JPH07228809A - Ink, ink jet recording process using the ink and apparatus for using the ink - Google Patents

Abstract

PURPOSE:To obtain an ink containing an anionic dye selected from a specific dye group, a liquid medium and a specific nitrogen compound as essential components, giving a printed record having excellent water-resistance and useful for high-quality recording. CONSTITUTION:This ink contains (A) at least one kind of anionic dye selected from the group consisting of anthraquinone dye, benzoquinone dye, naphthoquinone dye, xanthene dye, triphenylmethane dye, quinoline dye, indigoid dye, azine die, oxazine dye, thiazine dye and methine dye, (B) a liquid medium (e.g. a water-soluble organic solvent such as diethylene glycol) and (C) a nitrogen compound having a >=6C hydrocarbon group and >=2 nitrogen atoms [preferably a nitrogen compound of formula I (R1 and R4 are each an alkylamino, carboxyl, etc.; n is an integer of 2-4; m is an integer of 1-99), e.g. phenyltriethylenetetramine] as essential components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink, an ink jet recording method using the ink, and an ink jet device having the ink, and more specifically, an acidic paper or a neutral paper used in general offices. TECHNICAL FIELD The present invention relates to an ink which is excellent in water resistance of a printed record on so-called plain paper and can perform high-quality recording, an inkjet recording method using the ink, and an inkjet device having the ink.

[0002]

2. Description of the Related Art Conventionally, various compositions of inks for writing instruments (fountain pens, felt-tip pens, water-based ballpoint pens, etc.) and inkjet inks have been reported. In particular, in recent years, there has been an increasing demand for water resistance of printed matter on plain paper such as copy paper, report paper, notebooks and notepapers commonly used in offices.
Detailed research and development have been conducted from various aspects such as ink composition and physical properties. For example, JP-A-2-296878 and JP-A-2-255876 propose that a water-based ink composition contains a polyamine to improve the water resistance of a printed record.

[0003]

[Problems to be solved by the invention] However,
In the inks as described above, the mechanism for improving the water resistance is basically largely due to salt formation with respect to the hydrophilic base portion of the dye, so that clogging and stability of the ink may be impaired. Further, there is a problem in storage stability that the ink itself is discolored due to decomposition of polyamine during storage of the ink. From this, it has been considered that the above ink contains a dissolution stabilizer for the purpose of improving the stability of the ink, but in this case, the dissolution stabilizer must be added in a large amount. Therefore, the image quality of a printed record formed using such an ink deteriorates. In particular, in ink jet recording, fixing of the ink recorded on a recording material such as plain paper is largely due to natural permeation and evaporation of the recording material, so that the deterioration of image quality becomes a problem.

Further, Japanese Patent Application Laid-Open No. 57-57760 proposes a method of improving the water resistance of a printed record by incorporating an amphoteric surfactant in the ink. However, the water resistance of the above-mentioned ink is affected by the type of recording material. That is, depending on the surface pH of the recording material, the type of sizing agent, the type of cellulose, etc., there are recording materials having good water resistance, and there are recording materials having severe stains on the characters and poor water resistance. Further, the above-mentioned ink was inferior in practicality because the ink became viscous and clogging occurred even though the recorded matter had good water resistance. In general, an amphoteric surfactant contains many impurities in its components, and thus there is a problem that the reliability of the ink and the image quality are deteriorated. As described above, the quality of printed matter,
An ink which has excellent water resistance and practicality, excellent ink reliability, and gives a printed material having good water resistance regardless of the material to be recorded has not been found yet.

Therefore, the object of the present invention is to adversely affect the image quality of the printed matter when printing is performed on so-called plain paper such as acid paper or neutral paper used in general offices. Without giving it, the printed matter has sufficient water resistance, has no problem even for long-term storage, and enables high-quality printing without nozzle clogging. An object of the present invention is to provide an ink that can be used, an inkjet recording method using the ink, and an inkjet device having the ink.

[0006]

The above objects can be achieved by the present invention described below. That is, the present invention is at least one selected from the group consisting of anthraquinone dyes, benzoquinone dyes, naphthoquinone dyes, xanthene dyes, triphenylmethane dyes, quinoline dyes, indigoid dyes, azine dyes, oxazine dyes, thiazine dyes and methine dyes. Anionic dye, liquid medium, hydrocarbon group having 6 or more carbon atoms and 2
An ink comprising an essential component of a nitrogen compound containing at least one nitrogen atom at the same time, an inkjet recording method using the ink, and an inkjet device having the ink.

[0007]

[Function] The polyamine compound interacts with the negatively charged portion such as the sulfone group or the carboxyl group of the azo direct dye or the acid dye in the aqueous solution, so that the dye becomes insoluble and the printed matter It is already known that the water resistance is greatly improved. However, since the primary amino group of the polyamine compound decomposes the azo group of the dye molecule, there is a problem that discoloration occurs during storage as an ink. If the primary amino group is replaced with a secondary or tertiary amino group in order to improve this, the fading property of the ink can be suppressed to some extent, but this time, the water resistance of the printed matter is as high as that of the primary amino group. It did not improve, and the performance was insufficient in terms of both prevention of discoloration and water resistance. The present inventor has solved the above-mentioned problem of water resistance by introducing a hydrophobic group having a large molecular weight into the polyamine compound to increase the hydrophobicity of the entire molecule of the polyamine compound. The prevention of discoloration was solved by using an anionic dye having no azo group in the molecular structure as a dye.

[0008]

Preferred Embodiments Next, preferred embodiments will be described.
The present invention will be described in more detail. The nitrogen compound used in the ink of the present invention has a hydrocarbon group having a carbon number of 6 or more as a hydrophobic group, and in principle, the compound should be water-soluble. If the number of carbon atoms in the hydrocarbon group is less than 6, the printed matter cannot have sufficient water resistance. On the other hand, when the number of carbon atoms of the hydrocarbon group exceeds 48, the nitrogen compound becomes difficult to dissolve in the liquid medium of the ink, and the liquid stability of the obtained ink is impaired. In order to balance the hydrophobicity and water solubility of the nitrogen compound used in the present invention, in addition to the above-mentioned hydrophobic group, a hydrophilic group such as a hydroxyl group, a carboxyl group, a sulfone group or a salt thereof is used as the nitrogen compound. May be introduced into. Further, the nitrogen compound needs to have two or more nitrogen atoms, and if the nitrogen compound in the nitrogen compound is one, the nitrogen compound becomes difficult to dissolve in the liquid medium of the ink, and the liquid stability of the ink is Be damaged.

Examples of the above-mentioned nitrogen compounds preferable for use in the present invention include salts of an alkyl group, a carboxyl group and a carboxyl group, which have a primary amino group, a secondary amino group or a tertiary amino group. , A polyamine compound having a sulfone group and a salt group of a sulfone group, and more preferable examples of the nitrogen compound include the following general formula (1)
The compound shown by is mentioned.

[0010]

[Chemical 2] [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are carbon atoms having 1 to 48 carbon atoms which may be substituted with an alkylamino group, a carboxyl group or a salt group thereof, a sulfone group or a salt group thereof. It represents a hydrogen group or a hydrogen atom, at least one of which is a hydrocarbon group having 6 or more carbon atoms, n is an integer of 2 to 4, and m is an integer of 1 to 99. ]

As a more preferable nitrogen compound, at _{least one} of R ₁ , R ₂ , R ₃ and R ₄ of the compound of the general formula (1) is a carboxyl group or a salt thereof, a sulfone group or a salt thereof. It is a compound which is an organic group having a group. Specific examples of these nitrogen compounds include diamine derivatives such as ethylenediamine, propylenediamine, tetramethylenediamine and pentamethylenediamine;
Derivatives of polyamines such as 1,2,3-triaminopropane, tris (2-aminoethyl) amine and tetra (aminomethyl) methane; diethylenetriamine, triethylenetetramine, tetraethylenepentamine and heptaethyleneoctamine Derivatives of polyalkylene polyamines, in which at least one of hydrogen atoms bonded to nitrogen atoms of these polyamines is substituted with a hydrocarbon group having 6 or more carbon atoms, preferably 6 to 48 carbon atoms, and the like. Can be mentioned. Specific examples of the hydrocarbon group include an alkyl group such as a hexyl group which may have a substituent, an octyl group and a lauryl group, an aromatic group such as a phenyl group which may have a substituent, a naphthyl group and an anthranyl group. Group groups can be mentioned. For example, specifically, octyldiethylenetriamine, lauryldiethylenetriamine, phenyldiethylenetriamine, 1,3-dihexyldiethylenetriamine, phenyltriethylenetetramine, hexyltriethylenetetramine, octyltriethylenetetramine, 1,1′-dioctyltriethylenetetramine,
Octyl tetraethylene pentamine, lauryl triethylene tetramine, 1,1'-dioctyl tetraethylene pentamine, lauryl tetraethylene pentamine, 1,
1'-diphenyl tetraethylene pentamine and decyl heptaethylene octamine are mentioned. Preferred other compounds are lauryl heptaethylene octamine, tetradecyl heptaethylene octamine, and 1,1 ′.
-Dilauryl heptaethylene octamine, 1,1'-ditetradecyl heptaethylene octamine, etc. are mentioned.

[0012]

[Chemical 3] However, the present invention is not limited to these specific examples.

The above nitrogen compound is used in the ink of the present invention in an amount of about 5 to 3 per 100 parts by weight of the anionic dye described below.
00 parts by weight, more preferably about 20 to 200 parts by weight. If the amount of the nitrogen compound used is less than 5 parts by weight, it is insufficient in terms of improving water resistance.
If it exceeds 300 parts by weight, the effect of improving the water resistance is saturated and the viscosity of the ink remarkably increases, so that the recording characteristics and the reliability around the apparatus and the head are insufficient.

If the dye used in the present invention is anionic, water resistance is imparted by the addition of the nitrogen compound (polyamine compound), but in order to prevent discoloration due to decomposition of the azo group in the dye, The dye used in the ink of the invention is a dye having no azo group in its molecular structure, for example, anthraquinone type, benzoquinone type, naphthoquinone type, xanthene type, triphenylmethane type, quinoline type, indigoid type, azine type, oxazine type. Anionic dyes other than azo dyes such as thiazine dyes, methine dyes and stilbene dyes are used.

Specific examples of the anionic dyes other than the azo type dyes include C.I. I. Direct Yellow 39,
C. I. Direct Blue 41, C.I. I. Direct Blue 106, C.I. I. Direct Blue 108, C.I.
I. Direct Black 62, C.I. I. Acid Yellow 1, C.I. I. Acid Yellow 3, C.I. I. Acid Yellow 7, C.I. I. Acid Red 49, C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I.
I. Acid Red 80, C.I. I. Acid red 8
2, C.I. I. Acid Red 83, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 94, C.I. I. Acid Red 289, C.I.
I. Acid Red 306, C.I. I. Acid red 3
56, C.I. I. Acid Violet 15, C.I. I. Acid Violet 31, C.I. I. Acid Violet 34, C.I. I. Acid Violet 41, C.I. I.
Acid Violet 43, C.I. I. Acid Violet 48, C.I. I. Acid Violet 49, C.I.
I. Acid Violet 51, C.I. I. Acid Blue 1, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Acid Blue 22, C.I. I. Acid Blue 23, C.I. I.
Acid Blue 25, C.I. I. Acid Blue 27,
C. I. Acid Blue 40, C.I. I. Acid Blue 41, C.I. I. Acid Blue 43, C.I. I. Acid Blue 45, C.I. I. Acid Blue 54, C.I. I. Acid Blue 59, C.I. I. Acid Blue 62, C.I.
I. Acid Blue 74, C.I. I. Acid blue 7
8, C.I. I. Acid Blue 80, C.I. I. Acid Blue 82, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I.
I. Acid Blue 100, C.I. I. Acid blue 1
02, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. Acid Blue 112, C.I.
I. Acid Blue 126, C.I. I. Acid blue 1
27, C.I. I. Acid Blue 129, C.I. I. Acid Blue 138, C.I. I. Acid Blue 143, C.I.
I. Acid Blue 182, C.I. I. Acid blue 1
83, C.I. I. Acid Blue 202, C.I. I. Acid Blue 204, C.I. I. Acid Blue 205, C.I.
I. Acid Green 3, C.I. I. Acid Green 5, C.I. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I.
Acid Green 27, C.I. I. Acid green 3
6, C.I. I. Acid Green 40, C.I. I. Acid Green 41, C.I. I. Acid Green 44, C.I.
I. Acid Brown 13, C.I. I. Acid Brown 27, C.I. I. Acid Brown 103, C.I. I. Acid Black 2, C.I. I. Acid Black 48, C.I.
I. Acid Black 50, C.I. I. Reactive Blue 1, C.I. I. Reactive Blue 2, C.I. I. Reactive Blue 4, C.I. I. Reactive Blue 5, C.I.
I. Reactive Blue 17, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 27, C.I. I.
Reactive Blue 29, C.I. I. Reactive Blue 32, C.I. I. Reactive Blue 44, C.I. I. Reactive Blue 46 and C.I. I. Reactive Green 7 and the like are mentioned, and among these, particularly preferable anionic dyes include, for example, C.I. I. Direct blue 4
1, C.I. I. Direct Blue 106, C.I. I. Direct Blue 108, C.I. I. Direct black 62,
C. I. Acid Yellow 1, C.I. I. Acid Yellow 3, C.I. I. Acid Yellow 7, C.I. I. Acid Red 49, C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I.
I. Acid Red 92, C.I. I. Acid Red 9
4, C.I. I. Acid Red 289, C.I. I. Acid Blue 1, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Acid Blue 22, C.I. I. Acid Blue 23, C.I.
I. Acid Blue 25, C.I. I. Acid blue 2
7, C.I. I. Acid Blue 40, C.I. I. Acid Blue 41, C.I. I. Acid Blue 43, C.I. I. Acid Blue 45, C.I. I. Acid Blue 54, C.I.
I. Acid Blue 59, C.I. I. Acid blue 6
2, C.I. I. Acid Blue 74, C.I. I. Acid Blue 78, C.I. I. Acid Blue 80, C.I. I. Acid Blue 82, C.I. I. Acid Blue 83, C.I.
I. Acid Blue 90, C.I. I. Acid Blue 9
3, C.I. I. Acid Blue 100, C.I. I. Acid Blue 102, C.I. I. Acid Blue 103, C.I.
I. Acid Blue 104, C.I. I. Acid blue 1
12, C.I. I. Acid Blue 126, C.I. I. Acid Blue 127, C.I. I. Acid Blue 129, C.I.
I. Acid Blue 138, C.I. I. Acid blue 1
43, C.I. I. Acid Blue 182, C.I. I. Acid Blue 183, C.I. I. Acid Blue 203, C.I.
I. Acid Blue 204, C.I. I. Acid blue 2
05, C.I. I. Acid Black 2, C.I. I. Acid Black 48, C.I. I. Acid Black 50, C.I.
I. Reactive Blue 1, C.I. I. Reactive Blue 2, C.I. I. Reactive Blue 4, C.I. I. Reactive Blue 5, C.I. I. Reactive Blue 17,
C. I. Reactive Blue 19, C.I. I. Reactive Blue 27, C.I. I. Reactive Blue 29, C.I.
I. Reactive Blue 32, C.I. I. Reactive Blue 44 and C.I. I. Reactive Blue 46 and the like can be mentioned.

The amount of the above dye used in the ink of the present invention is not particularly limited, but it is generally 0.1 to 15% by weight, preferably 0.
The amount is preferably 5 to 10% by weight, more preferably 0.5 to 6% by weight. A suitable medium for use in the ink of the present invention is water or a mixed solvent of water and a water-soluble organic solvent. As the water, it is preferable to use deionized water instead of general tap water containing various ions.

As the water-soluble organic solvent used by mixing with water, for example, methyl alcohol, ethyl alcohol,
n-propyl alcohol, isopropyl alcohol, n
-Butyl alcohol, sec-butyl alcohol, te
rt-butyl alcohol, isobutyl alcohol, n-
C1-C5 alkyl alcohols such as pentanol; amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as dioxane; polyethylene glycol, polypropylene glycol, etc. Polyalkylene glycols; alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, and diethylene glycol contain 2 to 6 carbon atoms. Alkylene glycols; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomer Lower alkyl ethers of polyhydric alcohols such as ethyl (or ethyl) ether; lower dialkyl ethers of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether, tetraethylene glycol (or ethyl) ether; sulfolane, N-methyl 2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned.

In the ink of the present invention, an appropriate one is selected from the above organic solvents and used. In the case of the dye used in the present invention, diethylene glycol or thiodiglycol is used particularly from the viewpoint of preventing clogging of the ink. Is preferred,
From the viewpoint of image density and ejection stability, a nitrogen-containing cyclic compound or a polyalkylene oxide ether compound is preferable, and from the viewpoint of frequency response, use of a lower alcohol or a surfactant is preferable. Therefore, a preferable solvent composition in the present invention is a composition containing various components as described above in addition to water.

The content of the water-soluble organic solvent in the ink of the present invention is generally 2 to 80% by weight, preferably 3 to 70% by weight, more preferably 4 to 10% by weight based on the total weight of the ink.
It is in the range of 60% by weight. The amount of water used is 10 to 97.5% by weight of the total ink, preferably 35 to 97.5.
%, And more preferably 45-97.5% by weight.

In addition to the above components, the ink of the present invention may contain a pH adjusting agent, a viscosity adjusting agent, a surface tension adjusting agent and the like, if necessary. Examples of the pH adjusting agent include various organic amines such as diethanolamine and triethanolamine; inorganic alkali agents such as alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; organic acids such as lithium acetate. Salts: Organic acids, mineral acids and the like can be mentioned. The ink of the present invention has a viscosity of 1 to 25 ° C.
It preferably has a physical property of 20 cps, preferably 1 to 15 cps, a surface tension of 20 dyn / cm or more, preferably 25 dyn / cm or more, and a pH of about 4 to 10.

The recording method in which the ink of the present invention is used is
An inkjet recording method is effective as a method, and as a recording material, any recording material such as general plain paper (for example, high-quality paper, medium-quality paper, bond paper), coated paper or a plastic film for OHP is used. But it can be used. INDUSTRIAL APPLICABILITY The ink of the present invention is particularly suitable when applied to an inkjet recording method of the type that ejects ink due to the bubbling phenomenon of the ink due to thermal energy, and has the characteristic that ejection is extremely stable and satellite dots do not occur. is there. However, in this case, adjustment of thermal properties (for example, specific gravity, thermal expansion coefficient, thermal conductivity, etc.) may be required.

The ink of the present invention is particularly preferably used in an ink jet recording system in which droplets are ejected for recording by the action of heat energy, but it goes without saying that it can also be used as a general writing instrument. The recording method of the present invention for performing recording using the ink of the present invention is an inkjet recording method in which thermal energy corresponding to a recording signal is applied to the ink in the chamber of the recording head, and droplets are generated by the energy. A recording apparatus to which such an ink jet recording method is applied will be described below.

FIG. 1 and FIG. 2 show an example of the head structure, which is the main part of the structure. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a cross-sectional view taken along the line AB of FIG. The head 13 is a glass, ceramics, or plastic plate having a groove 14 through which ink passes, and a heating head 15 used for thermal recording (thin film head is shown in the drawing, but not limited to this). It is obtained by bonding and. The heat generating head 15 is composed of a heat generating resistor layer 18 made of silicon oxide or the like, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.

The ink 21 is a discharge orifice (fine hole) 2
It is filled up to 2, and the pressure P forms the meniscus 23. Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact therewith, and the meniscus 23 is generated by the pressure. And ink 21
Are ejected and become small ink droplets 24 from the orifice 22 and fly toward the recording material 25.

FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is made by bonding a glass plate 27 having multi-grooves 26 and a heating head 28 similar to that described in FIG. Figure 4
Shows an example of an ink jet recording apparatus incorporating this head. In FIG. 4, reference numeral 65 denotes a recording head having ejection energy generating means, which ejects ink to a recording material facing the ejection port surface where ejection ports are arranged for recording, and 66 denotes a recording head 65 mounted to perform recording. A carriage for moving the head 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is a motor 6.
It is connected to a belt 69 driven by 8 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move in the recording area and the area adjacent thereto. Reference numeral 51 is a paper feed section for inserting a recording material, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the ejection opening surface of the recording head 65, and as the recording progresses, the paper discharge roller 53.
The paper is ejected to the paper ejecting section where is arranged.

Reference numeral 61 denotes a blade serving as a wiping member, one end of which is held by a blade holding member to serve as a fixed end in the form of a cantilever. Blade 61
Is arranged at a position adjacent to the recording area of the recording head 65, and in the case of this example, is held in a protruding form in the movement path of the recording head 65. Reference numeral 62 denotes a cap, which is arranged at a home position adjacent to the blade 61, and has a configuration in which it moves in a direction perpendicular to the moving direction of the recording head 65 and comes into contact with the ejection surface to perform capping. 63 more
Is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the movement path of the recording head 65. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and dust on the ink ejection port surface.

In the above configuration, when the recording head 65 returns to the home position after the recording is completed, the head recovery unit 64
The cap 62 is retracted from the moving path of the recording head 65, but the blade 61 is projected in the moving path.
As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to project into the movement path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same position as the above-mentioned position during wiping. As a result, even during this movement, the ejection port surface of the recording head 65 is wiped. The above-described movement of the recording head 65 to the home position is performed not only at the end of recording or at the time of ejection recovery but also at the home position adjacent to the recording area at a predetermined interval while the recording head 65 moves in the recording area for recording. To, and with this movement, the wiping is performed.

The ink jet recording apparatus in which the ink of the present invention is used is not limited to the above-described head and ink cartridge as separate bodies, but those in which they are integrated as shown in FIG. Is also preferably used. In FIG. 6, 70 is an inkjet cartridge,
An ink absorber impregnated with ink is housed therein, and the ink in the ink absorber is ejected as ink droplets from a head portion 71 having a plurality of orifices. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. The inkjet cartridge 70 is used in place of the recording head 65 shown in FIG. 4, and is detachable from the carriage 66.

[0029]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The inks of Examples 1 to 5 of the present invention were prepared using the components shown in Table 1 below. Also, the inks of Comparative Examples 1 to 10 were prepared using the components shown in Table 2.

[0030]

[Table 1] Ink components of Examples

[0031]

[0032]

[Table 2] Components of inks of comparative examples

[0033]

[Evaluation] The inks of the examples and comparative examples shown in Tables 1 and 2 above are subjected to recording by applying thermal energy to the ink in the recording head to generate droplets for recording. Head (orifice size 50 x 4
Table 3 shows the evaluation results of ejection stability, sticking recovery property, water resistance of the printed matter, and storage stability of the ink when printing is performed by mounting in a recording device having 0 μm, driving voltage 30 V and frequency 4 KHz). The contents and conditions of each evaluation item are as follows.

Ejection Stability 100 sheets of continuous slip paper were printed and evaluated according to the following criteria. ○: No abnormality ×: No ejection or print disorder occurred Fixing recovery (clogging) After leaving for 1 month in an environment of 35 ° C, after performing recovery operation (suction operation by pumping), print and print as follows. It was evaluated according to the standard. ◯: The normal printing state is restored within 5 times of the recovery operation. X: No ejection or print disorder occurs even after the recovery operation is performed 6 times or more.

Water resistance A continuous slip sheet on the market was printed by driving all nozzles at the same time to prepare a patch, which was naturally dried in a room for 24 hours. Then, the patch was placed in a petri dish and tap water was allowed to stand still. , Gently soaked, left for 5 minutes and then dried. -1 Remaining ratio of optical density of patch before and after immersion (optical density of patch after immersion / optical density of patch before immersion × 10
0;%) was calculated and evaluated according to the following criteria. ◯: Remaining optical density is 80% or more ×: Remaining optical density is less than 80% −2 The degree to which the dye in the printed portion of the paper flows out and redeposits on the white background is evaluated according to the following criteria. ◯: Contamination is inconspicuous ×: Contamination is remarkable

Storage stability 100 cc of each ink was placed in a Teflon airtight container and stored in a constant temperature bath at 60 ° C. for 1 month.
It was printed on 0 sheets and evaluated according to the following criteria. ○: No abnormality ×: No ejection, print disturbance or discoloration

[0038]

[Table 3] Evaluation results of Examples and Comparative Examples

[0039]

As described above, according to the present invention, by using an anionic dye together with a nitrogen compound having a hydrocarbon group having 6 or more carbon atoms and 2 or more nitrogen atoms, various types of plain paper can be obtained. It is possible to provide an ink that has excellent water resistance when printed on a printed sheet and does not clog the orifice of the inkjet head and has excellent storage stability. Furthermore, by using a dye containing no azo group as the anionic dye, discoloration during storage of the ink can be completely prevented.

[0040]

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a recording head according to an inkjet recording method of the present invention.

FIG. 2 is a schematic cross-sectional view showing a sectional view taken along the line AB of FIG.

FIG. 3 is a schematic external view showing an example of a multi-head in which a large number of heads in FIG. 1 are arranged.

FIG. 4 is a schematic perspective view showing an example of an ink jet recording apparatus incorporating the same head.

FIG. 5 is a schematic cross-sectional view showing an example of an ink cartridge that supplies ink to the head.

FIG. 6 is a schematic external view showing an example of a main part of an inkjet recording apparatus in which the same head and the same ink cartridge are integrated.

[0041]

[Explanation of symbols]

 13: Head 14: Ink Grooves 15, 28: Heating Head 16: Protective Layer 17: Aluminum Electrode 18: Heating Resistor Layer 19: Heat Storage Layer 20: Substrate 21: Ink 22: Discharge Orifice (Fine Hole) 23: Meniscus 24 : Ink droplet 25: Recording material 26: Multi groove 27: Glass plate

51: paper feed unit 52: paper feed roller 53: paper discharge roller 61: blade 62: cap 63: ink absorber 64: ejection recovery unit 65: recording head 66: carriage 67: guide shaft 68: motor unit 69 : Belt 70: Inkjet cartridge 71: Head 72: Atmosphere communication hole

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Shinichi Sato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Eriko Saito 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Co., Ltd. (72) Inventor Hisashi Teraoka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Norifumi Hattori 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Keiichi Murai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (19)

[Claims] 1. Anthraquinone-based, benzoquinone-based, naphthoquinone-based, xanthene-based, triphenylmethane-based,
At least one anionic dye selected from the group consisting of quinoline-based, indigoid-based, azine-based, oxazine-based, thiazine-based, and methine-based dyes, a liquid medium, a hydrocarbon group having 6 or more carbon atoms, and 2 or more An ink comprising a nitrogen compound which simultaneously contains a nitrogen atom as an essential component. 2. The ink according to claim 1, wherein the nitrogen compound is a polyamine derivative containing two or more amino groups. 3. The ink according to claim 2, wherein the nitrogen compound is a compound represented by the following general formula (1). [Chemical 1] [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are carbon atoms having 1 to 48 carbon atoms which may be substituted with an alkylamino group, a carboxyl group or a salt group thereof, a sulfone group or a salt group thereof. It represents a hydrogen group or a hydrogen atom, at least one of which is a hydrocarbon group having 6 or more carbon atoms, n is an integer of 2 to 4, and m is an integer of 1 to 99. ] 4. R ₁ , R ₂ and R of the compound of the general formula (1)
The ink according to claim 3, wherein at least one of ₃ and R ₄ is an organic group having a carboxyl group or a salt group group thereof, a sulfone group or a salt group thereof. 5. An ink jet recording method for recording on a recording material by ejecting ink droplets from an orifice according to a recording signal, wherein the ink is the ink according to claim 1. . 6. The ink jet recording method according to claim 5, wherein thermal energy is applied to the ink to eject ink droplets. 7. A recording unit comprising an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets, wherein the ink is the ink according to claim 1. unit. 8. The recording unit according to claim 7, wherein the head portion is a head that causes thermal energy to act on the ink to eject ink droplets. 9. The recording unit according to claim 7, wherein the ink containing portion contains an ink absorber inside. 10. The recording unit according to claim 7, wherein the ink containing portion is formed of polyurethane, cellulose, or polyvinyl acetate. 11. An ink cartridge having an ink containing portion containing ink, wherein the ink is
An ink cartridge, which is the ink described in 1. 12. The ink cartridge according to claim 11, wherein the ink containing portion has a liquid contact surface formed of polyolefin. 13. An ink jet recording apparatus comprising a recording unit having an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets, wherein the ink is the ink according to claim 1. An ink jet recording apparatus characterized by the above. 14. The head portion is a head which causes thermal energy to act on ink to eject ink droplets.
3. The inkjet recording device according to item 3. 15. The ink jet recording apparatus according to claim 13, wherein the ink containing portion contains an ink absorber inside. 16. The ink jet recording apparatus according to claim 13, wherein the ink containing portion is formed of polyurethane, cellulose, or polyvinyl acetate. 17. A recording head for ejecting ink droplets,
The ink according to claim 1, wherein the ink is an ink cartridge having an ink containing portion containing the ink, and an ink supplying portion for supplying the ink from the ink cartridge to a recording head. Characteristic inkjet recording device. 18. The ink jet recording apparatus according to claim 17, wherein the recording head is a head that causes thermal energy to act on ink to eject ink droplets. 19. The ink jet recording apparatus according to claim 17, wherein the ink containing portion has a liquid contact surface formed of polyolefin.