JP3302269B2 - INK, INK JET RECORDING METHOD USING THE SAME, AND APPARATUS USING THE INK - Google Patents

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 a device and a recording apparatus using the ink.

[0002]

2. Description of the Related Art Ink-jet inks of various compositions have been reported so far, and various studies have been made on the reliability of ink-jets. Today, high-speed printers are required, and accordingly, high-frequency responsiveness of ink is required. In addition, from the viewpoint of ecology, the life of the head has been extended, so that stricter reliability is required for inkjet inks. In addition, water resistance of so-called plain paper such as neutral paper, and color There is also a need for good color tones in images.

[0003]

When described INVENTION Problems to be Solved] In particular yellow ink, C. in KOKOKU 3-6193 JP
I. An ink using Direct Yellow 86 has been proposed. In this case, although the storage stability and fixation of the ink are considerably improved, the ejection property becomes unstable during continuous printing. Occurs. Also,
The water resistance and color tone of plain paper are not sufficient. Japanese Patent Application Laid-Open No. 5-194890 discloses C.I. I. Direct Yellow 86 and C.I. I. A yellow ink containing Acid Yellow 23 and JP-A-61-2771 have the following general formula (A):

[0004]

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(Where M ₁And M_TwoIs hydrogen atom, alkali
Indicates metal, ammonia or organic amine, same or different
It may be. X is alkylamido having 6 to 18 carbon atoms
And an alkoxyalkylamine residue. )
A yellow ink containing a dye represented by
However, all of these inks have good color tone
However, although the water resistance to plain paper is still sufficient
Absent.

[0006] EP 0468647 A1 proposes a yellow dye having excellent water resistance. When these inks having good water resistance are used in an ink jet printer, the water resistance is improved. May cause printing disturbance or non-ejection. In addition, there is also a problem that during continuous printing, the printing is disturbed and the ejection property becomes unstable.

[0007] As described above, a yellow ink which satisfies the reliability of the ink jet such as the print quality when performing continuous printing, satisfies the water resistance, and has a good color tone has not yet been found.

Accordingly, an object of the present invention is to provide an ink jet recording apparatus that has no problem with various reliability such as print quality and storage stability when continuous printing is performed, and has good water resistance to plain paper. An object of the present invention is to provide a yellow ink having a good color tone, an inkjet recording method using the same, and a device and a recording apparatus using the ink.

[0009]

The above object is achieved by the present invention described below. That is, the present invention provides at least 2
C. in a yellow ink containing at least one kind of yellow dye and a liquid medium for dissolving or dispersing the dye, a dye represented by the following general formula (1) at least in a free acid state;
I. The ink is characterized by containing Direct Yellow 86 . In the present invention, the state of the free acid
The main solubilizing group in SO ₃ H groups in state, L ^* a ^* b ^* chromaticity diagram with b
Yellow dyes located at ^* = xa ^* (3 ≦ x ≦ ∞) are preferred
C. I. Represents Direct Yellow 86.

[0010]

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[Wherein, Ar and Ar ₁ each represent an aryl group or a substituted aryl group, and at least one of Ar and Ar ₁ has a substituent selected from COOH or COSH. J and J ₁ are the following general formulas (2) and (3), respectively.
And a structure selected from the group consisting of (4).

[0012]

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(Wherein R ₅ is independently H, an alkyl group, a substituted alkyl group, an alkoxy group, a halogen, CN,
It is selected from ureido, and NHCOR _6. R ₆ is selected from H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group and a substituted aralkyl group. T represents an alkyl group, W represents H, CN, CONR ₁₀
R ₁₁ is selected from pyridium and COOH. (M)
Represents an alkylene chain having 2 to 8 carbon atoms, and B is selected from H, an alkyl group and COOH. )

Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ and R ₁₁ is selected from H, an alkyl group and a substituted alkyl group, L represents a divalent organic bonding group, and n represents 0 or 1. Is shown. X is a carbonyl group or the following general formula (5), (6) or (7)
It consists of the structure.

[0015]

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(Wherein Z is OR ₇ , SR ₇ , and NR ₈ R ₉
Wherein Y is selected from H, Cl, CN and Z, and E is selected from Cl and CN. R ₇ , R ₈ and R
₉ is H, alkenyl group, substituted alkenyl group, alkyl group, substituted alkyl group, aryl group, substituted aryl group,
Selected from aralkyl groups and substituted aralkyl groups,
R ₈ and R ₉ together with the nitrogen atom to which these groups are attached are 5
Form a 6-membered or 6-membered ring. )

Ar and Ar ₁ in the general formula (1) represent S
In the absence of O ₃ H groups, at least two COOH
When Ar and Ar ₁ in the general formula (1) have a SO ₃ H group,
It has at least as many groups selected from COOH groups or COSH groups as the number of SO ₃ H groups. ]

According to the present invention, there is provided an ink jet recording method for recording on a recording medium by discharging ink from an orifice according to a recording signal, wherein the ink is the above ink. is there.

According to the present invention, there is provided a recording unit including an ink storage section for storing ink and a head section for discharging the ink, wherein the ink is the above-described ink. .

According to the present invention, there is provided an ink cartridge provided with an ink containing section containing ink, wherein the ink is the above-mentioned ink.

According to the present invention, there is provided an ink jet recording apparatus including a recording unit having an ink containing section for containing ink and a head section for discharging the ink, wherein the ink is the above ink. Is an ink jet recording apparatus.

According to another aspect of the present invention, there is provided a recording head for discharging ink, an ink cartridge having an ink containing portion for containing ink, and an ink jet device having an ink supply portion for supplying ink from the ink cartridge to the recording head. In a recording apparatus, the ink is the above-described ink.

Hereinafter, the present invention will be described in detail. The present inventors have conducted intensive studies on various ink compositions. As a result, in a liquid medium containing two or more types of yellow dyes, the yellow dye represented by the general formula (1) and the free acid In the state of the above, the main solubilizing group is SO ₃ H group, and L ^* a ^*
b ^* chromaticity diagram in b ^* = x a ^* yellow ink (3 ≦ x ≦ ∞) a yellow dye which is located, characterized in that are used in combination is, ejection stability and long when the continuous printing It has been found that the ink has good reliability in storage and the like, and has good water resistance and color tone.

When the dye is used alone in the ink, the dye easily forms micelles. However, by coexisting with a dye having a different structure, a synergistic effect acts between the two to make it difficult to form micelles. It is presumed that the dye can always be stably dissolved in the ink, so it may have good reliability such as ejection stability when printing continuously and ejection stability after long-term storage. Is done. In particular, in the dye represented by the general formula (1), the main solubilizing group is a SO ₃ H group in a free acid state, and the dye is represented on an L ^* a ^* b ^* chromaticity diagram.
b ^* = By ^{x a * (3 ≦ x ≦} ∞) to be used in combination with yellow dye located, good reliability student can not be obtained with dye alone represented by the general formula (1) (when the continuous printing Discharge stability and discharge stability after long-term storage), as well as good water resistance and color tone.

For example, the dye represented by the general formula (1), the main solubilizing group is an SO ₃ H group, and the L ^* a ^* b ^* chromaticity diagram shows
When a yellow ink containing a yellow dye located at b ^* = x a ^* (3 ≦ x ≦ ∞) is used so that a ^* = 0 is obtained, a secondary color including preferable yellow is obtained. The color tone of red and green can be improved. For example, using one type of dye to improve the reliability of print quality and long-term storage stability when performing continuous printing rather than producing a color near a ^* = 0 Can be done.

The main solubilizing group is an SO ₃ H group, and L ^*
a ^* b ^* chromaticity diagram in b ^* = x a ^* the yellow dye is located in (3 ≦ x ≦ ∞) is a dye having a symmetrical structure across the organic linking group, better balanced dye In this case, since the structure becomes stable, the reliability is expected to be further improved. Among the yellow dyes, the yellow dye represented by the following general formula (8) has the best compatibility when used in combination with the general formula (1), and balances reliability such as ejection stability, water resistance, and color tone. Considering that it is the best.

It has also been found that when a monovalent alkali metal not contained in the dye is added to the ink, the balance between reliability such as ejection stability and water resistance becomes better. It is presumed that the reason is that an alkali metal not contained in the dye of the ink acts as a counter ion of the dye, and causes some synergistic effect.

[0028]

Next, preferred embodiments will be described in more detail. The ink of the present invention has at least 2
A yellow ink containing at least one kind of yellow dye and a liquid medium for dissolving or dispersing the dye, a dye represented by the following general formula (1) at least in a free acid state, and a main solubilizing group in a free acid state: There in SO ₃ H groups, an ink which is characterized by containing a yellow dye which is located to the L ^* a ^* b ^* chromaticity diagram in ^{b * = x a * (3} ≦ x ≦ ∞).

[0029]

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In the general formula (1), Ar and Ar ₁ each represent an aryl group or a substituted aryl group, and at least one of Ar and Ar ₁ has a substituent selected from COOH or COSH. J and J ₁ each have a structure selected from the group consisting of the following general formulas (2), (3) and (4).

[0031]

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(Wherein R ₅ is independently H, an alkyl group, a substituted alkyl group, an alkoxy group, a halogen, CN,
It is selected from ureido, and NHCOR _6. R ₆ is selected from H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group and a substituted aralkyl group. T represents an alkyl group, W represents H, CN, CONR ₁₀
R ₁₁ is selected from pyridium and COOH. (M)
Represents an alkylene chain having 2 to 8 carbon atoms, and B is selected from H, an alkyl group and COOH. )

Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ and R ₁₁ is selected from H, an alkyl group and a substituted alkyl group, L represents a divalent organic bonding group, and n represents 0 or 1. Is shown. X is a carbonyl group or the following general formula (5), (6) or (7)
It consists of the structure.

[0034]

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(Where Z is OR ₇ , SR ₇ , and NR ₈ R ₉
Wherein Y is selected from H, Cl, CN and Z, and E is selected from Cl and CN. R ₇ , R ₈ and R
₉ is H, alkenyl group, substituted alkenyl group, alkyl group, substituted alkyl group, aryl group, substituted aryl group,
Selected from aralkyl groups and substituted aralkyl groups,
R ₈ and R ₉ together with the nitrogen atom to which these groups are attached are 5
Form a 6-membered or 6-membered ring. When Ar and Ar ₁ in the general formula (1) have no SO ₃ H group, at least two COOH groups or CO 2
Having a group selected from the group consisting of SH and Ar in the general formula (1)
And when Ar ₁ has an SO ₃ H group, it has at least as many SO ₃ H groups as the group selected from COOH groups or COSH groups.

Next, the dye represented by the above general formula (1)
Among them, preferred dyes are shown. Dyeing represented by general formula (1)
Is a water-soluble group_ThreeH Group, and in the dye
The number of COOH groups is SO_ThreeH Dyes that are at least as many as the number of groups
Is preferred. In the dye represented by the general formula (1),
O_ThreeH Having no groups and at least two COOH groups
Is preferred. For dyes represented by the general formula (1)
Dyes having at least three COOH groups are preferred.
Good.

In the dye represented by the general formula (1),
at least one of r and Ar ₁ is at least one C
Dyes having a structure having an OOH group are preferred. In the dye represented by the general formula (1), a dye in which each of Ar and Ar ₁ has a structure having at least one COOH group is preferable. In the dye represented by the general formula (1),
A dye having a structure in which each of r and Ar ₁ has at least two COOH groups is preferred. In the dye represented by the general formula (1), a dye in which each of Ar and Ar ₁ is a dicarboxyphenyl group is preferable.

In the dye represented by the general formula (1), X
Has a structure represented by the general formula (5), and Z in the general formula (5) is NHC ₂ H ₄ OH, N (C ₂ H ₄ OH) ₂ ,
Dyes selected from NHR (R is an alkyl group having 1 to 6 carbon atoms) or morpholino are preferred. A dye in which the counter ion of the dye represented by the general formula (1) is selected from ammonia or an alkylamine is preferred.

The following formula (1) is particularly preferable.
Specific examples of the dye represented by are shown below, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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In the other dye used in the present invention, the main solubilizing group is an SO ₃ H group, and b ^* is shown on the L ^* a ^* b ^* chromaticity diagram ^.
= Xa ^* (3 ≦ x ≦ ∞). For example, C.I. I. Direct Yellow 86, C.I. I. Acid Yellow 36 and the like. Among the yellow dyes, those having a symmetrical structure with a linking group interposed therebetween are preferred, and among these, the dyes represented by the following general formula (8) in the form of a free acid are preferred. That is, at least two or more
And a liquid medium for dissolving or dispersing the dye.
At least in the form of free acid
And a dye represented by the above general formula (1)
An ink containing a yellow dye represented by (8) is preferred.
No.

[0046]

Embedded image In the dye represented by the general formula (8), A ₁ represents —CH ₃ ,
B ₁

[0047]

Embedded image (In the formula, X ₁ is the same as described above.)

The dye represented by the formula (1) is preferable in consideration of the compatibility with the dye represented by the general formula (1), and comprehensively relates to the ink properties such as water resistance and color tone, as well as reliability such as ejection stability. This is the most preferable combination when considered.

Specific examples of the yellow dye include C.I. I.
In the L ^* a ^* b ^* chromaticity diagram, b ^* =
and a yellow dye located at x a ^* (3 ≦ x ≦ ∞).

The total content of the dye represented by the general formula (1) and the yellow dye in the ink is 0.1%.
-30% by weight, more preferably 0.1-10% by weight.

When the dye represented by the above general formula (1) and the yellow dye are used, the respective ratios in the ink are appropriately determined, and are not particularly limited. The range of 5: 1 to 1: 1, more preferably the range of 4: 1 to 2: 1 is good in consideration of print quality, reliability for long-term storage, water resistance, color tone, and the like when continuous printing is performed. .

When the ratio of the dye represented by the general formula (1) to the yellow dye is such that a ^* = 0 in the L ^* a ^* b ^* chromaticity diagram, secondary colors including preferable yellow are obtained. The color tone of red and green can be made good. For example, when one kind of dye is used to produce a color near a ^* = 0,
The case of using the mixed dye of the present invention is more preferable than the case of using one type of dye because the print quality and the reliability such as long-term storage during continuous printing are improved.

The counter ion of the dye represented by the general formula (1) is preferably selected from ammonia or an alkylamine, and the main solubilizing group is a SO ₃ H group in a free acid state, and L ^* a ^* b ^* chromaticity diagram in the b ^* = x a ^*
The counter ion of the yellow dye located at (3 ≦ x ≦ ∞) is preferably selected from alkanolamines or alkali metals. The reason is not so serious, but is because the dissolution stability of the dye becomes better.

Further, the ink of the present invention preferably contains a monovalent alkali metal which is not contained in the dye. It is considered that the reason is that alkali metal not contained in the dye in the ink acts as a counter ion of the dye and produces some synergistic effect, thereby improving the balance between reliability and water resistance. The content of the monovalent alkali metal in the ink is in the range of 0.01 to 10.0% by weight, preferably 0.1 to 5% by weight, and more preferably 0.1 to 3% by weight.

The pH of the ink used in the present invention is preferably 9 or more. When the pH is 9 or more, it becomes more advantageous in terms of reliability such as print quality, fixation, and long-term storage properties when continuously discharged.

The ink of the present invention contains volatile base components such as ammonia and alkylamine.
Since these volatilize over time, urea, ethylene urea, propylene urea, thiourea,
It is preferable to include a urea derivative such as diethyl urea. The content of urea or urea derivative in the ink is 0.0
The range is from 1 to 20, preferably from 0.1 to 15% by weight.

Further, a penetrant such as alcohol or ether may be contained in order to improve solid uniformity and fixability. The ink content of the penetrant is in the range of 0.01 to 15% by weight, more preferably 0.01 to 10% by weight.

The liquid medium for dissolving or dispersing 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, for example, amides such as dimethylformamide and dimethylacetamide; ketones such as acetone; ethers such as tetrahydrafuran and dioxane; polyalkylene glycol such as polyethylene glycol and polypropylene glycol. Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, etc. Glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether Lower alkyl ethers of polyhydric alcohols and the like; N- methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
Examples include cyclic amide compounds such as triethanolamine, sulfolane, dimethyl sulfoxide, 2-pyrrolidone and 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.
More preferably, it is in the range of 3 to 30% by weight. The content of water in the ink is in the range of 30 to 95% by weight. If the amount is less than 30% by weight, the solubility of the dye becomes poor, and the viscosity of the ink becomes high. on the other hand,
If the content is more than 95% by weight, the amount of the evaporating component is too large, so that sufficient fixing properties cannot be satisfied.

It is preferable that the ink according to the present invention contains various additives in addition to the above components, in order to further improve the dissolution stability of the dye in the ink. That is, there is no problem even if a volatile base component such as ammonia or alkylamine is contained in the ink. Further, urea, a urea derivative, and various additives may be contained. Further, as a pH adjuster, a salt of a strong acid or strong base, an amine or the like may be contained. In addition to the above components, if necessary, a surfactant, a rust inhibitor, a fungicide, an antioxidant, an evaporation promoter,
Additives such as chelating agents and water-soluble polymers may be added.

The ink according to the present invention can be used as a general water-based writing instrument, but is particularly suitable for application to an ink jet recording method of a type in which the ink is ejected by thermal energy, and the ejection becomes extremely stable, There is a feature that generation of dots does not occur.
However, in this case, the thermal physical property value (for example, specific heat, thermal expansion coefficient, thermal conductivity, etc.) may be adjusted.

Further, the ink according to the present invention solves the problem of the water resistance of the ink of the print recorded matter when recorded on plain paper or the like, and at the same time, improves the matching of the ink itself with the ink jet head. As 2
Surface tension at 5 ° C. is 30 to 68 dyne / cm, more preferably 30 to 50 dyne / cm, and viscosity is 15 c
P or less, preferably 10 cP or less, more preferably 5 cP or less
It is desirable to adjust to P or less.

As a method and apparatus suitable for performing recording using the ink of the present invention, there is provided ink jet recording in which thermal energy corresponding to a recording signal is applied to ink in a chamber of a recording head, and the ink is ejected by the thermal energy. And an ink jet recording apparatus.

FIGS. 1, 2 and 3 show examples of the structure of a head which is a main part of the apparatus. The head 13 includes a glass, ceramic or plastic plate having a groove 14 through which ink passes, and a heating head 15 used for thermal recording (a head is shown in the figure, but is not limited to this).
And can be obtained in close contact. The heating head 15 has a protective film 16 made of silicon oxide or the like, 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 good heat dissipation such as alumina.

The ink 21 has a discharge orifice (fine hole) 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 of the heating head 15 indicated by n rapidly generates heat, and bubbles are generated in the ink 21 in contact with the area.
The meniscus 23 is protruded by the pressure, the ink 21 is ejected, becomes a recording droplet 24 from the orifice 22, and flies toward the recording material 25.

FIG. 3 is an external view of a multi-head in which many 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 with reference to FIG.

FIG. 1 shows a head 1 along an ink flow path.
3 is a sectional view, and FIG. 2 is a cross-sectional view taken along a line AB in FIG. 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, and forms a cantilever. The blade 61 is provided at a position adjacent to a recording area of the recording head.

In the case of this embodiment, the recording head is held in a form protruding into the moving path of the recording head. 62 is a cap,
It is arranged at the home position adjacent to the blade 61,
The recording head is configured to move in a direction perpendicular to the direction of movement of the recording head, contact the ejection port surface, and perform capping. 6 more
Reference numeral 3 denotes an ink absorber disposed adjacent to the blade 61, and is held in a form protruding into the movement path of the recording head, similarly to the blade 61. 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 moisture, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a recording head having discharge energy generating means for discharging ink onto a recording material facing a discharge port surface provided with discharge ports to perform recording, and 66 is provided with the recording head 65. And a carriage for moving the recording head 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown).
As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and the adjacent area.

Reference numeral 51 denotes an insertion portion for inserting a recording material, and reference numeral 52 denotes a feeding roller driven by a motor (not shown). With such a configuration, the recording material is fed to a position facing the discharge port surface of the recording head, and is discharged to a discharge unit provided with a discharge roller 53 as recording proceeds.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the head recovery unit 6
The cap 62 of 4 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection port surface of the recording head 65 is wiped. When capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62 moves so as to protrude 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 position as the position at the time of wiping. As a result, even in this movement, the ejection port surface of the recording head 65 is wiped.

The movement of the print head to the home position is not only at the end of printing or at the time of ejection recovery, but also at a predetermined interval while the printing head moves through the printing area for printing. Position, and the wiping is performed along with the movement.

FIG. 5 is a view showing an example of an ink cartridge containing ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink storage portion that stores the supply ink, 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. An ink absorber 44 receives the waste ink. It is preferable for the present invention that the ink container has a liquid contact surface made of polyolefin, particularly polyethylene.

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 from each other as described above, but is also suitable for the 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 storage portion for storing ink, for example, an ink absorber is stored, and the ink in the ink absorber has a plurality of orifices. Head part 71
Are ejected as ink droplets from the ink. As the material of the ink absorber, it is preferable for the present invention to use polyurethane, cellulose or polyvinyl acetate.

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

[0079]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on weight unless otherwise specified.

Examples 1 to 4 The following components were mixed, sufficiently stirred and dissolved, and filtered under pressure through a fluoropore filter having a pore size of 0.45 μm (trade name: manufactured by Sumitomo Electric Industries, Ltd.). Then, each of the inks of this example was adjusted. In addition, the pH of the salt component of each compound
Was adjusted to about 9.5.

Ink composition of Example 1 Acetyleneol EH (manufactured by Kawaken Fine Chemicals) 1 part Urea 8 parts Glycerin 8 parts Ethylene glycol 8 parts Water 72.1 parts I. Guilec Yellow 86 (x = 7.3) 0.5 part Dye (1) 1.7 parts Lithium hydroxide 0.2 part Triethanolamine 0.5 part (Note) x in the yellow dye is 2. 5% ink was printed on copy paper: 4024 (trade name, manufactured by Xerox Corporation), and b ^* = x on the L ^* a ^* b ^* chromaticity diagram when the chromaticity was measured.
The value at the position of a ^* is shown.

Ink composition of Example 2 Ethylene oxide-provylene oxide copolymer 1 part (MH50, manufactured by Asahi Denka Co., Ltd.) Thiourea 5 parts 2-Pyrodoline 8 parts Triethylene glycol 8 parts Water 74.8 parts C . I. Guilec Yellow 86 (x = 7.3) 0.8 part Dye (2) 1.7 parts Ammonium sulfate 0.3 part Sodium hydroxide 0.4 part

Ink composition of Example 3 Acetylene EH (manufactured by Kawaken Fine Chemicals) 1 part Urea 8 parts Diethylene glycol 10 parts Thiodiglycol 10 parts C.I. I. Guilec Yellow 86 (x = 7.3) 0.5 parts Dye (3) 1.7 parts Water 67.5 parts Diethanolamine 0.8 parts Lithium acetate 0.5 parts

Ink composition of Example 4 Acetylene EH (manufactured by Kawaken Fine Chemicals) 1 part Urea 8 parts Glycerin 8 parts Ethylene glycol 8 parts Water 72.6 parts I. Guilec Yellow 86 (x = 7.3) 0.5 parts Dye (1) 1.7 parts Sodium hydroxide 0.2 parts Triethanolamine 0.5 parts

Comparative Example 1 An ink was prepared by replacing the dye (1) in the composition of Example 1 with pure water.

Comparative Example 2 In the composition of Example 1, C.I. I. Except for Guilec Yellow 86 (x = 7.3), it was replaced with pure water to prepare an ink.

Comparative Example 3 In the composition of Example 1, C.I. I. Except for Guilec Yellow 86 (x = 7.3), the ink was prepared by replacing it with Dye (2).

Comparative Example 4 In the composition of Example 1, C.I. I.
The ink was adjusted in place of Acid Yellow 23.

Comparative Example 5 In the composition of Example 1, the dye (1) and C.I. I. With the exception of Guilec Yellow 86 (x = 7.3), they were C.I. I. The ink was adjusted in place of Guilect Yellow 142.

(Evaluation Method and Evaluation Criteria) (1) Evaluation of Chromaticity Solid is printed on copy paper: 4024 (trade name, manufactured by Xerox Corporation), and the chromaticity is measured by high-speed spectrophotometer: CMS-500.
Using a mold (Murakami Color Research Laboratory)
Check the position on the chromaticity diagram and check the neutral position ( a ^*
= 0, ○, Δ. ◎: −2 ≦ a ^* ≦ 2, b ^* ≧ 0 ○: −10 ≦ a ^* ≦ −2, −2 ≦ a ^* ≦ 10, b ^* ≧ 0 Δ: a ^* ≦ −10, 10 ≦ a ^* , b ^* ≧ 0

(2) Evaluation of Water Resistance After filling a predetermined ink into a printer and printing alphanumeric characters and solid portions on a commercially available acidic paper, the printer was stopped.
After leaving the printed matter for one hour or more, the print density was adjusted to Macbeth RD9.
15 (trade name: manufactured by Macbeth). Thereafter, the printed matter was immersed in a container filled with water for 3 minutes or longer, left to dry naturally, the print density was measured again, the remaining rate of the print density was determined, and the water resistance was evaluated.

[0092]

(Equation 1) ：: Residual rate of print density is 80% or more to 100% or less △: Residual rate of print density is 60% to less than 80% ×: Residual rate of print density is less than 60%

(3) Evaluation of print quality after continuous printing (evaluation of durability) The printer was continuously printed for 24 hours in a thermostat at 35 ° C., and thereafter the print quality was visually observed and evaluated according to the following criteria. did. ：: Normal printing can be performed. △: Printing is slightly disturbed, but printing can be performed without any problem in actual use. ×: Non-discharge or printing is disturbed.

(4) Evaluation of eye clogging property (adhesion recovery property) Ink jet printer (trade name: BJC600J,
(Manufactured by Canon Inc.) in a constant temperature bath at 35 ° C. for one month, and then left at room temperature for 24 hours. After performing a recovery operation (suction operation by pumping), printing was performed, and evaluation was performed according to the following criteria. ：: Return to normal printing state within 5 recovery operations △: Return to normal printing state after 6 to 10 recovery operations ×: Non-discharge or print disturbance after 6 to 10 recovery operations

(5) Evaluation of long-term storage property at high temperature Put bottles sealed with each ink in a container, leave for 3 months in an environment of 50 ° C., filter the ink with a filter paper, and place on a filter paper. The presence or absence of aggregates was visually observed and evaluated according to the following criteria. ：: No aggregates at all 凝集: Slight aggregates observed, but no problem on printing △: Slight aggregates observed, printing slightly scumming ×: Many aggregates, no ejection Cause

(6) Evaluation of long-term storage property at low temperature Each bottle sealed with each ink was put in a container, left for 3 months in an environment of 5 ° C., and the ink was filtered with filter paper.
The presence or absence of aggregates on the filter paper was visually observed and evaluated according to the following criteria. ◎: No agglomerates at all ○: Slight agglomerates are observed, but there is no problem on printing △: Slight agglomerates are observed, and printing is slightly scumming ×: There are many agglomerates, Cause non-discharge

Table 1 shows the above evaluation results of each of the examples and comparative examples.

[0098]

[Table 1]

[0099]

As described above, according to the ink of the present invention, durability and long-term storage stability are excellent, water resistance and color tone are good, and there is no problem when used in an ink jet recording system. An ink that can perform highly reliable recording can be obtained.

Further, according to the ink jet recording method and the recording apparatus of the present invention, highly reliable recording excellent in clogging resistance at the nozzle tip can be performed by using the above ink.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a head section of an ink jet recording apparatus.

FIG. 2 is a cross-sectional view of a head section of the inkjet recording apparatus.

FIG. 3 is an external perspective view of a head obtained by multiplying the head shown in FIG. 1;

FIG. 4 is a perspective view illustrating an example of an ink jet recording apparatus.

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

FIG. 6 is a perspective view of a recording unit.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 13 Head 14 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 Discharge orifice 23 Meniscus 24 Recording droplet 25 Recording material 26 Multi-groove 27 Glass plate 28 Heating Head 40 Ink Container 42 Plug 44 Ink Absorber 45 Ink Cartridge 51 Insertion Section 52 Feeding Roller 53 Discharge Roller 61 Blade 62 Cap 63 Ink Absorber 64 Discharge Recovery Section 65 Recording Head 66 Carriage 70 Recording Unit 71 Head Section 72 Atmospheric communication port

Continuation of the front page (56) References JP-A-8-325493 (JP, A) JP-A-7-97541 (JP, A) JP-A-7-238245 (JP, A) JP-A-7-150086 (JP) JP-A-5-155004 (JP, A) JP-A-2-233781 (JP, A) JP-A-61-2771 (JP, A) JP-A-5-194890 (JP, A) 4-233975 (JP, A) JP-A-9-76623 (JP, A) International publication 95/29208 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00- 11/20 CA (STN) REGISTRY (STN)

Claims (32)

(57) [Claims] [1 claim] and at least two or more of the yellow dye in the yellow ink comprising a liquid medium dissolving or dispersing the dye, the dye represented by the state of at least the free acid by the following general formula (1), C. I. Direct yellow
86. An ink comprising: Embedded image [Wherein, Ar and Ar ₁ each represent an aryl group or a substituted aryl group, and at least one of Ar and Ar ₁ is a C
It has a substituent selected from OOH or COSH. J
And J ₁ each have a structure selected from the group consisting of the following general formulas (2), (3) and (4). Embedded image (Wherein R ₅ is independently H, alkyl, substituted alkyl, alkoxy, halogen, CN, ureido and N
HCOR _{6 is} selected. R ₆ is selected from H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group and a substituted aralkyl group. T represents an alkyl group, and W is selected from H, CN, CONR ₁₀ R ₁₁ , pyridium and COOH. (M) represents an alkylene chain having 2 to 8 carbon atoms, B represents H, an alkyl group and COOH
Is selected from ) R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ and R ₁₁
Are each independently selected from H, an alkyl group and a substituted alkyl group, L represents a divalent organic bonding group, and n represents 0 or 1. X is a carbonyl group or the following general formula (5);
It has the structure of (6) or (7). Embedded image Wherein Z is selected from OR ₇ , SR ₇ , and NR ₈ R ₉ , Y is selected from H, Cl, CN and Z, and E is Cl
And CN. R ₇ , R ₈ and R ₉ are each H,
An alkenyl group, a substituted alkenyl group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group and a substituted aralkyl group, wherein R ₈ and R ₉ together with the nitrogen atom to which these groups are attached Form a six-membered or six-membered ring. ) Ar and Ar in the general formula (1)
_{If 1} does not have an SO ₃ H group, at least two C
When Ar and Ar ₁ in the general formula (1) have a SO ₃ H group having a group selected from an OOH group or a COSH group, at least a group selected from a COOH group or a COSH group is an SO ₃ H group. Or more. ] 2. The dye represented by the general formula (1) has an SO ₃ H group as a water-soluble group, and the number of COOH groups in the dye is equal to or more than the number of SO ₃ H groups. 2. The ink according to 1. 3. A dye represented by the general formula (1):
The ink according to claim 1, having no SO ₃ H group and having at least two COOH groups. 4. A dye represented by the general formula (1):
The ink of claim 1 having at least three COOH groups. 5. A dye represented by the general formula (1):
At least one of Ar and Ar ₁ is The ink according to claim 1 which is a structure having at least one COOH group. 6. A dye represented by the general formula (1):
The ink according to claim 1 each of Ar and Ar ₁ has a structure having at least one COOH group. 7. A dye represented by the general formula (1):
The ink according to claim 1 each of Ar and Ar ₁ has a structure having at least two COOH groups. 8. A dye represented by the general formula (1):
The ink according to claim 1 each of Ar and Ar ₁ are dicarboxyphenyl groups. 9. A dye represented by the general formula (1):
X has a structure represented by the general formula (5), and Z in the general formula (5) is NHC ₂ H ₄ OH, N (C ₂ H ₄ OH) ₂ ,
The ink according to claim 1, wherein the ink is selected from NHR (R is an alkyl group having 1 to 6 carbon atoms) or morpholino. 10. The ink according to claim 1, wherein the counter ion of the dye represented by the general formula (1) is selected from ammonia or an alkylamine. 11. A dye represented by the general formula (1) and C.I.
I. 2. The ink according to claim 1, wherein the content of Direct Yellow 86 in the ink is 0.1 to 30% by weight in total. 12. A dye represented by the general formula (1) and C.I.
I. 2. The ink according to claim 1, wherein the content of Direct Yellow 86 with respect to the ink is 0.1 to 10% by weight in total. 13. A dye represented by the general formula (1) and C.I.
I. The content ratio of Direct Yellow 86 is 5: 5 by weight.
The ink according to claim 1, wherein the ratio is from 1 to 1: 1. 14. A dye represented by the general formula (1) and C.I.
I. 4 with a content ratio by weight of Direct Yellow over 86:
The ink according to claim 1, wherein the ratio is 1 to 2: 1. 15. The ink according to claim 1, wherein the pH of the ink is 9 or more.
The ink according to the above. 16. An ink containing urea , ethylene urea, and urea.
Group consisting of ropylene urea, thiourea and diethyl urea
The ink according to claim 1, comprising at least one member selected from the group consisting of: 17. The ink according to claim 1, wherein the ink contains a penetrant. 18. An ink jet recording method in which ink is ejected from an orifice in accordance with a recording signal to perform recording on a recording medium, wherein the ink is the ink according to claim 1. Description: 19. The ink jet recording method according to claim 18, wherein the ink is ejected by applying thermal energy to the ink. 20. A recording unit comprising an ink containing section containing ink and a head section for ejecting the ink, wherein the ink is the ink according to claim 1. Description: 21. The head portion, according to claim 2 is a head for discharging ink droplets by applying thermal energy to the ink
0 recording unit. 22. The recording unit according to claim 20 , wherein the ink containing section contains an ink absorber inside. 23. The ink accommodating portion, polyurethane, recording unit according to claim 20 or 22, wherein is formed by cellulose or polyvinyl acetate. 24. An ink cartridge provided with an ink containing section containing ink, wherein the ink is provided.
An ink cartridge characterized by being the ink described in (1). 25. The ink cartridge according to claim 24, wherein the ink containing section has a liquid contact surface formed of polyolefin. 26. An ink jet recording apparatus comprising: a recording unit having an ink containing section for containing ink; and a head section for discharging the ink, wherein the ink is the ink according to claim 1. Description: Inkjet recording apparatus. 27. The head according to claim 2, wherein the head is a head for ejecting ink droplets by applying thermal energy to the ink.
7. The ink jet recording apparatus according to 6 . 28. The ink jet recording apparatus according to claim 26 , wherein the ink containing section contains an ink absorber inside. 29. The ink jet recording apparatus according to claim 26 , wherein the ink containing section is formed of polyurethane, cellulose, or polyvinyl acetate. 30. An ink jet recording apparatus comprising: a recording head for discharging ink; an ink cartridge having an ink containing section for containing ink; and an ink supply section for supplying ink from the ink cartridge to the recording head. An ink jet recording apparatus, wherein the ink is the ink according to claim 1. 31. A recording head according to claim 3 is a head for discharging ink by applying thermal energy to the ink
0. The inkjet recording apparatus according to item 0 . 32. The ink jet recording apparatus according to claim 30, wherein the ink containing section has a liquid contact surface formed of polyolefin.