0 parts by weight.
[Structural Formula (8) -1]

<1 -M> dye ink above <1 -C> ink, except for changing the dye 4.0 parts by weight represented by the Symbol structural formula (7) -1 using the same formulation and method A magenta ink for ink jet recording was obtained.
[Structural Formula (7) -1]

The dye <1 -Y> Ink the <1 -M> ink, except for changing the dye 4.5 parts by weight represented by the Symbol structural formula (5) -1 using the same formulation and method A yellow ink for inkjet recording was obtained.
[Structural Formula (5) -1]

[Example 2 ]
< 2- K> Ink The material having the following formulation was dissolved in ion-exchanged water and filtered through a 0.2 μm filter to obtain a black ink for inkjet recording.

-Duasyn Black HEF-SF Liquid 45.0 parts by weight (Direct Black 168, dye concentration 20%, manufactured by Clariant)
-0.3 part by weight of the material represented by the structural formula (1) -2-0.05 part by weight of the fluorosurfactant represented by the structural formula (2) -2-9.0 part by weight of glycerin- 1,3-butanediol 26.0 parts by weight 2-ethyl-1,3-hexanediol 2.0 parts by weight 2-amino-2-ethyl-1,3-propanediol 0.7 parts by weight Proxel LV (Avecia, antiseptic and antifungal agent) 0.1 parts by weight ・ Remaining amount of ion-exchanged water
100 parts by weight

The dye <2 -C> Ink the <2 -K> ink, instead of the dye 4.5 parts by weight represented by the Symbol structural formula (8) -2, 11.0 parts by weight of glycerin, 1, A cyan ink for inkjet recording was obtained using the same formulation and method except that 3-butanediol was changed to 33.0 parts by weight.
[Structural Formula (8) -2]

< 2- M> Ink Using the same formulation and method except that the dye of the < 2- C> ink was changed to 4.0 parts by weight of the dye represented by the structural formula (7) -1. A magenta ink for inkjet recording was obtained.

The dye <2 -Y> Ink the <2 -M> ink, except for changing the dye 4.5 parts by weight represented by the Symbol structural formula (6) -1 using the same formulation and method A yellow ink for inkjet recording was obtained.
[Structural Formula (6) -1]

[Example 3 ]
< 3- K> Ink A material having the following formulation was dissolved in ion-exchanged water and filtered through a 0.2 μm filter to obtain a black ink for ink jet recording.

・ BAYSCRIPT Black SP liquid 45.0 parts by weight (dye concentration 30%, manufactured by LANXESS)
-0.4 part by weight of the material represented by the structural formula (1)-1-0.05 part by weight of the fluorosurfactant represented by the structural formula (2)-3-9.0 part by weight of glycerin- 1,3-butanediol 27.0 parts by weight 2-ethyl-1,3-hexanediol 2.0 parts by weight 2-amino-2-ethyl-1,3-propanediol 0.5 parts by weight Proxel LV (Avecia, antiseptic and antifungal agent) 0.1 parts by weight ・ Remaining amount of ion-exchanged water
100 parts by weight

< 3- C> Ink The dye of the above < 3- K> ink is changed to 4.5 parts by weight of the dye represented by the structural formula (8) -1, and glycerin is changed to 11.0 parts by weight. -A cyan ink for inkjet recording was obtained using the same formulation and method except that the butanediol was changed to 33.0 parts by weight.

<3 -M> dye ink above <3 -C> ink, except for changing the dye 4.0 parts by weight represented by the Symbol structural formula (7) -2 using the same formulation and method A magenta ink for ink jet recording was obtained.
[Structural Formula (7) -2]

<3 -Y> dye represented by the ink above <3 -M> dye ink, and the dye 3.0 parts by weight represented by the structural formula (5) -1, the formula (6) -1 A yellow ink for inkjet recording was obtained using the same formulation and method except that the amount was changed to 1.5 parts by weight.

[Example 4 ]
< 4- K> Ink A material having the following formulation was dissolved in ion-exchanged water and filtered through a 0.2 μm filter to obtain a black ink for ink jet recording.

-Duasyn Black HEF-SF Liquid 30.0 parts by weight (Direct Black 168, dye concentration 20%, manufactured by Clariant)
-0.4 weight part of material represented by following structural formula (1) -3-0.1 weight part of fluorosurfactant represented by following structural formula (2) -4-16.0 weight part of glycerol 1,3-butanediol 30.0 parts by weight 2-ethyl-1,3-hexanediol 1.5 parts by weight 2-amino-2-ethyl-1,3-propanediol 0.5 parts by weight Proxel LV (Avecia, antiseptic and antifungal agent) 0.1 parts by weight ・ Remaining amount of ion-exchanged water
100 parts by weight

［構造式（２）−４］
（Ｒｆ１：−Ｃ_３Ｆ_７、ｋ＝２１、Ｑ：−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_３Ｆ_７）

[Structural Formula (1) -3] (R ¹ , R ² : —C ₆ H ₁₃ , R ³ , R ⁴ : —CH ₃ , j = 2)
2,6,9,19-tetramethyltetradecane-6,9-diol

[Structural Formula (2) -4]
_{(Rf1: -C 3 F 7,} k = 21, Q: -CH 2 CH (OH) CH 2 -C 3 F 7)

< 4- C> ink
A material having the following formulation was dissolved in ion-exchanged water and filtered through a 0.2 μm filter to obtain a cyan ink for inkjet recording.

-2.5 weight part of dye represented by said structural formula (8) -1
-0.4 weight part of material represented by said structural formula (1) -3
-0.1 weight part of fluorine-type surfactant represented by the said Structural formula (2) -4
・ Glycerin 19.0 parts by weight
・ 3,0 parts by weight of 1,3-butanediol
・ 1.5 parts by weight of 2-ethyl-1,3-hexanediol
・ 0.5 parts by weight of 2-amino-2-ethyl-1,3-propanediol
・ Proxel LV (Abesia, antiseptic / antifungal agent) 0.1 parts by weight
・ Ion exchange water remaining
100 parts by weight

< 4- M> ink
The dyes of the <4-C> ink, by using the same formulation and method except for changing the dye 2.0 parts by weight represented by the structural formula (7) -1, Lee inkjet recording magenta Ink was obtained.

< 4- Y> ink
The dyes of the <4-M> ink, except for changing the dye represented by the structural formula (5) -1 using the same formulation and method to obtain the i inkjet recording yellow ink.

[Comparative Example 1 ]
<12-K, 12-C, 12-M, 12-Y> Ink The fluorine-based surfactant represented by the structural formula (2) -1 used in Example 1 is represented by the following structural formula (2) -5. A black, cyan, magenta, and yellow ink jet recording ink was obtained using the same formulation and method except that the materials shown were changed.
[Structural Formula (2) -5] (Rf ¹ : -C ₄ F ₉ , k = 45)

[Comparative Example 2 ]
<13-K, 13-C, 13-M, 13-Y> Ink The fluorinated surfactant represented by the structural formula (2) -3 used in Example 3 was replaced with Zonyl FS-300 [polyoxyalkylene. (C2-3) -2-perfluoroalkyl (C4-16) ethyl ether, solid content 40%, manufactured by DuPont Co., Ltd.), using the same formulation and method, black, cyan, magenta, yellow Each ink for inkjet recording was obtained.

[Comparative Example 3 ]
<14-K, 14-C, 14-M, 14-Y> Ink The same except that the fluorine-based surfactant represented by Structural Formula (2) -3 used in Example 3 was not added. Black, cyan, magenta and yellow ink jet recording inks were obtained using the formulation and method.

The following tests (1) to (5) were performed for each ink prepared in the above examples and comparative examples and evaluated.
(1) Measurement of surface tension The surface tension at 25 ° C. was measured using a CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd. The results are shown in [Table 1] and [Table 2].
(2) Measurement of flash point The flash point was measured according to the method described in JIS-K2265 using the Cleveland open flash point test method. The results are shown in [Table 1] and [Table 2].

(3) Defoaming property test 10 ml of recording ink stored at 50 ° C. for 1 month after preparation is placed in a 100 ml graduated cylinder at 10 ° C. and constant until the volume of the recording ink and bubbles reaches 100 ml. Pressure air was injected, and the injection of air was stopped after 30 seconds or when the total volume of the recording ink and bubbles reached 100 ml. Then, the time from when the air injection was stopped until the total volume of the recording ink and bubbles reached 20 ml was measured as the defoaming time, and the following criteria were used for evaluation. The results are shown in [Table 1] and [Table 2]. A and B are allowable ranges.
[Defoaming evaluation criteria]
A: Defoaming time of less than 10 seconds B: Defoaming time of 10 seconds or more and less than 30 seconds C: Defoaming time of 30 seconds or more and less than 300 seconds D: Defoaming time of 300 seconds or more

(4) Measurement of ejection stability Each ink is filled in an ink cartridge, set in an ink jet printer (IPSiO G707: manufactured by Ricoh) having the structure shown in FIGS. 1 to 2, and the ejection stability is evaluated by the following method. Went.
Print continuously for 10 minutes using a printer with a nozzle plate set, put a moisturizing cap with ink on the head surface, leave the printer in a 50 ° C 60% RH environment for one month, and then clean it. And returned to the same level as before. Thereafter, an intermittent printing test was performed under the following conditions to evaluate discharge stability.
That is, after printing the print pattern chart continuously for 20 sheets, it is put into a resting state in which printing is not performed for 20 minutes, and this is repeated 50 times. After a total of 1000 copies are printed, the same chart is printed again. The presence or absence of streaks, white spots, and jet disturbance in the 5% chart solid part was visually evaluated. In the above print pattern, each ink was printed at 100% duty in a chart in which each color printing area was 5% in the total area of the paper. The printing conditions were a recording density of 300 dpi and one-pass printing. The evaluation criteria are as follows, and the evaluation results are shown in [Table 1] and [Table 2]. Ranks A and B are allowable ranges.
〔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 disturbance are observed in the solid portion.
D: Streaks, white spots, and jet turbulence are observed throughout the solid portion.

(5) Color bleed Red, cyan and yellow on the recording medium formed by mixing magenta, cyan, yellow and magenta and yellow on the recording medium using the above-described printer in which each recording ink is filled in an ink cartridge. Printing was performed using My Paper (manufactured by Ricoh Co., Ltd.) as a test paper, using a printing pattern for printing black ink characters in a solid image portion made of green color ink formed by color mixing. The printing conditions were 100% duty, the recording density was 300 dpi, and one-pass printing. The color bleed between the color ink and the black ink was visually evaluated. The evaluation criteria are as follows. Although the evaluation results are shown in [Table 3], A and B are allowable ranges.
〔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 blurred but can be recognized.
D: Color bleed occurs and it is difficult to recognize black characters.

DESCRIPTION OF SYMBOLS 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 105 Operation part 111 Upper cover 112 Front cover front 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper placement part 142 Paper 143 Feed roller 144 Separator pad 145 Guide 151 Transport belt 152 Counter roller 153 Transport guide 154 Pressing member 155 Pressure roller 156 Charging roller 157 Transport roller 158 Tension roller 161 Guide member 171 Separating claw 172 Paper discharge roller 173 Paper discharge roller 181 Double-sided feeding Paper unit 182 Manual paper feed unit 200 Ink cartridge

JP 2002-138226 A JP 2006-316243 A

Claims (7)

In an inkjet recording ink set comprising at least black, cyan, magenta, and yellow inks, each ink is at least a water-soluble dye, a water-soluble solvent, a fluorosurfactant, and a compound represented by the following structural formula (1) and it contains water, the fluorine-based surfactant, an inkjet recording ink set which is a compound represented by the following structural formula (2).
[Structural formula (1)]
^{_{HOR 1 R 3 C- (CH 2}} ) j -CR 2 R 4 OH
In the above formula, R ¹ and R ² are each independently an alkyl group having 3 to 6 carbon atoms, R ³ and R ⁴ are each independently an alkyl group having 1 to 2 carbon atoms, and j is It is a natural number of 1-6.
[Structural formula (2)]
^{_{Rf 1 -CH 2 CH (OH)}} CH 2 O- (CH 2 CH 2 O) k -Q
However, in the above formula, Rf ¹ is _-C 3 _{F 7} or _-C 4 _F 9, Q is _-C b _{H 2b +} 1 (b is a natural number of _{11~19), - CH 2 CH (} OH) CH 2 - C ₃ F _7, or represents _{-CH 2 CH (OH) CH 2} -C 4 F 9, k is 20 to 35.   The ratio between the content S of the water-soluble solvent and the content W of water is in the range of 0.7 ≦ S / W ≦ 1.6, and each ink has no flash point. Item 2. An ink set for inkjet recording according to Item 1. The ink set for inkjet recording according to claim 1 or 2, wherein the water-soluble dye used in the yellow ink is represented by the following structural formula (5) or structural formula (6).
[Structural formula (5)]

[Structural formula (6)]

In the above formula, A and B are alkoxy groups, T is an alkanolamino group, D is —SO ₃ M (M is an alkali metal), and t is 1. The ink set for inkjet recording according to claim 1 or 2, wherein the water-soluble dye used in the magenta ink is represented by the following structural formula (7).
[Structural formula (7)]

However, in said formula, X is hydrogen or an aryl group, Z is hydrogen or a halogen, M is an alkali metal. The ink set for inkjet recording according to claim 1 or 2, wherein the water-soluble dye used in the cyan ink is represented by the following structural formula (8).
[Structural formula (8)]

However, in said formula, M is an alkali metal or quaternary ammonium, t is an integer of 0-3, u is an integer of 1-2.   An ink jet recording method, comprising: using the ink set for ink jet recording according to any one of claims 1 to 5;   A recorded matter recorded using the ink set for ink jet recording according to claim 1.

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