JP2015017206A - Ink-jet recording ink, ink-jet recording method and ink-jet recording apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink-jet recording ink having excellent discharge reliability with less nozzle clog and injection curve, allowing both weather-resistance and color development properties, having improved filter permeability, and enabling improved life of a flow passage member and reliability of an apparatus.SOLUTION: An ink-jet recording ink includes water, an organic solvent and a coloring agent. The coloring agent is C.I. Acid orange 33. The C.I. Acid orange 33 includes a high polar component A and a low polar component B having lower polarity than the high polar component A. The mass ratio (B/A) of the high polar component A and the low polar component B is 1.2 or lower. The mass ratio (B/A) of the high polar component A and the low polar component B is preferably 0 or higher and 0.8 or lower.

Description

  The present invention relates to an inkjet recording ink, an inkjet recording method, and an inkjet recording apparatus.

The ink jet recording method is a recording method in which ink droplets are ejected and attached to a recording medium for recording. Since the recording process is simple, it is possible to increase the number of colors at a low cost, and to perform multi-printing for non-contact printing. This is a recording method that can easily improve the printing quality and can perform high-speed recording without noise. Therefore, in recent years, it has been widely used from home printers to commercial printers.
Since it is widely used, the image quality of the inkjet recording method is continuously improved, and not only the four process colors (cyan, magenta, yellow, black) but also light ink (light cyan, light magenta, gray) And special colors (red, blue, green) have also been used. By increasing the number of colors, it is possible to reduce the graininess of the printed image and expand the color space.
The image quality by the ink jet recording method can satisfy a photographic image from a character image, and in recent years, with the spread of digital cameras and scanners, it has been widely used as a method for outputting a photograph instead of a silver salt photograph. Therefore, in order to compare print output images based on images on a computer display, the user is demanding color development close to that of a display, and color development superior to silver salt photography is demanded. Therefore, ink jet recording apparatuses that require high color development for photographic use have become apparatuses that use inks of a plurality of colors other than process colors (see Patent Documents 1 to 3).

  In this way, when the color is increased in order to widen the color development region of the ink jet, dyes having different hues such as red, green, and blue are required. In particular, the red to orange region is strongly demanded for color development because of the hue that forms the human face color, and there is also a problem that the influence of fading is strongly recognized as a change in face color. In addition, it is difficult to ensure the ejection reliability of dye inks with good weather resistance and color developability, nozzle clogging and jet bending are likely to occur, and all the performance cannot be satisfied at present.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is excellent in ejection reliability with less nozzle clogging and jet bending, can achieve both weather resistance and color development, improve filter liquid permeability, increase the life of the flow path member and the reliability of the apparatus. An object of the present invention is to provide an ink for ink jet recording.

  The ink for inkjet recording of the present invention as a means for solving the above problems comprises water, an organic solvent, and a colorant, and the colorant is C.I. I. Acid Orange 33, and the C.I. I. Acid Orange 33 includes a high polarity component A and a low polarity component B having a lower polarity than the high polarity component A, and a mass ratio (B / A) between the high polarity component A and the low polarity component B is 1.2 or less.

  According to the present invention, it is possible to solve the above-mentioned problems and achieve the above-mentioned object, to have excellent ejection reliability with little nozzle clogging and jet bending, to achieve both weather resistance and color development, and to pass through a filter. An object of the present invention is to provide an ink for ink jet recording which improves liquidity and can improve the life of the flow path member and the reliability of the apparatus.

FIG. 1 is a schematic diagram illustrating an example of an ink cartridge. FIG. 2 is a schematic view including the case of the ink cartridge of FIG. FIG. 3 is a perspective view showing an example of an ink jet recording apparatus. FIG. 4 is a schematic diagram illustrating an example of an ink jet recording apparatus. FIG. 5 is a schematic enlarged view showing an example of an ink jet head of the ink jet recording apparatus. FIG. I. It is a figure which shows the FT-IR absorption spectrum of the high polar component A in Acid Orange 33. FIG. I. It is a figure which shows the FT-IR absorption spectrum of the low polar component B in Acid Orange 33.

(Inkjet recording ink)
The ink for inkjet recording of the present invention contains water, an organic solvent, and a colorant, preferably contains a surfactant and a penetrating agent, and further contains other components as necessary.

  In the inkjet recording ink of the present invention, the colorant is C.I. I. Acid Orange 33, and the C.I. I. Acid Orange 33 includes a high polarity component A and a low polarity component B having a lower polarity than the high polarity component A, and a mass ratio (B / A) between the high polarity component A and the low polarity component B is 1.2 or less.

<Colorant>
Water-soluble dyes C.I. I. By using Acid Orange 33 and using a dye ink that develops a hue from red to orange, a wide color gamut that cannot be obtained by the process color can be developed.

C. above. I. Acid Orange 33 is represented by the following structural formula, but what is produced by a general azo dye synthesis method and supplied to the market is a mixture of four or more components.

Among these, the color of the two components is orange and the content is large. The two components were separated and recovered by liquid chromatography, and the FT-IR absorption spectra of the high polarity component A and the low polarity component B having a lower polarity than the high polarity component A were shown in FIG. FIG.
As shown in FIG. 6, the highly polar component A has a strong absorption attributed to an azo bond at a position of 1620 cm ⁻¹ . On the other hand, as shown in FIG. 7, the low polar component B has strong absorption attributed to an azo bond at the position of 1590 cm ⁻¹ , and both have different structures due to different absorption peak positions. It is believed that there is.
C. above. I. When comparing the absorption of the position of the absorption and 1590 ± 10 cm ^-1 of 1620 positions of ± 10 cm ^-1 in the FT-IR spectra of Acid Orange 33,
The highly polar component A is a compound having a large absorption at a position of 1620 ± 10 cm ⁻¹ .
The low polar component B is a compound having a large absorption at a position of 1590 ± 10 cm ⁻¹ . I. The polarities of the high polarity component A and the low polarity component B in Acid Orange 33 are relative indicators, but in the present invention, C.I. I. Acid Orange 33 is evaluated from the solubility in the benzyl alcohol phase when extracted with benzyl alcohol (dielectric constant 13.1), and the high polarity component A is a component having a solubility in the benzyl alcohol phase of less than 3 g / L. The low polarity component B is a component having a solubility in the benzyl alcohol phase of 3 g / L or more. By dissolving the benzyl alcohol phase separated from the aqueous phase with a rotary evaporator and recovering the dissolved component, the solubility in the benzyl alcohol phase can be calculated from the recovered dye mass and the amount of benzyl alcohol used. The lower the solubility in benzyl alcohol, the more polar the dye.

In the ink for ink jet recording of the present invention, the mass ratio (B / A) of the content of the high polarity component A and the content of the low polarity component B is different, so that nozzle clogging, jet bending, It affects liquid permeability and ink repellency on the nozzle surface.
One of the high polarity component A and the low polarity component B may be a main component and the other may be a subcomponent, that is, the high polarity component A may be a main component, and the low polarity component B may be a main component. It does not matter. Here, the main component means a coloring component that is contained most in the total amount of the colorant.
In addition, C.I. I. The acid orange 33 only needs to contain at least the high-polarity component A, and those containing only the high-polarity component A (low-polarity component B is 0% by mass) are also included in the present invention. However, those containing only the low-polarity component B (high-polarity component A is 0% by mass) are included in the present invention because they are inferior in ink repellency, filterability, refilterability, and ejection reliability. I can't.

In the ink for inkjet recording of the present invention, the mass ratio (B / A) between the high polarity component A and the low polarity component B is 1.2 or less, preferably 1.0 or less, and preferably 0 or more and 0.8. The following is more preferable. The lower limit of the mass ratio (B / A) is not particularly limited unless the man-hours required for separation and purification are limited, but is preferably 0 or more. In the numerical range, the ink repellency with respect to the nozzle member can be ensured, and the jet bending is improved.
By setting the mass ratio (B / A) to 1.2 or less, liquid permeability can be secured, and long-term discharge reliability and apparatus life can be improved.

Here, the said mass ratio (B / A) can be calculated | required by isolate | separating, isolating and quantifying the dye currently used with a liquid chromatography.
Examples of the liquid chromatography include TLC (thin layer liquid chromatography) and HPLC (high performance liquid chromatography). If any of these analytical methods can be used to separate the coloring component of the dye, a desired developing solvent can be selected depending on the stationary phase.
Examples of the developing solvent for TLC include ethyl acetate, n-butyl acetate, chloroform, acetonitrile, pyridine, morpholine, acetone, 2-propanol, ethanol, methanol, water, and the like. These may be used individually by 1 type and may use 2 or more types together.

In addition to isolating and measuring mass, the separated dye can be calculated as a mass ratio by measuring different characteristics and converting the mass from a calibration curve. As an example, when using a visible absorption spectrum, obtain the maximum absorbance of the absorption spectrum in the visible region with respect to the dissolved concentration of each composition, convert the absorption spectrum to the concentration using a calibration curve, and calculate the concentration to mass ratio between the compositions. can do.
The same measurement can be performed using an IR spectrum, NMR, Mass spectrum, or the like, and an optimal measurement method can be selected depending on the measurement sensitivity, separation method, and separation state.
C. above. I. The method of adjusting the high-polarity component and the low-polarity component of Acid Orange 33 to the desired composition ratio is to separate the individual components by liquid chromatography as the most reliable method, and mix them to the desired mixing ratio. It is to use. However, if the method is used industrially, the separation cost becomes high. Therefore, the component ratio is changed by single or combined treatment such as activated carbon treatment, column chromatography, extraction, recrystallization, etc., and adjusted to the target composition ratio. It is preferable. These processing techniques are not limited to these.

C. above. I. Acid Orange 33 may be appropriately synthesized or a commercially available product. Examples of the synthesis method include synthesis by an azo coupling reaction using 4,4′-diamino-diphenylcyclohexane hydrochloride and 2-naphthol-6,8-disulfonic acid disodium salt, phenol and sodium nitrite as starting materials. can do.
Examples of the commercially available products include Winchem Industrial Co. Ltd .. , Hangzhou Sunshine Chemicals Co. , Ltd., Ltd. , Shijiazhang gangkuo chemical Co., Ltd. , Ltd., Ltd. , Taizhou Shengyu Chemical Co. , Ltd., Ltd. , Afine Chemicals Limited, Hangzhou Arundies Chemical Co. , Ltd., Zheijing Jinhua Hanlycome Chemical Co., Ltd. , Ltd., Trust Chem Co. , Ltd., Shao Xing Empire Import & Export Co. , Ltd., Ltd. , UNICORN COLORS, Qingdao Sanhuan Colorchem Co., Ltd. , Ltd., Ningbo Fuhao Chemical Co. , Ltd., Ltd. , SHIJIAZHAUNG KUNLI CHEMICAL Co. Ltd .. , Shuanghong Chemical Co. , Ltd., Dalian Shenglin I / E Co. , Ltd., APPEX DYESTUFF INDUSTRIES, Fine Shoji, Shanghai Joy International Trading Co., Ltd. , Ltd., Ltd. , B. R. Y. Chemicals Co. , Ltd., Ltd. , New Dragon Industrial Co. , Ltd., Ltd. It can obtain from.

  The inkjet recording ink includes the C.I. I. In addition to Acid Orange 33, different water-soluble dyes can be used as colorants. Thereby, a hue and a weather resistance can be adjusted. The C.I. I. Acid orange 33 can adjust the color tone of ink by mixing with cyan, magenta, yellow, black, and other dyes.

  Such C.I. I. Examples of the dye used by mixing with Acid Orange 33 include dyes classified as acidic dyes, direct dyes, basic dyes, reactive dyes, and food dyes in the following color index.

  Examples of the acid dyes and food dyes include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. 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; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Food Yellow 3, 4; I. Food red 7, 9, 14; I. Food black 1, 2, etc. are mentioned.

  Examples of the direct dye include C.I. I. Direct yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, 144; I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227; I. Direct orange 26, 29, 62, 102; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like.

  Examples of the basic dye include 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. 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; 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; I. Basic black 2, 8, etc. are mentioned.

  Examples of the reactive dye include C.I. I. Reactive black 3, 4, 7, 11, 12, 17; I. Reactive Yellow 1, 5, 11, 13, 14, 20, 21, 22, 25, 40, 47, 51, 55, 65, 67; I. Reactive Red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97; I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, and the like.

  In addition to the above dyes, other weather-resistant dyes can be used. Examples of the other weather-resistant dyes include, for example, Japanese Patent No. 4485053, Japanese Unexamined Patent Application Publication No. 2006-199922, Japanese Unexamined Patent Application Publication No. 2007-224274, Japanese Unexamined Patent Application Publication No. 2009-062515, Japanese Unexamined Patent Application Publication No. 2009-0662515, and WO2009. / 060654 pamphlet, JP-A-2005-008868, WO2006 / 0775706 pamphlet, JP-A-2003-192930, and Japanese Patent No. 4773581, and the like.

The content of the dye is preferably 1% by mass to 10% by mass and more preferably 4% by mass to 6% by mass as the total amount of the dye with respect to the inkjet recording ink. When the content is 1% by mass or more, the coloring power of the ink is increased, and the color development is sufficiently enhanced. When the content is 4% by mass or more, light resistance and ozone resistance can be further improved. On the other hand, by setting the content to 10% by mass or less, precipitation of the dye during drying can be suppressed, and discharge stability can be improved.
This is because the dye is in a cluster state in which a plurality of molecules are gathered in the vicinity at the time of drying. When printing at a dilute dye concentration, it is difficult to form a cluster after drying, and the dye is dyed as a single molecule. It is estimated that the environmental resistance deteriorates with increasing frequency.
In addition, since the dye is a water-soluble dye, it is solubilized by ionic dissociation in water as an organic salt. However, there is a limit to solubility, and the ink contains an organic solvent, so the solubility of the dye is often lowered. . When the water in the ink volatilizes, the dye that has been solubilized as a water-soluble component is deposited, resulting in an increase in ink viscosity and nozzle clogging. When the density is further increased, the coloring power per ink drop is increased, and the dot recognizability is increased, so that the graininess of the image tends to be deteriorated.

<Water>
There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water etc. are mentioned. It is done. These may be used individually by 1 type and may use 2 or more types together.

<Organic solvent>
It is preferable to add an organic solvent to the ink of the present invention for the purposes of inhibiting drying of the ink, penetrating into the recording medium, antibacterial and the like.
Examples of the organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, Etc.
Among these, preferred organic solvents include polyhydric alcohols having an equilibrium water content in an 80% RH environment at 23 ° C. of 30% by mass or more. Specific examples thereof include 1,2,3-butanetriol ( 38 mass%), 1,2,4-butanetriol (41 mass%), glycerin (49 mass%), diglycerin (38 mass%), triethylene glycol (39 mass%), tetraethylene glycol (37 mass%) ), Diethylene glycol (43% by mass), 1,3-butanediol (35% by mass), and the like.
Among these, glycerin and 1,3-butanediol are particularly preferably used because they can reduce the viscosity when containing water.

Further, if necessary, a water-soluble solvent having an equilibrium water content of less than 30% by mass can be used. Examples include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, cyclic ethers, amines, amides, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and other organic solvents. .
Examples of the polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 2- Methyl-2,4-pentanediol, hexylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 3-methyl-1,3-hexanediol, propylpropylene Diglycol etc. are mentioned.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monoethyl ether. And triethylene glycol dimethyl ether.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the cyclic ethers include epoxies, oxetanes, tetrahydrofurans, tetrahydropyrans, and crown ethers. Among these, oxetanes and tetrahydrofurans are preferable, and oxetanes are more preferable from the viewpoint of water solubility.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylmonoethanolamine, N-methyldiethanolamine, N-methylethanolamine, N-phenylethanolamine, and 3-aminopropyldiethylamine. Is mentioned.
Examples of the amide compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, β-methoxy-N, N-dimethyl. Examples include propionamide and β-butoxy-N, N-dimethylpropionamide. Formamide, N-methylformamide, N, N-dimethylformamide, and N, N-diethylformamide are also present as amide compounds, but are highly harmful and are not preferred for use. The amide compound has the effect of solubilizing the dye and has the effect of suppressing crystal precipitation during ink drying.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiglycol, and the like.

The content of the organic solvent is preferably 10% by mass to 50% by mass and more preferably 15% by mass to 40% by mass with respect to the inkjet recording ink. When the content is 15% by mass or more, the ejection stability is improved by slowing the drying speed of the ink, and the dye is prevented from crystallizing and fixing in the maintenance device of the ink jet recording apparatus. Improve operational reliability. On the other hand, when the content is less than 50% by mass, the dissolution of the dye can be maintained by securing the water content in the ink, and the crystallization of the dye due to the decrease in the water content in the ink can be suppressed. it can. Further, since the drying property on the paper is not greatly reduced, the color stabilization time on the glossy paper can be shortened.
In addition, in a dye ink containing 30% by mass or more of a water-soluble organic solvent, the drying speed of the ink is slow and the color stability immediately after printing an image is impaired. Therefore, the content of the organic solvent is more preferably 15% by mass to 30% by mass.

<Surfactant>
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, an acetylene glycol surfactant, and a fluorine surfactant. It is preferable to select a surfactant that does not impair the dispersion stability, depending on the combination of the colorant and the organic solvent.

Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, oxalate sulfonate, laurate, and polyoxyethylene alkyl ether sulfate salt.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene And ethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and the like.
Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Specific examples below are preferably used, but are not limited thereto. Examples include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, and dimethyl lauryl betaine.

  Examples of the surfactant include Nikko Chemicals Co., Ltd., Nippon Emulsion Co., Ltd., Nippon Shokubai Co., Ltd., Toho Chemical Co., Ltd., Kao Co., Ltd., Adeka Co., Ltd., Lion Co., Ltd., Aoki Oil Co., Ltd., Sanyo Chemical Industries Co., Ltd. Available from other surfactant manufacturers.

  The acetylene glycol surfactants are 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5- Examples thereof include acetylene glycols such as dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, 485 or TG manufactured by Air Products (USA)). Among these, Surfynol 465, 104 and TG are preferable from the viewpoint of showing good print quality.

Examples of the fluorosurfactant include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, and perfluoroalkylamine oxide. Examples thereof include a compound, a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, a sulfate ester salt thereof, and a fluorine-based aliphatic polymer ester.
A commercial item can be used as said fluorosurfactant, As this commercial item, for example, Surflon S-111, S-112, S-113, S121, S131, S132, S-141, S-145 (Manufactured by Asahi Glass Co., Ltd.), Fullard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (manufactured by Sumitomo 3M), FT -110, 250, 251, 400S (manufactured by Neos), Zonyl FS-62, FSA, FSE, FSJ, FSP, TBS, UR, FSO, FSO-100, FSN N, FSN-100, FS-300, FSK ( DuPont), Polyfox PF-136A, PF-156A, PF-151N (OMNOVA) and the like.

The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. However, those that do not decompose even at high pH are preferable. For example, side chain-modified polydimethylsiloxane, both-end-modified polydimethylsiloxane , One-end-modified polydimethylsiloxane, side-chain both-end-modified polydimethylsiloxane, and the like. As the modifying group, a polyether-modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group is particularly preferable because it exhibits good properties as an aqueous surfactant.
As such a surfactant, an appropriately synthesized product or a commercially available product may be used. Such commercially available products can be easily obtained from, for example, Big Chemie, Shin-Etsu Silicone, Toray Dow Corning Silicone, etc.

There is no restriction | limiting in particular as said polyether modified silicone type surfactant, According to the objective, it can select suitably, For example, the polyalkylene oxide structure represented with the following general formula (A) is Si of dimethylpolysiloxane. And compounds introduced into the partial side chain.
[General formula (A)]
However, in the said General formula (13), m, n, a, and b represent an integer. R and R ′ represent an alkyl group or an alkylene group.

  There is no restriction | limiting in particular as said polyether modified silicone type surfactant, What was synthesize | combined suitably may be used and a commercial item may be used. As said commercial item, KF-618, KF-642, KF-643 (all are Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (all are Japan Emulsion Co., Ltd.), FZ, for example. -2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (all are Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (all , Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (all are Toshiba Silicone Co., Ltd.), and the like.

The surfactant is not limited to these, and may be used alone or in combination. Even if it is not easily dissolved by itself in the recording liquid, it can be solubilized by mixing and exist stably.
The content of the surfactant is preferably 0.01% by mass to 5% by mass, and preferably 0.5% by mass to 2% by mass with respect to the ink for inkjet recording, from the viewpoint of exerting a penetrating effect. More preferred.
When the content is 0.01% by mass or more, it is possible to ensure permeability to a recording medium and wettability to an inkjet head. On the other hand, when the content is 5.0% by mass or less, it is possible to balance the permeability to the recording medium, and it is possible to suppress the show-through and improve the image density.

<Penetration agent>
The penetrant preferably contains at least one polyol having a solubility in water at 20 ° C. of 0.2% by mass or more and less than 5.0% by mass.
Among the polyols, examples of the aliphatic diol include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 2,2-diethyl-1,3. -Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1 , 2-diol, 2-ethyl-1,3-hexanediol, and the like. Among these, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol are preferable.

Other penetrants that can be used in combination are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, and diethylene glycol. Examples thereof include alkyl and aryl ethers of polyhydric alcohols such as monobutyl ether, propylene glycol monobutyl ether and tetraethylene glycol chlorophenyl ether, and lower alcohols such as ethanol.
The content of the penetrant is preferably 0.1% by mass to 4.0% by mass with respect to the ink jet recording ink. When the content is 0.1% by mass or less, quick drying is obtained and an image without blur is obtained. On the other hand, when the content is 4.0% by mass or less, the dispersion stability of the colorant is good, the nozzle is not easily clogged, the permeability to the recording medium is good, and the image density is high. Is high and can prevent the occurrence of show-through.

<Other ingredients>
There is no restriction | limiting in particular as said other component, It can select suitably as needed, For example, water dispersible resin, an image preservability improvement agent, a pH adjuster, antiseptic / antifungal agent, a chelating reagent, a rust preventive agent Oxygen absorbers, light stabilizers, and the like.

<< Water-dispersible resin >>
As the water-dispersible resin, those having excellent film-forming properties (image forming properties) and having high water repellency, high water resistance, and high weather resistance have high water resistance and high image density (high color developability). It is useful for image recording, and examples thereof include condensation-type synthetic resins, addition-type synthetic resins, and natural polymer compounds.
The particle size of the water-dispersible resin is related to the viscosity of the dispersion. When the composition is the same, the smaller the particle size, the larger the viscosity at the same solid content. The average particle size of the water-dispersible resin is preferably 50 nm or more so as not to have an excessively high viscosity when converted into an ink. When the particle size is several tens of microns, it becomes larger than the nozzle opening of the ink jet head and cannot be used. It is known that if particles having a large particle diameter exist in the ink even if they are smaller than the nozzle opening, the ejection property is deteriorated. The average particle size is preferably 500 nm or less, and preferably 150 nm or less in order not to impair the ink ejection properties.

The water-dispersible resin has a function of fixing the colorant to the paper surface, and it is desired to form a film at room temperature to improve the fixability of the colorant. For this purpose, the minimum film-forming temperature (MFT) is preferably room temperature or lower, and preferably 20 ° C. or lower. However, when the glass transition point is -40 ° C. or lower, the resin film becomes more viscous and the printed matter is tacky. Therefore, it is preferably a water dispersible resin having a glass transition point of −30 ° C. or higher.
Using such a water-dispersible resin makes it possible to improve image fixability, water resistance, and gas resistance. However, depending on the recording medium, the gloss may change due to the resin coating. End up. In addition, since a large amount of addition forms a film when the meniscus of the ink jet head is dried, addition of a resin solid content of 5% by mass or more is not preferable because it causes clogging of the nozzle and changes in glossiness.

<< Image preservability improver >>
An image preservability improver may be added to the ink for inkjet recording of the present invention.
Examples of the image preservability improver include hindered amine compounds, ultraviolet absorbers, antioxidants, and the like. Since an inkjet recording image is greatly affected by light and gas, it is preferable to add a hindered amine compound, an ultraviolet absorber, and an antioxidant.

-Hinder amine compounds-
As the hindered amine, for example, any of N—CH ₃ type, N—H type, and N—OR type can be used, but N—CH ₃ type and N—OR type are preferable. Some of these hindered amines are miscible with water by mixing with butyl carbitol or butyl cellosolve, but are preferably water-insoluble liquids or powders dispersed therein.
Examples of the water-dispersed hindered amine compound include TINUVIN 123DW manufactured by BASF, Adecanol UC-5225 and Adecanol UC-606 manufactured by ADEKA. Among these, TINUVIN 123DW in which a hindered amine compound is included and dispersed is particularly preferable because it has an effect on stability and ozone resistance when mixed with a dye.
Content of the said hindered amine compound is dependent on the dye density | concentration which should be protected, 1 mass%-10 mass% are preferable with respect to solid content of a dye, and 2 mass%-7 mass% are more preferable.

-UV absorber-
Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, hydroxyphenyltriazine ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, nickel complex ultraviolet absorbers, Examples include inorganic oxide fine particles.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.

  Examples of the salicylate UV absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

  Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

  Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis. (4-tert-octylferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octylferrate) triethanolamine nickel (II), and the like.

Examples of the inorganic oxide fine particles include zinc oxide fine particles and titanium oxide fine particles, and an average particle size of 50 nm or less is preferable from the viewpoint of transparency.
Among these, a hydroxyphenyl triazine type and a benzotriazole type are preferable, and these aqueous dispersions are preferable when added to the aqueous ink.
Examples of such an aqueous dispersion include TINUVIN 1130, TINUVIN 99DW, TINUVIN 400DW, TINUVIN 477DW manufactured by BASF, and UC-3140 manufactured by ADEKA. Among these, TINUVIN 477DW in which an ultraviolet absorber is included and dispersed in a resin is particularly preferable because of its high effect on ozone resistance.
The content of the ultraviolet absorber in the ink depends on the concentration of the dye to be protected, and is preferably 1% by mass to 10% by mass and more preferably 2% by mass to 7% by mass with respect to the solid content of the dye. preferable.

-Antioxidant-
Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenolic antioxidant (including hindered phenolic antioxidant) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-Butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-to (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

  Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propio Nate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like.

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl β. , Β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, and trinonylphenyl phosphite.

Since both are poorly water-soluble, it is preferable to add to the ink using a water dispersion. An example of such an aqueous dispersion is ADEKA SDX-2855.
There is no restriction | limiting in particular in content of the said antioxidant, Although it can select suitably according to the objective, 0 mass%-10 mass% are preferable.

The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 to 11 without adversely affecting the ink to be prepared, and can be appropriately selected according to the purpose. And alkali metal element hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like.
If the pH is less than 7 or exceeds 11, the amount of the ink-jet head or ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure may occur.
Examples of the 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 and quaternary ammonium hydroxide.
Examples of the phosphonium hydroxide include quaternary phosphonium hydroxide.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

<Method for producing ink for inkjet recording>
The ink for ink-jet recording of the present invention includes C.I. I. It is produced by dispersing or dissolving Acid Orange 33, an organic solvent, a surfactant, a penetrating agent, water, and other components as necessary in an aqueous medium, and stirring and mixing appropriately. The stirring and mixing can be performed, for example, with a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like, and can be performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. .

The physical properties of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity and surface tension are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 2 mPa · s to 20 mPa · s. By setting the ink viscosity at ejection to 3 mPa · s or more, there is an effect that residual vibration during ink ejection is less likely to occur, and vibration after ejection by the drive waveform can be easily suppressed, and the next ejection can be performed in a short time. It becomes suitable for high-speed printing. On the other hand, by suppressing the ink viscosity to 15 mPa · s or less, it becomes easy to stabilize the ejection performance. Since the viscosity changes depending on the use environment, it is preferable that the ink viscosity satisfies the above range within the expected use range, and the viscosity at 25 ° C. is more preferably 3 mPa · s to 10 mPa · s. The viscosity can be measured, for example, by adjusting the temperature to each temperature using a viscometer (RE-550L, manufactured by Toki Sangyo Co., Ltd.).

  The static surface tension of the ink is preferably 20 mN / m to 35 mN / m at 25 ° C., more preferably 20 mN / m to 40 mN / m or less. If the static surface tension is in this range, the permeability is high and effective in reducing bleeding, and the drying property on plain paper printing is good. In addition, since dot enlargement occurs on the surface of glossy paper, color development on glossy paper is improved. When the surface tension exceeds 40 mN / m, the spread of dots is suppressed due to the size of the glossy paper surface layer, and the amount of ink adhering increases in order to improve the concealing property. Longer time may be incurred. On the other hand, when the static surface tension is less than 20 mN / m, the nozzle plate of the ink jet head gets too wet, and wiping spots due to maintenance cause the ink to ooze out around the nozzle holes and cause non-uniform wettability. It may cause bending or non-ejection.

  There is no restriction | limiting in particular as a color of the said ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are used. When recording is performed using an ink set in which two or more of these colors are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are used in combination, a full color image can be formed. it can. Further, by using red, green, blue, orange, green, gray, light cyan, light magenta, and dark yellow inks other than the process colors, the color gamut of the full color image can be expanded and the graininess of the image can be reduced. Also, since the total amount of secondary color adhesion can be reduced, it is difficult to cause improper absorption of recording media, beading and bleeding can be reduced, and hue bending and hue change during drying can be reduced. .

The ink uses a piezoelectric element as pressure generating means for pressurizing the ink in the ink flow path, and deforms a vibration plate that forms the wall surface of the ink flow path to change the volume in the ink flow path to eject ink droplets. A so-called piezo type (refer to Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-59911). In other words, the diaphragm and the electrode that form the wall surface of the ink flow path are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the vibration plate and the electrode, thereby reducing the volume of the ink flow path. It can be used favorably in a printer equipped with any inkjet head such as an electrostatic type that changes and discharges ink droplets (see Japanese Patent Laid-Open No. 6-71882).
The ink can be used, for example, in a printer or the like having a function of accelerating print fixing by heating a recording medium and the ink at 50 ° C. to 200 ° C. before or after printing.

(ink cartridge)
The ink cartridge of the present invention contains the ink for ink jet recording of the present invention in a container, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like Preferred examples include those possessed.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 1 is a view showing an example of the ink cartridge of the present invention, and FIG. 2 is a view including a case (exterior) of the ink cartridge 200 of FIG.
As shown in FIG. 1, the ink cartridge 200 is filled into the ink bag 241 from the ink inlet 242 and 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. 2, the ink bag 241 is usually housed in a plastic cartridge case 244 and is detachably attached to various ink jet recording apparatuses.

  The ink cartridge of the present invention contains the ink for ink jet recording of the present invention and can be used by being detachably attached to various ink jet recording apparatuses, and is also detachably attached to the ink jet recording apparatus of the present invention described later. It is particularly preferable to use them.

(Inkjet recording method and inkjet recording apparatus)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means and control means.
The ink jet recording method of the present invention includes at least an ink flying step, and further includes other steps appropriately selected as necessary, for example, a stimulus generation step, a control step, and the like.

  The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

-Ink flying process and ink flying means-
The ink flying step is a step of forming an image by applying a stimulus to the inkjet recording ink of the present invention and causing the ink to fly.
The ink flying means is means for forming an image by applying a stimulus to the ink jet recording ink of the present invention and causing the ink to fly. There is no restriction | limiting in particular as this ink flying means, For example, a recording head etc. are mentioned.

  As the recording head, a piezoelectric element is used as a pressure generating means for pressurizing the ink in the ink flow path, and the diaphragm that forms the wall surface of the ink flow path is deformed to change the volume in the ink flow path to eject ink droplets. A so-called piezo type (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-61). No. 59911), the diaphragm and the electrode forming the wall surface of the ink flow path are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the diaphragm and the electrode, whereby the ink flow path inner volume is obtained. This includes any case of an electrostatic type in which ink droplets are ejected by changing the pressure (see Japanese Patent Laid-Open No. 6-71882).

  The stimulus can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, light, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor, etc. Examples include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a body, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.

  The flying mode of the ink jet recording ink is not particularly limited, and varies depending on the type of the stimulus.For example, when the stimulus is “heat”, the ink jet recording ink in the recording head Thermal energy corresponding to a recording signal is applied using, for example, a thermal head, bubbles are generated in the inkjet recording ink by the thermal energy, and the pressure of the bubbles causes the inkjet recording ink to be ejected from the nozzle holes of the recording head. And a method of ejecting and ejecting ink as droplets. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting the ink jet recording ink as droplets from the nozzle holes of the recording head.

  The size of the droplets of the inkjet recording ink to be ejected is preferably, for example, 31 pl to 40 pl, and the ejection jet speed is preferably 5 m / s to 20 m / s. The drive frequency is preferably 1 kHz or higher, and the resolution is preferably 300 dpi or higher. The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

There is no restriction | limiting in particular as a material of the ink repellent layer of the nozzle plate in the said recording head, According to the objective, it can select suitably, For example, a silicone type water repellent material, a fluorine type water repellent material, etc. are mentioned. Among these, silicone-based water repellent materials are preferable.
Examples of the silicone-based water repellent material include room temperature-curing liquid silicone resin or elastomer, which is applied to the surface of a substrate and polymerized and cured by being left in the air at room temperature to form an ink repellent film. It is preferable.
The silicone-based water-repellent material is a heat-curable liquid silicone resin or elastomer, and may be applied to the surface of the substrate and cured by heat treatment to form an ink-repellent film.
The silicone-based water repellent material is an ultraviolet curable liquid silicone resin or elastomer, and may be applied to the surface of the substrate and cured by irradiation with ultraviolet rays to form an ink repellant film.
The silicone water repellent material preferably has a viscosity of 1,000 cp (centipoise) or less.

  The 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, elastomer, etc. In addition to the ink repellency important in the present invention, it is heat resistant. It has various properties such as properties, releasability, defoaming properties, and tackiness. Silicone resins include room temperature curing, heat curing, ultraviolet curing, and the like, and can be selected according to the production method and usage.

As a method for forming the ink repellent layer containing the silicone resin on the nozzle surface, 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 Examples thereof include a method of forming by coating and the like, and an electrodeposition method. When forming the ink repellent layer, except for the electrodeposition method, the nozzle holes and the back of the nozzle plate are masked with a photoresist, a water-soluble resin, etc., and after forming the ink repellent layer, the resist is peeled off to remove only the nozzle plate surface. In addition, an ink repellent layer containing a silicone resin can be formed. In this case, care should be taken because a strong alkaline stripping solution will damage the ink repellent layer.
The thickness of the ink repellent layer containing the silicone resin is preferably 0.1 μm to 5.0 μm, and more preferably 0.1 μm to 1.0 μm. When the thickness is less than 0.1 μm, the durability against wiping deteriorates, and the ink repellency may deteriorate during long-term use. When the thickness exceeds 5.0 μm, the ink repellency has a thickness greater than necessary. The manufacturing cost may increase because of the layer.
The surface roughness (Ra) of the ink repellent layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.2 μm or less. By setting the surface roughness Ra to 0.2 μm or less, it is possible to reduce wiping residue during wiping.

Here, one aspect of carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings.
The ink jet recording apparatus shown in FIG. 3 stocks an apparatus main body 101, a paper feed tray 102 for loading paper loaded on the apparatus main body 101, and paper on which an image is recorded (formed) mounted on the apparatus main body 101. A paper discharge tray 103 and an ink cartridge loading unit 104. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201.
In the apparatus main body 101, as shown in FIGS. 4 and 5, the carriage 133 is slid in the main scanning direction by guide rods 131 and stays 132 which are horizontally mounted on left and right side plates (not shown). It is held movably and moved and scanned in the direction of the arrow in FIG. 5 by a main scanning motor (not shown).
The carriage 133 includes a plurality of ink jet recording heads 134 including four ink jet recording heads that eject recording ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). The ejection ports are arranged in a direction crossing the main scanning direction, and are mounted with the ink droplet ejection direction facing downward.
As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a heating resistor, a metal phase caused by a temperature change A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like as an energy generating means for discharging recording ink can be used.

In addition, 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 the ink for ink-jet recording of the present invention from the ink cartridge 1 of the present invention loaded in the ink cartridge loading section 105 via a recording ink supply tube (not shown).
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 feeding tray 103, a half-moon roller (feeding) that separates and feeds the paper 142 one by one from the paper stacking unit 141. A separation pad 144 made of a material having a large friction coefficient is provided opposite to the paper roller 143) and the paper feed roller 43, and the separation pad 144 is urged toward the paper feed roller 143 side.
As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° so as to follow the transport belt 151. A conveying guide 153 and a tip pressure roller 155 urged toward the conveying belt 151 by a pressing member 154, and a charging roller 156 as a charging means for charging the surface of the conveying belt 151. It has been.

  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 having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), and the surface layer. It has a back layer (medium resistance layer, earth layer) that is made of the same material and has resistance controlled by carbon. On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134. Note that, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed below the paper discharge roller 172.

A double-sided paper feeding unit 181 is detachably mounted on 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 it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. 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 approximately 90 °.

At this time, the conveyance belt 157 is charged by the charging roller 156, and the sheet 142 is conveyed by being electrostatically attracted to the conveyance belt 151. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103.
When the recording ink remaining amount near end in the sub tank 135 is detected, a required amount of recording ink is supplied from the ink cartridge 1 to the sub tank 135.
In this ink jet recording apparatus, when the recording ink in the ink cartridge 1 of the present invention is used up, the casing of the ink cartridge 201 can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge 201 can supply recording ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration. Accordingly, the ink cartridge 1 can be used even when the apparatus main body 101 is closed and installed, for example, in a rack or when an object is placed on the upper surface of the apparatus main body 101. Can be easily exchanged.
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.
Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method. For example, the ink jet recording apparatus, the facsimile apparatus, the copying apparatus, the printer / fax / copier multifunction machine, etc. It can be particularly preferably applied.

<Recording media>
The recording medium that is the target of the ink jet recording method of the present invention has at least one ink receiving layer on a support, and further includes other layers as necessary.
An ink jet recording medium comprising a lower layer containing silica, polyvinyl alcohol and a crosslinking agent on the support, comprising an upper layer containing alumina or colloidal silica and polyvinyl alcohol and substantially free of polyvinyl alcohol crosslinking agent. Is preferred.
The upper layer of such a recording medium is a recording medium printing surface, and the Beck smoothness of this surface is preferably 300 seconds or more. If it is 300 seconds or less, it is not preferable because the pixels are spread unevenly, the roundness is easily lost, and noise in photographic gradation is likely to occur.

The ink receiving layer has a multilayer structure of two or more layers, and the lower layer contains porous particles such as an inorganic oxide having a large specific surface area so that the ink can be absorbed quickly and the colorant can be fixed. Is preferred. Specific examples include silica or alumina. Among silicas, synthetic silica having an average primary particle size of 30 nm or less obtained by a vapor phase method and a BET specific surface area of 250 m ² / g or more is an ink absorptivity. And high gloss.
Examples of the alumina include β-alumina and γ-alumina.

In addition, colloidal silica or alumina having a small primary particle size and a large secondary particle size is preferably used for the upper layer corresponding to the surface of the recording medium, and colloidal silica particles treated with an aluminum salt can also be preferably used.
As the binder in the ink receiving layer, a hydrophilic binder that is highly transparent and can obtain higher permeability of the ink solvent is preferably used. In using the hydrophilic binder, it is important that the hydrophilic binder does not swell during the initial permeation of the ink solvent and block the gap, and a hydrophilic binder that does not easily swell near room temperature is preferably used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol. The lower layer can be formed into a gel-like structure by adding a crosslinking agent such as borax to polyvinyl alcohol, and dried in the gel structure, thereby forming an ink-receiving layer with a large gap and high liquid absorption.
As the base material of the recording medium, any of known paper, synthetic paper, resin-coated paper, film and the like can be used, but a non-ink-absorbing base material is preferable.
In particular, resin-coated paper used for photographic printing paper is more preferable as a media base material for reproducing photographic image quality.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.

(Production Example 1)
<Purification and separation of dye>
In a beaker, water-soluble dye C.I. I. Acid Orange 33 (trade name: ACID ORANGE 33, manufactured by New Dragon Industrial Co., Ltd.) 10 g was dissolved in 290 g of water, 5 g of activated carbon Shirasagi M (manufactured by Nippon Environmental Chemicals Co., Ltd.) was added, and 1 at 23 ° C. with a stirrer. Stir for hours. Thereafter, activated carbon was removed by vacuum filtration using a PP filter having a filter diameter of 5 μm, and then a 0.8 μm cellulose acetate filter was filtered under pressure. The filtrate was treated with a reverse osmosis membrane to remove inorganic salts such as alkali metal salts from the dye solution. This dye solution was concentrated with an evaporator to obtain a dye solution having a solid content of 10% by mass.
The obtained dye solution was filled with silica gel (Wakosil C-200, manufactured by Wako Pure Chemical Industries, Ltd.) using a mixed solvent of butyl acetate: ethanol: water = 35: 35: 30 (volume ratio) as a developing solvent. Separation and separation were performed using a column. In the separated product, a strong colored solution was dried with a rotary evaporator, and the obtained solid was dried with a vacuum dryer at 50 ° C. for 6 hours. I. A component of Acid Orange 33 was obtained.

At this time, the component obtained previously was designated as the low polarity component B, and the component obtained later was designated as the high polarity component A. These components were measured by ATR method with SpectrumOne FT-IR (manufactured by Perkin Elmer), and the FT-IR absorption spectra of FIGS. 6 and 7 were obtained.
About the obtained high polar component A and low polar component B, the solubility to benzyl alcohol was calculated | required as follows. The lower the solubility in benzyl alcohol (dielectric constant 13.1), the higher the polarity.
First, 1.8 g of dye was added to 20 mL of water and dissolved, and the mixture was added to a separatory funnel, and 40 mL of benzyl alcohol was also added and mixed well. Then, it was left still and the water layer and the benzyl alcohol layer were separated, and the benzyl alcohol layer was recovered. The operation of adding 40 mL of fresh benzyl alcohol to this aqueous layer, mixing and extracting was repeated three times, and 160 mL of benzyl alcohol in which the dye was dissolved was recovered. The benzyl alcohol layer was dried using a rotary evaporator, and the amount recovered of each component was evaluated.
The recovered amount of the benzyl alcohol layer of the high polarity component A was 0.08 g, and the solubility was 0.5 g / L. The recovered amount of the benzyl alcohol layer of the low polarity component B was 0.98 g, and the solubility was 6.1 g / L. From these results, it was found that the high polarity component A is higher in polarity than the low polarity component B.

(Examples 1-10 and Comparative Examples 1-3)
<Preparation of ink>
The ink was prepared according to the following procedure according to Tables 1 to 3.
First, an organic solvent, a surfactant, and water were mixed and stirred for 30 minutes to mix uniformly. The prepared dye and other components were added to the mixed solution, and the remaining amount of water was added so that the total amount was 95% by mass, followed by stirring for 30 minutes. A lithium hydroxide 10 mass% aqueous solution was added to the mixed solution to adjust the pH to 9, and the remaining amount of water was added so that the total amount was 100 mass%, followed by stirring for 30 minutes.
The prepared inks (100 mL) were saved for filterability evaluation, and the others were pressure filtered through a 0.2-μm cellulose acetate membrane filter with a diameter of 25 mm to remove coarse particles. Examples 1 to 10 and Comparative Example 1 Inkjet recording inks -3 were prepared.

  Next, various characteristics of each ink-jet recording ink produced were evaluated as follows. The results are shown in Tables 1 to 3.

<Evaluation of ink repellency to nozzle member>
A silicone resin (SR-2411, manufactured by Toray Dow Corning Silicone Co., Ltd.) is applied on the surface of the Ni electroforming nozzle with a dispenser, and heat-treated at 250 ° C. for 1 hour in the atmosphere to form a silicone layer having a thickness of about 0.5 μm Formed.
The prepared nozzle member was immersed in each ink jet recording ink at 50 ° C. for 7 days. After immersion, the nozzle member rinsed with pure water and naturally dried was further immersed in each ink jet recording ink at 25 ° C. for 30 seconds, and the ink repellency after pulling up was evaluated according to the following criteria.
〔Evaluation criteria〕
3: The ink repels substantially within 90 seconds after pulling up. 2: The ink which is immersed in about 90 seconds remains. 1: The ink remains in the entire immersed part.

<Filtration evaluation>
100 mL of each ink for ink jet recording was subjected to pressure filtration with a 0.2 μm cellulose acetate membrane filter having a diameter of 25 mm, and the number of filters used for filtration was counted to evaluate the filterability. The filtration method was assembling into a 20 mL syringe and then pressurizing by hand, and the filter was replaced when the filtration rate was less than 1 drop per second.
〔Evaluation criteria〕
3: 1 or less 2: 2 or more and less than 3 1: 3 or more

<Re-filterability evaluation>
The re-filterability of each ink for ink jet recording was subjected to pressure filtration at a pressure of 1 kgf / cm ^{2 with} a cellulose acetate membrane filter diameter of 0.2 μm and an air pressure of 1 kgf / cm ² . The following criteria were evaluated from the attenuation rate) and the maximum filtration rate.
〔Evaluation criteria〕
4: The slope attenuation rate is less than 15 [× 10 ⁻⁴ / sec] and the maximum filtration rate exceeds 1.0 [g / sec] 3: The attenuation rate is less than 15 [× 10 ⁻⁴ / sec] The maximum filtration rate is less than 1.0 [g / sec] 2: The attenuation rate is 15 to 25 [× 10 ⁻⁴ / sec] 1: The attenuation rate is greater than 25 [× 10 ⁻⁴ / sec] thing

<Printer evaluation>
Clean by passing pure water through the ink supply path including the print head of the printer (Ricoh Co., Ltd., IPSiO GX e3300), and thoroughly drain until the cleaning liquid is not colored. An evaluation printing apparatus was used. Further, each ink for ink jet recording was stirred for 30 minutes under a reduced pressure condition of 5 Pa to 10 Pa to degas the ink, and the ink cartridge was filled to obtain an ink cartridge for evaluation. After this ink cartridge was set in the printing apparatus and filled with ink, it was left overnight and printed on photographic paper Krispia (manufactured by Seiko Epson) in an environment of 40% RH at 23 ° C. Evaluation was performed as described above. The results are shown in Tables 1 to 3.

<< Evaluation of ejection reliability >>
The evaluation printing device was modified to check how long printing can be resumed without capping, cleaning, etc. during operation. The reliability was evaluated by changing the quantity. Standing in a 50% RH environment at 23 ° C. for 10 minutes, the dot position and the dot diameter state are increased 450 times from the printed image when dots with 75 dpi intervals are printed on photographic paper Krispia (Seiko Epson). After magnifying and observing, the following criteria were evaluated.
〔Evaluation criteria〕
5: No particular problem 4: Small change in dot diameter and within the limit of bending in the jet direction 3: Small jet bend 2: Large change in dot diameter but no clogging 1: Significant clogging occurred

The detail of the component of the brand name in Tables 1 to 3 is as follows.
* Surfactant: Surfynol 465 (acetylene glycol compound, manufactured by Nissin Chemical Co., Ltd.)
* Surfactant: Softanol EP-7025 (polyoxyalkylene secondary alcohol ether, manufactured by Nippon Shokubai Co., Ltd.)
* Proxel LV (manufactured by Avicia, 1,2-benzisothiazolin-3-one, fungicide)

From the results of Tables 1 to 3, when the mass ratio (B / A) of the high polarity component A and the low polarity component B is 1.2 or less, ink repellency, filterability, refilterability, and It was found that each of the discharge reliability had performance that could withstand use.
Further, if the mass ratio (B / A) is 1.0 or less, the filterability at the time of ink production is improved, and the jet bending at the time of ejection is reduced. I knew it was possible.
Furthermore, when the mass ratio (B / A) is 0 or more and 0.8 or less, the ink repellency, filterability, and refilterability are good, and the load is applied to the filter in the main body and the ink is very reliable. It was found that the ink can be reduced.

As an aspect of this invention, it is as follows, for example.
<1> It contains water, an organic solvent, and a colorant,
The colorant is C.I. I. Acid Orange 33, and the C.I. I. Acid Orange 33 includes a high polarity component A and a low polarity component B having a lower polarity than the high polarity component A, and a mass ratio (B / A) between the high polarity component A and the low polarity component B is It is an ink for ink jet recording characterized by being 1.2 or less.
<2> The ink for inkjet recording according to <1>, wherein a mass ratio (B / A) of the high polarity component A and the low polarity component B is 1.0 or less.
<3> The ink for inkjet recording according to any one of <1> to <2>, wherein a mass ratio (B / A) of the high polarity component A to the low polarity component B is 0 or more and 0.8 or less. .
<4> C.I. I. When comparing the absorption of the position of the absorption and 1590 ± 10 cm ^-1 of 1620 positions of ± 10 cm ^-1 in the FT-IR spectra of Acid Orange 33,
The high polar component A is a compound having a large absorption at a position of 1620 ± 10 cm ⁻¹ .
The ink for inkjet recording according to any one of <1> to <3>, wherein the low polarity component B is a compound having a large absorption at a position of 1590 ± 10 cm ⁻¹ .
<5> An ink cartridge comprising the ink for ink jet recording according to any one of <1> to <4> contained in a container.
<6> at least an ink flying step of recording an image by applying a stimulus to the ink for inkjet recording according to any one of <1> to <4> and causing the ink to fly;
In the ink jet recording method, the ink flying step is performed using a recording head having an ink repellent layer containing a silicone resin.
<7> At least ink flying means for recording an image by applying a stimulus to the ink for inkjet recording according to any one of <1> to <4> and causing the ink to fly.
An ink jet recording apparatus, wherein the ink flying means includes a recording head having an ink repellent layer containing a silicone resin.

200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge case

Japanese Patent No. 4793544 Japanese Patent No. 3900857 JP 60-49069 A

Claims (7)

Containing water, organic solvent, and colorant,
The colorant is C.I. I. Acid Orange 33, and the C.I. I. Acid Orange 33 includes a high polarity component A and a low polarity component B having a lower polarity than the high polarity component A, and a mass ratio (B / A) between the high polarity component A and the low polarity component B is An ink for ink jet recording, wherein the ink is 1.2 or less.   The ink for inkjet recording according to claim 1, wherein a mass ratio (B / A) of the high polarity component A and the low polarity component B is 1.0 or less.   The ink for inkjet recording according to any one of claims 1 to 2, wherein a mass ratio (B / A) of the high polarity component A and the low polarity component B is 0 or more and 0.8 or less. C. I. When comparing the absorption of the position of the absorption and 1590 ± 10 cm ^-1 of 1620 positions of ± 10 cm ^-1 in the FT-IR spectra of Acid Orange 33,
The high polar component A is a compound having a large absorption at a position of 1620 ± 10 cm ⁻¹ .
The ink for inkjet recording according to any one of claims 1 to 3, wherein the low polarity component B is a compound having a large absorption at a position of 1590 ± 10 cm ^-1 .   An ink cartridge comprising the ink-jet recording ink according to claim 1 contained in a container. At least an ink flying step of recording an image by applying a stimulus to the ink for inkjet recording according to any one of claims 1 to 4 and causing the ink to fly;
An ink jet recording method, wherein the ink flying step is performed using a recording head having an ink repellent layer containing a silicone resin. Applying a stimulus to the ink for ink jet recording according to any one of claims 1 to 4, and having at least ink flying means for flying the ink to record an image,
An ink jet recording apparatus, wherein the ink flying means has a recording head having an ink repellent layer containing a silicone resin.