JPH0860053A - Ink, ink jet recording method using the same, and apparatus using the same - Google Patents

Abstract

PURPOSE: To obtain an ink which provides a water- and light-resistant image when used for printing on plain paper, does not cause clogging at a nozzle tip, and is excellent in storage stability by incorporating a specific dye and an org. amine into the ink. CONSTITUTION: This ink contains at least one member selected from among dyes represented by formula I (wherein X<3> is a sulfo or carboxyl group; each X<4> is independently a substituent; m is 0-2; Y<1> and Y<2> are each alkyl or halogen; and Z<4> is carboxyl) and dyes represented by formula II (wherein L is a metal cation or H; Pc is a phthalocyanine ring; R<1> is H, optionally substd. alkyl, optionally substd. alkenyl, or optionally substd. aralkyl; R<2> is H. alkyl, alkoxy, halogen, or substd. amino; M<+> is an optionally substd. ammonium ion; and t+q is 3-4) and at least one org. amine pref. selected from among monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine.

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 apparatus using the ink, and more specifically, it has excellent water resistance and dissolution stability to plain paper and improved light resistance. The present invention also relates to an ink capable of obtaining a high-quality color image, an inkjet recording method using the same, and a device using such an ink.

[0002]

2. Description of the Related Art Hitherto, various compositions of ink jet ink have been reported. They are various dyes dissolved or dispersed in water or other organic solvents. In particular, in recent years, water resistance of printing when recorded on plain paper has been required, and on the other hand, detailed research and development have been made from various aspects such as ink composition and physical properties.

For example, JP-A-2-296878 and JP-A-2-255876 propose that an aqueous ink composition contains a polyamine. However, in such an ink, since the hydrophilic base portion of the dye is salted, the solubility of the dye is lowered, the reliability is lowered such as nozzle clogging, and bronze (association of dye) on the printed matter. As a result, uneven printing may occur or the density may not appear. In addition, it is possible to include a large amount of a dissolution stabilizer in the ink for the purpose of increasing the solubility of the dye, but in this case, a large amount of the dissolution stabilizer must be added, and the ink is formed using such an ink. The image quality of the recorded matter deteriorated.

Further, in JP-A-3-91577, the dye has a carboxyl group and further has an ammonium salt group or a volatile substituted ammonium salt group, so that the dye or the ammonia on the recording material is It has been proposed to improve the water resistance by volatilizing the amine and converting the carboxyl group into a free acid. However, even in this case, even if the initial solubility of the dye is good, the solubility of the dye is lowered due to gradual evaporation of ammonia or amine from the ink, and the nozzle clogging prevention and ink Often causes a decrease in stability. Further, for the same reason, bronzing easily occurs on a recording material, particularly acid paper. In addition, various proposals have been made for ink compositions having excellent water resistance using existing dyes and novel structural dyes, but none of them satisfy all the above conditions.

Further, EP0559310A1 and EP
In 0559309A2, compounds represented by the following structural formulas (c) and (d) are proposed. [Wherein, X ³ is a sulfone group or a carboxyl group, X ⁴ is independently a substituent, m is an integer of 0 to 2, Y ¹ and Y ² are each an alkyl group or a halogen atom, and Z ⁴ is Represents a carboxyl group. ]

[0006] [Wherein L is a metal cation or a hydrogen atom, Pc is a phthalocyanine ring, R ¹ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or a substituted aralkyl group, and R ² is A hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or any substituted amino group, M ⁺ represents an ammonium ion or a substituted ammonium cation, and (t + q) represents an integer of 3 to 4. ]

However, these compounds are essentially insoluble in water and solvents. Therefore, although it is possible to improve the water resistance as compared with conventional dyes for ink, even if the ink is formed by dissolving it in water or a solvent, for example, the cartridge containing ink in the cartridge, If left unattended for a long time, water and solvent evaporate, the ink becomes highly viscous, dries, and finally solidifies, making it difficult to print. Such a state is called sticking.). Similarly, when ink is ejected from a nozzle during printing and ink is not ejected from the nozzle for a certain time (for example, about 1 minute), the next first droplet from the nozzle is ejected. When the ink is ejected, stable ejection cannot be performed and printing may be disturbed, which may cause inconvenience (hereinafter, such a state is referred to as poor uniformity).

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to form a recorded image having good water resistance and improved light resistance on various plain papers, and to obtain an image quality after recording. Ink that does not have a bad influence on the nozzle, prevents clogging at the nozzle tip, and ensures reliability such as storage stability,
An object of the present invention is to provide an inkjet recording method using the ink and a device using the ink. A further object of the present invention is to provide an ink with excellent reliability in which stable ink droplets are formed when ink is ejected again after the ink ejection is stopped, and printing is not disturbed.

[0009]

The above object can be achieved by the present invention described below. That is, the present invention provides the following structural formula (a)
And an ink containing at least one dye represented by (b) and an organic amine, an inkjet recording method using the ink, and a device using the ink. [Wherein, X ³ is a sulfone group or a carboxyl group, X ⁴ is independently a substituent, m is an integer of 0 to 2, Y ¹ and Y ² are each an alkyl group or a halogen atom, and Z ⁴ is Represents a carboxyl group. ] [Wherein L is a metal cation or a hydrogen atom, Pc is a phthalocyanine ring, R ¹ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or a substituted aralkyl group, and R ² is A hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or any substituted amino group, M ⁺ represents an ammonium ion or a substituted ammonium cation, and (t + q) represents an integer of 3 to 4. ]

[0010]

The present inventor can form a recorded image with good water resistance on various plain papers and with improved light resistance, and does not adversely affect the image quality after recording, and the nozzle In order to provide an ink that secures reliability such as anti-clogging property and storage stability, as a result of intensive studies on various ink compositions, as a result, an ink containing a coloring material and a liquid medium that dissolves the same is An ink containing a dye represented by (a) or (b) and an organic amine does not impair the water resistance originally possessed by the dye and has excellent ink dissolution stability, that is, it does not cause clogging at the nozzle tip. It was further found that the image quality after recording was good.

The reason for this is that although the ammonia contained in the ink usually volatilizes at the nozzle tip or is stored for a long period of time and the dye becomes a free acid, the solubility of the dye decreases.
It is considered that the inclusion of the organic amine in the ink prevents the dye from becoming a free acid, increases the solubility of the dye, and prevents the dye from becoming insoluble. Furthermore, by adding a surfactant to the ink, the solubilizing effect prevents the dye molecules from associating, so the dye is dissolved and stabilized, and a synergistic effect of preventing clogging and sticking at the nozzle tip is obtained. I found that I could be.

It has also been found that the addition of a nitrogen-containing compound other than an organic amine to the ink has the effect of further increasing the solubility of the dye. Further, by adding at least one of hydroxide and alkali metal salt to the ink, the ink has excellent dissolution stability without impairing the water resistance originally possessed by the dye, that is, clogging at the nozzle tip. It was found that the image quality after recording did not occur and the image quality was good.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. Examples of the organic amine used in the present invention include monoethanolamine, diethanolamine, triethanolamine, ethylmonoethanolamine, n-butylmonoethanolamine, dimethylethanolamine, ethylethanolamine, ethyldiethanolamine, n-butyldiethanolamine, di-n-butyl. Examples thereof include, but are not limited to, ethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

The content of the organic amine is not particularly limited, but is preferably 0.01 to 10.0% by weight of the ink, more preferably 0.1 to 5.0% by weight. Examples of the dye used in the present invention include at least one dye represented by the following structural formulas (a) and (b). [Wherein, X ³ is a sulfone group or a carboxyl group, X ⁴ is independently a substituent, m is an integer of 0 to 2, Y ¹ and Y ² are each an alkyl group or a halogen atom, and Z ⁴ is Represents a carboxyl group. ]

[0015] [Wherein L is a metal cation or a hydrogen atom, Pc is a phthalocyanine ring, R ¹ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or a substituted aralkyl group, and R ² is A hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or any substituted amino group, M ⁺ represents an ammonium ion or a substituted ammonium cation, and (t + q) represents an integer of 3 to 4. ]

The content of the dye is not particularly limited, but is preferably in the range of 0.2 to 10.0% by weight of the total ink,
More preferably, it is in the range of 0.5 to 8.0% by weight. Specific examples of more preferred compounds represented by formula (a) are shown below.

[0017]

[0018]

[0019]

[0020]

Specific examples of more preferable compounds represented by the general formula (b) are shown below.

[0022]

[0023]

[0024]

[0025]

[0026]

The liquid medium for dissolving the above dye used in the present invention is preferably a mixture of water and a water-soluble organic solvent. Specific examples of the water-soluble organic solvent include amides such as dimethylformamide and dimethylacetamide;
Ketones such as acetone; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiene. 2 to 6 alkylene groups such as glycol, hexylene glycol and diethylene glycol
Alkylene glycols containing 1 carbon atom; lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether; monohydric alcohols such as ethanol and isopropyl alcohol; N- Methyl-2-pyrrolidone,
1,3-Dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, 2-pyrrolidone, ε-
Examples thereof include cyclic amide compounds such as caprolactam and imide compounds such as succinimide. However, the present invention is not limited to these. The content of the water-soluble organic solvent is generally 5 with respect to the total amount of the ink.
-40% by weight is preferable, and more preferably 5-30% by weight.

The surfactant used in the present invention includes:
Anionic surfactants such as fatty acid salts, higher alcohol ester salts, alkylbenzene sulfonates, higher alcohol phosphate salts; cationic surfactants such as aliphatic amine salts and quaternary ammonium salts; higher alcohol ethylene oxide adducts , Alkylphenol ethylene oxide adduct, aliphatic ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, fatty acid amide ethylene oxide adduct, higher alkylamine ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, polyhydric alcohol Nonionic surfactants such as fatty acid esters and fatty acid amides of alkanolamines; amphoteric surfactants such as amino acid type and betaine type are used. There is no particular limitation, but more preferably, a nonionic surfactant such as ethylene oxide adduct of higher alcohol, ethylene oxide adduct of alkylphenol, ethylene oxide-propylene oxide copolymer, ethylene oxide adduct of acetylene glycol, etc. To use.
Further, the number of added moles of the ethylene oxide adduct is 4
The range of -20 is particularly preferable.

The amount of the surfactant added is not particularly limited, but it is preferably in the range of 0.01 to 10.0% by weight, more preferably 0.1 to 5.0% by weight, based on the total weight of the ink. . If it is less than 0.01% by weight, the solubilizing effect cannot be sufficiently expected, depending on the kind of the surfactant, and 10.0
When the content exceeds the weight%, the initial viscosity of the ink becomes too large, which is not preferable.

Examples of the nitrogen-containing compound other than the organic amine used in the present invention include urea, thiourea, ethylene urea, alkyl urea, alkyl thiourea, dialkyl urea and dialkyl thiourea, but are not limited thereto. Not something. Urea is particularly preferably used. The content of the nitrogen-containing compound is not particularly limited, but is preferably in the range of 0.01 to 20.0% by weight, and more preferably in the range of 0.1 to 15.0% by weight of the total ink.

The hydroxide used in the present invention includes, but is not limited to, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide. It is not something that will be done. The content of the hydroxide is not particularly limited, but is preferably in the range of 0.01 to 10.0% by weight, and more preferably 0.1 to 5.0% by weight of the total ink.
Range.

The alkali metal salts used in the present invention include lithium acetate, sodium acetate, potassium acetate, beryllium acetate, magnesium acetate, calcium acetate, lithium nitrate, sodium nitrate, potassium nitrate, beryllium nitrate, magnesium nitrate, calcium nitrate, Lithium phosphate, sodium phosphate, potassium phosphate, beryllium phosphate, magnesium phosphate, calcium phosphate, lithium carbonate, sodium carbonate, potassium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, lithium oxalate, sodium oxalate, oxalic acid Examples thereof include, but are not limited to, potassium, beryllium oxalate, magnesium oxalate, calcium oxalate, and the like. Although the content of the alkali metal salt is not particularly limited, it is preferably in the range of 0.01 to 10.0% by weight, and more preferably in the range of 0.1 to 5.0% by weight, based on the entire ink.

Examples of the sulfates used in the present invention include sodium sulfate, lithium sulfate, potassium sulfate, ammonium sulfate, gallium sulfate, calcium sulfate, barium sulfate, beryllium sulfate and magnesium sulfate, but are not limited thereto. Not a thing. The content of the sulfate salt is not particularly limited, but is 0.01 to 0.01% of the entire ink.
A range of 10.0% by weight is preferable, and a range of 0.
It is in the range of 1 to 5.0% by weight. In the ink of the present invention, in addition to the above components, if necessary, a pH adjusting agent, a viscosity adjusting agent,
Antiseptic, antioxidant, evaporation accelerator, rust preventive, fungicide,
You may mix | blend additives, such as a chelating agent.

For the ink of the present invention, an ink jet system in which a recording signal is applied to the ink of the recording head and droplets are ejected by the generated thermal energy is preferably used. An example of the configuration of the recording head, which is the main part of the apparatus, is shown in FIGS. The head 13 includes a glass, ceramics or plastic plate having a groove 14 through which ink passes, and a heating head 15 (thin film head is shown in the figure, but not limited to this) used for thermal recording. Obtained by gluing. The heating head 15 includes a protective film 16 made of silicon oxide or the like and aluminum electrodes 17-1 and 17.
-2, a heating resistor layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate having a good heat dissipation property such as alumina.

The ink 21 is a discharge orifice (fine hole) 2
2, the meniscus 23 is formed by the pressure P. Here, 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,
The meniscus 23 is projected by the pressure, the ink 21 is ejected, becomes a recording droplet 24 from the ejection orifice 22, and flies toward the recording material 25. FIG. 3 shows a schematic view of a recording head in which a large number of the heads shown in FIG. 1 are arranged. The recording head is manufactured by closely adhering a glass plate 27 having a multi-groove 26 to a heating head 28 similar to that described in FIG. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a sectional view taken along the line AB of FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating the head. In FIG. 4, reference numeral 61 is a blade serving as a wiping member, one end of which is held by a blade holding member to be a solid end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head, and in the case of this example, is held in a protruding form in the movement path of the recording head. 6
Reference numeral 2 denotes a cap, which is arranged at a home position adjacent to the blade 61, has a configuration that moves in a direction perpendicular to the moving direction of the recording head and contacts the ejection port surface to perform capping. Further, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the moving path of the recording head. The blade 61, the cap 62, and the absorber 63 form an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a recording head having ejection energy generating means, which ejects ink onto a recording material facing the ejection port surface where the ejection ports are arranged for recording, and 66 denotes a recording head in which the recording head 65 is mounted. A carriage for moving 65. The carriage 66 is swingably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 (not shown) driven by a motor 68. As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area.

Reference numeral 51 designates a paper feed section for inserting a recording material, and 5
A paper feed roller 2 is 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, and as recording progresses, the recording material is ejected to the ejection unit provided with the ejection roller 53. In the above structure, when the recording head 65 returns to the home position after the recording is completed, the cap 62 of the head recovery unit 64 is retracted from the movement path of the recording head 65.
The blade 61 projects into the movement 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 port 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, the ejection opening surface of the recording head 65 is wiped even during this movement. The above-mentioned movement of the recording head to the home position is performed not only at the end of recording or at the time of ejection recovery, but also at a predetermined interval to the home position adjacent to the recording area while the recording head moves in the recording area for recording. However, the wiping is performed along with this movement.

FIG. 5 is a diagram showing an example of an ink cartridge in which the ink is supplied to the head through an ink supply member, for example, a tube. Here, 40 is an ink containing portion containing the ink for supply, for example, an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into this stopper 42, the ink in the ink bag 40 can be supplied to the head. Reference numeral 44 is an absorber that receives waste ink. As the ink containing portion, the liquid contact surface with the ink is polyolefin,
Those formed of polyethylene are particularly preferable for the present invention. The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separate from each other as described above, and is preferably used in the one in which they are integrated as shown in FIG.

In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink containing portion which has absorbed ink, for example,
The ink absorber is housed, and the ink in the ink absorber is ejected as ink droplets from the head portion 71 having a plurality of orifices. As a material for the ink absorber, for example, polyurethane can be used. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head shown in FIG.
It is detachable from the carriage 66.

In FIG. 7, reference numeral 100 is a recording head element, which includes an ink ejecting section 102, an ink supply tank section 104, a wiring board 105 provided with wiring for transmitting a signal for driving an ejection energy generating element, and supporting them. The base plate 106 and so on. The ink ejection unit 102 is an ejection port 102 formed on a surface facing a recording medium.
A has a liquid passage extending inward, an ejection energy generating element such as an electrothermal converter disposed in each liquid passage, and a common liquid chamber communicating with each liquid passage. Ink supply tank unit 10
The reference numeral 4 functions as a sub-tank that receives the ink supply from the ink tank 110 side and guides the ink to the common liquid chamber in the ejection unit 102.

Further, the base plate 106 can be made of aluminum or the like, and also functions as a heat dissipation plate for suppressing heat generation of the recording head element due to driving of the electrothermal converter. Reference numeral 112 denotes an ink absorber, which is disposed in the ink tank 110 and is impregnated with ink, and can be formed by using a porous body or fiber made of the above-mentioned material. 114 is a lid member of the ink tank 110. Denoted at 107 is a protrusion provided on the recording head element 100.
A taper is provided to facilitate the connection with 10.
Reference numeral 117 denotes the element housing portion 110 of the ink tank 110.
It is an opening provided in the wall portion 117A of A, engages with the protrusion 107, and the engagement between the recording head element 100 and the ink tank 110 is performed.

Reference numeral 118 denotes an abutting member provided in the element accommodating portion 110A for facilitating the work for mounting the recording head element 100 and for ensuring the mounted state, and engages with the rear end surface of the base plate 106.
Reference numeral 119 is a protrusion for positioning the recording head element 100, and 120 is a supply port for supplying ink from the ink tank 110 into the recording head element 100. Incidentally, in the recording apparatus used in the present invention, the ink jet recording apparatus in which thermal energy is applied to the ink to eject the ink droplets has been taken as an example above, but the present invention is not limited to the piezo method using a piezoelectric element, etc. The same can be applied to the inkjet recording apparatus of.

[0045]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following description, "part" and "%" are based on weight unless otherwise specified. All water used was deionized water.

Examples 1 to 10 First, the following components were mixed and dissolved, and then pressure-filtered with a membrane filter having a pore size of 0.22 μm (trade name: Fluoropore filter, manufactured by Sumitomo Electric Co., Ltd.). An ink was prepared. Ink composition of Example 1 Compound 1 below 3 parts Glycerin 10 parts Thiodiglycol 5 parts Diethanolamine 1 part Water 81 parts

[0047]

Ink Composition of Example 2 Compound 2 below 4 parts glycerin 7.5 parts thiodiglycol 7.5 parts triethanolamine 1 part water 80 parts

[0049]

Ink composition of Example 3 Compound 3 below 4 parts Glycerin 5 parts Ethylene glycol 20 parts Diethanolamine 2 parts Acetylenol EH (Kawaken Fine Chemicals) 2 parts Water 67 parts

[0051]

Ink composition of Example 4 Compound 4 below 3 parts glycerin 9.5 parts ethylene glycol 8.5 parts dimethylethanolamine 1 part ethylene oxide-propylene oxide copolymer (MH-50, manufactured by Asahi Denka Co., Ltd. ) 5 parts water 73 parts

[0053]

Ink composition of Example 5 Compound 5 below 6 parts thiodiglycol 10 parts ethylene glycol 10 parts triethanolamine 3 parts acetylenol EH (Kawaken Fine Chemicals) 3 parts urea 10 parts water 58 parts

[0055]

Ink composition of Example 6 Compound 6 below 2.5 parts thiodiglycol 10.5 parts ethylene glycol 10.5 parts monoethanolamine 2 parts ethylene oxide-propylene oxide copolymer (MH-50, (Asahi Denka Co., Ltd. 2 parts Urea 5 parts Sodium hydroxide 1 part Water 66.5 parts

[0057]

Ink composition of Example 7 Compound 7 below 2.5 parts Glycerin 7.5 parts Ethylene glycol 7.5 parts Diethylethanolamine 3 parts Acetylenol EH (Kawaken Fine Chemicals Co.) 3 parts Urea 5 parts Lithium acetate 2 parts Water 69.5 copies

[0059]

Ink composition of Example 8 Compound 8 below 3 parts glycerin 7 parts thiodiglycol 7 parts diethanolamine 3 parts ethylene oxide-propylene oxide copolymer (MH-50, manufactured by Asahi Denka Co., Ltd.) 1 part urea 7 Part lithium hydroxide 1 part sodium sulfate 1 part water 70 parts

[0061]

Ink composition of Example 9 Compound 9 below 3 parts glycerin 7 parts thiodiglycol 7 parts diethanolamine 3 parts acetylenol EH (manufactured by Kawaken Fine Chemicals) 1 part urea 7 parts lithium acetate 2 parts ammonium sulfate 1 part water 69 parts

[0063]

Ink composition of Example 10 Compound 10 below 3 parts glycerin 7.5 parts thiodiglycol 7.5 parts triethanolamine 1 part ethylene oxide-propylene oxide copolymer (MH-50, (Asahi Denka Co., Ltd. 1 part Urea 8 parts Lithium acetate 0.2 parts Sodium sulfate 0.5 parts Water 71.3 parts

[0065]

Ink Compositions of Comparative Examples 1 to 10 In each of the ink compositions of Examples 1 to 10, organic amines, surfactants, nitrogen-containing compounds, hydroxides, alkali metal salts and sulfates were removed from the respective ink compositions, and The inks of Comparative Examples 1 to 10 were prepared by supplementing the shortage with deionized water.

Evaluation Test Next, Examples 1 to 10 and Comparative Examples 1 to 10 obtained as described above.
Each of the inks is used to perform printing using an on-demand type inkjet printer that uses a heating element as an ink jet energy source as an inkjet recording device, and (1) clogging, (2) firstness, and (3) ) Each evaluation test of water resistance was performed according to the following criteria. The obtained results are shown in Table 1 below. The plain papers used for evaluation are the following three papers. SK: Canon NP Dry SK (acid paper) PB: Plover Bond (neutral paper) XX: Xerox 4024 (neutral paper)

[Evaluation Method and Evaluation Criteria] (1) Evaluation of Clogging Property (Fixing Recovery Property) After being left in a constant temperature bath at 35 ° C. for 1 month, it was left at room temperature for 24 hours to carry out recovery operation (suction operation by pumping). Printing was performed, and evaluation was performed according to the following criteria. ◯: The printing state returns to normal within five recovery operations. Δ: The printing state returns to normal after 6 to 10 times of recovery operation. ▼: No ejection or disorder of printing occurs even after performing recovery operation 10 times.

(2) Evaluation of monotonous property After being left in a thermo-hygrostat of 15 ° C./10% for 1 hour, an ink droplet was ejected from a certain nozzle, the nozzle was not used for 1 minute, and then the The degree of ejection stability when ink droplets were ejected from the nozzle was evaluated according to the following criteria. ◯: Normal printing can be performed. Δ: Printing can be performed without any problems in actual use, although there is some printing disorder. ▼: There is ejection failure or irregular printing.

(3) Evaluation of Water Resistance After filling the printer with a predetermined ink and printing the alphanumeric characters and the solid portion on the three plain papers, the printing was stopped, and after leaving for 1 hour or more, the print density Macbeth RD915
(Product name: manufactured by Macbeth Co.) is measured. After that, the printed matter was immersed in a container filled with water for 5 minutes, then left standing and dried, the print density was measured again, and the residual rate of the print density was obtained to evaluate the water resistance. Good: The residual density of printed matter is 80% or more. B: The residual density of the printed matter is 65% or more and less than 80%. ▼: The residual density of printed matter is less than 65%.

Table 1: List of evaluation test results

[0072]

As described above, according to the present invention, it is possible to form a recorded image having good water resistance and improved light resistance on various plain papers, which adversely affects the image quality after recording. It is possible to provide an ink that ensures reliability such as prevention of clogging at the tip of the nozzle and storage stability, an inkjet recording method using the same, and a device using such an ink. Further, according to the present invention, a stable ink droplet is formed when the ink is ejected again after the ink ejection is stopped, and it is possible to provide the ink having the excellent reliability in which the printing is not disturbed.

[0073]

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a head of an inkjet recording apparatus.

FIG. 2 is a cross-sectional view of a head of an inkjet recording device.

FIG. 3 is an external perspective view of a head in which the head shown in FIG. 1 is multi-headed.

FIG. 4 is a perspective view showing an example of an inkjet recording apparatus.

FIG. 5 is a vertical sectional view of an ink cartridge.

FIG. 6 is a perspective view showing an example of a recording unit.

FIG. 7 is an exploded perspective view showing an example of a recording unit.

[0074]

[Explanation of symbols]

 13: Head 14: Ink Groove 15: Heating Head 16: Protective Film 17: Aluminum Electrode 18: Heating Resistor Layer 19: Heat Storage Layer 20: Substrate 21: Ink 22: Discharge Orifice (Fine Hole) 23: Meniscus 24: Recording Liquid Droplet 25: Recording material 26: Multi groove 27: Glass plate 28: Heating head 40: Ink bag 42: Plug 44: Ink absorber 45: Ink cartridge 51: Paper feed section 52: Paper feed roller 53: Paper ejection roller 61 : Blade 62: Cap 63: Ink absorber 64: Ejection recovery part 65: Recording head 66: Carriage 67: Guide shaft 68: Motor 69: Belt 70: Recording unit 71: Head part 72: Atmosphere communication port 100: Recording head element 102: Ink ejection part 102A: Ejection port 104: Ink supply tank part 105: Line board 106: Base plate 107: Projection part 110: Ink tank 110A: Element storage part 112: Ink absorber 114: Lid member 117: Opening 117A: Wall part of element storage part 118: Abutting member 119: Positioning projection 120: Supply port

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C09D 11/02 PTG D06P 5/00 111 A (72) Inventor Yoshihisa Takizawa 3-chome Shimomaruko, Ota-ku, Tokyo No. 30-2 Canon Inc. (72) Inventor Satoshi Nagashima 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Mayumi Yamamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (32)

[Claims] 1. An ink containing at least one dye represented by the following structural formulas (a) and (b) and an organic amine. [Wherein, X ³ is a sulfone group or a carboxyl group, X ⁴ is independently a substituent, m is an integer of 0 to 2, Y ¹ and Y ² are each an alkyl group or a halogen atom, and Z ⁴ is Represents a carboxyl group. ] [Wherein L is a metal cation or a hydrogen atom, Pc is a phthalocyanine ring, R ¹ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or a substituted aralkyl group, and R ² is A hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or any substituted amino group, M ⁺ represents an ammonium ion or a substituted ammonium cation, and (t + q) represents an integer of 3 to 4. ] 2. The ink according to claim 1, further comprising a surfactant. 3. The ink according to claim 1, further containing a nitrogen-containing compound other than the organic amine. 4. The ink according to claim 1, further comprising at least one of hydroxide and alkali metal salt. 5. The ink according to claim 1, further comprising a sulfate salt. 6. The organic amine is monoethanolamine,
The ink according to claim 1, wherein the ink is at least one selected from diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine. 7. The content of organic amine in the ink is 0.0
The ink according to claim 1, which is in the range of 1 to 5.0% by weight. 8. The ink according to claim 2, wherein the surfactant is an ionic surfactant, a nonionic surfactant, an amphoteric surfactant, or a mixture of two or more thereof. 9. The ink according to claim 2, wherein the surfactant is a nonionic surfactant. 10. The surfactant contains at least one selected from ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkylphenols, ethylene oxide-propylene oxide copolymers, and ethylene oxide adducts of acetylene glycol. Inks 2-9. 11. The content of the surfactant is 0.
The ink according to claim 2, which is in a range of 01 to 10.0% by weight. 12. The ink according to claim 3, wherein the nitrogen-containing compound is urea or a derivative thereof. 13. The content of the nitrogen-containing compound is in the range of 0.01 to 20.0% by weight of the ink.
Ink described in. 14. The ink according to claim 4, wherein the hydroxide is at least one selected from sodium hydroxide, lithium hydroxide, potassium hydroxide and ammonium hydroxide. 15. The ink has a hydroxide content of 0.0.
The ink according to claims 4 to 14, which is in the range of 1 to 5.0% by weight. 16. The alkali metal salt is sodium acetate,
16. At least one selected from lithium acetate, potassium acetate, sodium nitrate, lithium nitrate, potassium nitrate, sodium phosphate, lithium phosphate, potassium phosphate, sodium carbonate, lithium carbonate and potassium carbonate. ink. 17. The ink according to claim 4, wherein the content of the alkali metal salt is in the range of 0.01 to 5.0% by weight of the ink. 18. The ink according to claim 5, wherein the sulfate is at least one selected from sodium sulfate, lithium sulfate, potassium sulfate and ammonium sulfate. 19. The ink has a sulfate content of 0.01.
The ink according to any one of claims 5 to 18, which is in the range of 5.0 wt%. 20. 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 any one of claims 1 to 19. Recording method. 21. The ink jet recording method according to claim 20, wherein thermal energy is applied to the ink to eject ink droplets. 22. 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 any one of claims 1 to 19. Recording unit. 23. The head portion is a head which causes thermal energy to act on ink to eject ink droplets.
Recording unit described in. 24. The recording unit according to claim 22, wherein the ink containing portion is formed of polyurethane, cellulose, or polyvinyl acetate. 25. An ink cartridge comprising an ink containing portion containing ink, wherein the ink is
An ink cartridge according to any one of claims 1 to 19. 26. The ink cartridge according to claim 25, wherein the ink containing portion has a liquid contact surface formed of polyolefin. 27. 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 any one of claims 1 to 19. An inkjet recording apparatus characterized by the following. 28. The head section is a head for ejecting ink droplets by applying thermal energy to the ink.
The inkjet recording device according to item 1. 29. The ink jet recording apparatus according to claim 27, wherein the ink containing portion is made of polyurethane, cellulose or polyvinyl acetate. 30. A recording head for ejecting ink droplets,
An ink according to any one of claims 1 to 19, 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 the recording head. An inkjet recording method characterized by the above. 31. The ink jet recording apparatus according to claim 30, wherein the recording head is a head which applies thermal energy to ink to eject ink droplets. 32. The ink jet recording apparatus according to claim 30, wherein the ink containing portion has a liquid contact surface formed of polyolefin.