JPH07268262A - Ink, ink jet recording method using the same, and apparatus using the same - Google Patents

Abstract

PURPOSE:To obtain an ink which gives a record excellent in water resistance and fixing properties and is excellent in clogging prevention and long-term storage stability by compounding a specific dye, a specific compd., and a liq. medium for dissolving or dispersing them. CONSTITUTION:An ink comprises a dye with the state of free acid represented by formula I {wherein R1, R2, and R2' are carboxyl. sulfo, OH, amino, 1-2C alkyl, or H; R3 to R6 are each carboxyl, sulfo, amino, OH, alkylamido, or H; and X is a group of formula II or III [wherein R7 is carboxyl, sulfo, or II; and R8 and R9 are each Rt, alkylamido, or a group of formula IV (wherein n is 1-5; and m is 0 or 1)]}, at least one compd. selected from the group consisting of a sec. amine (deriv.), a tert. amine (deriv.), and their combined compds, and having at least one group selected from the group consisting of alkyl, carboxyl (salt), and sulfo (salt) groups (e.g. C12H25NHC3H6NHC2H4 COONa), and a liq. medium for dissolving or dispersing the dye and the compd.

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. The present invention relates to an ink capable of performing high-quality recording of a recorded matter having high water resistance when printed on so-called plain paper, an inkjet recording method using the same, and a device using the ink.

[0002]

2. Description of the Related Art Writing instruments (fountain pens, felt-tip pens,
Regarding water-based inks and ink-jet inks for water-based ballpoint pens, etc., various compositions have been reported. In particular, in recent years, there has been an increasing demand for improving the water resistance of printed matter on plain paper such as copy paper, report paper, notebooks, and notepapers that are commonly used in offices. For example, Japanese Patent Laid-Open No. 2-296878. JP-A-2-255876 and JP-A-2-255876 propose that a water-based ink composition contains a polyamine to improve the water resistance of a printed record.

[0003]

[Problems to be solved by the invention] However,
In the inks as described above, the mechanism for improving the water resistance is basically largely due to salt addition to the hydrophilic base of the dye, so that clogging resistance, ink stability, and solubility of the dye in the ink are problems. Becomes Further, since bronzing (association of dyes) occurs on the printed matter, print unevenness may occur or the density may not be particularly high on acid paper. From this, in the ink as described above, for example, for the purpose of improving 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, since a large amount of dissolution stabilizer has to be added, the image quality and fixability of the printed and recorded matter formed using such an ink deteriorate. Particularly, in ink jet recording, since the fixability of the ink recorded on the recording material such as plain paper largely depends on the natural permeation and evaporation to the recording material, it is preferable to include a large amount of the dissolution stabilizer in the ink. Absent.

Further, JP-A-3-91577 proposes a method for 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 done. However, even in this case, although the dissolution stability in the initial stage of the ink is good, the dissolution stability and clogging resistance of the dye gradually deteriorate because ammonia or substituted ammonia volatilizes over time. Further, there is a problem in that the water resistance level varies depending on the paper type. In this way, the ink is stable for a long period of time, and when an image is formed using such an ink, the image is of high quality and also has good water resistance and fixability, and further, it is resistant to clogging. However, no excellent ink has been proposed yet.

Therefore, the object of the present invention is to obtain excellent image quality of the printed matter when printing is performed on so-called plain paper such as acid paper and neutral paper used in general offices. And has good water resistance and fixability, and
An object of the present invention is to provide an ink that has excellent resistance to clogging and has no problem even during long-term storage, an inkjet recording method using the same, and a device using the ink.

[0006]

The above object can be achieved by the present invention described below. That is, the present invention provides a dye characterized by being represented by the following general formula (I) in a free acid state, a secondary amine, a derivative of a secondary amine, a tertiary amine and a tertiary amine. At least one compound selected from a derivative and a respective composite compound, wherein the compound is an alkyl group, a carboxyl group, a salt of a carboxyl group,
An ink comprising a compound having at least one group selected from the group consisting of a sulfone group and a salt of a sulfone group, and a liquid medium for dissolving or dispersing these.

[Chemical 6] In the above general formula (I), R ₁ , R ₂ and R ₂ ′ are each a carboxyl group, a sulfone group, a hydroxyl group, an amino group, and a carbon number of 1 to 1.
R ₃ , R ₄ and R ₅ selected from the alkyl group of 2 and hydrogen atom
And R ₆ are selected from a carboxyl group, a sulfone group, an amino group, a hydroxyl group, an alkylamide group and a hydrogen atom.

X has a structure represented by the following general formula (II) or (III).

[Chemical 7] In the formula, R ₇ is selected from a carboxyl group, a sulfone group and a hydrogen atom. R ₈ and R ₉ are selected from the group consisting of a carboxyl group, a sulfone group, an alkylamide group, a structure represented by the following formula, and hydrogen.

[Chemical 8]

[0008]

The present inventors have conducted diligent studies on various ink compositions in order to improve the water resistance of a printed record with a water-soluble ink. As a result, the dye of the general formula (I), a secondary amine, At least one compound selected from a secondary amine derivative, a tertiary amine, a tertiary amine derivative, and a composite compound of each, and the compound is an alkyl group,
An ink comprising at least 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, and a liquid medium in which these are dissolved or dispersed. ,
A print-recorded product obtained as if a fixing accelerator were added, which has an average good fixing property regardless of the paper type and does not cause bronze (association of dyes) on the paper surface due to the paper type. It was found that the ink is of high quality and has not only good water resistance, but also good resistance to clogging, and has no problem in long-term storage.

Although the mechanism thereof is not clear, in the speculation area, the dye of the general formula (I), the secondary amine,
At least one selected from a secondary amine derivative, a tertiary amine, a tertiary amine derivative, and a complex compound of each.
Structural compatibility of both compounds, the compounds 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. Image quality of printed matter on plain paper such as acid paper or neutral paper,
It is considered that it was possible to provide an ink having good water resistance and fixability, and having no problem in clogging resistance and long-term storage.

[0010]

Preferred Embodiments Next, the preferred embodiments will be described in more detail. The ink according to the present invention is selected from a dye represented by the following general formula (I), a secondary amine, a derivative of a secondary amine, a tertiary amine, a derivative of a tertiary amine and a composite compound of each. 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 (hereinafter, referred to as (Abbreviated as secondary amine) and a liquid medium for dissolving or dispersing these.

[Chemical 9] In the above general formula (I), R ₁ , R ₂ and R ₂ ′ are each a carboxyl group, a sulfone group, a hydroxyl group, an amino group, and a carbon number of 1 to 1.
R ₃ , R ₄ and R ₅ selected from the alkyl group of 2 and hydrogen atom
And R ₆ are selected from a carboxyl group, a sulfone group, an amino group, a hydroxyl group, an alkylamide group and a hydrogen atom.

X has a structure represented by the following general formula (II) or (III).

[Chemical 10] In the formula, R ₇ is selected from a carboxyl group, a sulfone group and a hydrogen atom. R ₈ and R ₉ are selected from the group consisting of a carboxyl group, a sulfone group, an alkylamide group, a structure represented by the following formula, and hydrogen.

[Chemical 11]

The dyes represented by the general formula (I) are considered below, but the present invention is not limited thereto. Further, two or more kinds of these dyes may be used at the same time.

[0013]

[Chemical 12]

[0014]

[Chemical 13]

[0015]

[Chemical 14]

[0016]

[Chemical 15]

Among these, preferred dyes are dyes 1, 2, and
3,4,5,6,7,8,9,10,14, more preferably Dyes 1,2,3,4,5,6,7, and more preferably Dyes 1,3,4, 7 At least one compound selected from these dyes and a secondary amine, a derivative of a secondary amine, a tertiary amine, a derivative of a tertiary amine and a composite compound of each, and the compound is an alkyl group. , Carboxyl groups, salts of carboxyl groups,
Particularly good water resistance can be obtained by combining with a compound having at least one type of group selected from the group consisting of sulfone groups and salts of sulfone groups.

At least one compound selected from the group consisting of a secondary amine or a derivative of a secondary amine, a tertiary amine or a derivative of a tertiary amine, and a complex thereof used in the present invention. And the compound is
The compound having at least one substituent 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 may be any compound as long as it satisfies the above structure. Particularly, as shown in FIG. 7, it is preferable that the compound has a peak having the minimum solubility in the pH range of the ink of 4 to 10.

That is, when a compound having a peak having a minimum solubility in the pH range of 4 to 10 is formed on acid paper and neutral paper, an insolubilized film is formed at the interface between the ink and the atmosphere. Therefore, the effect of improving the water resistance becomes remarkable.

Further, by adding a compound having a peak having a minimum solubility in the range of pH 4 to 10, it is possible to improve the fixing property while improving the feathering. In addition, the ink does not spread because it has a small affinity with the sizing agent present on the paper surface, while the ink has a high affinity with cellulose, so it is noticeable that the ink penetrates in the direction perpendicular to the paper. This is because the balance of these two effects is the best.

Among such compounds, the compounds represented by the following general formula (IV) are particularly preferable.

[Chemical 16] (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. R ₃ is (CH ₂ ) _b- X ₂
Alternatively, R ₄ —Y or a hydrogen atom is represented, and b is an integer of 1 to 4. R ₄ represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom. Z represents _{(NR 5 C q H 2q)} c (NHC n H 2n) d, q and n are an integer from 2 to 4, c + d is an integer of 0 to 50. Y represents _{(NR 6 C m H 2m)} e (NHC p H 2p) f, m and p are integer of 2 to 4, the e + f is an integer of 0 to 50. R ₅ represents _{(CH 2) g -X 3,} g is an integer of 1 to 4. R ₆ represents _{(CH 2) h -X 4,} 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 of a carboxyl group, a sulfone group, a salt of a sulfone group or a hydrogen atom. The compound of the general formula (IV) has at least one compound 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 (IV), in consideration of the stability of the ink performance, X ₁ , X ₂ , X ₃ and X ₄ are each a carboxyl group salt, a sulfone group salt or hydrogen. It is preferably selected from the group consisting of atoms. The reason for this is that when X ₁ , X ₂ , X ₃ and X ₄ are each selected from a carboxyl group or a sulfone group, the compound of the general formula (IV) forms a cyclic compound, so that the ink performance and reliability are improved. This is because it is easy to reduce The particularly preferable compounds contained in the general formula (IV) are listed below, but the present invention is not limited to these compounds, and two or more kinds of these compounds can be used at the same time.

(Compound 1)

[Chemical 17] (Compound 2)

[Chemical 18] (Compound 3)

[Chemical 19]

(Compound 4)

[Chemical 20] (Compound 5)

[Chemical 21] (Compound 6)

[Chemical formula 22]

(Compound 7) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) ₂ N
HCH ₂ COONa (Compound 8) C ₁₅ H ₃₁ NHC ₂ H ₄ COOLi (Compound 9) C ₃ H ₇ (NHC ₂ H ₄ ) ₂ NHCH ₂ COO
Na (compound 10) C ₁₂ H ₂₅ NHC ₂ H ₄ COONa (compound 11) C ₁₂ H ₂₅ (NHC ₂ H ₄ ) NHCH ₂ COO
Li

(Compound 12) C ₁₂ H ₂₅ (NHC ₂ H ₄ ) NH
C ₂ H ₄ SO ₃ Li (Compound 13) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) NHCH ₂ SO ₃ N
a (Compound 14) C ₂₀ H ₄₁ (NHC ₂ H ₄ ) NHCH ₂ SO ₃ N
H ₄ (Compound 15) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) ₂ NHC ₂ H ₄ CO
ONH ₄ (Compound 16) C ₂₅ H ₅₁ (NHC ₂ H ₄ ) ₃ NHCH ₂ SO ₃
Li (Compound 17) C ₁₅ H ₃₁ (NHC ₂ H ₄ ) NHCH ₂ SO ₃ H
・ N (CH ₂ CH ₃ ) ₃

(Compound 18) C ₁₀ H ₂₁ (NHC ₂ H ₄ ) ₃ NH
_{C 2 H 4 COOH · NH (} CH 2 CH 3) 2 ( Compound _{19) C 12 H 25 (NHC} 2 H 4) 2 NHCH 2 COO
NH ₄ (Compound 20) C ₅ H ₁₁ (NHC ₂ H ₄ ) ₂ NHCH ₂ COO
Na (compound 21) C ₇ H ₁₅ (NHC ₂ H ₄ ) ₂ C ₂ H ₄ COONa (compound 22) C ₁₂ H ₂₅ (NHC ₂ H ₄ ) ₄ NHCH ₂ COO
Na

(Compound 23)

[Chemical formula 23] (Compound 24)

[Chemical formula 24]

(Compound 25) C ₁₂ H ₂₅ NHC ₃ H ₆ NHC
H ₂ COONH ₄ (Compound 26) C ₁₂ H ₂₅ NHC ₃ H ₆ NHC ₂ H ₄ COON
a (Compound 27) C ₈ H ₁₇ NHC ₃ H ₆ NHC ₃ H ₆ NHC ₂ H
₄ COONa (Compound 28) C ₁₂ H ₂₅ NHC ₃ H ₆ NHC ₂ H ₄ COOL
i

(Compound 29)

[Chemical 25] (Compound 30)

[Chemical formula 26]

A mixture of water and a water-soluble organic solvent is preferably used as a liquid medium for dissolving or dispersing the above-mentioned specific dyes and compounds constituting the ink according to the present invention. Specific examples of the water-soluble organic solvent used in the present invention include amides such as dimethylformamide and dimethylacetamide; ketones such as acetone; ethers such as tetrahydrofuran and dioxane; polyethylene glycol and polypropylene. Polyalkylene glycols such as glycols; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol and other alkylene groups having 2 to 6 carbon atoms Alkylene glycols containing atoms; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl ( Lower alkyl ethers of polyhydric alcohols such as ethyl) ether; N-
Cyclic amide compounds such as methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethanolamine, sulfolane, dimethylsulfoxide, 2-pyrrolidone and ε-caprolactam, and imide compounds such as succinimide. Can be mentioned.

The ink according to the present invention preferably contains various additives in order to improve the dissolution stability of the dye in the ink. That is, volatile base components such as ammonia and alkylamine are contained in the ink, but since these volatilize volatilize over time and the dissolution stability of the dye gradually deteriorates, urea or a urea derivative is used as an alkali supplier. Is preferably contained. The content of urea or urea derivative in the ink is in the range of 0.01 to 20% by weight, preferably 0.1 to 15% by weight.

Further, when divalent metal ions are present in the ink, a problem of kogation, which is peculiar to ink jet recording such as burning of a heater, occurs. In order to satisfy inkjet recording suitability and prevent such kogation, EDT
It is preferable to add an acidic component such as A, a carboxylic acid compound such as hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, maleic acid, succinic acid or citric acid, if necessary. The content of the acidic component in the ink is in the range of 0.01 to 10% by weight,
Preferably 0.1 to 5.0% by weight, more preferably 0.1.
1 to 3.0% by weight.

In addition, as described above, it is also a preferred embodiment to contain a monovalent metal ion in the ink for the purpose of dissolving stability of the dye and preventing kogation. The content of monovalent metal ions in the ink is 0.01 to 10.0.
The range of weight% is preferably 0.1 to 5.0% by weight, more preferably 0.1 to 3.0% by weight. Further, these monovalent metal ions may be contained as counter ions of the dye.

Further, when the ink according to the present invention is used in an ink jet recording method, it is preferable to adjust the pH of the ink to 9 or more by using the above additives and the like. That is, the ink jet recording method is different from a water-based ballpoint pen or the like, in that there is no contact between the recording material and the ink, and clogging cannot be solved by pressing the pen tip at the time of recording like stationery. It is preferable that the solubility of the ink is improved by maintaining the pH of 9 or more. The ink according to the present invention contains, in addition to the above components, a surfactant, a rust preventive, a preservative, a fungicide, an antioxidant, a reduction inhibitor, an evaporation accelerator, and a chelating agent, if necessary. , Various additives such as water-soluble polymers may be contained.

As described above, the amount of the dye represented by the above general formula (I) added to the ink in the free acid state is as follows.
It depends largely on the purpose, dye type, and ink composition,
The amount is in the range of 0.1 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. When the amount of the dye added to the ink is less than 0.1% by weight, sufficient printing density cannot be obtained, while when the amount added is more than 15% by weight, the dissolution stability of the dye is deteriorated.

The amount of the compound represented by the general formula (IV) added to the ink also depends largely on the use, purpose, colorant species, and ink composition, but is 0.01-2.
It is in the range of 0% by weight, preferably in the range of 0.1 to 10% by weight. Further, the ratio of the dye and the compound represented by the general formula (IV) in the ink cannot be generally stated from the structural compatibility, but for example, in the case of general use, the ratio in the ink is The ratio of the dye contained to the compound represented by the general formula (IV) is preferably in the range of 1: 3 to 8: 1.

The content of the water-soluble organic solvent, which is a liquid medium for dissolving or dispersing the dye and the compound, is generally preferably 1% to 40%, more preferably 3% to 40% by weight based on the total weight of the ink. It is in the range of 30%. 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 dye, which is a coloring material, is deteriorated, and the viscosity of the ink is increased, which is not preferable. On the other hand, if the amount 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 due to the bubbling phenomenon of the ink due to thermal energy, and the ejection is 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 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 are 25 ° C. Surface tension at 30-68 dyne / c
m, 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 in plain paper, the amount of water contained in the ink according to the present invention is preferably 50% by weight or more and 98% by weight or less, more preferably 60% by weight or less. It is not less than 95% by weight and not more than 95% by weight.

As a method and an apparatus suitable for recording using the ink according to the present invention, thermal energy corresponding to a recording signal is applied to the ink in the chamber of the recording head, and the thermal energy causes a droplet to be generated. Examples thereof include an inkjet recording method and an inkjet recording device.

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 (thin film is shown in the figure, but not limited to this). It is obtained by bonding and. The heating head 15 has a good heat dissipation property such as a protective film 16 made of silicon oxide, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome, a heat storage layer 19, and alumina. It consists of a substrate 20.

The ink 21 has a discharge orifice (fine hole) 2
2, the meniscus 23 is formed by the pressure P. Now, when electrical signal information is applied to the aluminum electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly heats up, and bubbles are generated in the ink 21 in contact with the area, and the pressure causes The meniscus 23 protrudes, the ink 21 is ejected and becomes an ink droplet 24, which is ejected from the ejection orifice 22 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 adhering a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG. 1 is a cross-sectional view of the head 13 along the ink flow path,
FIG. 2 is a sectional view taken along the line AB of FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating the above 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 65, and in the case of this example, is held in a form protruding in the movement path of the recording head 65. Reference numeral 62 denotes a cap of the ejection port surface of the recording head 65, which is disposed at a home position adjacent to the blade 61, moves in a direction perpendicular to the moving direction of the recording head 65, contacts the ink ejection port surface, and caps. Is provided. Further, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the movement path of the recording head 65.

The blade 61, the cap 62 and the ink absorber 63 constitute an ejection recovery section 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 onto a recording material facing the ejection port surface where the ejection ports are arranged to perform recording.
Reference numeral 6 denotes a carriage on which the recording head 65 is mounted and which is moved. The carriage 66 slidably engages with a 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 designates a paper feed section for inserting a recording material, and 5
A paper feed roller 2 is driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the ejection port surface of the recording head 65, 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 cap 62 of the ejection recovery unit 64 is retracted from the movement path of the recording head 65, but the blade 61 is projected 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.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same position as the above-mentioned position during wiping. As a result, the ejection opening surface of the recording head 65 is wiped even during this movement. The above-described movement of the recording head 65 to the home position is performed not only at the end of recording or at the time of ejection recovery, but also at the home position adjacent to the recording area at a predetermined interval while the recording head 65 moves in the recording area for recording. And the wiping is performed in accordance with this movement.

FIG. 5 is a diagram showing an example of an ink cartridge 45 in which ink is supplied to the head via an ink supply member, for example, a tube. Where 4
Reference numeral 0 is an ink containing portion containing 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 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 separately provided 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 containing portion containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a head portion having a plurality of orifices. The ink is ejected from 71 as an ink droplet.

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. The recording unit 70 is used in place of the recording head shown in FIG. 4, and is detachable from the carriage 66.

[0052]

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 7 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. Filter and Examples 1-7
Each of the inks according to the present invention was prepared. Also, the pH of the ink was adjusted to about 9.5 with the salt component of each compound.

Ink composition of Example 1 -Compound 26 3 parts-Thiodiglycol 10 parts-Water 79 parts-Dye 1 2.5 parts-Ammonium sulfate 0.5 parts-Urea 5 parts

Ink composition of Example 2 Compound 20 2 parts 2-Pyrrolidone 10 parts Water 84 parts Dye 4 3 parts Sodium bisulfite 1 part

Ink composition of Example 3 Compound 15 3 parts Thiodiglycol 10 parts 28% ammonia water 1 part Water 77 parts Dye 2 4 parts Urea 5 parts

Ink composition of Example 4 Compound 24 2 parts Ethylene glycol 7 parts Water 81.5 parts Dye 15 3 parts Urea 7 parts Lithium acetate 0.5 parts

Ink composition of Example 5 -Compound 25 3 parts-Thiodiglycol 7 parts-Water 79.5 parts-Dye 1 2.5 parts-Ammonium sulfate 0.5 parts-Sodium hydroxide 0.2 parts-C. I. Direct Yellow 0.3 parts ・ Urea 7 parts

Ink composition of Example 6 -Compound 19 2 parts-Ethylene glycol 5 parts-Thiodiglycol 5 parts-Water 78 parts-Dye 3 3 parts-Urea 6 parts-Sodium acetate 1 part

Ink composition of Example 7 -Compound 25 3 parts-Thiodiglycol 10 parts-Water 84 parts-Dye 1 2.5 parts-Ammonium sulfate 0.5 parts

Comparative Examples 1 to 6 In the compositions of Examples 1 to 4, the compounds represented by the general formula (IV) were removed from the respective compositions, and the deficiency was supplemented with pure water. The inks of Comparative Examples 1 to 4 were used. Also, the ink of Comparative Example 5 was prepared by replacing Compound 25 of Example 1 with dimethyldodecylbetaine. In addition, the ink of Comparative Example 6 was prepared by removing 6 of Example 1 and adding 6 parts of isopropyl alcohol and 76 parts of water.

Next, Examples 1 to 7 obtained above
Using the inks of Comparative Examples 1 to 6 and an on-demand type ink jet printer using a heating element as an ink discharge energy source as an ink jet recording device, a printing test was conducted. ) Clogging resistance, (3) Evaluation of print quality, (4) Bronze,
The evaluations of (5) fixability and (6) long-term storability were conducted 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 26 V, resistance value of heating resistor 1
It was performed at 50Ω and a frequency of 6 kHz.

<Evaluation Method and Evaluation Criteria> (1) Water Resistance (A) A printer was filled with a predetermined ink to print alphanumeric characters and solid portions on 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.). After that, the printed matter was immersed in a container filled with water for 3 minutes or more, allowed to stand and air-dried, and the printed density was measured again. The residual rate of the printed matter density was determined to evaluate the water resistance. ⊚: The residual density of printed matter is 90% or more. ◯: Residual rate of printed matter density is 80% or more and less than 90%. B: The residual density of printed matter is 66% or more and less than 80%. X: The residual density of printed matter is less than 66%.

Water resistance (B) A printer was filled with a predetermined ink to print alphanumeric characters and a solid portion 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, left to stand and naturally dried to measure the printed density again, and the residual rate of the printed matter density was determined to evaluate the water resistance. ⊚: The residual density of printed matter is 90% or more. ◯: Residual rate of printed matter density is 80% or more and less than 90%. B: The residual density of printed matter is 66% or more and less than 80%. X: The residual density of printed matter is less than 66%.

(2) Evaluation of clogging property (sticking recovery property) The printer was left in a constant temperature bath at 35 ° C. for 1 month and then left at room temperature for 24 hours to perform a recovery operation (suction operation by pumping). It was printed later and evaluated according to the following criteria. ⊚: The printing state returns to normal within three recovery operations. ◯: The printing state returns to normal after 3 to 5 times of recovery operation. Δ: The printing state returns to normal after 6 to 10 times of recovery operation. X: No ejection or print disorder occurs even after performing the recovery operation 10 times.

(3) Evaluation of printing quality (A) After printing alphanumeric characters on a commercially available acidic paper with a printer and leaving the printed material for 1 hour or more, the sharpness of the characters and the whiskers generated from the characters by visual observation with a microscope. The degree of bleeding was 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.

Evaluation of printing quality (B) After printing alphanumeric characters on a commercially available neutral paper with a printer and leaving the printed material for 1 hour or more, the sharpness of the character and the beard-like character generated from the character by a microscope and visual inspection. The degree of bleeding was 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 are many beard-like blurs. X: Characters are not sharp and have many beard-like blurs.

(4) Evaluation of bronze on recorded matter After printing the solid portion on a commercially available acidic paper with a printer and leaving it for 1 hour or more, the degree of gloss (bronze) with a reddish solid portion was measured. The following criteria evaluated. ○: The solid part is not reddish. Δ: The solid part has a little reddish tint. X: The solid part is reddish on the entire surface.

(5) Evaluation of Fixability (A) After printing alphanumeric characters on a commercially available acid paper with a printer, 1
After 0, 20, 30, 40, 50 and 60 seconds, rubbing with a filter paper (No. 2 (trade name) manufactured by Toyo Roshi Kaisha, Ltd.) was carried out, and judgment was made based on several seconds until the printed portion became dirty (20 ± 5 ° C., 5
(Measured at 0 ± 10% RH), and evaluated according to the following criteria. A: Less than 6 seconds. ◯: 6 seconds or more and less than 16 seconds. Δ: 16 seconds or more and less than 31 seconds. X: 31 seconds or more.

Evaluation of Fixability (B) After printing alphanumeric characters on a commercially available neutral paper with a printer, 1
After 0, 20, 30, 40, 50 and 60 seconds, rubbing with a filter paper (No. 2 (trade name) manufactured by Toyo Roshi Kaisha, Ltd.) was carried out, and judgment was made based on several seconds until the printed portion became dirty (20 ± 5 ° C., 5
(Measured at 0 ± 10% RH), and evaluated according to the following criteria. A: Less than 6 seconds. ◯: 6 seconds or more and less than 16 seconds. Δ: 16 seconds or more and less than 31 seconds. X: 31 seconds or more.

(6) Evaluation of long-term storability Each ink was placed in a bottle container tightly stoppered, left in an environment of 50 ° C. for 3 months, and the ink was filtered with 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.

[0072]

[Table 1] Table 1 Evaluation results

[0073]

[Table 2] Table 2 Evaluation results

[0074]

As described above, according to the present invention, when printing recording is performed on so-called plain paper such as acidic paper and neutral paper used in general offices, the type of paper is changed. In addition, high-quality printed and printed matter with good water resistance and fixability can be obtained, and bronze of the dye in the ink does not occur, excellent clogging resistance and no problem for long-term storage. Ink is provided.

[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.

FIG. 7 is a graph showing the relationship between pH and solubility of compounds used in the present invention.

[Explanation of symbols]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location B41M 5/00 E C09D 11/02 PTF PTG (72) Inventor Shinichi Sato 3 Shimomaruko, Ota-ku, Tokyo No. 30-2 Canon Inc. (72) Mayumi Yamamoto 3-30-2 Shimomaruko Ota-ku, Tokyo Canon Inc. (72) Satoshi Nagashima 3-30-2 Shimomaruko Ota-ku, Tokyo Canon Inc. (72) Inventor Nofumi Hattori 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (33)

[Claims] 1. A dye characterized by being represented by the following general formula (I) in the form of a free acid, a secondary amine, a derivative of a secondary amine, a tertiary amine and a derivative of a tertiary amine. And at least one compound selected from the respective composite compounds, wherein the compound is 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. An ink comprising: a compound having: and a liquid medium that dissolves or disperses the compound. [Chemical 1] In the general formula (I), R ₁ , R ₂ and R ₂ ′ are each a carboxyl group, a sulfone group, a hydroxyl group, an amino group, and a carbon number of 1 to 1.
Selected from the alkyl group and hydrogen atom of 2, R ₃ , R ₄ and R
₅ and R ₆ are selected from a carboxyl group, a sulfone group, an amino group, a hydroxyl group, an alkylamide group and a hydrogen atom.
X has a structure represented by the following general formula (II) or (III). [Chemical 2] In the formula, R ₇ is selected from a carboxyl group, a sulfone group and a hydrogen atom. R ₈ and R ₉ are selected from the group consisting of a carboxyl group, a sulfone group, an alkylamide group, a structure represented by the following formula, and hydrogen. [Chemical 3] 2. The ink according to claim 1, wherein the dye represented by formula (I) has at least one carboxyl group as a water-soluble group. 3. In the dye represented by the general formula (I),
Having a carboxyl group and a sulfone group as a water-soluble group,
The ink according to claim 1, wherein the number of carboxyl groups of the dye is equal to or more than the number of sulfone groups. 4. The ink according to claim 1, wherein the dye represented by formula (I) has a counter ion composed of a volatile component. 5. The ink according to claim 4, which is a dye whose counter ion is ammonia or alkylamine. 6. When X in the dye represented by formula (I) is represented by formula (II), R ₇ is hydrogen or X has a structure represented by formula (III). Claim 1
Ink described in. 7. The ink according to claim 1, wherein when X in the dye represented by formula (I) is represented by formula (III), R ₈ and R ₉ have a structure represented by the following formula. [Chemical 4] 8. A secondary amine, a derivative of a secondary amine,
At least one compound selected from a tertiary amine, a derivative of a tertiary amine, and a composite compound of each, and the compound is an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group, or a salt of a sulfone group. The compound having at least one group selected from the group consisting of
The ink according to claim 1, which has a peak having a minimum solubility in the range of 4 to 10. 9. A secondary amine, a derivative of a secondary amine,
At least one compound selected from a tertiary amine, a derivative of a tertiary amine, and a composite compound of each, and the compound is an alkyl group, a carboxyl group, a salt of a carboxyl group, a sulfone group, or a salt of a sulfone group. The ink according to claim 1, wherein the compound having at least one group selected from the group consisting of is represented by the following general formula (IV). [Chemical 5] (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. R ₃ is (CH ₂ ) _b- X ₂
Alternatively, R ₄ —Y or a hydrogen atom is represented, and b is an integer of 1 to 4. R ₄ represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom. Z represents _{(NR 5 C q H 2q)} c (NHC n H 2n) d, q and n are an integer from 2 to 4, c + d is an integer of 0 to 50. Y represents _{(NR 6 C m H 2m)} e (NHC p H 2p) f, m and p are integer of 2 to 4, the e + f is an integer of 0 to 50. R ₅ represents _{(CH 2) g -X 3,} g is an integer of 1 to 4. R ₆ represents _{(CH 2) h -X 4,} h is from 1 to 4
Is an integer. 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. The compound of the general formula (IV) has at least one compound 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. ) 10. In the formula of the compound represented by formula (IV), 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 9. 11. A compound represented by the general formula (IV), wherein R ₁ and R ₄ are each an alkyl group having 1 to 32 carbon atoms, and c
The ink according to claim 10, wherein + 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 12. 12. The ink according to claim 1, further comprising a volatile base component or a monovalent metal component. 13. The ink according to claim 1, further comprising a volatile base component and a monovalent metal component. 14. The ink according to claim 12, wherein the volatile base component is ammonia or an alkylamine. 15. The ink according to claim 12, wherein the monovalent metal component is selected from sodium and lithium. 16. The ink according to claim 1, wherein the ink contains urea or a urea derivative.
Ink described in. 17. The ink according to claim 1, wherein the pH is 9 or more. 18. The ink according to claim 17, wherein an acid salt is used as a kogation inhibitor. 19. An ink jet recording method for recording on a recording material by ejecting ink droplets from an orifice according to a recording signal, wherein the ink is the ink according to claim 1 or 12.
An ink jet recording method, which is the ink according to claim 13. 20. The ink jet recording method according to claim 19, wherein thermal energy is applied to the ink to eject ink droplets. 21. An ink according to claim 1, 12, or 13 in a recording unit having an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets. A recording unit characterized in that. 22. The head portion is a head which causes thermal energy to act on ink to eject ink droplets.
The recording unit according to 1. 23. The recording unit according to claim 21, wherein the ink containing portion contains an ink absorber inside. 24. The recording unit according to claim 21, wherein the ink containing portion is formed of polyurethane, cellulose, or polyvinyl acetate. 25. An ink cartridge comprising an ink containing portion containing ink, wherein the ink is the ink according to claim 1, 12 or 13. 26. The ink cartridge according to claim 25, wherein the ink containing portion has a liquid contact surface formed of polyolefin. 27. An ink jet recording apparatus comprising a recording unit having an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets, wherein the ink is the ink according to claim 1, claim 12 or claim 10. Item 13
An ink jet recording apparatus, which is the ink according to item 1. 28. The head section is a head for causing thermal energy to act on ink to eject ink droplets.
7. The inkjet recording device according to 7. 29. The ink jet recording apparatus according to claim 27, wherein the ink containing portion contains an ink absorber inside. 30. The ink jet recording apparatus according to claim 27, wherein the ink containing portion is made of polyurethane, cellulose, or polyvinyl acetate. 31. A recording head for ejecting ink droplets,
An ink jet recording apparatus comprising an ink cartridge having an ink containing portion containing ink and an ink supply portion for supplying ink from the ink cartridge to a recording head, wherein the ink is the ink according to claim 1, claim 12 or claim 13. An ink jet recording apparatus, which is the ink according to item 1. 32. The ink jet recording apparatus according to claim 31, wherein the recording head is a head which causes thermal energy to act on ink to eject ink droplets. 33. The ink jet recording apparatus according to claim 31, wherein the ink containing portion has a liquid contact surface formed of polyolefin.