JP6237010B2 - Ink set for ink jet recording, ink cartridge, ink jet recording apparatus, ink jet recording method, and ink recorded matter - Google Patents

Description

  The present invention relates to an ink for ink jet recording, an ink cartridge, an ink jet recording apparatus, an ink jet recording method, and an ink recorded matter.

  Inkjet printers have been remarkably popular due to their low noise and low running costs, and color printers that can print on plain paper have been actively put on 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 described above, and the ink to be used is selected from the characteristics that are prioritized according to the application.

  Inks used for ink jet recording generally contain water as a main component and contain a colorant and a water-soluble solvent such as glycerin for the purpose of preventing clogging. As the colorant, a dye has been used because of its excellent color developability and stability, but it cannot be said that the light resistance and water resistance of the image are sufficient. The water resistance is improved to some extent by improving the ink jet recording paper having an ink absorbing layer, but the plain paper is not satisfactory.

  In order to compensate for these drawbacks, inks using pigments as colorants have begun to be used. Although the light resistance, water resistance, etc. of the image are greatly improved, the color development is poor due to interference of light of different wavelengths and phases due to multiple reflections of light inside the pigment. Color development is said to be inferior.

  As a method for compensating for the decrease in color developability when such a pigment is used, a method of improving the color developability by coating pigment particles with a resin is used. According to this method, the fixability and gas resistance are further improved by the resin, which greatly contributes to dispersion stability. However, the current situation is less than that of dyes.

  Patent Documents 1 to 3 include C.I. I. Pigment red 122 and C.I. I. Pigment Violet 19 solid solution, C.I. I. Pigment violet 19 and C.I. I. Pigment Red 202 solid solution and C.I. I. There is a description of providing a high color ink set by using Pigment Yellow 155. However, C.I. I. Pigment red 122 and C.I. I. Pigment Violet 19 solid solution and C.I. I. There is no description of the combination of Pigment Yellow 155. Furthermore, since there is no description of the water-soluble solvent to be used, it is not suitable for a high-speed continuous book machine that requires quick drying.

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, an object of the present invention is to provide an ink set for ink jet recording which improves color development, particularly red, which is insufficient with conventional pigment inks, and also has quick drying properties.

The above-mentioned problem is solved by the following ink set for ink jet recording of the present invention [1].
[1] An ink set for inkjet recording comprising a combination of at least a plurality of inks of different hues comprising a pigment, a water-soluble solvent and water,
Including yellow ink and magenta ink as the ink,
The yellow ink is C.I. I. Pigment yellow 155,
The magenta ink is C.I. I. Pigment red 122 and C.I. I. Pigment violet 19;
C. in the magenta ink. I. Pigment red 122 and C.I. I. The mixing ratio with Pigment Violet 19 is 20:80 to 80:20 on a mass basis,
The water-soluble solvent includes at least one selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, N, N-dimethyl-β-methoxypropionamide and N, N-dimethyl-β-butoxypropionamide <br> An ink set for ink jet recording characterized by the above.

  By defining the color index of yellow pigment and magenta pigment, and water-soluble solvent, the ink set for ink jet recording is provided which improves color development, especially red, which is insufficient with conventional pigment inks, and also has quick drying properties. be able to.

It is perspective explanatory drawing seen from the front side of the inkjet recording device. It is a schematic block diagram explaining the whole structure of the mechanism part of the inkjet recording device shown in FIG. It is the schematic which shows an ink cartridge. It is the schematic which shows the modification of an ink cartridge.

Hereinafter, the present invention will be described in more detail.
The ink set for ink-jet recording of the present invention is an ink set for ink-jet recording comprising a combination of at least a plurality of inks of different hues comprising a pigment, a water-soluble solvent and water, and the yellow ink pigment is C.I. I. Pigment Yellow 155, and the magenta ink pigment is C.I. I. Pigment red 122 and C.I. I. Pigment Violet 19 and the water-soluble solvent is selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, N, N-dimethyl-β-methoxypropionamide and N, N-dimethyl-β-butoxypropionamide. It contains at least one kind.

  The magenta pigment is C.I. I. Pigment red 122 and C.I. I. Pigment violet 19 mixture or solid solution was used, and the yellow pigment was changed to C.I. I. Pigment Yellow 155 combined with color development, high chroma and high brightness red area color reproducibility, magenta ink that does not cause clogging in inkjet recording head, ink cartridge containing yellow ink, and An ink jet recording method and ink recorded matter using excellent magenta ink and yellow ink are provided.

  The ink constituting the ink set for ink-jet recording of the present invention uses water as a liquid medium. The following water-soluble solvents are used for the purpose of preventing ink drying, improving dispersion stability, and preventing curling on plain paper. Is used. A plurality of these water-soluble solvents may be used in combination.

Specific examples of the water-soluble solvent include the following.
Glycerin, ethylene glycol, diethylene glycol, isopropylideneglycerol, 1,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, trimethylolethane, ethylene glycol , Diethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, Polyhydric alcohols such as 1,2,4-butanetriol, 1,2,3-butanetriol, petriol;

  Polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether;

  Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone , Ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds; formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethyl-β-methoxypropionamide, N, N-dimethyl-β- Amides such as butoxypropionamide;

  Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine; sulfur-containing compounds such as dimethylsulfoxide, sulfolane, thiodiethanol; 3-ethyl-3-hydroxymethyloxetane, propylene carbonate, ethylene carbonate etc;

  Among these water-soluble solvents, 3-ethyl-3-hydroxymethyloxetane, isopropylideneglycerol, N, N-dimethyl-β-methoxypropionamide, and N, N-dimethyl-β-butoxypropionamide are particularly preferable. These can obtain an excellent effect for preventing curling in plain paper.

  The mass ratio of the pigment and the water-soluble solvent has a great influence on the ink ejection stability from the head. If the amount of the water-soluble solvent is small even though the pigment solid content is high, water evaporation near the ink meniscus of the nozzle proceeds, resulting in ejection failure. The blending amount of the water-soluble solvent is preferably 10 to 70% by mass, more preferably 20 to 50% by mass with respect to the whole ink. Ink within this range is very good in drying, storage and reliability tests.

  In the present invention, the C.I. I. Pigment red 122 and C.I. I. The mixing ratio with respect to pigment violet 19 (mass basis) is preferably 20:80 to 80:20. C. I. Pigment Violet 19 is a compound represented by the following structural formula (1) -1 (unsubstituted quinacdrine). I. Pigment Red 122 is a compound (2,9-dimethylquinacrine) represented by the following structural formula (1) -2 in which quinacrine is modified with methyl. The mixing ratio is preferably 25:75 to 75:25. When the former is 20 or more, both color developability and dispersibility are improved. By being 80 or less, the expected color development can be provided.

In addition, C.I. I. Pigment red 122 and C.I. I. There are two types of mixing of the pigment violet 19: one in which two coloring materials (pigment, surfactant and water are included) and the other in which the pigment is made into a solid solution. A solid solution is a mixed crystal (state crystallized in a mixed state) of a plurality of pigment molecules.
The amount of solid solution produced can be confirmed by observing the peak intensity of 2θ = with respect to the Bragg angle (2θ ± 0.2 °) of CuKα rays (wavelength: 1.541Å) with respect to X-rays. The production amount of the solid solution can be adjusted by adjusting the mixing conditions and the like when producing the solid solution from the pigment mixture.

（式中、Ｒは炭素数１〜２０のアルキル基、アリル基、アラルキル基を表し、ｌは０〜７の整数を表し、nは２０〜２００の整数を表す。） Any dispersant may be used for the color pigment ink in the present invention, but by using a compound represented by the following general formula (1), the average particle size is small, and the standard deviation in the particle size distribution is small. An aqueous pigment ink can be obtained.

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an allyl group, or an aralkyl group, l represents an integer of 0 to 7, and n represents an integer of 20 to 200.)

  In the general formula (1), n is preferably 20 or more and 100 or less, more preferably 30 or more and 50 or less. When n is less than 20, the dispersion stability tends to be lowered, the average particle size is large, and satisfactory chroma cannot be obtained due to the ink standard having a large standard deviation in the particle size distribution. On the other hand, when n is larger than 100, the viscosity of the ink increases, and printing by the ink jet method tends to be difficult. As the compound represented by the general formula (1), POE (n = 40) β naphthyl ether is more preferable.

  If necessary, the ink for inkjet recording of the present invention has a penetrating agent, a pH adjuster, an antiseptic / antifungal agent, a rust inhibitor, an antioxidant, an ultraviolet absorber, an oxygen absorber, a light stabilizer, and an anti-kogation agent. A conventionally known additive such as an agent can be appropriately selected and added.

-Penetration agent-
By adding a penetrant to the ink, the surface tension is reduced, the ink filling property to the nozzle is improved, the ejection stability is improved, and the recording medium after the ink droplets land on the recording medium. Feathering and color bleed can be reduced due to faster penetration into the skin. As the penetrating agent, a surfactant or a solvent having penetrability is used.

  Surfactants are broadly classified into anionic surfactants, nonionic surfactants, and amphoteric surfactants according to hydrophilic groups, and can be broadly classified into fluorine surfactants, acetylene surfactants, etc. according to hydrophobic groups. it can.

  Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate, and the like.

Nonionic surfactants include, for example, polyols, glycol ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylenes. Examples thereof include alkylamide and acetylene glycol.
Fluorosurfactants include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide, perfluoro. An alkyl ether compound etc. are mentioned, The fluorine-type surfactant represented by following Structural formula (2) can be used especially preferable.

As acetylene glycol surfactants, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5 An acetylene glycol type such as dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, 485 or TG from Air Products (USA)) can be used, particularly Surfynol 465, 104 and TG indicate good print quality.
As the permeable solvent, a polyol having 8 or more carbon atoms such as 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, or glycol ether can be used. .

  The said surfactant can be used individually or in mixture of 2 or more types. According to a preferred embodiment of the present invention, the amount of penetrant added to the entire ink is preferably used in a ratio range of 0.01% to 5% by weight, more preferably 0.03% to 2% by weight. is there. If the amount of the surfactant is small, the spread of dots after printing is poor, and the dot diameter becomes small, so that the solid image is poorly filled and the image density and saturation are lowered. If the amount of the surfactant is too large, foaming is likely to occur, and problems such as failure to discharge due to the foam blocking the flow path in the nozzle may occur.

-PH adjuster-
By adding a pH adjusting agent to keep it alkaline, the dispersion state can be stabilized and the ejection can be stabilized. In addition, when the pH is 11 or more, the amount of the ink jet head and the ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure occur. It is more preferable to add the pH adjuster when kneading and dispersing the pigment in water together with the dispersant than after adding the pigment and the additive such as a water-soluble solvent and penetrant after kneading and dispersing. This is because dispersion may be destroyed by adding some pH adjusters.

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, and 2-amino-2-ethyl-1,3-propanediol. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of 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.

-Antiseptic and fungicide-
As antiseptic / antifungal agents, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol and the like can be used in the present invention.

-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, phosphorus-based antioxidants, and the like.

-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 the recording liquid that can be used in the present invention.
Kogation is a malfunction in a thermal head that discharges recording liquid by using the force that foams the recording liquid by instantaneously heating the recording liquid by passing an electric current through the heater. When the recording liquid is heated This is a phenomenon in which alteration occurs in the recording liquid component and the altered substance adheres to the heater. When kogation occurs, heating by the heater is not normally performed, and the discharge force becomes weak, or in the worst case, the recording liquid does not discharge. Therefore, an anti-kogation agent can be added to the recording liquid that can be used in the present invention 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, acid having amino group and / or salt thereof, methyl group or methylene group. An ammonium salt of an acid having a group and a carboxyl group.

-Recording device-
The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, such as an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like.
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 FIG. 2, a carriage (133) is slidable in the main scanning direction by a guide rod (131) and a stay (132), which are horizontally extending guide members. And moving and scanning by the main scanning motor.
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 the ink supply tube and is 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). Opposed to the half-moon roller [sheet feeding roller (143)] that separates and feeds the sheet one by one, and the separation pad (144) made of a material having a large friction coefficient, this separation pad (144) 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 having a thickness of about 40 μm without resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), It has the same material as the surface layer and a back layer (medium resistance layer, earth layer) that has been 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) of the present invention 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.

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

The ink cartridge will be described with reference to FIGS. Here, FIG. 3 is a schematic diagram illustrating an example of the ink bag 241 of the ink cartridge of the present invention, and FIG. 4 is a schematic diagram illustrating the ink cartridge 200 in which the ink bag 241 of FIG. 3 is accommodated in the cartridge case 244. is there.
As shown in FIG. 3, ink is filled into the ink bag 241 from the ink inlet 242 and air remaining in the ink bag is exhausted, and then the ink inlet 242 is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port 243 made of a rubber member and supplied to the apparatus. The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 4, it is usually housed in a plastic cartridge case 244 and used as an ink cartridge 200 detachably mounted on various ink jet recording apparatuses.
The ink cartridge of the present invention is particularly preferably used by being detachably mounted on the above-described ink jet recording apparatus of the present invention.

（式中、Ｒは炭素数１〜２０のアルキル基、アリル基、アラルキル基を表し、ｌは０〜７の整数を表し、nは２０〜２００の整数を表す。）
［３］前記一般式（１）で示される化合物がＰＯＥ（ｎ＝４０）βナフチルエーテルであることを特徴とする［２］に記載のインクジェット記録用インクセット。
［４］［１］〜［３］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で使用されるマゼンタインクであって、顔料、水溶性溶剤及び水からなり、前記顔料としてＣ．Ｉ．ピグメントレッド１２２及びＣ．Ｉ．ピグメントバイオレット１９を含み、前記マゼンタインクにおけるＣ．Ｉ．ピグメントレッド１２２とＣ．Ｉ．ピグメントバイオレット１９との混合比が質量基準で２０：８０〜８０：２０であり、前記水溶性溶剤が３−エチル−３−ヒドロキシメチルオキセタン、Ｎ，Ｎ−ジメチル−β−メトキシプロピオンアミド及びＮ，Ｎ−ジメチル−β−ブトキシプロピオンアミドよりなる群から選ばれる少なくとも一種を含むことを特徴とするマゼンタインク。
［５］［４］に記載のマゼンタインクを収容したことを特徴とするインクカートリッジ。［６］［１］〜［３］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のインクを吐出させて記録を行う方式のヘッドを備えたことを特徴とするインクジェット記録装置。
［７］［６］に記載のインクジェット記録装置を用いて印字することを特徴とするインクジェット記録方法。
［８］［７］に記載のインクジェット記録方法で印字されたことを特徴とするインク記録物。
［９］画像支持体が紙であることを特徴とする［８］に記載のインク記録物。 The present invention relates to the following ink set for inkjet recording [1], and includes the following [2] to [10] as embodiments.
[1] An ink set for inkjet recording comprising a combination of at least a plurality of inks of different hues comprising a pigment, a water-soluble solvent and water,
Including yellow ink and magenta ink as the ink,
The yellow ink is C.I. I. Pigment yellow 155,
The magenta ink is C.I. I. Pigment red 122 and C.I. I. Pigment violet 19;
C. in the magenta ink. I. Pigment red 122 and C.I. I. The mixing ratio with Pigment Violet 19 is 20:80 to 80:20 on a mass basis,
The water-soluble solvent contains at least one selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, N, N-dimethyl-β-methoxypropionamide and N, N-dimethyl-β-butoxypropionamide. Ink set for ink jet recording characterized.
[ 2 ] The pigment is dispersed in the ink by a compound represented by the following general formula (1), and the amount of the compound used is 0.3 to 2 with respect to the pigment 1 on a mass basis. The ink set for inkjet recording according to [1] .

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an allyl group, or an aralkyl group, l represents an integer of 0 to 7, and n represents an integer of 20 to 200.)
[ 3 ] The ink set for ink jet recording according to [2] , wherein the compound represented by the general formula (1) is POE (n = 40) β naphthyl ether.
[ 4 ] A magenta ink used in the ink set for ink jet recording according to any one of [1] to [ 3 ], comprising a pigment, a water-soluble solvent, and water. I. Pigment red 122 and C.I. I. Pigment Violet 19 and C.I. in the magenta ink. I. Pigment red 122 and C.I. I. The mixing ratio with Pigment Violet 19 is 20:80 to 80:20 on a mass basis, and the water-soluble solvent is 3-ethyl-3-hydroxymethyloxetane, N, N-dimethyl-β-methoxypropionamide and N, A magenta ink comprising at least one selected from the group consisting of N-dimethyl-β-butoxypropionamide.
[ 5 ] An ink cartridge containing the magenta ink according to [ 4 ]. [ 6 ] An ink jet recording apparatus comprising a head of a system for performing recording by discharging ink of the ink set for ink jet recording according to any one of [1] to [ 3 ].
[ 7 ] An inkjet recording method, wherein printing is performed using the inkjet recording apparatus according to [ 6 ].
[ 8 ] An ink record printed by the ink jet recording method according to [ 7 ].
[ 9 ] The ink recorded matter according to [ 8 ], wherein the image support is paper.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a present Example at all.
In addition, the number of parts in an Example represents a mass part.

[Preparation of color pigment dispersion]
<Pigment / Dispersant>
To prepare the ink, a color pigment dispersion was first prepared.
The pigment types (α to ε) used are shown in Table 1 below, and the dispersant types (I to VI) used for dispersing the pigment are shown in Table 2 below.
Pigment β is C.I. I. Pigment red 122 and C.I. I. Pigment Violet 19 is formed into a solid solution.

<Basic formulation of color pigment dispersion>
The basic formulation for preparing dispersions a to r was as follows.
Pigment (pigment types: α, β, γ, δ, ε) 200 parts Dispersant (dispersant types: I, II, III, IV, V, VI) 75 parts High purity water remaining (total: 1000 parts)

(Preparation of dispersions a to e and j to r)
Regarding dispersions a to e and j to r, first, the pigment and the dispersant were premixed at a blending ratio shown in Table 3 below to obtain a mixed slurry. Using a disk-type media mill (UAM type, Kotobuki Kogyo Co., Ltd.), 0.03 mm zirconia beads and a filling rate of 70% were used for circulation dispersion (retention time 20 min) at a peripheral speed of 6 m / s and a liquid temperature of 10 ° C. for 20 min. Then, after centrifuging coarse particles with a centrifuge (Model 7700 manufactured by Kubota Corporation) for 8000 G for 20 min, the mixture is filtered using a filter having a diameter of 1.2 μm, and dispersions a to e, j to r was obtained.
(Preparation of dispersions f to i)
The dispersion types f to i were prepared by mixing the dispersion types d and e at a mixing ratio shown in Table 3.

[Preparation of ink]
<Basic formulation of ink>
The basic formula of the ink was as follows.
Dispersion (dispersion type: a to r) 25.0 parts Glycerin 5.0 parts Water-soluble solvent 15.0 parts Polyoxyethylene (3) alkyl (C13) sodium ether acetate 0.5 part 2-ethyl-1, 3-hexanediol 3.0 parts 2-amino-2-ethyl-1,3-propanediol 0.5 part Proxel LV (manufactured by Arch Chemicals Japan, antiseptic / antifungal agent) 0.1 part urethane resin (XW-75) -W920, manufactured by Mitsui Chemicals Co., Ltd.) 2.0 parts High purity water remaining (total: 100 parts)

In the ink formulation shown in Table 4 below, after obtaining a mixture of a dispersion species and a water-soluble solvent by the following preparation method, filtration with a membrane filter having a pore diameter of 0.8 μm, vacuum deaeration, and filtration, Ink jet recording inks (inks 1 to 19) of Examples and Comparative Examples were obtained.
In Table 4, 3-ethyl-3-hydroxymethyloxetane is “EHO”, N, N-dimethyl-β-methoxypropionamide is “MMP”, and N, N-dimethyl-β-butoxypropionamide is used. Each was abbreviated as “MBP”.

<Ink preparation method>
After adding the following components (1) to (8), the mixture was stirred for 30 minutes to prepare [Vehicle].
Next, each of the following components (9) and (10) was added to the obtained [vehicle] and stirred for 1 hour to prepare an ink.
(1) Glycerin (2) 1,3-Butanediol (3) 2-Ethyl-1,3-hexanediol (4) Water-soluble solvent (5) Polyoxyethylene (3) Alkyl (C13) Sodium ether acetate (6 ) 2-Amino-2-ethyl-1,3-propanediol (7) Proxel LV
(8) High purity water (9) Dispersion (10) Urethane resin

[ Examples 1 to 3, 6 to 14, Reference Examples 1 and 2, Comparative Examples 1 to 4]
Inks 1 to 19 were combined as shown in Table 5 to prepare ink sets of Examples 1 to 3, 6 to 14, Reference Examples 1 and 2, and Comparative Examples 1 to 4.
Examples 4 and 5 are missing numbers.
The inks of Examples 1 to 3, 6 to 14, Reference Examples 1 and 2, and Comparative Examples 1 to 4 were filled into an ink pack for an ink jet printer IPSiO GX e5500 (manufactured by Ricoh), Inc., and an ink cartridge. It was created.
The ink set was evaluated by the evaluation method described below using each ink set.
The evaluation results are shown in Table 5.

[Evaluation 1: Evaluation of curl]
The ink set for ink-jet recording prepared in Examples and Comparative Examples was set by filling the printer IPSiO GX e5500 (manufactured by Ricoh) having the structure shown in FIGS. The printing test paper used was the following recording paper A, and a recording density of 600 × 300 dpi and an A4 solid image were printed with one pass. The ink adhesion amount is adjusted to 300 to 340 mg / A4, the image 10 minutes after the end of printing is placed on a flat desk with the printing surface facing down, and the distance between the paper edge and the reference surface is scaled. It measured using. The average value of the measured values at the right and left edges of the paper was taken as the curl amount. The results of evaluation based on the following criteria are shown in Table 5. ○ and Δ are acceptable ranges.
(Evaluation paper)
Recording paper A: BP-PAPER GF-500 (A4, manufactured by Canon)
(Evaluation criteria)
○: Less than 5 mm Δ: 5 mm or more and less than 20 mm ×: 20 mm or more

[Evaluation 2: Y monochrome image evaluation (saturation of image)]
The optical densities of the solid image portions of the examples and comparative examples were measured with a spectrocolorimeter (X-Rite 938) and evaluated according to the following criteria.
Image sharpness (saturation) is printed on Xerox 4200 made by Xerox Co., Ltd., and a solid image of the image sample is measured with an Xrite densitometer and plotted on a chromaticity diagram. Say the distance from the top origin. More specifically, (a ² + b ² ) ^{1/2 is referred} to for the a value and b value on the chromaticity diagram.
(Evaluation criteria)
~ Saturation ~
○: Saturation 80 or more △: Saturation 75 or more and less than 80 ×: Saturation 75 or less

[Evaluation 3: M monochrome image evaluation (saturation of image)]
In the evaluation 2, the yellow ink was replaced with magenta ink, and the M single color image evaluation (image saturation) was performed in the same manner as in the evaluation 2 except that the evaluation criteria were as follows.
(Evaluation criteria)
~ Magenta pigment ink saturation ~
○: Saturation 70 or more △: Saturation 65 or more and less than 70 ×: Saturation 65 or less

[Evaluation 4: Evaluation of R secondary color image (saturation of image)]
The inks for ink jet recording in Examples and Comparative Examples were filled in the Ricoh ink jet printer IPSiO GX e5500 having the structure shown in FIGS. 1 and 2, and a solid image was printed in one pass. For printing evaluation, the recording paper A described below was used for printing, and the brightness was measured with a reflective color spectrocolorimetric densitometer X-Rite 938 (manufactured by X-Rite).
The saturation C * = ((a *) ² + (b *) ² ) ^1/2 is calculated from the obtained a * and b * values, and the saturation of the standard color (Japan color ver. ² ) is calculated. calculates the ratio k = C * / C * ₀ and a value C * _0, and evaluated according to the evaluation criteria below. The results are shown in Table 5, and the rank ○ is an acceptable range.
(Evaluation paper)
Recording paper A: BP-PAPER GF-500 (A4, manufactured by Canon)
(Evaluation criteria)
○: 1.1> k ≧ 1.0
Δ: 1.0> k ≧ 0.9
×: 0.9> k

[Evaluation 5: Evaluation of ejection stability]
An ink jet printer IPSiO GX e5500 manufactured by Ricoh Co., Ltd. was placed in a constant temperature and humidity chamber, and the environment in the tank was set to a temperature of 32 ° C. and a humidity of 30% RH. Next, after printing the following print pattern charts continuously for 20 sheets, the printer enters a pause state in which printing is not performed for 20 minutes, and this is repeated 50 times. Judged.

-Print pattern chart-
In the printing pattern, each ink was printed at a duty of 100% in a chart in which the printing area in the image area is 5% of the printing area of each color in the entire area of the paper. The printing conditions were a recording density of 300 dpi and one-pass printing.
(Evaluation criteria)
○: No omission △: Within 10 omissions ×: More than 10 omissions

[Evaluation 6: Evaluation of ink storage stability]
Each ink was put in a polyethylene container, sealed, stored at 70 ° C. for 3 weeks, and then the particle size, surface tension, and viscosity were measured and evaluated according to the rate of change from the initial physical properties as follows.
(Evaluation criteria)
○: Within 10% △: Within 30% ×: Over 50%

Next, the evaluation results in Table 5 will be examined.
(1) When comparing the example with the comparative example, the former is one of evaluation of curl, Y single color image evaluation, M single color image evaluation, R secondary color image evaluation, ejection stability evaluation, and ink storage stability evaluation. It was better. This is because the ink set of the comparative example is yellow, magenta does not use a specific color index, and the water-soluble solvent does not use a specific solvent.
(2) When Examples 2 and 3 are compared with Reference Examples 1 and 2, Examples 2 and 3 are superior to Reference Example 1 in M image evaluation and R secondary color image evaluation. 3 was superior to Reference Example 1 in M image evaluation, R secondary color image evaluation, and ink storage stability evaluation. This is because Examples 2 and 3 are magenta pigments C.I. I. Pigment red 122 and C.I. I. This is because the mixing ratio of the pigment violet 19 is within the specific range defined in the embodiment [2].
(3) When Examples 6 and 7 were compared with Examples 8, 9, and 10, Examples 6 and 7 were superior to Examples 8 to 10 in Y image evaluation. This is because the dispersant used in Examples 6 and 7 satisfies the numerical range (20 to 200) for n defined by the general formula (1) of the previous embodiment [3].
(4) When Example 1 is compared with Examples 6 and 7, Example 1 is superior to Examples 6 and 7 in ink storage stability evaluation and ejection stability evaluation Y, respectively. This is because the dispersant used in Example 1 is POE (n = 40) β naphthyl ether defined in the above embodiment [4].

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

JP 2005-048019 A JP 2009-197093 A Special table 2008-504399

Claims (9)

An ink set for inkjet recording comprising a combination of at least a plurality of inks of different hues comprising a pigment, a water-soluble solvent and water,
Including yellow ink and magenta ink as the ink,
The yellow ink is C.I. I. Pigment yellow 155,
The magenta ink is C.I. I. Pigment red 122 and C.I. I. Pigment violet 19;
C. in the magenta ink. I. Pigment red 122 and C.I. I. The mixing ratio with Pigment Violet 19 is 20:80 to 80:20 on a mass basis,
The water-soluble solvent contains at least one selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, N, N-dimethyl-β-methoxypropionamide and N, N-dimethyl-β-butoxypropionamide. Ink set for ink jet recording characterized. The pigment is dispersed in the ink by a compound represented by the following general formula (1), and the amount of the compound used is 0.3 to 2 with respect to the pigment 1 on a mass basis. 2. An ink set for inkjet recording according to 1 .

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an allyl group, or an aralkyl group, l represents an integer of 0 to 7, and n represents an integer of 20 to 200.) The ink set for ink jet recording according to claim 2 , wherein the compound represented by the general formula (1) is POE (n = 40) β naphthyl ether. A magenta ink used in the ink set for ink jet recording according to any one of claims 1 to 3 , comprising a pigment, a water-soluble solvent, and water. I. Pigment red 122 and C.I. I. Pigment Violet 19 and C.I. in the magenta ink. I. Pigment red 122 and C.I. I. The mixing ratio with Pigment Violet 19 is 20:80 to 80:20 on a mass basis, and the water-soluble solvent is 3-ethyl-3-hydroxymethyloxetane, N, N-dimethyl-β-methoxypropionamide and N, A magenta ink comprising at least one selected from the group consisting of N-dimethyl-β-butoxypropionamide. An ink cartridge containing the magenta ink according to claim 4 . An ink jet recording apparatus comprising the head of the method of performing recording by ejecting ink jet recording ink set according to any of claims 1-3. 7. An ink jet recording method comprising printing using the ink jet recording apparatus according to claim 6 . An ink recorded matter printed by the ink jet recording method according to claim 7 . The ink recorded matter according to claim 8 , wherein the image support is paper.

Images