JPH07238247A - Ink, ink jet recording method using the same and equipment using the same - Google Patents

Abstract

PURPOSE:To obtain an ink good in water resistance, printed image quality and settability when recorded on plain paper therewith, thus suitable for ink jet recording, comprising a coloring material, urea (derivative), a primary- tertiary amine (derivative) and a liquid medium. CONSTITUTION:This ink comprises a coloring material (pref. a direct dye, sulfone group-bearing dye or a dye having N in portions except divalent organic bond group), urea (derivative), a primary tertiary amine (derivative), a complex compound thereof [pref. a compound of the formula [R1 is a 1-48C alkyl, carboxyl, sulfone or H; R2 is (CH2)a-x1 ((a) is 1-4) or H; R3 is (CH2)b-x2 ((b) is 1-4), H, etc.; Z is (NR5CqH2q)c(NHCnH2n)d ((q) and (n) each is 2-4; (c+d) is 0-50; R5 is (CH2)g-x3 ((g) is 1-4); X1-X3 each is carboxyl (salt), sulfone (salt) or H]}, and a liquid medium.

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. More specifically, acidic paper, neutral paper, etc. used in general offices, etc. An ink excellent in water resistance and capable of obtaining a printed image with high image quality and excellent in stability when recording is performed on so-called plain paper, an inkjet recording method using the same, and a device using the ink. Regarding

[0002]

2. Description of the Related Art Writing instruments (fountain pens, felt-tip pens,
With regard to inks for water-based ballpoint pens and the like, and ink jet inks, various compositions have been reported. In particular, in recent years, there has been an increasing demand for water resistance of printed matter on plain paper such as copy paper, report paper, notebooks, and notepapers that are commonly used in offices, and various aspects such as ink composition and physical properties have been demanded. Detailed research and development is being carried out.

For example, in JP-A-57-57760, an amphoteric surfactant is used in the ink, or in JP-A-2-296878 and JP-A-2-25587.
Japanese Patent Laid-Open No. 6-1994 proposes to improve the water resistance of a printed record by including a polyamine in the water-based ink composition.

[0004]

[Problems to be solved by the invention] However,
The following problems have been found in the above-mentioned conventional techniques.
That is, in the inks as described above, the mechanism for improving the water resistance is largely due to the salt increase to the water-immersed base portion of the dye, so that the stability of the ink and the solubility of the dye in the ink become problems. Therefore, in order to improve the stability of the ink and the solubility of the dye in the ink, it has been made to include a dissolution stabilizer in the ink. In this case, the dissolution stabilizer to be contained in the ink is Since a large amount must be put in, the image quality of the printed record formed using such an ink deteriorates. In particular, in ink jet recording, fixing of the ink recorded on a recording material such as plain paper is largely due to natural permeation and evaporation of the recording material, so that the deterioration of image quality becomes a problem.

Further, in JP-A-3-91577, when a dye has a carboxyl group, and further an ammonium salt or a volatile substituted ammonium salt is used, ammonia or amine is volatilized on the recorded matter and is liberated. It has been proposed to improve water resistance by becoming an acid. However, in this case, even if the initial solubility of the ink is good, the dissolution stability of the dye is lowered due to the gradual evaporation of ammonia or amine in the ink. Further, there is a problem that the water resistance level varies depending on the paper type. As described above, an ink having good water resistance, quality of printed matter and excellent ink reliability has not been proposed yet.

Therefore, an object of the present invention is to solve the above-mentioned problems, and when printing and recording are carried out on so-called plain paper generally used in offices and the like, the printed and recorded matter has sufficient water resistance. An object of the present invention is to provide an ink having good image quality and fixability and having no problem in long-term storage, an ink jet recording method using the ink, and a device using the ink.

[0007]

The above object can be achieved by the present invention described below. That is, the present invention dissolves or disperses at least a coloring material, urea or a urea derivative, at least one compound selected from primary to tertiary amines or their derivatives and complex compounds thereof, and the like. An ink comprising a liquid medium, an inkjet recording method using the ink, and a device using the ink.

[0008]

The inventors of the present invention have made extensive studies on various ink compositions in order to improve the water resistance of a printed matter by using a water-based ink and solve the above-mentioned problems of the prior art.
Ink comprising at least a coloring material, urea or a urea derivative, at least one compound selected from primary to tertiary amines or their derivatives and complex compounds thereof, and a liquid medium for dissolving or dispersing these The inventors of the present invention have found that the water resistance of a print-recorded product to be obtained can be remarkably improved by using the.

Further, the first to third grades among the above-mentioned constituents.
When at least one compound selected from a primary amine or a derivative thereof and a complex compound thereof has at least one group of an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group or a salt of a sulfone group, It was found that the solubility of the ink is good, and the fixability of the ink and the printing quality are also good.

Furthermore, at least one compound selected from the primary to tertiary amines or their derivatives and their complex compounds in the above-mentioned constituents is a compound represented by the above general formula (I). In the case of the above, not only the solubility of the ink and the stability of the ink when stored for a long period of time are improved, but also when the recording material is printed on acid paper or neutral paper, It was found that the ink has good drying property and the print quality is not impaired. Furthermore, it was found that the reliability of the inkjet recording system is not impaired even when such an ink is used for inkjet recording.

Although these reasons are not clear, if it is intentionally predicted, it is considered to be due to the following reasons. That is, at least one compound selected from primary to tertiary amines or derivatives thereof and complex compounds thereof is an alkyl group, a carboxyl group, a salt group of a carboxyl group, a sulfone group or a salt of a sulfone group. Has a group,
Moreover, when recording is performed using the ink of the present invention containing the compound as a constituent, the ink applied on the recording material forms a water-insoluble film at the interface with the atmosphere. This time,
When urea or a urea derivative is contained in the liquid ink inside the insoluble film, the growth of the insoluble film is suppressed, and the ink forms a flow path only in the recording material direction, and the recording material is quickly It is thought that this is because it penetrates into. Further, at this time, it is considered that the printing quality is improved because the ink is prevented from bleeding on the surface of the recording material due to the influence of the insoluble film. Further, the water resistance is also expected to be improved due to the influence of the insoluble film. Among these, particularly preferable are inks in which a primary to tertiary amine, a derivative thereof or a complex compound thereof contains a compound represented by the general formula (I).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The urea derivative contained in the ink according to the present invention is at least one selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alcohol and ethylene oxide added to the nitrogen atom of urea. The content of the urea derivative or urea in the ink is 0.1 to 20 wt% based on the total weight of the ink.
%, Preferably 1 to 15 wt%, more preferably 1.5
Is in the range of 8 wt%.

Next, as the primary to tertiary amines, their derivatives or their complex compounds contained in the ink according to the present invention, the following general formulas (i) and (i) are preferable.
Examples thereof include compounds represented by i) or the general formula (I).
Incidentally, the composite compound means a compound having, for example, a secondary amine group and a tertiary amine group at the same time in one molecule. _{(I) NH 2 (C m} H 2m NH) q H m is an integer of 1 to 4, q is an integer of 1-6. _{(Ii) C k H 2k +} 1 NH (C s H 2s NH) u H k is 1 to 48 integer, s is an integer from 1 to 4, u is an integer of 0-5.

Specifically, the following compounds may be mentioned.

(Compound 1) NH ₂ C ₂ H ₄ NH ₂ (Compound 2) NH ₂ (C ₂ H ₄ NH) ₂ H (Compound 3) NH ₂ (C ₂ H ₄ NH) ₃ H (Compound 4) NH ₂ (C ₂ H ₄ NH) ₄ H (Compound 5) NH ₂ CH ₂ COOH (Compound 6) NH ₂ C ₂ H ₄ NHCH ₂ SO ₃ H (Compound 7) NH ₂ (C ₂ H ₄ NH) ₂ CH ₂ COOH (Compound 8) NH ₂ (C ₂ H ₄ NH) ₃ CH ₂ COOH (Compound 9) C ₄ H ₉ NHC ₂ H ₄ NH ₂ (Compound 10) C ₆ H ₁₃ NH ₂ (Compound 11) C ₈ H ₁₇ NH (C ₂ H ₄ NH) ₂ H (Compound 12) C ₈ H ₁₇ NHC ₃ H ₆ NH ₂ (Compound 13) C ₁₂ H ₂₅ NHC ₃ H ₆ NH ₂

(Compound 14)

[Chemical 2] (Compound 15)

[Chemical 3] (Compound 16)

[Chemical 4]

(Compound 17)

[Chemical 5] (Compound 18)

[Chemical 6]

(Compound 19)

[Chemical 7]

(Compound 20) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) ₂
NHCH ₂ COONa (Compound 21) C ₁₅ H ₃₁ NHC ₂ H ₄ COOLi (Compound 22) C ₃ H ₇ (NHC ₂ H ₄ ) ₂ NHCH ₂ COO
Na (compound 23) C ₁₂ H ₂₅ NHC ₂ H ₄ COONa (compound 24) C ₁₂ H ₂₅ (NHC ₂ H ₄ ) NHCH ₂ CO
OLi

(Compound 25) C ₁₂ H ₂₅ (NHC ₂ H ₄ ) N
HC ₂ H ₄ SO ₃ Li (Compound 26) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) NHCH ₂ SO ₃
Na (Compound 27) C ₂₀ H ₄₁ (NHC ₂ H ₄ ) NHCH ₂ SO ₃
NH ₄ (Compound 28) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) ₂ NHC ₂ H ₄ C
OONH ₄ (Compound 29) C ₂₅ H ₅₁ (NHC ₂ H ₄ ) ₃ NHCH ₂ SO
₃ Li (Compound 30) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) NHCH ₂ SO ₃
H ・ N (CH ₂ CH ₃ ) ₃

(Compound 31) C ₁₀ H ₂₁ (NHC ₂ H ₄ ) ₃
NHC ₂ H ₄ COOH.NH (CH ₂ CH ₃ ) ₂ (Compound 32) C ₁₂ H ₂₅ (NHC ₂ H ₄ ) ₂ NHCH ₂ CO
ONH ₄ (Compound 33) C ₅ H ₁₁ (NHC ₂ H ₄ ) ₂ NHCH ₂ CO
ONa (Compound 34) C ₇ H ₁₅ (NHC ₂ H ₄ ) ₂ C ₂ H ₄ COON
a (Compound 35) C ₁₂ H ₂₅ (NHC ₂ H ₄ ) ₄ NHCH ₂ CO
ONa

(Compound 36)

[Chemical 8] (Compound 37)

[Chemical 9]

(Compound 38) C ₁₂ H ₂₅ NHC ₃ H ₆ NH
CH ₂ COONH ₄ (Compound 39) C ₁₂ H ₂₅ NHC ₃ H ₆ NHCH ₂ COO
Na (Compound 40) C ₈ H ₁₇ N (CH ₃ ) C ₂ H ₄ N (CH ₃ ) C ₂
H ₄ NHC ₂ H ₄ COONa (Compound 41) C ₁₂ H ₂₅ NHC ₃ H ₆ N (CH ₃ ) C ₂ H ₄
COOLi

(Compound 42)

[Chemical 10] (Compound 43)

[Chemical 11]

Considering the water resistance, the print quality and the storage stability of the above compounds, the compounds of the general formulas (I) and (i
Those of i) are preferable, and when considering the ink jet recording method, the compounds of the general formula (I) are preferable.
Further, among the compounds of general formula (I), the compounds represented by the specific examples of compounds 14 to 43 are particularly preferable. Further, the content of the compound represented by the general formula (I) used in the present invention as described above in the ink largely depends on the use, purpose, color material type, and ink composition, but is preferably , 0.01 to 20% by weight, more preferably 0.1 to 10.0% by weight.

The coloring material used in the ink according to the present invention is not particularly limited, and various coloring materials such as dyes and pigments may be used. Among these, the ease of making ink,
Considering the stability of the ink and the ink, for example, an acid dye, a basic dye and a direct dye are easy to use, and the coloring material particularly effective in the present invention is a dye having direct property. Further, it is particularly preferable when the dye having directivity has a sulfone group. Further, among the direct dyes, those having a nitrogen atom in the portion excluding the divalent organic linking group are also preferable.

Among these, particularly preferable are dyes in which the coloring material has a cyclic compound forming a 5- or 6-membered ring with at least an amino group or a nitrogen atom. Specific examples of the color material as described above include, for example, CI direct black 168, CI direct black 154,
CI Direct Yellow 142, CI Direct Yellow 86, CI Direct Red 227, CI Direct Blue 199, CI Direct Blue 90,
CI Food Black 1, CI Food Black 2 and the following general formulas (II), (III), (IV) in the form of the following free acids:
A coloring material composed of the compound represented by (V) or (VI) is also conceivable, but is not limited thereto.

A coloring material represented by the following general formula (II) in the form of a free acid: Pc (SO ₃ H) _t (SO ₂ —NR ¹ —L—NR ² —X—NR ³ —G) _q (II) [In the formula, Pc is a gold-containing phthalocyanine nucleus, R ¹ , R ² and R
Each ³ independently represents H, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or a substituted aralkyl group. L represents a divalent organic connecting group. X
Are each independently a carbonyl group or the following (2) to (4)
It represents a group represented by the formula.

[0029]

[Chemical 12]

(In the formula, each Z is independently NR ⁴ R ⁵ , S
Represents R ⁶ or OR ⁶ , and Y is independently H, Cl, Z,
Represents SR ⁷ or OR ⁷ , and E is Cl or CN independently.
Represents R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, and R ⁴ and R ⁵ are nitrogen atoms. To form a 5- or 6-membered ring. ) G represents a colorless organic residue substituted with 1 or 2 thiocarboxyl groups or carboxyl groups, and t + q is 3 to 4
Is an integer. ].

As the compound represented by the general formula (II),
Specific examples include the following.

[0032]

[Chemical 13]

Colorant represented by the following general formula (III) in the form of free acid: Ar ¹ N = NJX (NR ¹ LNR ² X) _n JN = NAr ² (III) [wherein J represents the following formula: .

[Chemical 14]Also, Ar¹And Ar²Are each independently an aryl group or a group
A substituted aryl group, wherein Ar¹And Ar²At least one of
Independently represents a substituent selected from COOH and COSH by 1
Have more than one. R¹And R² Are independently H, an alkyl group,
Substituted alkyl group, alkenyl group or substituted alkenyl group
, L represents a divalent organic linking group, and n represents 0 or 1.
You X is independently a carbonyl group or the following (2) to
It represents a group represented by the formula (4).

[0034]

[Chemical 15](In the formula, each Z is independently NR³ R^Four, SR^FiveOr OR^Five
, Y is independently H, Cl, Z, SR⁶Or O
R⁶And E each independently represents Cl or CN.
R³, R^Four, R^FiveAnd R⁶Are each independently H, an alkyl group,
Substituted alkyl group, alkenyl group, substituted alkenyl group,
Reel group, substituted aryl group, aralkyl group or substituted aralkyl group
Represents a rualkyl group, R³Or R^FourIs 5 or 6 together with the nitrogen atom
Form a member ring. ) Further, the compound represented by the general formula (III) is at least S
O₃Selected from the group consisting of COOH and COSH in the same number as H
It has an exposed group. ]

As the compound represented by the general formula (III),
Specific examples include the following.

[0036]

[Chemical 16]

[0037]

[Chemical 17]

A coloring material represented by the following general formula (IV) in the form of a free acid:

[Chemical 18] [Wherein R ₁ and R ₂ are each selected from a carboxyl group, hydrogen and a hydroxyl group, R ₃ is selected from a carboxyl group, a sulfone group and hydrogen, and R ₄ , R ₅ and R ₆ are each an amino group. Group, carboxyl group, sulfone group and hydrogen.) The compound represented by the general formula (IV) has the same or more carboxyl groups as the sulfone group. ]

Specific examples of the compound represented by the general formula (IV) include the following.

[0040]

[Chemical 19]

Coloring agent represented by the following general formula (V) in the form of free acid:

[Chemical 20]   [(Wherein R₁And R₂Are each independently carboxyl
A group, a sulfone group and a hydrogen atom, R₃And R_Four
Are each independently a hydrogen atom, OCH₃, OC₂H_Five, NH
COCH₃, CH₃, C₂H_Five, NHCH₂COOH and N
HC₂H_FourR selected from COOH_Five, R₆And R₇Is a husband
Independently, hydrogen atom, carboxyl group, sulfone group and
Selected from amino groups. The compound represented by the general formula (V) is a sulfone.
It has at least as many carboxyl groups as there are groups. ]

Specific examples of the compound represented by the general formula (V) include the following.

[0043]

[Chemical 21]  

Colorant represented by the following general formula (VI) in the form of free acid:

[Chemical formula 22]   (In the formula, R₁And R₂Are each independently a hydrogen atom,
From a sil group, a sulfone group and an alkyl group having 1 to 2 carbon atoms
Selected, X and Y are NR₃R_FourAnd NR_FiveR₆Select from
Be exposed. R₃And R_FourIs an alkyl group, a substituted alkyl group,
Aryl group, substituted aryl group, aralkyl group, substituted ara
From alkyl group, alkoxyl group and substituted alkoxyl group
Selected, R₅Is a hydrogen atom, an alkyl group, a substituted alkyl
Group, alkenyl group, substituted alkenyl group, aralkyl group,
Substituted aralkyl group, alkoxyl group and substituted alkoxy
R selected from R group₆Is replaced by COSH or COOH
Represents a colorless organic residue. )

Specific examples of the compound represented by the general formula (VI) include the following.

[0046]

[Chemical formula 23]  

There are no particular restrictions on the amount of each of the various coloring materials used as described above, but in general, it is preferably in the range of 0.1 to 15% by weight, more preferably 0% by weight, based on the total weight of the ink. 0.1 to 10% by weight.

In addition, when the pH adjusting agent is added to the ink according to the present invention, it is preferable that the pH of the ink is adjusted to the alkaline side in order to improve print recording properties. Specifically, it is preferable that the pH is 9 or higher. As the pH adjuster used in this case, various basic components or acidic components are used, but particularly good are ammonia, volatile basic components such as amines, and acidic components,
A combination of sulfuric acid, acetic acid, hydrochloric acid and phosphoric acid. Incidentally, the ink according to the present invention, in addition to the above components, if necessary, a water-soluble organic solvent, a surfactant, a rust preventive, an antiseptic, a fungicide, an antioxidant, a reduction inhibitor, an evaporation accelerator, It may contain various additives such as chelating agents and water-soluble polymers.

The liquid medium 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 tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Ethylene glycol, propylene glycol, butylene glycol,
Alkylene glycols having an alkylene group of 2 to 6 carbon atoms such as triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol; glycerin; ethylene glycol monomethyl (or ethyl) ether , Diethylene glycol monomethyl (or ethyl) ether,
Lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether; N
-Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethanolamine, sulfolane,
Examples thereof include cyclic amide compounds such as dimethyl sulfoxide, 2-pyrrolidone and ε-caprolactam, and imide compounds such as succinimide.

The content of the water-soluble organic solvent is generally preferably 1% to 40% by weight, more preferably 3% to 30%, based on the total weight of the ink. Further, the content of water in the ink is used in the range of 30 to 95% by weight. If it is less than 30% by weight, the solubility of the coloring material 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 a sufficient fixing property.

The ink according to the present invention 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, the ejection is extremely stable, and satellite dots are generated. There is a feature that it does not exist. 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 water resistance of the printed matter when recorded on plain paper or the like, and at the same time improves the matching with the ink jet 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. Therefore, in order to adjust the ink to the above physical properties and solve the problem of plain paper, the amount of water contained in the ink according to the present invention is 50% by weight or more and 98% by weight or less, preferably 60% by weight or more. It is preferably 95% by weight or less.

The ink according to the present invention is particularly suitable for use in an ink jet recording method in which droplets are ejected by the action of heat energy for recording, but it can also be used as a general writing instrument. As a method and apparatus suitable for performing recording using the ink according to the present invention, a method and apparatus for applying thermal energy corresponding to a recording signal to ink in a chamber of a recording head and generating droplets by the thermal energy Is 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 made by bonding glass, ceramics or a plastic plate having a groove 14 through which ink is passed, and a heating head 15 (a head is shown in the drawing, but not limited to this) used for thermal recording. Obtained. The heating head 15 includes a protective film 16 made of silicon oxide and an aluminum electrode 17.
1, 17-2, a heating resistor layer 18 made of nichrome, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina.
It depends on and. The ink 21 reaches the ejection orifice (fine hole) 22 and the meniscus 23 is generated by the pressure P.
Is formed. Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heat generation head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact with the area, and the meniscus 23 is generated by the pressure. Are ejected, the ink 21 is ejected, and becomes a recording droplet 24 from the orifice 22 and flies toward the recording material 25. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG. 1 shows the head 13 along the ink flow path.
2 is a cross-sectional view of FIG. 2, and FIG. 2 is a sectional view taken along line AB of 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, 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 moving path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61, and has a configuration in which it moves in a direction perpendicular to the moving direction of the recording head 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,
The recording head is held in a protruding form in the moving path of the recording head.
The blade 61, the cap 62, and the absorber 63 constitute a discharge recovery unit 64, and the blade 61 and the absorber 6
3 removes water, dust and the like from 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 port is arranged for recording, and 66 has the recording head 65 mounted. It is 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 (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 due to the end of recording or the like, the cap 62 of the head recovery section 64 is retracted from the movement path of the recording head 65, but the blade 61 projects into the movement path. There is. 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. Recording head 6
When 5 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the above-described position at the time of wiping. As a result, the ejection opening surface of the recording head 65 is wiped even during this movement. To move the recording head to the home position,
Not only at the end of recording or at the time of ejection recovery, the recording head moves to the home position adjacent to the recording area at a predetermined interval while moving in the recording area for recording, and the wiping is performed with this movement. .

FIG. 5 is a diagram showing an example of an ink cartridge in which 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. 44
Is an absorber that receives waste ink. It is preferable for the present invention that the ink containing portion has a liquid contact surface with ink formed 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 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 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 acetal 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 shown in FIG.
The recording head is used instead of the recording head and is detachable from the carriage 66.

[0060]

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 8 The following components were mixed, thoroughly stirred and dissolved, and then pressurized with a fluoropore filter (trade name: manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.45 μm. The ink according to the present invention was prepared by filtration. Also, the pH was adjusted to about 9.5 with the salt component of each compound.

Ink composition of Example 1- Ammonium salt of dye (IV) -1 2 parts-Thiodiglycol 10 parts-Water 79 parts-Compound 38 2.5 parts-Urea 4 parts-Ammonium sulfate 0.5 parts

Ink composition of Example 2 Ammonium salt of Dye (V) -1 2.5 parts 2-Pyrrolidone 10 parts Compound 39 4 parts Urea 6 parts Ammonium phosphate 0.5 parts Water 77 parts

Ink composition of Example 3 Dye (ΙI) -1 2 parts thiodiglycol 10 parts isopropyl alcohol 4 parts succinate salt of compound 12 4 parts urea 5 parts ammonium sulphate 1 part water 74 parts

Ink composition of Example 4 C.I. I. Direct Red 227 2 parts-Diethylene glycol 5 parts-Thiodiglycol 5 parts-Compound 33 4.5 parts-Urea 5 parts-Water 78.5 parts

Ink composition of Example 5 C.I. I. Direct Black 168 2nd copy C.I. I. Food Black 1 1 part-Thiodiglycol 10 parts-Ethanol 3 parts-Compound 3 4 parts-Urea 3 parts-Water 77 parts

Ink composition of Example 6 C.I. I. Direct Blue 199 2 parts Dipropylene glycol 10 parts Compound 5 parts of acetic acid salt, 1,1-diethanol Urea 4 parts of _{13 [NH 2 CON (CH 2} CH 2 OH) 2] · Water 79 parts

Ink composition of Example 7 C.I. I. Direct Blue 90 2 parts ・ Diethylene glycol 10 parts ・ Compound 7 5 parts ・ 1,1-Diethylurea 2.5 parts ・ Water 80.5 parts

Ink composition of Example 8 C.I. I. Food Black 2 3 parts-Pyrrolidone 5 parts-Thiodiglycol 5 parts-Compound 4 4 parts-Urea 3 parts-Water 79 parts

Comparative Examples 1 to 5 In the compositions of Examples 1 to 5, the compounds represented by the general formula (I) were removed from each composition, and the deficiency was supplemented with pure water. The inks of Examples 1 to 4 were used.

Comparative Example 6 The ink of Comparative Example 6 was prepared by removing the urea derivative from the composition of Example 6 and supplementing the deficiency with water.

Comparative Example 7 The ink of Comparative Example 7 was prepared by removing the compound 7 and the urea derivative from the composition of Example 7 and supplementing the deficiency with water.

Comparative Example 8 The ink of Comparative Example 8 was prepared by removing urea from the composition of Example 8 and supplementing the shortage with water.

Next, Examples 1 to 8 obtained above
Using the inks of Comparative Examples 1 to 8 and an ink jet recording apparatus, an on-demand type ink jet printer using a heating element as an ink discharge energy source was used to perform a printing test. Evaluations of 2) frequency response, (3) evaluation of printing quality, (4) storage stability, and (5) fixing property were performed according to the following criteria. The obtained results are shown in Tables 1 and 2 below. The printing conditions of the above-mentioned ink jet recording apparatus are as follows: drive voltage 26V, resistance value of heating resistor 150Ω and frequency 4
Performed at KHz.

<Evaluation Method and Evaluation Criteria> (1) Water Resistance A printer is filled with a predetermined ink, and (A) commercially available acid paper and (B) commercially available neutral paper are printed with alphanumeric characters and solid portions. After that, the printing is stopped, the printed matter is left for one hour or more, and the print density is measured by Macbeth RD915 (trade name: manufactured by Macbeth Co.). Then, the printed matter was dipped in a container filled with water for 3 minutes, allowed to stand and dried, the print density was measured again, the residual rate of the print density was determined, and the water resistance was evaluated. ◯: The residual rate of printed matter density is 80% or more. Δ: The residual rate of printed matter density is 66% or more and 79% or less. X: The residual density of printed matter is 65% or less.

(2) Frequency Responsiveness The printed state of the obtained printed matter, that is, the state of scratches or white spots and the state of defective landing points such as splash and twist, was visually observed and evaluated. ◯: The ink follow-up condition with respect to the frequency is almost good, and in character printing, no blur, white spots, or landing point defects are not observed, but slight blur is observed in solid printing. Δ: No smearing or white spots are observed in character printing, but defective landing points are partially observed. Further, in solid printing, blurring and white spots are seen in about 1/3 of the whole solid printing. X: Many solid lines and white spots in solid printing, and a large number of thin lines and defective landing points in character printing.

(3) Evaluation of print quality Alphanumeric characters were printed on (A) commercially available acidic paper and (B) commercially available neutral paper with a printer, and the printed matter was left standing for 1 hour or more, and then visually and microscopically. The sharpness of characters and the degree of whisker-like bleeding generated from the characters were evaluated. ⊚: Characters are sharp and have no beard-like bleeding. ◯: The characters are sharp, but some beard-like bleeding occurs. Δ: Characters are not sharp. Or, there is a little beard-like bleeding. X: Characters are not sharp and have many beard-like blurs.

(4) Storage stability The ink was hermetically placed in a bottle container, left for 6 months in an environment of 70 ° C., filtered with a filter paper, and the presence or absence of aggregates was visually evaluated. ◯: There is no aggregate. Δ: Aggregates are slightly seen. X: There are many aggregates.

(5) Fixability After printing the solid portion on commercially available acidic paper, the printed portion was rubbed with sillbon paper, and the presence or absence of stains was observed over time after printing. evaluated. ◯: No stain after 10 seconds. Δ: No stain after 15 seconds. X: No stain after 20 seconds.

[0080]

[Table 1] Table 1 Evaluation results

[0081]

[Table 2] Table 2 Evaluation results

[0082]

As described above, according to the present invention, when print recording is performed on so-called plain paper such as acid paper and neutral paper used in general offices, etc. There is provided an ink and an inkjet recording method capable of obtaining a printed / recorded material excellent in water resistance without adversely affecting the above. Furthermore, according to the present invention, the stability of the ink is good even after storage for a long period of time, and it is possible to perform highly reliable recording without any problem even when used in an inkjet recording system.

[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]

 61: Wiping member 62: Cap 63: Ink absorber 64: Ejection recovery section 65: Recording head 66: Carriage

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Eriko Saito Eriko Saito 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Mayumi Yamamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Shinichi Sato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (29)

[Claims] 1. A liquid for dissolving or dispersing at least a coloring material, urea or a urea derivative, at least one compound selected from primary to tertiary amines or their derivatives and complex compounds thereof, and a solution for dissolving or dispersing them. An ink comprising a medium. 2. A primary to tertiary amine or a derivative thereof or a complex compound thereof is selected from the group consisting of an alkyl group, a carboxyl group, a salt group of a carboxyl group, a sulfone group and a salt group of a sulfone group. At least one chosen
The ink of claim 1 having one group. 3. The ink according to claim 1, wherein the primary to tertiary amine, a derivative thereof or a complex compound thereof is a compound represented by the following general formula (I). [Chemical 1] (In the formula, R ₁ represents an alkyl group having 1 to 48 carbon atoms, a carboxyl group, a salt of a carboxyl group, a sulfone group, a salt of a sulfone group or a hydrogen atom, and R ₂ is (CH ₂ ) _a- X ₁ or hydrogen. Represents an atom, and a is an integer of 1 to 4. R ₃ is (C
H ₂ ) _b —X ₂ or R ₄ —Y or a hydrogen atom, and b is 1 to
It is an integer of 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 are integers of 2 to 4, and c + d is 0 to 5
It is an integer of 0. Y is _{(NR 6 C m H 2m)} e (NHC p H 2p) f
Where m and p are integers of 2 to 4 respectively, and e + f is 0 to 5
It is an integer of 0. R ₅ represents _{(CH 2) g -X 3,} g is an integer of 1 to 4. R ₆ represents (CH ₂ ) _h —X ₄ , and h
Is an integer of 1 to 4. X ₁ , X ₂ , X ₃ and X ₄ are each selected from the group consisting of a carboxyl group, a salt group of a carboxyl group, a sulfone group, a salt group of a sulfone group and a hydrogen atom. Also, at least one or more carboxyl groups,
It has a carboxyl group salt, a sulfone group or a sulfone group salt. ) 4. A compound represented by the general formula (I), X ₁ ,
The ink according to claim 3, wherein X ₂ , X ₃ and X ₄ are each selected from the group consisting of a salt group of a carboxyl group, a salt group of a sulfone group and a hydrogen atom. 5. X _{1 of} the compound represented by formula (I),
The ink according to claim 3, wherein each of X ₂ , X ₃ and X ₄ is a volatile nitrogen-containing compound having a carboxyl group or a sulfone group. 6. R ₁ in the compound represented by formula (I)
And R ₄ are each an alkyl group having 1 to 32 carbon atoms, c + d
The ink according to claim 3, wherein e and f are integers of 0 to 16 and a, b, g, and h are integers of 1 to 2, respectively. 7. The ink according to claim 3, wherein the compound represented by the general formula (I) has an alkyl group having 1 to 32 carbon atoms. 8. The ink according to claim 3, wherein the compound represented by formula (I) has an alkyl group having 4 to 24 carbon atoms. 9. The ink according to claim 3, wherein the compound represented by formula (I) has an alkyl group having 6 to 18 carbon atoms. 10. The ink according to claim 3, wherein the compound represented by the general formula (I) has two or more nitrogen atoms. 11. The ink according to claim 1, wherein the coloring material is a direct dye. 12. The ink according to claim 1, wherein the coloring material is a dye having a sulfone group. 13. The ink according to claim 1, wherein the coloring material is a dye having a nitrogen atom in a portion excluding the divalent organic linking group. 14. The ink according to claim 1, wherein the pH of the ink is adjusted to 9 or more. 15. An inkjet 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 ink according to claim 1. . 16. The ink jet recording method according to claim 15, wherein thermal energy is applied to the ink to eject ink droplets. 17. 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. 18. The head unit is a head which causes thermal energy to act on ink to eject ink droplets.
The recording unit according to 7. 19. The recording unit according to claim 17, wherein the ink containing portion contains an ink absorber inside. 20. The recording unit according to claim 17, wherein the ink containing portion is formed of polyurethane, cellulose, or polyvinyl acetate. 21. An ink cartridge comprising an ink containing portion containing ink, wherein the ink is
An ink cartridge, which is the ink described in 1. 22. The ink cartridge according to claim 21, wherein the ink containing portion has a liquid contact surface formed of polyolefin. 23. An ink according to claim 1, wherein the ink is an ink jet recording apparatus including a recording unit having an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets. An ink jet recording apparatus characterized by the above. 24. The head portion is a head for causing thermal energy to act on ink to eject ink droplets.
3. The inkjet recording device according to item 3. 25. The ink jet recording apparatus according to claim 23, wherein the ink containing portion contains an ink absorber inside. 26. The ink jet recording apparatus according to claim 23, wherein the ink containing portion is formed of polyurethane, cellulose, or polyvinyl acetate. 27. 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. 28. The ink jet recording apparatus according to claim 27, wherein the recording head is a head which causes thermal energy to act on ink to eject ink droplets. 29. The ink jet recording apparatus according to claim 27, wherein the ink containing portion has a liquid contact surface formed of polyolefin.