JPH06271802A - Ink, inkjet recording method using the same, and equipment using the ink - Google Patents

Abstract

(57) [Abstract] [Purpose] An ink that gives high quality images even when recorded on plain paper without causing bleeding or bleeding problems on the recording material To provide an inkjet recording method using the same and a device using the ink. An ink containing at least a coloring agent, a water-soluble organic solvent, and water containing a compound represented by the following general formula (1), and an ink jet recording method using the same And equipment using such ink. [Chemical 1]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink capable of forming a high-speed, high-quality color image on a so-called plain paper such as copy paper or bond paper, an ink jet recording method using the ink, and the ink. Regarding the equipment used.

[0002]

2. Description of the Related Art In recent years, in personal computers, displays have been colorized from desktop types to laptop types and notebook types, and since application software that makes full use of color expression has been announced, printers have been announced. Color recording can be said to be the most anticipated field. Among various recording methods used in these, the inkjet recording method forms ink droplets by various ink ejection methods, and forms them on a recording material such as paper, processed paper, plastic film and cloth. The recording is performed by attaching the recording head to the recording head and is quiet because the recording head and the recording material do not contact each other.
It has the advantages that high-speed printing is possible and color recording is easy. In the ink jet recording method, the following characteristics have been conventionally required for the ink. (1) No bleeding occurs in the printed portion on the recording material (2) High storage stability of the ink (3) High safety in use Further, in the ink jet recording method for performing color recording, (4) When different colors are printed adjacent to each other on the recording material, there is no bleeding of different colors caused by unfixed ink droplets (5) It is required that the color solid part of the obtained printed matter is particularly uniform and that there be no color unevenness.

[0003]

However, even when the conventional ink is used as it is as an ink for color ink jet recording, there is a problem that bleeding is severe and an image is not formed. Therefore, it has been attempted to suppress bleeding by using a dedicated recording material having good ink absorption, which is called coated paper. Also, when printing on so-called plain paper such as copy paper or bond paper, printing is performed while waiting for ink droplets in the printing section to settle in order to prevent bleeding, so the printing speed is very slow. was there. As described above, the current situation is that the conventional ink has almost no paper selectivity. For the purpose of improving the bleeding of printed matter and the fixability of ink droplets on plain paper, which is the above-mentioned problem, a method of recording with an ink having a pH of a strong alkali (for example, JP-A-Sho 5)
No. 6-57862), a method of recording using an ink to which a large amount of a surfactant is added (for example, Japanese Patent Laid-Open No. Sho 5).
No. 5-29546 and Japanese Patent Laid-Open No. 56-5871) have been tried.

However, even when printing is performed using these inks, improvement in bleeding is not always sufficient, and even when the bleeding is relatively small, among the characteristics required for the above-mentioned ink, (1) There is a problem that the bleeding of the printing section appears remarkably and there is a problem that the reliability is not sufficient. For color inkjet recording, high-speed and high-quality images can be obtained even when recorded on plain paper. The current situation is that there has never been ink. Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, the obtained image does not cause a problem of bleeding or bleeding on a recording material, and high-speed printing is possible even when recorded on plain paper. Another object of the present invention is to provide an ink that gives a high-quality image, an inkjet recording method using the ink, and a device using the ink.

[0005]

[Means and Actions for Solving Problems] The above objects are
The following is achieved by the present invention. That is, the present invention is an ink containing at least a coloring agent, a water-soluble organic solvent, and water, and containing a compound represented by the following general formula (1).

[Chemical 2] (However, R _{1 to} R ₄ represent any of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group, and a substituted or unsubstituted phenyl group, and m + n is an arbitrary number in the range of 0 to 50. And l (el) is 2 or more.)

[0006]

The present inventors have conducted diligent research on an ink which prevents bleeding and gives a uniform color image without color unevenness. As a result, the ink containing the compound represented by the above general formula (1) is extremely effective. The present invention has been completed by finding that it is effective for. The reason why the ink of the present invention containing the above compound is effective in preventing bleeding and forming a uniform image without color unevenness is speculated as follows. The most important factors controlling bleeding prevention and color uniformity of recorded images are
It is considered that the wettability of the ink to the recording material. Among the recording materials, especially plain paper, the density of the fibers on the surface is not uniform, and the fixing of the ink is slow in the areas where the fibers are dense.
Bleeding may occur or image color unevenness may occur. Since the ink of the present invention has good wetting property on a recording material, the ink fixing selectivity due to the fiber density of paper is no longer present, and bleeding and color unevenness of an image may occur on any part of the paper. It is thought that it will not occur. Further, the ink having a very good wetting property is excellent in the roundness of dots forming an image because of the color uniformity, and a higher quality image can be obtained.

An ink containing a compound having one triple bond is also excellent in color uniformity, but the ink of the present invention is
In comparison with an ink containing a compound having one such triple bond, the ink of the present invention is
The effect was even better. Although the reason for the above is not clear, the compound represented by the general formula (1) having two or more triple bonds contained in the ink of the present invention has a molecular weight higher than that of a compound having one triple bond. The electron density inside is higher, and the hydrophobic part in the molecule (the part containing triple bond)
Is rigid and does not cause structural changes so freely,
It is presumed that the orientation is extremely orderly with respect to the surface of the ink, and the interaction with the recording material is effectively exerted to exert a strong wetting property.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The addition amount of the compound represented by the following general formula (1) contained in the ink of the present invention is generally preferably in the range of 0.001 to 20% by weight of the total weight of the ink, and more preferably Is 0.0
It is from 01 to 5% by weight. Further, m + n in the formula is preferably an arbitrary number in the range of 0 to 50.

[0009]

[Chemical 3]

Specific examples of the compound represented by the above general formula (1) are shown below, but the structure thereof is not limited thereto.

[0011]

[Chemical 4]

[0012]

[Chemical 5]

As the liquid medium constituting the ink of the present invention, a general water-soluble organic solvent can be used without any particular problem. For example, polyethylene glycol,
Polyalkylene glycols such as polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1, 2,
Alkylene glycols having an alkylene group of 2 to 6 carbon atoms, such as 6-hexanetriol, hexylene glycol, diethylene glycol and thiodiglycol;
Glycerin; lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n -Butyl alcohol,
Alcohols such as sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, benzyl alcohol, cyclohexanol; amides such as dimethylformamide, dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; tetrahydrofuran, dioxane, etc. Ethers of
N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3
And nitrogen-containing heterocyclic ketones such as dimethyl-2-imidazolidinone.

Among these, preferable water-soluble organic solvents include ethylene glycol, triethylene glycol,
Hexylene glycol, diethylene glycol, glycerin, thiodiglycol, ethyl alcohol, isopropyl alcohol, cyclohexanol, etc., and the content thereof is generally 1 to 35% with respect to the total weight of the ink.
It is desirable that the range is.

Examples of dyes used in the ink of the present invention include direct dyes, acid dyes, basic dyes, reactive dyes, disperse dyes and vat dyes. The content of these dyes is determined depending on the type of liquid medium component, the characteristics required for the ink, etc., but is generally 0.5 with respect to the total weight of the ink.
-15 wt%, preferably 1-7 wt%.

The main components of the ink of the present invention are as described above, but in addition thereto, anti-clogging agents such as urea and its derivatives; viscosity modifiers such as polyvinyl alcohol, celluloses and water-soluble resins; diethanolamine, tri A pH adjusting agent such as ethanolamine and a buffer solution, an antifungal agent, various surfactants and the like can be added as necessary within a range not hindering the purpose of the present invention. Further, in order to prepare an ink used in an ink jet recording method of charging the ink, it is preferable to add a specific resistance adjusting agent such as an inorganic salt such as lithium chloride, ammonium chloride and sodium chloride.

The ink of the present invention is particularly suitable for use in an ink jet recording system in which droplets are ejected by the action of heat energy for recording, but it can also be used as another ink jet recording method or a general writing tool. There is no limit. A recording device suitable for recording using the ink of the present invention is a device that applies thermal energy corresponding to a recording signal to the ink in the chamber of the recording head and generates a droplet by the energy.

An example of the structure of the recording head, which is the main part, is shown in FIGS. 1, 2 and 3. The head 13 is made of glass, ceramics, a plastic plate, or the like having a groove 14 through which ink passes, and a heating head 15 having a heating resistor used for heat-sensitive recording (a head is shown in the drawing, but is not limited to this. It is not a thing) and is obtained by adhering. The heating head 15 has a protective film 1 formed of silicon oxide or the like.
6, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.

The ink 21 is a discharge orifice (fine hole) 2
It is filled up to 2, and the pressure P forms the meniscus 23. Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly heats up, bubbles are generated in the ink 21 in contact with the area, and the meniscus 23 is generated by the pressure. Is ejected, the ink 21 is ejected, and becomes a recording droplet 24 from the orifice 22 and flies toward the recording material 25. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is made by bonding a glass plate 27 having multi-grooves 26 and a heating head 28 similar to that described in FIG. 1 is a sectional view of the head 13 taken along the ink flow path, and 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 this head. In FIG. 4, reference numeral 61 is a blade as a wiping member, and one end of the blade is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head, and in the case of this example, is held in a protruding form in the moving path of the recording head. 6
Reference numeral 2 denotes a cap, which is arranged 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 comes into contact with the ejection surface to perform capping. 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 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 dust from the surface of the ink ejection port. 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 is slidably engaged with a guide shaft 67, and a part of the carriage 66 is a motor 68.
It is connected to a belt 69 driven by (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move in the recording area and the area adjacent thereto.

Reference numeral 51 is a paper feed section for inserting a recording material, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the ejection opening surface of the recording head, and as recording progresses, the recording material is ejected to the ejection unit provided with the ejection roller 53.

In the above structure, when the recording head 65 returns to the home position due to the end of recording or the like, the head recovery section 64.
The cap 62 is retracted from the moving path of the recording head 65, but the blade 61 is projected in the moving path.
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 moving 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, even during this movement, the ejection port surface of the recording head 65 is wiped. The above-mentioned movement of the recording head to the home position is performed not only at the end of recording and 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 moves in the recording area for recording. Then, with this movement, the wiping is performed.

FIG. 5 is a sectional view 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. Here, 40 is an ink containing portion containing the ink for supply, for example,
It is 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. An ink absorber 44 receives the waste ink.

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, and the one in which they are integrated as shown in FIG. 6 is also preferable. 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. Reference numeral 72 is 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 65 shown in FIG. 4, and is detachable from the carriage 66.

To carry out the recording method of the present invention, for example, a recording apparatus in which four recording heads shown in FIG. 3 are arranged on a carriage is used. FIG. 7 shows an example thereof. 8
Recording heads 1, 82, 83, and 84 are for ejecting recording inks of black, cyan, magenta, and yellow, respectively. The head is arranged in the above-described recording apparatus and ejects recording ink of each color according to a recording signal. Although FIG. 7 shows an example in which four recording heads are used, the present invention is not limited to this, and as shown in FIG. 8, one recording head ejects all inks of black, cyan, magenta, and yellow. You may. When the ink contained in the recording unit has been consumed, it can be reused by refilling it with the ink of the present invention.

[0028]

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. The dyes and contents of the black, cyan, magenta and yellow inks used in the examples and comparative examples are as follows. -Black: CI Food Black 2 2 parts Dye A 1.2 parts below Dye B 0.8 parts below-Yellow: CI Direct Yellow 86 2.5 parts-Cyan: CI Acid Blue 9 3.5 parts-Magenta: Dyes below C 3.5 parts

Dye A

[Chemical 6] Dye B

[Chemical 7] (However, Q ₁ represents a phenyl group or a naphthyl group substituted with a group selected from a lower alkylcarbonylamino group and a lower alkoxy group, or a naphthyl group substituted with an SO ₃ M group, and Q ₂ represents SO ₃ Represents a phenyl group substituted by an M group or a phenyl group substituted by a lower alkoxy group, Q ₃ represents an unsubstituted or SO ₃ M group substituted phenyl group or a naphthyl group, and R ₁ and R ₂ represent a lower group Represents a group selected from an alkyl group, a lower alkoxy group and a lower alkylcarbonylamino group, R ₃ represents a hydrogen atom or a phenyl group substituted with a SO ₃ M group, n is 0 or 1, and M is an alkali Represents a metal or ammonium.)

Dye C

[Chemical 8] (However, Y represents a hydrogen atom, a methyl group, a methoxy group, an acetylamino group or a nitro group, and may form a benzene ring together with the carbon atom at the 3-position of the benzene ring B. On the other hand, X Represents any of an acetyl group, a benzoyl group, a paratoluenesulfonyl group and a 4-chloro-6-hydroxy-1,3,5-triazin-2-yl group, and M ¹ , M ² and M ³ are each It is a base selected from alkali metals, ammonium and amines.)

<Example 1> Dyes (black, yellow, cyan, magenta) Parts by weight of each of the above-mentioned dyes-Glycerin 8 parts-Urea 5 parts-Thiodiglycol 8 parts-NO. Compound of 1 1 part-Pure water Remainder After thoroughly stirring the composition of the above ink, the pore size was 0.22
μm Fluoropore filter (Sumitomo Electric Industries, Ltd .:
The ink of this example was obtained by pressure filtration under the trade name).

<Example 2> Dyes (black, yellow, cyan, magenta) Weight parts of the respective dyes described above: Glycerin 8 parts, urea 5 parts, thiodiglycol 8 parts, NO. Compound of 2 16 parts / pure water Remainder The composition of the above ink was prepared in the same manner as in Example 1 to obtain the ink of this example.

<Example 3> Dyes (black, yellow, cyan, magenta) Parts by weight of each of the above-mentioned dyes-Glycerin 8 parts-Urea 5 parts-Thiodiglycol 8 parts-NO. Compound of 3 0.5 part Cyclohexanol 1 part Pure water Remainder The composition of the above ink was prepared in the same manner as in Example 1 to obtain the ink of this example.

<Example 4> Dyes (black, yellow, cyan, magenta) Parts by weight of each of the above-mentioned dyes-Glycerin 8 parts-Urea 5 parts-Thiodiglycol 8 parts-NO. Compound of No. 4 10 parts Pure water Remainder The composition of the above ink was prepared in the same manner as in Example 1 to obtain the ink of this example.

<Example 5> Dyes (black, yellow, cyan, magenta) Weight parts of each of the above-mentioned dyes-Glycerin 8 parts-Urea 5 parts-Thiodiglycol 8 parts-NO. Compound of 5 5 parts / pure water Remainder The composition of the above ink was prepared in the same manner as in Example 1 to obtain the ink of this example.

<Comparative Example 1> Dyes (black, yellow, cyan, magenta) Weight parts of each of the dyes described above: 5 parts of glycerin; 5 parts of urea; 6 parts of thiodiglycol; balance of pure water The composition was prepared in the same manner as in Example 1 to obtain the ink of this comparative example.

<Evaluation> Next, the obtained inks of Examples 1 to 5 and Comparative Example 1 were used to perform recording on commercially available copy paper and bond paper. As the inkjet recording apparatus used, a recording apparatus similar to that shown in FIG. 4 was used, and a color image was formed using the four recording heads shown in FIG. As the recording head used here, the same recording head as that used in the inkjet printer BJC-820J (manufactured by Canon: trade name) was used. The drive conditions for the recording heads, that is, the conditions for energizing the heaters were that the applied voltage was 28 V, the pulse width was 3.2 μsec and the drive frequency was 5 kHz for each head. The method and conditions of each evaluation item are as follows. The evaluation results are shown in Table 1.

(1) Bleeding A color sample was printed so that different colors were adjacent to each other, and the state of bleeding was visually observed and evaluated according to the following criteria. The colors used were black, yellow, cyan, and magenta, and red and green, which were made by overprinting and mixing two of the three colors, yellow, cyan, and magenta,
There are seven colors of blue. ◯: No bleeding is observed at all boundaries Δ: Bleeding is noticeable at red, green, and blue boundaries where a large amount of ink adheres x: Bleeding is remarkable at almost all boundaries

(2) Color Uniformity The uniformity of solid color portions was visually evaluated and evaluated. ◯: No difference in color tone Δ: Partially uneven color tone X: Uneven color tone

(3) Occurrence rate of bleeding Commercially available copy paper and bond paper were continuously printed so that 300 dots did not contact each other, and naturally dried in a room for 24 hours, and then irregularly or irregularly bleeding under a microscope. The number of dots generated was counted, and the percentage was evaluated according to the following criteria. ○: 10% or less △: 10 to 20% ×: 21% or more

(4) Storage stability The ink was placed in a heat-resistant glass bottle in an amount of 100 cc, sealed tightly and stored in a constant temperature layer at 60 ° C. for 2 months, and then mounted in a printer for printing and evaluation. ◯: No abnormality X: No ejection, print disorder or discoloration

(5) Clogging property (fixing recovery property) The printer is filled with a predetermined ink, and after printing alphanumeric characters continuously for 10 minutes, the printing is stopped and left for one month without a cap or the like. After that, a nozzle clogging recovery operation was performed, printing was performed again, and the number of recovery operations was evaluated until the normal printing state without character blurring and chipping was reproduced. ◯: Normal printing is possible with 1-5 recovery operations. △: Normal printing is possible with 6-10 recovery operations. ×: Normal printing is possible with 11 or more recovery operations.

[0043]

[Table 1] Table 1 Evaluation results

[0044]

As described above, according to the present invention, even when high-speed printing is performed on plain paper, there is no bleeding, bleeding, and color unevenness, and the dot shape has good circularity and high image quality. An ink is provided from which an image is obtained. Further, such an ink is particularly suitable as an inkjet recording ink of a system in which thermal energy is applied to perform recording.

[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 portion of the inkjet recording apparatus.

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 perspective view showing a recording unit in which a plurality of recording heads used in an embodiment of the present invention are arranged.

FIG. 8 is a perspective view of another recording head used in the present invention.

[Explanation of symbols]

 13 head 15 heat generating head 21 ink 25 recording material 28 heat generating head 40 ink bag 44 ink absorber 45 ink cartridge 61 wiping member 65 recording head 66 carriage 70 recording unit 71 head portion 72 atmosphere communicating hole

Claims (16)

[Claims] 1. An ink containing at least a colorant, a water-soluble organic solvent, and water, which contains a compound represented by the following general formula (1). [Chemical 1] (However, R _{1 to} R ₄ represent any of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group, and a substituted or unsubstituted phenyl group, and m + n is an arbitrary number in the range of 0 to 50. Yes, l is 2 or more.) 2. The ink according to claim 1, wherein the content of the compound represented by the general formula (1) is 0.001 to 20% by weight. 3. The ink according to claim 1, wherein the water-soluble organic solvent is a polyhydric alcohol, a monohydric alcohol or a derivative thereof. 4. An ink jet recording method for ejecting ink droplets from an orifice in response to a recording signal to record on a recording material, wherein the ink is the ink according to claim 1. . 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 4, wherein a plurality of color inks of yellow, magenta, cyan and black are used and the inks of two or more colors are applied to the recording medium so as to be in contact with each other. 7. A recording unit comprising an ink containing section for containing ink and a head section for ejecting the ink as ink droplets, wherein the ink is the ink according to claim 1. unit. 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 provided with an ink containing portion for containing ink, wherein the ink is the ink according to claim 1. 10. The ink container has a bag structure.
The ink cartridge described in. 11. The ink cartridge according to claim 9, wherein the ink containing portion has a liquid contact surface formed of polyolefin. 12. A refilling method comprising filling the ink according to claim 1 in an ink containing portion of the recording unit according to claim 7 or the ink cartridge according to claim 9. 13. An ink jet recording apparatus provided with the recording unit according to claim 7, wherein the ink is the ink according to claim 1. 14. The inkjet recording apparatus according to claim 13, wherein the recording unit includes a carriage. 15. An ink jet recording apparatus comprising the ink cartridge according to claim 9 and a head. 16. The ink jet recording apparatus according to claim 15, further comprising an ink supply system for supplying ink contained in an ink cartridge to a recording head.