JPH08302256A - Ink and ink jet recording and recording apparatus using the same - Google Patents

Abstract

PURPOSE: To obtain an ink excellent in preventing the disorder of printing caused when discharging ink after discharging the first one drop of ink from a nozzle and unusing for a time, having good water resistance to plain paper, stable also in long-period storage, and to carry out ink jet recording using the ink and to provide a recording apparatus using this ink. CONSTITUTION: This ink contains (A) a coloring agent, (B) a defoaming agent, (C) a compound having at least one kind of group selected from secondary amine, a derivative of the secondary amine, a tertiary amine and a derivative of the tertiary amine and their complex and having at least one kind of group selected from an alkyl group, a carboxylic group, a salt of carboxylic group, sulfone group and a salt of sulfone group and (D) a liquid medium for dissolving or dispersing these components. An ink jet recording method and a recording apparatus using this ink are provided.

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, an apparatus and a recording apparatus using the ink.

[0002]

2. Description of the Related Art Conventionally, ink jet inks having various compositions have been reported. In particular, today, water resistance of ink to plain paper is required, and for example, JP-A-2-296878 discloses that a water-based ink composition contains a polyamine to improve water resistance of a printed record. Is proposed.

Further, Japanese Patent Laid-Open No. 3-91577 discloses that
A method of improving water resistance by using a dye having a carboxyl group and having the carboxyl group converted to an ammonium salt or a volatile substituted ammonium salt has been proposed.

[0004]

However, in the ink as disclosed in the former Japanese Patent Application Laid-Open No. 2-296878, the mechanism for improving the water resistance is largely due to the salt increase to the hydrophilic base portion, and thus the ink resistance is high. Clogging, ink stability and dye solubility in the ink are problems. In such ink, for example,
For the purpose of improving the stability of the ink and the solubility in the ink, it has been made to include a dissolution stabilizer in the ink, but in this case, it is necessary to add a large amount of the dissolution stabilizer. The image quality and fixability of the printed record formed using the ink deteriorate. In particular, in ink jet recording, it is not preferable to include a large amount of a dissolution stabilizer in the ink because it largely depends on natural permeation and evaporation of a recording material such as plain paper.

On the other hand, in the latter ink as disclosed in Japanese Patent Laid-Open No. 3-91577, since a dye in which a carboxyl group is changed to an ammonium salt or a volatile substituted ammonium salt is used, the initial ink is used. Although the solubility stability in is also good, ammonia or substituted ammonia volatilizes over time, so the dissolution stability and clogging resistance of the dye gradually deteriorate, and there is also a problem of variation in water resistance level depending on the paper type. Become.

Therefore, in Japanese Patent Laid-Open No. 6-128515, at least one kind selected from secondary amines, secondary amine derivatives, tertiary amines, tertiary amine derivatives and their respective composite compounds is disclosed. By using an ink, which is a compound, and in which the compound has at least one group selected from the group consisting of an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group, and a salt of a sulfone group, It has been proposed to improve the water resistance of plain paper such as acid paper and neutral paper.

Certainly, when this ink is used, there is no problem even for long-term storage, and the water resistance is considerably improved, but under various severe environments (especially in an environment where the viscosity of the ink increases). In the following, when the ink is not ejected from a nozzle for a certain period of time (for example, about 1 minute) after ejecting an ink droplet from a nozzle during printing, If the first drop of ink is ejected, stable ejection cannot be performed, and printing may be disturbed.
This phenomenon is called firstness. ) Was slightly reduced.

The present invention has been made in view of such prior arts, and an object thereof is to provide a so-called plain paper such as acid paper or neutral paper which is excellent in ink-jetting property in an ink jet recording apparatus. It is an object of the present invention to provide an ink which has good water resistance to the ink and has no problem in long-term storage, an ink jet recording method using the ink, and a recording apparatus using the ink.

[0009]

The above object can be achieved by the present invention described below. That is, the present invention provides (A) colorant,
(B) an antifoaming agent, (C) a secondary amine, a derivative of a secondary amine, a tertiary amine, a derivative of a tertiary amine, and at least one compound selected from the respective composite compounds, And a compound having at least one group selected from the group consisting of an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group, and a salt of a sulfone group, and (D) a liquid medium in which they are dissolved or dispersed. The ink is characterized by containing.

Further, according to the present invention, there is provided an ink jet recording method for recording on a recording material by ejecting ink droplets from an orifice in response to a recording signal, wherein the ink is the above ink. Is.

Further, according to the present invention, in a recording unit provided with an ink containing portion containing ink and a head portion for ejecting the ink as an ink droplet, the ink is the above-mentioned ink. It is a unit.

Further, the present invention is an ink cartridge having an ink containing portion containing ink, wherein the ink is the above-mentioned ink.

Further, the present invention is 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 above ink. It is an inkjet recording apparatus characterized by the above.

Further, the present invention comprises a recording head for ejecting ink droplets, an ink cartridge having an ink accommodating portion for accommodating ink, and an ink supply portion for supplying ink from the ink cartridge to the recording head. In the inkjet recording apparatus, the ink is the above-mentioned ink.

The present invention will be described in detail below. The inventors of the present invention have conducted extensive studies on various ink compositions in order to improve ink repellency, and as a result, in a coloring agent and a liquid medium in which the coloring agent is dissolved or dispersed, at least an antifoaming agent and a second defoaming agent are used. At least one compound selected from a primary amine, a secondary amine derivative, a tertiary amine, a tertiary amine derivative and a composite compound thereof, and the compound is an alkyl group, a carboxyl group or a carboxyl group. When a compound having at least one kind of group selected from the group consisting of a salt of 1), a sulfone group, and a salt of a sulfone group is contained, the compound has excellent unifoaming property and sufficient water resistance, and is suitable for long-term storage. Also found that good ink was obtained.

Inkjet printers can be used in a variety of environments. In particular, it has been found that the ink-releasing property tends to be severe at low temperature and low humidity, but the reason why the defoaming agent is contained in the ink is very good, although the reason is not clear. Although it is in the range of estimation, it is considered that the film of the defoaming agent covers the ink surface, so that the evaporation of the ink is suppressed and the one-shot property is improved.

Next, the preferred embodiments of the present invention will be described in more detail. The ink of the present invention comprises (A) colorant,
(B) an antifoaming agent, (C) a secondary amine, a derivative of a secondary amine, a tertiary amine, a derivative of a tertiary amine, and at least one compound selected from the respective composite compounds, And a compound having at least one group selected from the group consisting of an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group, and a salt of a sulfone group, and (D) a liquid medium in which they are dissolved or dispersed. It is characterized by containing.

More preferably, (C) is at least one compound selected from a secondary amine, a secondary amine derivative, a tertiary amine, a tertiary amine derivative, and a composite compound thereof, And the compound is an alkyl group,
A compound having at least one group selected from the group consisting of a carboxyl group, a salt of a carboxyl group, a sulfone group, and a salt of a sulfone group is an ink represented by the following general formula (I).

[0019]

Embedded image

(In the formula, R ₁ represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom, and R ₂ represents (CH ₂ ) _a —X ₁
Alternatively, it represents a hydrogen atom, and a is an integer of 1 to 4. R _{3
Is, (CH 2) b -X 2} , represents R ₄ -Y or a hydrogen atom, b represents an integer of 1-4. R ₄ has 1 to 4 carbon atoms
8 represents an alkyl group or a hydrogen atom. Z is (NR ₅ C _q
H _2q ) _c (NHC _n H _2n ) _d , where q and n are 2 to 4
, And c + d represents an integer of 0 to 50. Y is (NR _{6
C m H 2m) e (NHC} p H 2p) represents _f, m and p are 2
Is an integer of 4 and e + f is an integer of 0 to 50. R ₅ represents _{(CH 2) g -X 3,} g is an integer of 1-4.
R ₆ represents _{(CH 2) h -X 4,} h is an integer of 1-4. X ₁ , X ₂ , X ₃ and X ₄ are each selected from the group consisting of a carboxyl group, a salt of a carboxyl group, a sulfone group, a salt of a sulfone group or a hydrogen atom. Further, the compound of the general formula (I) has at least one selected from the group consisting of a carboxyl group, a salt of a carboxyl group, a sulfone group and a salt of a sulfone group. )

In the compound of the general formula (I), in consideration of stability of ink performance and the like, in particular, X ₁ , X ₂ , X ₃ and X ₄ are respectively carboxyl group salts, sulfone group salts or It is preferably selected from the group consisting of hydrogen atoms.

The reason for this is that X ₁ , X ₂ , X ₃ and X ₄
However, when selected from a salt of a carboxyl group, a salt of a sulfone group, or a hydrogen atom, it is possible to prevent the compound of the general formula (I) from forming a cyclic compound and easily deteriorating the performance and reliability of the ink. Because you can.

In the formula of the compound represented by the general formula (I), R ₁ and R ₄ are each an alkyl group having 1 to 32 carbon atoms, c + d and e + f are each an integer of 0 to 16, a,
It is preferable that each of b, g and h is an integer of 1 to 2.

The preferred compounds contained in formula (I) are listed below, but the present invention is not limited to these compounds, and two or more of these compounds may be used at the same time. I can.

[0025]

Embedded image

[0026]

[Chemical 4]

[0027]

Embedded image

[0028]

[Chemical 6]

The content of the above compound in the ink is in the range of 0.01 to 20% by weight, and the content is 0.
If it is less than 01% by weight, sufficient water resistance of printing cannot be obtained, and if it exceeds 20% by weight, it is not preferable in view of long-term storage stability under severe conditions such as low temperature. Further, the content is more preferably 0.1 to 10% by weight.

The antifoaming agent used in the present invention includes fats and oils, fatty acids, fatty acid esters, alcohols, ethers, phosphate esters, amines, amides, metal soaps, and sulfates. System, silicon system, and the like. These can be used alone or in combination of two or more.

Among these, the antifoaming agent having a siloxane bond is preferable. This is because the defoaming agent having a siloxane bond is more effective in improving the foaming property than other types of defoaming agents.

Specific examples of the defoaming agent will be given below, but the present invention is not limited thereto. CA-123, C
A-220, CA-330, CB-442, CC-11
8, CC-218, CC-222, CC-438, CD
-432, CE-120R, CE-457, CK-14
0 (Nissan Dishome / Nippon Yushi Kagaku Co., Ltd.)

X-22-161AS, X-22-161
A, X-22-161B, KF-8012, KF-39
3, KF-859, KF-860, KF-861, KF
-867, KF-869, KF-880, KF-800
2, KF-8004, KF-8005, KF-858,
KF-864, KF-865, KF-868, KF-8
003, KF-105, X-22-163A, X-22
-163B, X-22-163C, KF-1001, K
F-101, X-22-169AS, X-22-169
B, KF-102, X-22-162B, X-22-1
62C, X-22-3701E, X-22-3710,
X-22-160AS, KF-6001, KF-600
2, KF-6003, X-22-4015, X-22-
164B, X-22-164C, X-22-2404,
X-22-167B, KF-2001, KF-200
2, X-22-170DX, X-22-173DX, X
-22-174DX, X-22-176DX, KF-8
57, KF-862, KF-8001, X-22-36
67, X-22-3939A, KF-351, KF-3
52, KF-353, KF-354, KF-355, K
F-615, KF-945, KF-618, KF-60
11, KF-6015, KF-6004, KF-41
0, KF-412, KF-413, KF-414, KF
-910, X-22-800, X-22-715, X-
22-904, KF-905, KF-700, KF-8
51, X-22-801B, KF-3935, X-22
-819, X-22-820, X-22-821, X-
22-822, FL100, KS604 (Shin-Etsu Chemical Co., Ltd.)

Dehydrans A, B, C, D, E,
Same F, same G, same K, same L, same 130, same 671, same 97
5, 1019, 1208, 1227, 129
3, 1513, 1620, 1981, 240,
Four Master 111, SN Deformer 414, 4
85, 381, 5013, 470, Nopco 267
-A, DF-122-NS (manufactured by San Nopco), Surfynol 104A, 104E, 104H, 6
1, TG-E, 440, 465, 485 (manufactured by Nisshin Chemical Co., Ltd.) and the like.

The addition amount of the defoaming agent in the ink is preferably 0.001 to 5% by weight, and if it is less than 0.001% by weight, sufficient effect on the firstness is not exhibited, while if it exceeds 5% by weight. Inconveniences such as a decrease in solubility of the dye and deterioration of dispersibility of the defoaming agent in the ink occur. Further, the content is preferably 0.001 to 3% by weight,
More preferably, it is 0.01 to 3% by weight.

The colorant used in the present invention can be appropriately selected and used, but many of conventionally known dyes and pigments are effective.

The dye effectively used in the present invention is
The ink as described above can satisfy the reliability, and generally, for example, direct dye, basic dye, acid dye, food dye, vat dye, soluble vat dye, disperse dye, oil-soluble In addition to dyes and mordant dyes, nurene dyes, naphthol dyes, reactive dyes, chrome dyes, azoic dyes,
Examples include water-soluble or oil-soluble dyes such as cationic dyes. Of these, particularly preferred are water-soluble direct dyes,
It is a basic dye or an acid dye.

The content of these coloring agents in the ink is in the range of 0.1 to 15% by weight, and more preferably 0.1 to 15.
It is in the range of 10% by weight.

In addition to the above components, the ink of the present invention may optionally contain a water-soluble organic solvent, a surfactant, a pH adjusting agent, an anticorrosive agent, an antifungal agent, an antioxidant, an evaporation accelerator, and a chelating agent. Additives such as agents and water-soluble polymers may be added.

The liquid medium which dissolves or disperses the above-mentioned coloring agent and defoaming agent and the compound represented by the general formula (I) used in the present invention is a mixture of water and a water-soluble organic solvent. preferable. Specific examples of the water-soluble organic solvent include, for example, amides such as dimethylformamide and dimethylacetamide; ketones such as acetone; ethers such as tetrahydrafuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Kinds; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Alkylene glycols in which the alkylene group such as hexylene glycol and diethylene glycol contains 2 to 6 carbon atoms; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ethers; N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, 2-pyrrolidone,
Examples include cyclic amide compounds such as ε-caprolactam and imide compounds such as succinimide.

In general, the content of the water-soluble organic solvent is preferably 1 to 40% by weight based on the total weight of the ink,
It is more preferably in the range of 3 to 30% by weight.

The content of water in the ink is 30 to 95.
Used in the range of weight percent. If it is less than 30% by weight, the solubility of the colorant is deteriorated and the viscosity of the ink is increased, which is not preferable. On the other hand, if it is more than 95% by weight, the amount of vaporized components is too large to satisfy the sufficient fixing property.

The ink according to the present invention can be used as a general water-based writing instrument, but is particularly suitable when applied to an ink jet recording method of the type in which the ink is ejected by the bubbling phenomenon of the ink due to thermal energy, and the ejection is performed. It is extremely stable and does not generate satellite dots. However, in this case, the thermal property value (for example, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

Further, the ink according to the present invention solves the problem of the water resistance of the printed matter when recorded on plain paper or the like, and at the same time improves the matching with the inkjet head, the physical properties of the ink itself. As 2
It is desirable that the surface tension at 5 ° C. is adjusted to 30 to 68 dyne / cm, and the viscosity is adjusted to 15 cP or less, preferably 10 cP or less, more preferably 5 cP or less.

As a suitable method and apparatus for performing recording using the ink of the present invention, an ink jet which applies thermal energy corresponding to a recording signal to the ink in the chamber of the recording head and causes the thermal energy to generate droplets. A recording method and an inkjet recording device can be mentioned.

An example of the head structure, which is the main part of the apparatus, is shown in FIGS. 1, 2 and 3. The head 13 is a glass, ceramic, or plastic plate having a groove 14 through which ink passes, and a heating head 15 used for heat-sensitive recording (a head is shown in the drawing, but is not limited to this).
It can be obtained by closely attaching and. The heating head 15 includes a protective film 16 made of silicon oxide and an aluminum electrode 17-1.
17-2, heating resistor layer 1 formed of nichrome or the like
8, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.

The ink 21 has a discharge orifice (fine hole) 2
2, the meniscus 23 is formed by a pressure (not shown).

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,
The meniscus 23 is projected by the pressure, the ink 21 is ejected, becomes a recording droplet 24 from the orifice 22, and is ejected toward the recording material 25.

FIG. 3 shows an external view of a multi-head in which a large number of the heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG.

Incidentally, FIG. 1 shows the head 1 along the ink flow path.
3 is a cross-sectional view of FIG. 3, and FIG. 2 is a sectional view taken along the line AB of FIG. 1. FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head.

In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed 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.

Further, in the case of this example, the recording head is held in a protruding form in the moving path. 62 is a cap,
It is arranged at the home position adjacent to the blade 61,
The recording head is moved in a direction perpendicular to the moving direction to come into contact with the ejection port surface to perform capping. 6 more
Reference numeral 3 denotes an ink absorber arranged 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 ink absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the ink absorber 63 remove water, dust, and the like on the ink ejection port surface.

Reference numeral 65 denotes a recording head which has an ejection energy generating means and ejects ink to a recording material facing the ejection port surface where the ejection ports are arranged for recording, and 66 is mounted with the recording head 65. And a carriage for moving the recording head 65. The carriage 66 slidably engages with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 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 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 port surface of the recording head, and is ejected to a paper ejection unit provided with a paper ejection roller 53 as the recording progresses.

In the above structure, when the recording head 65 returns to the home position after recording is completed, the head recovery unit 6
The fourth cap 62 is retracted from the movement path of the recording head 65, but the blade 61 is projected in 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 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 at the same positions as the above wiping positions. As a result, even during this movement, the ejection port surface of the recording head 65 is wiped.

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 the home adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. The wiper is moved to the position, and the wiping is performed along with the move.

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 container, the liquid contact surface with the ink is polyolefin
Particularly, polyethylene is 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 separated as described above, but is preferably one in which they are integrated as shown in FIG. Used.

In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink containing portion containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a plurality of orifices. Head portion 71
It is configured to be ejected as an ink droplet from. It is preferable for the present invention to use polyurethane, cellulose or polyvinyl acetate as the material of the ink absorber.

Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. This recording unit 70 is
It is used in place of the recording head shown in FIG. 4, and is detachable from the carriage 66.

[0062]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, "part" and "%" are based on weight unless otherwise specified.

Examples 1 to 3 The following components were mixed, thoroughly stirred and dissolved, and then pressure-filtered with a fluoropore filter (trade name: manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.45 μm. Then, the inks of this example were adjusted. In addition, the pH of the salt component of each compound
Was adjusted to about 9.5.

Ink composition compound 28 of Example 1 1.5 parts Urea 8 parts Ethylene glycol 7 parts Water 80.3 parts C.I. I. Direct Black 195 2.5 parts Potassium hydroxide 0.1 part Diethanolamine 0.5 part Dehydrane 1513 0.1 part

Ink composition compound of Example 2 26 parts 2 parts thiourea 5 parts 2-pyrodrine 10 parts water 79.6 parts C.I. I. Food Black 2 3 parts Lithium acetate 0.1 part KS604 0.3 part

Ink compound 12 of Example 3 1 part Urea 8 parts Thiodiglycol 7 parts C.I. I. Direct Blue 199 3 parts Isopropyl alcohol 0.5 parts Water 79.6 parts Triethanolamine 0.5 parts Sodium hydroxide 0.1 parts Surfynol 440 0.3 parts

Comparative Example 1 The ink of Comparative Example 1 was prepared by removing the defoaming agent from the composition of Example 1 and replacing it with pure water.

Comparative Example 2 The ink of Comparative Example 2 was prepared by removing the defoaming agent and the compound 26 from the composition of Example 2 and replacing it with pure water.

Comparative Example 3 The ink of Comparative Example 3 was prepared by removing the defoaming agent from the composition of Example 3 and replacing it with pure water.

(Evaluation Method and Evaluation Criteria) (1) Evaluation of One-Wetness The inkjet printer was left in a thermo-hygrostat at a temperature of 5 ° C. and a humidity of 10 RH% for 1 hour or more, and then an ink droplet was ejected from a nozzle. The nozzle was not used for 1 minute, and the degree of ejection stability when an ink droplet was ejected from the nozzle was visually evaluated according to the following criteria. ◯: Normal printing is possible Δ: Characters are slightly disturbed, but there is no problem in actual use ×: No ejection or disturbance of printing

(2) Evaluation of water resistance (A) A printer was filled with a predetermined ink to print alphanumeric characters and solid portions on a commercially available acid paper, and then the printing was stopped.
After leaving the printed matter for 1 hour or more, the print density is changed to Macbeth RD9.
Measurement is carried out with 15 (trade name: manufactured by Macbeth Co.). Then, the printed matter was dipped in a container filled with water for 3 minutes or more, allowed to stand and naturally dried, and the print density was measured again, and the residual rate of the print density was determined to evaluate the water resistance.

[0072]

[Equation 1]

⊚: Residual print density is 90% or more ◯: Residual print density is 80% to 89% Δ: Residual print density is 66% to 79% x: Residual print density 65% or less

(3) Evaluation of water resistance (B) A printer was filled with a predetermined ink to print alphanumeric characters and solid portions on a commercially available neutral paper, and then the printing was stopped.
After leaving the printed matter for 1 hour or more, the print density is changed to Macbeth RD9.
Measurement is carried out with 15 (trade name: manufactured by Macbeth Co.). Then, the printed matter was dipped in a container filled with water for 3 minutes or more, allowed to stand and naturally dried, and the print density was measured again, and the residual rate of the print density was determined to evaluate the water resistance.

⊚: Remaining print density is 90% or more ○: Remaining print density is 80% to 89% Δ: Remaining print density is 66% to 79% ×: Remaining print density 65% or less

(4) Evaluation of long-term storability Each ink was placed in a bottle container tightly sealed and left in an environment of 50 ° C. for 3 months, and the ink was filtered through a filter paper to visually check for the presence of aggregates. And observed according to the following criteria.

◯: There is no aggregate. Δ: A few aggregates are seen. X: There are many aggregates.

Table 1 shows the above evaluation results.

[0079]

[Table 1]

[0080]

As described above, according to the ink of the present invention, the ink is excellent in ink-releasing property, has good water resistance to so-called plain paper such as acid paper and neutral paper, and is stable even for long-term storage. Even when used in a recording system, an ink capable of performing highly reliable recording without any problems can be obtained.

Further, according to the ink jet recording method and recording apparatus of the present invention, it is possible to obtain a high-quality image having excellent ink releasability and excellent water resistance when recorded on plain paper, using the above ink. You can

[Brief description of drawings]

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

FIG. 2 is a cross-sectional view of a head portion 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 of a recording unit.

[Explanation of symbols]

 13 Head 14 Ink Groove 15 Heating Head 16 Protective Film 17-1, 17-2 Aluminum Electrode 18 Heating Resistor Layer 19 Heat Storage Layer 20 Substrate 21 Ink 22 Ejection Orifice (Micropore) 23 Meniscus 24 Ink Droplet 25 Recording Material 26 Multi-groove 27 Glass plate 28 Heat-generating head 40 Ink accommodating part 42 Plug 44 Ink absorber 45 Ink cartridge 51 Paper feeding part 52 Paper feed roller 53 Paper discharge roller 61 Blade 62 Cap 63 Ink absorber 64 Discharge recovery part 65 Recording head 66 Carriage 67 Guide shaft 68 Motor 69 Belt 70 Recording unit 71 Head part 72 Atmosphere communication port 73 Substrate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Hakada 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (20)

[Claims] 1. (A) Colorant, (B) Defoaming agent, (C) Second
Derivatives of secondary amines, secondary amines, tertiary amines, tertiary
At least one compound selected from the group consisting of derivatives of primary amines and respective complex compounds, and the compound is at least selected from the group consisting of an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group, and a salt of a sulfone group. An ink comprising a compound having one type of group, and (D) a liquid medium in which they are dissolved or dispersed. 2. At least one compound selected from the above-mentioned (C) secondary amine, secondary amine derivative, tertiary amine, tertiary amine derivative, and composite compound thereof, The compound having at least one group selected from the group consisting of an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group and a salt of a sulfone group is a compound represented by the following general formula (I): The ink according to 1. Embedded image (In the formula, R ₁ represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom, R ₂ represents (CH ₂ ) _a- X ₁ or a hydrogen atom, and a is an integer of 1 to 4. ₃ is (CH ₂ )
_b -X _2, represents R ₄ -Y or a hydrogen atom, b represents an integer of 1-4. R ₄ represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom. Z is (NR ₅ C _q H _2q ) _c (NHC
_n H _2n ) _d , q and n represent an integer of 2 to 4, and c + d represents an integer of 0 to 50. Y is (NR ₆ C _m H _2m ) _e (N
HC _p H _2p) represents _f, m and p are integer of 2 to 4, e +
f represents an integer of 0 to 50. R ₅ is (CH _{2) g} -X ₃
And g represents an integer of 1 to 4. R ₆ is (CH ₂ ) _h
It represents -X _4, h is an integer of 1-4. X ₁ , X ₂ ,
X ₃ and X ₄ are each selected from the group consisting of a carboxyl group, a salt of a carboxyl group, a sulfone group, a salt of a sulfone group and a hydrogen atom. The compound of the general formula (I) is at least one selected from the group consisting of a carboxyl group, a salt of a carboxyl group, a sulfone group and a salt of a sulfone group.
Have one or more. ) 3. In the formula of the compound represented by the general formula (I), X ₁ , X ₂ , X ₃ and X ₄ are each selected from the group consisting of a carboxyl group salt, a sulfone group salt and a hydrogen atom. The ink according to claim 2. 4. In the formula of the compound represented by the general formula (I), R ₁ and R ₄ are each an alkyl group having 1 to 32 carbon atoms,
The ink according to claim 2, wherein c + d and e + f are each an integer of 0 to 16 and a, b, g and h are each an integer of 1 to 2. 5. The ink according to claim 1, wherein the antifoaming agent (B) has a siloxane bond. 6. An ink jet recording method for ejecting ink droplets from an orifice in response to a recording signal to perform recording on a recording material, wherein the ink is the ink according to claim 1. . 7. The ink jet recording method according to claim 6, wherein thermal energy is applied to the ink to eject ink droplets. 8. 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. 9. The recording unit according to claim 8, wherein the head portion is a head that causes thermal energy to act on the ink to eject ink droplets. 10. The recording unit according to claim 8, wherein the ink containing portion contains an ink absorber inside. 11. The recording unit according to claim 8, wherein the ink containing portion is formed of polyurethane, cellulose or polyvinyl acetate. 12. An ink cartridge comprising an ink containing portion containing ink, wherein the ink is
An ink cartridge, which is the ink described in 1. 13. The ink cartridge according to claim 12, wherein the ink containing portion has a liquid contact surface formed of polyolefin. 14. 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. 15. The head unit is a head for applying thermal energy to ink to eject ink droplets.
4. The inkjet recording device according to 4. 16. The ink jet recording apparatus according to claim 14, wherein the ink containing portion contains an ink absorber inside. 17. The ink jet recording apparatus according to claim 14, wherein the ink containing portion is made of polyurethane, cellulose or polyvinyl acetate. 18. 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. 19. The ink jet recording apparatus according to claim 18, wherein the recording head is a head which applies thermal energy to ink to eject ink droplets. 20. The ink jet recording apparatus according to claim 18, wherein the ink containing portion has a liquid contact surface formed of polyolefin.