JP3123000B2 - Ink jet recording ink, ink jet recording method using the same, and device using the ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink for ink-jet recording, an ink-jet recording method using the same, and a device using such an ink. Ink jet recording ink that can perform good recording on uncoated paper such as high-quality paper, neutral paper, bond paper, and so-called plain paper and recycled paper used in offices and the like. The present invention relates to an ink jet recording method using the same and an apparatus using the ink.

[0002]

2. Description of the Related Art Writing instruments (fountain pens, felt-tip pens,
A variety of compositions have been reported for inks for aqueous ballpoint pens and the like, and inks for inkjets. In particular, the composition and physical properties of the ink have been used in recent years so that good recording can be performed on plain paper such as copy paper, report paper, notebooks, stationery, bond paper, and continuous slip paper that are commonly used in offices. Detailed research and development has been done from various aspects such as. For example, in general, ink contains a high-boiling organic solvent such as glycol for the purpose of preventing drying and preventing clogging, etc.When recording is performed on plain paper having a high degree of size using such an ink. In some cases, the ink hardly penetrates into the paper and the drying property of the recording part is poor. Was.

On the other hand, Japanese Patent Application Laid-Open No. 55-29546 proposes a method in which a large amount of a surfactant is added to ink to increase the permeability of the ink into the paper. However, in this case, bleeding occurs very frequently depending on the type of paper, ink drops from the pen tip when filled in a writing instrument, or when the ink is filled in an ink jet head, the head may be damaged. Lee depending on the structure conditions
The ink jet recording ink receded from the orifice surface so that ejection was not performed, and conversely, the entire orifice surface was wet and the ink was not ejected.

Further, JP-A-54-104933 and JP-B-62-14189 disclose an ink jet printer.
A method of adding N, N-bis (polyoxyethylene (or propylene))-P-toluenesulfonic acid amide or the like to a recording ink is disclosed, and this method is effective for improving the solubility of a dye. However, in order to sufficiently prevent clogging, it is necessary to use a considerably large amount of an organic solvent such as a polyhydric alcohol in combination, so that the drying property on a recording material such as paper is poor. Even after the elapse of time, there is a problem that stains are generated by contact, and therefore, a combination of a surfactant is also required to improve permeability to paper, and as a result, bleeding occurs and printing quality is sufficient. Not.

Further, when used for ink-jet recording and ink ejection is interrupted, if water or the like evaporates, the above-mentioned compound recedes from the orifice surface, and the clogging prevention property is poor. Various improvements other than the above have been attempted so far, but an ink jet that sufficiently solves all the above-mentioned problems of dryness, print quality, and clogging.
At present, no recording ink has been known so far.

[0006]

The object of the invention is a problem in trying to solve] Accordingly, the present invention also can prevent clogging of the printer head in the pause and the long-term stop or the like of printers apparatus, the recovery even in the unlikely event clogged it sex is easy and in which it is possible to form a high-quality image consisting of irregular bleeding less round dots on plain paper
Kujetto recording ink, is to provide a device using the inkjet recording method and such an ink using the same.

[0007]

The above object is achieved by the present invention described below. That is, the present invention relates to an ink jet recording method for plain paper containing a recording agent and a liquid medium for dissolving or dispersing the same.
An aqueous ink used for jet recording contains an organic amine salt of tricarboxylic acid , and is based on the total weight of the ink.
An ink for inkjet recording on plain paper, characterized by containing 1 to 40% by weight of a water-soluble organic solvent .
An inkjet recording method using the same and a device using the ink.

[0008]

SUMMARY OF] The present inventors have clogging prevention of the nozzle at the time of recording, as less high-quality image blurring of the ink jet recording in <br/> click on plain paper is obtained, for various ink compositions After careful examination, inkjet recording
Incorporation of an organic amine salt of a tricarboxylic acid into the ink for ink improves dye solubility in a state where the ink is concentrated due to evaporation of water, so that clogging can be prevented. Even when the volatile components in the ink are completely evaporated, the organic amine salt of tricarboxylic acid remains with the dye, so that the strong coagulation and precipitation of the dye can be relaxed, and the recovery is much easier than before. I learned that In addition, an inkjet recording ink containing an organic amine salt of a tricarboxylic acid,
When ejected as droplets from a nozzle of the printer head is evaporated on plain paper, by rapid ink changes associated with osmotic, organic amine salts of a tricarboxylic acid to rapidly thicken and crystallization, printing It has been found that the obtained dots maintain a round shape with less irregular bleeding.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. As the organic amine salt of tricarboxylic acid used in the present invention, citric acid, isocitric acid, tricarballylic acid, hemimellitic acid, trimellitic acid, trimesic acid, naphthalene tricarboxylic acid and the like can be used as the tricarboxylic acid. Ethanolamine, as an organic amine to be reacted with an acid,
Use of various alkanolamines such as diethanolamine, triethanolamine, monomethylethanolamine, and dimethylethanolamine; aliphatic amines such as ethylamine, diethylamine and triethylamine; and aromatic amines such as aniline, benzylamine and triphenylamine. Can be done. These tricarboxylic acids and organic amines may be used in combination of two or more.

The proportion of the organic amine salt of tricarboxylic acid used in the present invention in the ink is about 0.1 to 20% by weight, preferably 0.5 to 10% by weight.
The color material used in the present invention is a color index (Col.
or Index), almost all water-soluble acid dyes, direct dyes, basic dyes and reactive dyes can be used. Further, any dye which is not described in the color index can be used as long as it is a water-soluble dye. The use amount of these dyes is not particularly limited, but is generally 0.1 to 15 with respect to the total weight of the ink.
The range of weight% is suitable, more preferably 0.1 to 10% by weight.

[0011] The inkjet recording ink of the present invention comprises water-soluble organic solvent out of the above components, <br/> surfactant optionally, pH adjusting agents, rust inhibitors, antiseptic agents, antifungal Agent,
Various additives such as antioxidants, evaporation promoters, chelating agents, and water-soluble polymers may be added. The liquid medium used in the present invention is a mixture of water and a water-soluble organic solvent.
You. 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, triethylene glycol, 1, 2, 6
Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms such as hexanetriol, thiodiglycol, hexylene glycol, 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, dimethylsulfoxide and the like.

The content of the water-soluble organic solvent is generally from 1% to 40% by weight based on the total weight of the ink.
More preferably, it is in the range of 3% to 30%. Particularly, the amount of the wetting agent such as polyhydric alcohol generally used for the purpose of preventing clogging is required to be used in a large amount due to the effect of preventing clogging of the organic amine salt of tricarboxylic acid used in the present invention. On the contrary, when the content was 40% by weight or more, the result was that the print fixability on paper and the print quality deteriorated. Further, the content of water in the ink for ink jet recording is more preferably 30 to 9 from the viewpoints of solubility of the coloring material, viscosity of the ink, sufficient fixing properties, density of printed matter, and the like.
Used in the range of 5% by weight.

The ink for ink jet recording of the present invention is:
It is particularly suitable when applied to an ink jet recording method of a type in which the ink is ejected by the bubbling phenomenon of the ink due to thermal energy, and has a feature that the ejection becomes extremely stable and satellite dots are not generated. However, in this case, the thermal physical property value (for example, specific heat, thermal expansion coefficient, thermal conductivity, etc.) may be adjusted. Further, the ink jet recording ink of the present invention solves the problem of ink bleeding and the drying property and penetrability of the recorded matter when recorded on plain paper, and at the same time, improves the matching with the ink jet head. Physical properties of 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, adjusting the ink jet recording ink to the above physical properties,
In order to solve the problem in plain paper, the amount of water contained in the ink of the present invention is preferably from 50% by weight to 98% by weight, more preferably from 60% by weight to 95% by weight. is there.

The ink jet recording ink of the present invention comprises:
It is particularly suitably used in an ink jet recording method in which recording is performed by discharging droplets by the action of thermal energy.
You. The ink jet recording ink of the present invention (hereinafter simply referred to as
As a method and apparatus suitable for performing printing using "ink", a method and apparatus for applying thermal energy corresponding to a print signal to ink in a chamber of a print head and generating droplets by the thermal energy Is mentioned.

FIGS. 1, 2 and 3 show examples of the configuration of a head which is a main part of the apparatus. The head 13 is formed by bonding a glass, ceramic or plastic plate having a groove 14 through which ink passes, and a heating head 15 (a head is shown in the figure, but is not limited to this) used for thermal recording. Is obtained. The heating head 15 includes a protective film 16 made of silicon oxide or the like, and an aluminum electrode 17.
-1, 17-2, heat generating resistor layer 18 made of nichrome or the like, heat storage layer 19, substrate 20 having good heat dissipation such as alumina
Is made up of The ink 21 reaches a discharge orifice (fine hole) 22 and forms a meniscus 23 by the pressure P. Now, when an electric signal is applied to the electrodes 17-1 and 17-2, an area indicated by n of the heating 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. but projects the ink 21 is ejected, the recording droplets 24 from the orifice 22, usually
Fly towards paper 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 with reference to FIG. FIG. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a cross-sectional view taken along line AB in FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, and forms a cantilever. The blade 61 is disposed at a position adjacent to a recording area of the recording head, and in this example, is held in a form protruding into the movement 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 the cap moves in a direction perpendicular to the direction in which the print head moves and comes into contact with the ejection port surface to perform capping. Further, an absorber 63 is provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding into the movement path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a recording head which has discharge energy generating means and discharges ink on plain paper facing the discharge port surface where discharge ports are arranged to perform recording, and 66 denotes a recording head on which a recording head 65 is mounted. Is a carriage for performing the movement. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and the adjacent area. Reference numeral 51 denotes a paper feed unit for inserting plain paper, and reference numeral 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, plain paper is fed to a position facing the discharge port surface of the recording head, and is discharged to a discharge section provided with discharge rollers 53 as recording proceeds.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the cap 62 of the head recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. I have. As a result, the ejection port surface of the recording head 65 is wiped. When capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62 moves so as to protrude into the movement path of the recording head. 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 position at the time of wiping described above. As a result, the ejection port surface of the recording head 65 is also wiped during this movement. The movement of the recording head to the home position described above
Not only at the end of recording and at the time of ejection recovery, but also at a predetermined interval, the recording head moves to a home position adjacent to the recording area while moving the recording area for recording, and the wiping is performed along with this movement. .

FIG. 5 is a diagram showing an example of an ink cartridge containing ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink storage portion that stores the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the head. 44
Is an absorber for receiving waste ink. It is preferable for the present invention that the ink container has a surface in contact with the ink made of polyolefin, particularly polyethylene. The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separated as described above, but may be suitably used in an integrated one as shown in FIG.

In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink storage section containing ink, for example, an ink absorber is stored, and the ink in the ink absorber has a plurality of orifices. Head part 71
Are ejected as ink droplets from the ink. It is preferable for the present invention to use polyurethane, cellulose or polyvinyl acetal as a 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 has the configuration shown in FIG.
The recording head is used in place of the recording head shown in FIG.

[0021]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on weight unless otherwise specified. Examples 1 to 5 The following components were mixed, sufficiently stirred and dissolved, and filtered under pressure with a fluoropore filter having a pore size of 0.45 μm (trade name: manufactured by Sumitomo Electric Industries, Ltd.) to obtain 5 types of the present invention. Was prepared. Ink composition of Example 1 I. Direct Black 154 4 parts Diethylene glycol 10 parts Ethylene glycol 10 parts Isocitrate diethanolamine salt 5 parts Water 71 parts Ink composition of Example 2 I. Food Black 2 3 parts Glycerin 5 parts Thiodiglycol 5 parts Isopropyl alcohol 3 parts Diethanolamine citrate 3 parts Water 81 parts Ink composition of Example 3 I. Direct Yellow 86 2 parts Triethylene glycol 15 parts Ethyl alcohol 5 parts Tricarballylic acid diethylamine salt 8 parts Water 70 parts Ink composition of Example 4 I. Acid Red 35 3 parts Polyethylene glycol # 200 12 parts Diethylenglycol monophenyl ether 3 parts Hemimellitic acid diethylethanolamine salt 6 parts Water 76 parts Ink composition of Example 5 I. Food Black 2 4 parts Glycerin 10 parts Ethylene glycol 15 parts Trimesic acid triethylamine salt 5 parts Water 66 parts

COMPARATIVE EXAMPLES 1-5 Except for removing the organic amine salt of tricarboxylic acid contained in the inks of Examples 1-5, the components in which the content was replaced with water were treated in the same manner as in Example 1 to obtain a comparative example. Inks 1 to 5 were obtained.
Next, using the obtained inks of Examples 1 to 5 and Comparative Examples 1 to 5, an inkjet printer BJ-130 (trade name: Canon Inc.) using a heating element as an ink ejection energy source as an inkjet recording apparatus. Was used to evaluate print drying property, clogging evaluation and print quality evaluation. Table 1 shows the results.

[Evaluation Method and Evaluation Criteria] (1) Evaluation of clogging property After printing a predetermined number of alphanumeric characters continuously for 10 minutes by filling the printer with a predetermined ink, the printing is stopped, and a cap is put on the printer for 30 days. Leave (Leave condition: 40 ° C, 10 ± 5% R)
H) After that, the nozzle clogging recovery operation was performed, alphanumeric characters were printed again, and the determination was made based on the number of recovery operations and the presence / absence of defective portions such as blurred or missing characters. ：: Printing equivalent to the initial state is possible with 0 to 3 recovery operations. Δ: Printing equivalent to the initial state is possible with 4 to 9 recovery operations. ×: Printing equivalent to the initial state is possible after 10 or more recovery operations. (2) Print quality evaluation After printing on a commercially available copy paper (XEROX 4024), leave it for one hour or more, and then bleed at the dot level.
The sharpness of the edge was evaluated under environmental conditions of 25 ° C. and 60% RH. ：: no bleeding, and the edge is sharp. Δ: Some bleeding was observed, and the edge was slightly blurred. ×: There is much bleeding and the edges of the dots are also blurred. (3) Drying property of printing Regarding the drying property of printing, after printing alphanumeric characters on a commercially available continuous slip paper with a printer, 10, 20, 30, 40,
After 50 and 60 seconds, it was rubbed with a filter paper (No. 2 (trade name) manufactured by Toyo Roshi Kabushiki Kaisha) and judged based on the number of seconds until the printed portion was not stained (measured at 20 ± 5 ° C., 50 ± 10% RH). ). ：: within 15 seconds. Δ: 16 to 30 seconds. X: 31 seconds or more.

[Table 1]

[0024]

As described above, according to the present invention, there is no bleeding with respect to ordinary plain paper and recycled paper generally used in offices such as copy paper, report paper, notebooks and stationery, and excellent quality. In addition, recording with good permeability can be performed.
Further, according to the ink of the present invention, it is possible to perform highly reliable recording without causing clogging of a pen tip of a writing instrument or a nozzle of an inkjet head.

[Brief description of the drawings]

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

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

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

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

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

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

[Explanation of symbols]

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-51-139408 (JP, A) JP-A-58-183768 (JP, A) JP-A-50-6408 (JP, A) 252469 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 CA (STN) REGISTRY (STN)

Claims (15)

(57) [Claims] An aqueous ink used for ink-jet recording on plain paper containing a recording agent and a liquid medium for dissolving or dispersing the same, containing an organic amine salt of tricarboxylic acid, and based on the total weight of the ink. An ink for inkjet recording on plain paper, comprising 1 to 40% by weight of a water-soluble organic solvent. 2. An ink composition comprising 3 to 30% by weight of the total weight of the ink.
The ink according to claim 1, further comprising a water-soluble organic solvent. 3. An amount of 13 to 25% by weight based on the total weight of the ink.
The ink according to claim 1, which contains a water-soluble organic solvent. 4. The content of the organic amine salt of tricarboxylic acid is in the range of 0.1 to 20% of the total weight of the ink.
The ink according to the above. 5. An ink-jet recording method in which an aqueous ink containing a recording agent and a liquid medium for dissolving or dispersing the same is ejected from an orifice in accordance with a recording signal to perform recording on plain paper. An ink-jet recording method on plain paper, comprising an amine salt and 1 to 40% by weight of a water-soluble organic solvent based on the total weight of the ink. 6. An ink composition comprising 3 to 30% by weight of the total weight of the ink.
The ink jet according to claim 5, comprising a water-soluble organic solvent.
Record method. 7. An amount of 13 to 25% by weight based on the total weight of the ink.
6. The ink-jet printer according to claim 5, which comprises a water-soluble organic solvent.
Jet recording method. 8. The ink jet recording method according to claim 5 , wherein the ink is ejected by applying thermal energy to the ink. 9. A recording unit comprising an ink containing section containing ink and a head section for ejecting the ink as ink droplets, wherein the ink is the ink according to claim 1. unit. 10. The head portion, claim including a head that ejects ink droplets by applying thermal energy to the ink 9
A recording unit according to item 1. 11. An ink cartridge provided with an ink storage section for storing ink, wherein the ink is provided.
An ink cartridge characterized by being the ink described in (1). 12. An ink jet recording apparatus comprising : an ink storage section for storing ink; and a recording unit having a head section for discharging the ink as ink droplets, wherein the ink is the ink according to claim 1. An ink jet recording apparatus comprising: 13. The ink jet printer according to claim 1, wherein the head section includes a head for ejecting ink droplets by applying thermal energy to the ink.
3. The ink jet recording apparatus according to 2. 14. A recording head for discharging ink droplets,
2. An ink jet recording apparatus, comprising: an ink cartridge having an ink containing section containing ink; and an ink supply section for supplying ink from the ink cartridge to a recording head, wherein the ink is the ink according to claim 1. Characteristic inkjet recording device. 15. A recording head for ejecting ink droplets by applying thermal energy to ink.
15. The ink jet recording apparatus according to 14 .