JPH06316684A - Ink, recording method using the ink and recording apparatus using the method - Google Patents

Abstract

PURPOSE:To provide an ink containing a specific dye and a liquid medium, having excellent bleeding resistance of image, resolution, thermal stability, light resistance and discoloration resistance in room and useful for the printing on a coated paper, etc. CONSTITUTION:This ink contains (A) a dye consisting of the compound of the formula [Y is a 5-12C (branched) alkyl; Z is benzoyl, SO2, C6H5 or SO2C6H4- CH3; M is an alkali metal or ammonium] and (B) a liquid medium. Preferably, the content of the component A in the ink is 0.5-10wt.%, the component B contains 2-80wt.% of a polyhydric alcohol and polyhydric alcohol ether and 10-97.5wt.% of water and the pH of the ink is 3-10.5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink, a recording method using the same, and an apparatus using the same, more specifically,
The present invention relates to an ink having improved bleeding of an image recorded on a recording material having an ink receiving layer composed of a binder and a pigment on its surface, a recording method using the same, and a device using the same.

[0002]

2. Description of the Related Art Conventionally, an aqueous ink in which a water-soluble dye is dissolved in an aqueous medium has been used as an ink for ink jet recording. In these conventional inks, (1) an image with sufficient density is provided (2) good drying property on the recording material (3) little bleeding of the printed image (4) water, alcohol, etc. The recorded image does not flow out even if it comes into contact with it, or it is sufficiently readable even if it flows out (water resistance) (5) Excellent light resistance (6) No clogging of the pen tip or nozzle

(7) No problems such as blurring of the recorded image when recording continuously or when recording is started after being left for a long time (ejection stability) (8) Ink is stable during storage ( 9) During use, no problem will occur even if it comes into contact with the member that constitutes the recording means. (10) It is required that there is no problem with the safety of the user, including a negative Ames test. In addition to the above requirements, the ink jet recording method using energy is required to have (11) excellent heat resistance and not to have a bad influence on the thermal energy generating means.

Examples of black ink for plain paper satisfying the above requirements are disclosed in JP-A-1-135880 and JP-A-1-193.
Japanese Patent Laid-Open No. 62-199667 discloses an example of a color ink for forming a full-color image. However, these precedents do not satisfy all the above performances. In particular, when forming a full-color image, a problem that has not yet been solved is the problem of image bleeding when stored for a long period of time. When producing a full-color image, a recording material (so-called coated paper) having an ink receiving layer composed of a pigment and a binder on its surface is usually used in order to obtain a clear image. The blurring of the image is remarkable when the coated paper is used.

Among the four colors of black, cyan, magenta and yellow which form a full-color image, magenta tends to bleed, and in extreme cases, a magenta outline is produced in the printed portion. As a result, the image quality is significantly deteriorated. Examples of magenta dyes are disclosed in JP-A-58-1762.
77, JP-A-59-78273, JP-A-6.
0-81266, JP-A-62-190271, JP-A-62-199665-7, JP-A-1-
See JP-A-53976. These dyes have good light resistance, but have poor color tone, good water resistance and bleeding, but poor light resistance, good light resistance and water resistance, but discolored indoors. There are merits and demerits in both cases.

Further, Japanese Patent Laid-Open No. 62-18773 discloses that
As a hydrophobic structure portion in the dye, C _n H _{2n + 1} (n is 8 to
Dyes having an integer of 20) and Example 2 exemplifies dyes having the following structures.

[Chemical 7] However, the above dyes have problems in light resistance and storage stability.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to satisfy the above-mentioned general performance requirements, and to prevent the image from bleeding even when printed on coated paper for a long period of time and to have a light resistance. It is an object of the present invention to provide a magenta ink capable of giving an image having excellent properties and less likely to cause indoor discoloration, a recording method using the same, and a device using the same.

[0008]

The above object can be achieved by the present invention described below. That is, the present invention is an ink containing at least a dye and a liquid medium, wherein the dye is represented by the following general formula (I), a recording method using the ink, and an apparatus using the ink.

[Chemical 8] (In the above general formula, Y is an alkyl group having 5 to 12 carbon atoms which may be branched, Z is a benzoyl group, -SO ₂ C ₆ H ₅
Or a —SO ₂ C ₆ H ₄ —CH ₃ group. M represents an alkali metal or ammonium. )

[0009]

By using the dye of the above-mentioned general formula (I) as the dye in the ink, it is possible to obtain an ink which gives an image with less bleeding after storage on coated paper. Furthermore,
It is possible to provide an image having high image quality, excellent resolution, little discoloration, and excellent fastness. Further, the ink of the present invention can be stably used for a long period of time even when applied to an ink jet recording method in which ink is ejected by the action of thermal energy, without deposits on the heater. Further, there is no change in physical properties or precipitation of solid matter during storage. Further, by using a dye having a specific structure as a coloring material for the ink, the general required performance as described above is satisfied, and further, after printing on coated paper, there is little blurring of the image even when stored for a long period of time. It is possible to give an image that is excellent in light resistance and is unlikely to cause indoor discoloration.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The dye used in the present invention is
In general, Na salts of water-soluble groups such as sulfonic acid groups are generally used, but the present invention is not limited to Na salts, and K, Li, N
Salts of organic amines such as H ₃ and alcohol amines have the same effect, and the present invention also includes these salts. Specific examples of the dye represented by the general formula (I) include the following dyes. The substituent Y in the above general formula is C ₅ to C because it gives a good magenta color and prevents bleeding.
₁₂ alkyl groups (which may be branched) are preferred. When a substituent is added via an amino group, the color tone is largely deviated from magenta.

[0011]

[Chemical 9]

The amount of the dye used in the ink of the present invention is not particularly limited, but generally 0.1 to 15% by weight, preferably 0.3 of the total weight of the ink.
An amount of 10 to 10% by weight, more preferably 0.5 to 6% by weight is more preferable. A suitable aqueous medium for use in the ink of the present invention is water or a mixed solvent of water and a water-soluble organic solvent. As the water, it is preferable to use deionized water, not general water containing various ions.

As the water-soluble organic solvent used by mixing with water, a solvent known as a water-soluble organic solvent for ink jet recording is used. In particular, glycerin or polyethylene oxide having a degree of polymerization of 3 to 6 is preferable to prevent ink clogging, and a nitrogen-containing cyclic compound or a polyalkylene oxide ether compound is preferable from the viewpoint of image density and ejection stability, and further has a good frequency response. The use of lower alcohols and surfactants is preferred. Therefore, the preferred solvent composition in the present invention is a composition containing various components as described above in addition to water.

The content of the water-soluble organic solvent in the ink is generally in the range of 2 to 80% by weight, preferably 3 to 70% by weight, more preferably 4 to 60% by weight based on the total weight of the ink. Also, the water used is 10% by weight of the total ink.
As described above, the proportion is preferably 10 to 97.5% by weight or more, and when the amount of water is small, a large amount of low-volatile organic solvent remains in the formed image, and migration of dyes and bleeding of images become serious. This is not preferable because it causes problems.

Further, the ink of the present invention may contain a pH adjusting agent, a viscosity adjusting agent, a surface tension adjusting agent and the like, if necessary, in addition to the above components. Examples of the pH adjuster include various organic amines such as diethanolamine and triethanolamine, inorganic alkali salts such as alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, and organic acids such as lithium acetate. Examples thereof include salts, organic acids and mineral acids.

The ink of the present invention as described above has a viscosity at 25 ° C. of 1 to 20 cps, preferably 1 to 15 cps.
And the surface tension is 30 dyn / cm or more, preferably 40
It preferably has a physical property of dyn / cm or more and a pH of about 3 to 10.5. In the recording method using the ink of the present invention, the ink jet method is effective as a method, and as the recording material, it is effective to use a coated paper which gives an image excellent in sharpness and resolution. .

The ink jet system may be any conventionally known system and is not particularly limited, but in the present invention,
For example, the system described in Japanese Unexamined Patent Publication No. 54-59936 discloses a system and apparatus for causing a rapid volume change in ink under the action of thermal energy and ejecting the ink from a nozzle by the action force due to this state change. Is useful.

Next, an example of the ink jet recording apparatus of the present invention, which is suitable for recording using the above-mentioned ink of the present invention, will be described below. An example of the head configuration, which is the main part of the apparatus, is shown in FIGS. 1, 2 and 3. Head 13
Is adhered to a glass, ceramic or plastic plate having grooves 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 heat generating head 15 has a good heat dissipation property such as a protective film 16 formed of silicon oxide, aluminum electrodes 17-1 and 17-2, a heat generating resistor layer 18 formed of nichrome, a heat storage layer 19, and alumina. It consists of Kisaka 20.

The ink 21 is a discharge orifice (fine hole) 2
2, the meniscus 23 is formed by the pressure P. Now, aluminum electrodes 17-1 and 17-2
When the electric signal information is applied to the area, the area of the heating head 15 indicated by n rapidly generates heat, and the ink 21 in contact with the area is heated.
Bubbles are generated in the
The ink 21 is ejected, and the recording droplet 24 is discharged from the orifice 22.
And fly toward the recording material 25.

FIG. 3 shows an external view of a multi-head in which a large number of the heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG. 2 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.

In order to maintain the ink of the present invention at its operating temperature (head temperature control temperature during recording), the substrate 20 is heated to
It may be carried out by a method such as adjusting the temperature of the entire head to a constant temperature. In this way, the viscosity of the ink of the present invention held at the operating temperature becomes lower than that in the non-operating state due to the action of the compound having the thermoreversible gelation property, and the ejection property of the head becomes sufficiently good.

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 by the recording head, and in the case of this example,
The recording head 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 absorber provided adjacent to the blade 61 and, like the blade 61, 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 section 64.
Also, the absorber 63 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 ports are arranged for recording, and 66 denotes a recording head 65 mounted to move the recording head 65. It is a carriage for performing. The carriage 66 slidably engages with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor 68. As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area.

Reference numeral 51 designates a paper feeding 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, and is ejected to a paper ejection unit provided with a paper ejection roller 53 as the recording progresses. In the above configuration, 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 unit 64 is retracted from the movement path of the recording head 65.
1 projects in the movement path. As a result, the ejection port surface of the recording head 65 is wiped. The cap 62
When the cap 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 positions as the above wiping positions. As a result, the ejection opening surface of the recording head 65 is wiped even during this movement. The above-mentioned movement of the recording head to the home position is performed not only at the end of recording or at the time of ejection recovery, but also at a predetermined interval to the home position adjacent to the recording area while the recording head is moving in the recording area for recording. However, the wiping is performed along with this movement.

FIG. 5 is a diagram showing an example of an ink cartridge in which the ink is supplied to the head through an ink supply member, for example, a tube. Here, 40 is an ink containing portion containing the 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. Reference numeral 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 above-described head and ink cartridge which are separate bodies, but is preferably suitable for those 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. 3, and is detachable from the carriage 66.

As the recording material used in the present invention, any recording material such as ordinary plain paper, coated paper, plastic film for OHP, etc. can be used, and particularly when coated paper is used The effect is played. In general, coated paper is made of plain paper or high-quality paper as a base material and an ink receiving layer made of a pigment and a binder is provided on the surface of the base paper. Here, the paper fiber of the base material is used in the ink receiving layer. Including paper that contains a mixture of.

[0030]

EXAMPLES Next, examples and comparative examples will be described in more detail. In the text,% is based on weight unless otherwise specified. To check the degree of bleeding, a dye that does not cause bleeding (CI Direct Blue 199) was mixed with the dye used in the present invention to prepare an ink, and the degree of bleeding was determined. The used dye was synthesized by the conventional method as follows. After pn-decylaniline-0-sulfonic acid was dissolved, it was diazotized with sodium nitrite and coupled with benzoyl H acid at pH 4-7. After completion of the reaction, sodium sulfate was added and salting out and filtration were performed. After redissolving this in water,
Add isopropyl alcohol to precipitate and desalt, N
A dye of o.1 was obtained. The dyes No. 2 to No. 3 were synthesized in the same manner.

Example 1 No. 1 dye 1.5% C.I. I. Direct Blue 199 1.5% Diethylene glycol 30% Ion-exchanged water 67%

Example 2 No. 2 dye 1.5% C.I. I. Direct Blue 199 1.5% Diethylene glycol 20% Polyethylene glycol (average molecular weight 300) 10% Ion-exchanged water 67%

Example 3 No. 3 dyestuff 1% C.I. I. Direct Blue 199 1% Diethylene glycol 15% N-Methyl-2-pyrrolidone 15% Ion-exchanged water 68%

Examples 4 to 6 C.I. I. Direct Blue 199 was replaced with the magenta dye described in each Example to prepare magenta single color inks, and Examples 4 to 6 were prepared. The above components were sufficiently mixed and dissolved in a container, and pressure-filtered with a Teflon filter having a pore diameter of 0.22 μm to obtain an ink of the present invention. Inkjet printer BJ-130A using these inks with a heating element as a source of ink ejection energy
(Canon, 48 nozzles), and solid printing of 15 mm × 30 mm was performed on the following recording materials A and B.
It was then tested for bleed, weather resistance and discoloration.
The weather resistance and discoloration tests were carried out only on 4 to 6 in the above examples.

"Bleed acceleration test method": printed matter at 30 ° C /
After being left in an environment of 80% RH for 48 hours, the degree of bleeding was observed. No bleeding was observed in any case, and good results were obtained. "Weather resistance test method" Light exposure tester (Tester name: Ci35
fade-ometer Production company name: Atlas
Electric Devices Co. Chica
go, Illinois. ), The color difference ΔE ^* _ab before and after the test was measured. In each case, ΔE ^* _ab was 15 or less, and the degree of discoloration was small and good results were obtained. "Promotion method of fading": The printed matter is left for 120 minutes in a shaded tank where the ozone concentration is kept within the range of 3 ± 2 ppm, and the color difference ΔE ^* _ab of the printed matter before and after the test is measured (JIS.
According to Z 8730), Δ
E ^* _ab was 10 or less, and the degree of discoloration was small and good results were obtained. Recording material A: Sharp inkjet coated paper Recording material B: Canon PixelPro coated paper

For comparison, an ink was prepared by mixing the following components in the same manner as in the example, and solid printing was performed on the recording materials A and B by the same recording device as above. When a bleeding test and a discoloration test were performed using this printed matter, Comparative Example 1 showed large bleeding and discoloration, and Comparative Examples 2, 3 and 4 had little bleeding, but the discoloration as a single magenta color was large. .

Comparative Example 1 C. I. Acid Red 35 1.5% C.I. I. Direct Blue 199 1.5% Diethylene glycol 30% Ion-exchanged water 67%

Comparative Example 2 C. I. Reactive Red 23 1.5% C.I. I. Direct Blue 199 1.5% Diethylene glycol 20% Polyethylene glycol (average molecular weight 300) 10% Ion-exchanged water 67%

Comparative Example 3 C. I. Reactive Red 23 3% Diethylene glycol 20% Polyethylene glycol (average molecular weight 300) 10% Ion-exchanged water 67%

Comparative Example 4 Dye of the following structure 3%

[Chemical 10] Thiodiglycol 5% Urea 5% Glycerin 5% Isopropyl alcohol 5% Ion-exchanged water 77%

[0041]

According to the present invention as described above, by using the dye of the general formula (I) as the dye in the ink, it is possible to obtain an ink giving an image with less bleeding after storage on coated paper. Can be done. Further, it is possible to provide an image having high image quality and excellent resolution, and having little discoloration and excellent fastness. Further, the ink of the present invention can be stably used for a long period of time even when applied to an ink jet recording method in which ink is ejected by the action of thermal energy, without deposits on the heater.
Further, there is no change in physical properties or precipitation of solid matter during storage. Further, by using a dye having a specific structure as a coloring material for the ink, the general required performance as described above is satisfied, and further, after printing on coated paper, there is little blurring of the image even when stored for a long period of time. It is possible to give an image that is excellent in light resistance and is unlikely to cause indoor discoloration.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a recording head according to an inkjet recording method of the present invention.

FIG. 2 is a schematic cross-sectional view showing a sectional view taken along the line AB of FIG.

FIG. 3 is a schematic external view showing an example of a multi-head in which a large number of heads in FIG. 1 are arranged.

FIG. 4 is a schematic perspective view showing an example of an ink jet recording apparatus incorporating the same head.

FIG. 5 is a schematic cross-sectional view showing an example of an ink cartridge that supplies ink to the head.

FIG. 6 is a schematic external view showing an example of a main part of an inkjet recording apparatus in which the same head and the same ink cartridge are integrated.

[Explanation of symbols]

 13: Head 14: Ink Groove 15: Heating Head 16: Protective Layer 17: Aluminum Electrode 18: Heating Resistor Layer 19: Heating Layer 20: Substrate 21: Ink 22: Discharge Orifice 23: Meniscus 24: Ink Droplet 25: Cover Recording material 26: Multi-groove 27: Glass plate 28: Heating head 40: Ink bag 42: Pillar 44: Ink absorber 45: Ink cartridge 51: Paper feeding section 52: Paper feeding roller 52: Paper discharging roller 61: Blade 62: Cap 63: Ink absorber 64: Ejection recovery section 65: Recording head 66: Carriage 67: Guide shaft 68: Motor section 69: Belt 70: Inkjet cartridge

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // C09B 29/30 CLA 7306-4H

Claims (15)

[Claims] 1. An ink containing at least a dye and a liquid medium, wherein the dye is represented by the following general formula (I). [Chemical 1] (In the above general formula, Y is an alkyl group having 5 to 12 carbon atoms which may be branched, Z is a benzoyl group, -SO ₂ C ₆ H ₅
Or a —SO ₂ C ₆ H ₄ —CH ₃ group. M represents an alkali metal or ammonium. ) 2. The ink according to claim 1, containing 0.5 to 10% by weight of the dye represented by formula (I) and 2 to 80% by weight of a polyhydric alcohol or a polyhydric alcohol ether. 3. Containing 0.5 to 10% by weight of the dye of the general formula (I), 2 to 80% by weight of polyhydric alcohol or polyhydric alcohol ether, and 10 to 97.5% by weight of water. The ink according to claim 1, having a pH of 3 to 10.5. 4. In an inkjet recording method for recording an ink droplet on an image recording material by ejecting an ink droplet from an orifice in response to a recording signal, the ink contains at least a dye and a liquid medium, and the dye has the following general formula (I). An inkjet recording method characterized by: [Chemical 2] (In the above general formula, Y is an alkyl group having 5 to 12 carbon atoms which may be branched, Z is a benzoyl group, -SO ₂ C ₆ H ₅
Or a —SO ₂ C ₆ H ₄ —CH ₃ group. M represents an alkali metal or ammonium. ) 5. The ink jet recording method according to claim 4, wherein thermal energy is applied to the ink to eject ink droplets. 6. The ink jet recording method according to claim 5, wherein the recording material is coated paper. 7. A recording unit comprising an ink containing section containing ink and a head section for ejecting the ink as ink droplets, wherein the ink, at least a dye and a liquid medium are contained, and the dye is represented by the following general formula: A recording unit represented by I). [Chemical 3] (In the above general formula, Y is an alkyl group having 5 to 12 carbon atoms which may be branched, Z is a benzoyl group, -SO ₂ C ₆ H ₅
Or a —SO ₂ C ₆ H ₄ —CH ₃ group. M represents an alkali metal or ammonium. ) 8. The recording unit according to claim 7, wherein the head portion is a head that causes thermal energy to act on the ink to eject ink droplets. 9. An ink cartridge having an ink containing portion containing ink, wherein the ink contains at least a dye and a liquid medium, and the dye is represented by the following general formula (I). cartridge. [Chemical 4] (In the above general formula, Y is an alkyl group having 5 to 12 carbon atoms which may be branched, Z is a benzoyl group, -SO ₂ C ₆ H ₅
Or a —SO ₂ C ₆ H ₄ —CH ₃ group. M represents an alkali metal or ammonium. ) 10. The ink cartridge according to claim 9, wherein the ink containing portion has a liquid contact surface formed of polyolefin. 11. An ink jet recording apparatus comprising a recording unit having an ink containing section containing ink and a head section for ejecting the ink as ink droplets, wherein the ink contains at least a dye and a liquid medium,
An ink jet recording apparatus, wherein the dye is represented by the following general formula (I). [Chemical 5] (In the above general formula, Y is an alkyl group having 5 to 12 carbon atoms which may be branched, Z is a benzoyl group, -SO ₂ C ₆ H ₅
Or a —SO ₂ C ₆ H ₄ —CH ₃ group. M represents an alkali metal or ammonium. ) 12. The head unit is a head for causing thermal energy to act on ink to eject ink droplets.
1. The inkjet recording device according to 1. 13. An ink jet recording apparatus comprising a head for ejecting ink droplets, an ink cartridge having an ink containing portion containing ink, and an ink supply portion for supplying ink from the ink cartridge to the recording head, An ink jet recording apparatus, wherein the ink contains at least a dye and a liquid medium, and the dye is represented by the following general formula (I). [Chemical 6] (In the above general formula, Y is an alkyl group having 5 to 12 carbon atoms which may be branched, Z is a benzoyl group, -SO ₂ C ₆ H ₅
Or a —SO ₂ C ₆ H ₄ —CH ₃ group. M represents an alkali metal or ammonium. ) 14. The ink jet recording apparatus according to claim 13, wherein the recording head is a head that causes thermal energy to act on ink to eject ink droplets. 15. The ink jet recording apparatus according to claim 14, wherein the ink containing portion has a liquid contact surface formed of polyolefin.