JP2003165936A - Water-base ink composition and inkjet recording method and inkjet recorder using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an inkjet recording ink exhibiting dispersion or dissolution stability without causing a change in the size of ink drops and a change in the delivery velocity of ink drops, poor ink delivery, and a like problem. <P>SOLUTION: The water-base ink is an ink used in an inkjet printer in which a member coming into contact with the ink is at least partially made of silicon, glass, or a membrane thereof on which any one of an oxide, a nitride, a metal, and an organic compound is formed, wherein the zeta potential between the member and a colorant is 0 to -50 mV at a pH of 6.5-11.5. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to ink-jet recording in which at least a part of a member which comes into contact with ink is silicon, glass, or an oxide, nitride, metal,
A film provided with any of organic compounds (silicon is either single crystal silicon or polysilicon, or glass is borosilicate glass, photosensitive glass, quartz glass, soda-lime glass, or silicon , The film provided on any of the glasses is any one of silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, and polyimide. Regarding recording method.

[0002]

2. Description of the Related Art In recent years, the ink jet recording system has been rapidly spread in recent years because of its advantages such as small size, low price, low running cost and low noise. Electrophotographic transfer paper, printing paper, typewriter paper, wire. Dot printer paper, word processor paper, letter paper,
Inkjet printers that can print on various non-coated plain papers such as report papers are also on the market. This inkjet printer includes an inkjet printer of the type that uses glass or silicon or silicon oxide in view of easiness of fine processing, processing accuracy, process and the like.

The ink used in such an ink jet printer is generally composed of a coloring agent and a wetting agent (polyhydric alcohol or ethers thereof) which are dispersed or dissolved in a solvent, and a solvent, and if necessary, a penetrating agent, It contains an antifungal agent, an antiseptic agent, a dispersant, etc., but when this ink is filled in the above glass or an ink jet printer using silicon or silicon oxide and used or left for a long time, the glass in contact with the ink or Further, silicon and silicon oxide are eluted. As a result, the design accuracy of the inkjet printer is lowered, and the size of the ink droplets and the ejection speed of the ink droplets change, which deteriorates the image quality, and in the worst case, ejection failure occurs. Further, since the bonding strength is lowered by elution of glass or silicon or silicon oxide at the bonded portion, ejection failure or in the worst case, the bonded portion is peeled off and malfunctions.

Particularly in an ink jet printer in which the liquid chamber member is made of glass, silicon, or silicon oxide,
Since the dimensional accuracy of the liquid chamber, which requires precision, is reduced, the above-mentioned problem remarkably occurs.

Further, the fluid resistance portion is made of glass or silicon,
In an ink jet printer composed of silicon oxide, the fluid resistance changes due to the elution of glass, silicon, or silicon oxide, and the size of the ink droplets and the ejection speed of the ink droplets change remarkably and the image quality deteriorates. Or, in the worst case, ejection failure occurs.

Further, in the ink jet printer in which the diaphragm is made of glass, silicon, or silicon oxide,
Because the thickness of the diaphragm is reduced, the size of the ink droplets and the ejection speed of the ink droplets are changed, and ejection failure occurs, which deteriorates the image quality.Finally, the diaphragm becomes thin and can withstand vibration. Without damage.

In an ink jet printer whose nozzle is made of glass, silicon, or silicon oxide,
Since the diameter of the nozzle becomes large, the size of the ink droplet, the ejection speed of the ink droplet changes, and ejection failure occurs, which deteriorates the image quality.

In addition, in the ink from which glass, silicon, or silicon oxide is eluted, the dissolution or dispersion stability of the colorant is lowered, and the colorant is deposited to cause clogging. Further, the eluted glass, silicon, or silicon oxide itself becomes supersaturated by evaporation of a solvent such as water and is deposited on the nozzle surface or the like to cause clogging.

Since these problems have not been solved under the present circumstances, it was possible to use the head for a relatively short period of time, for example, when the ink filled in advance was used up, the head was replaced together. In order to solve these problems, an inkjet printer is disclosed in JP-A-5-15.
As disclosed in 5023, WO98-42513, and the like, there is a method of providing an inorganic or organic material layer such as SiN, TiN, or TiO on glass or silicon or silicon oxide to prevent it. This is glass or silicon,
Some of them have the effect of preventing the elution of silicon oxide, but the manufacturing process increases the number of steps, resulting in a large cost, resulting in a very expensive inkjet printer. Further, these films are likely to have pinholes, and it is difficult to form them uniformly, and defects often occur in the films.
In some cases, depending on the method and structure of the head, the film formation itself cannot be incorporated in the process. Furthermore, recent experiments have revealed that certain types of black dyes cannot prevent the elution even if these layers are provided, and other color materials also show elution exceeding the standard value in the long term. It has also been confirmed in some cases.

As the ink, JP-A-9-123437 is used.
In U.S. Pat. No. 5,968,839, a method has been proposed in which urea is added to the ink to stably dissolve it in the ink even if glass or silicon or silicon oxide is eluted, to prevent precipitation.
Since there is no effect of preventing elution of glass, silicon, or silicon oxide itself, glass, silicon, or silicon oxide cannot be used in a portion where accuracy is required. Therefore, a film of silicon or silicon or a silicon oxide which can be relatively easily formed by thermal oxidation, and further, SiN, TiN or TiO on silicon or a silicon oxide.
Ink that does not elute even on a substrate provided with a layer of an inorganic material or an organic material such as is required.

Japanese Patent Publication No. 7-51687 describes an ink in which the content of sodium ions is regulated. Further, JP-A-5-331391 defines the contents of sodium and potassium.
In JP-A-333542 and JP-A-9-25441, there are inks in which the contents of sodium and potassium are regulated.

The applicant of the present invention has proposed an ink containing a specific dye and quaternary ammonium as a counter ion in the ink in Japanese Patent No. 1677642, and in Japanese Patent No. 2085163 discloses the ink containing the dye in the ink. Inks containing quaternary phosphonium ions have been proposed. These are clogging and kogation.
n), the problems such as storage stability were solved. After that, glass or silicon in contact with the ink, silicon oxide, further silicon, SiN on the silicon oxide,
The phenomenon of elution of the substrate has become known by providing a layer of inorganic or organic material such as TiN or TiO. Therefore, when the ink proposed above was examined again, it was found that the dissolution of the substrate was not sufficiently solved.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation, and at least a part of a member in contact with ink is silicon, glass, or an oxide, a nitride, a metal, or an organic compound thereof. A film provided with either (single crystal silicon or polysilicon, or glass is borosilicate glass, photosensitive glass, quartz glass, or soda-lime glass,
Or a film provided on either silicon or glass is any one of silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, and polyimide) As ink for ink, by preventing elution of glass, silicon, silicon oxide, etc. that come into contact with ink, changes in ink droplet size and ejection speed of ink droplets, ejection defects are prevented, and ink dispersion or dissolution stability It is an object of the present invention to provide an excellent inkjet recording ink.

[0014]

As a result of earnest research, the inventors of the present invention have found that even if the content of a specific element such as sodium or potassium is reduced, clogging or kogation may be effective. It has been found that the elution of glass, silicon, silicon oxide, etc. in contact with the ink cannot be prevented, and that it becomes possible by using the zeta potential of the ink and the zeta potential between the member and the coloring material. That is,
By using an ink having a zeta potential of −20 mV or less at a pH of 6.5 to 11.5, or a zeta potential between a member and a coloring material at a pH of 6.5 to 11.5 is 0 to −50 mV. By using the ink that is
We have found that it is possible to prevent the elution of glass, silicon, silicon oxide, etc. that come into contact with the ink, and have found that all of the above problems can be solved.

Further, at this time, the oxidation / reduction current value between the member and the ink is 0 to 0-5.0 to 5.0 Vvs SCE (to the saturated calomel electrode).
It was also revealed that the characteristics were 1.0 μA / cm ² (Pt.). The present invention has been made based on these findings.

The above problems of the present invention are as follows (1) to (32).
Achieved by (1) An ink used in an inkjet printer in which at least a part of a member in contact with the ink is formed of silicon, glass, or a film in which any one of oxide, nitride, metal, and organic compound is provided. And a zeta potential between the member and the coloring material at a pH of 6.5 to 11.5 is 0 to -50 mV.

(2) It is used for an ink jet printer in which at least a part of the member which comes into contact with the ink is formed of silicon, glass, or a film in which any one of oxide, nitride, metal and organic compound is provided. The ink has a zeta potential of −6.5 at pH 6.5 to 11.5.
A water-based ink composition, which has a zeta potential of 20 mV or less and a member-coloring material of 0 to -50 mV.

(3) The aqueous ink composition as described in (1) or (2) above, wherein the coloring material is contained in a resin or contains colored resin fine particles colored with the coloring material.

(4) The above (1) to (1) characterized by containing a cationic ion and / or a cationic substance.
The aqueous ink composition according to any one of (3).

(5) The aqueous ink composition as described in (4) above, wherein the cationic compound is a cationic resin, a cationic surfactant and / or a cationic coloring material.

(6) The aqueous ink composition as described in (5) above, wherein the cationic coloring material is a cationic dye, a cationic carbon black or a cationic pigment.

(7) The above (1) to (1) characterized by containing a phosphonium ion represented by the following general formula (1):
The aqueous ink composition according to any one of (3). General formula (1)

[Chemical 5] (In the formula, Ra, Rb, Rc, and Rd represent a linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a halogenated alkyl group, a substituted or unsubstituted phenyl group, and X ⁻ Represents a counter ion.)

(8) The above (1) to (1), which contains an acetylene compound represented by the following general formula (2):
The aqueous ink composition according to any one of (3). General formula (2)

[Chemical 6] (However, R ^{1 to} R ⁶ are linear alkyl groups having 1 to 5 carbon atoms,
m and n represent the integer of 0-20. )

(9) The above (1) to (1) characterized by containing a sulfonium ion represented by the following general formula (3):
The aqueous ink composition according to any one of (3). General formula (3)

[Chemical 7] (In the formula, Ra, Rb and Rc are linear, branched, cyclic alkyl groups having 1 to 4 carbon atoms, hydroxyalkyl groups,
It represents a halogenated alkyl group or a substituted or unsubstituted phenyl group, and X ⁻ represents a counter ion. )

(10) The above (1), which contains an arsonium ion represented by the following general formula (4):
The aqueous ink composition according to any one of to (3). General formula (4)

[Chemical 8] (In the formula, Ra, Rb, Rc, and Rd represent a linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a halogenated alkyl group, a substituted or unsubstituted phenyl group, and X ⁻ Represents a counter ion.)

(11) The aqueous ink composition as described in any of (1) to (3) above, which contains a boron compound.

(12) The aqueous ink composition as described in any of (1) to (3) above, which contains beryllium ions (Be ²⁺ ).

(13) The aqueous ink composition as described in any of (1) to (3) above, which contains aluminum ions (Al ³⁺ ).

(14) The aqueous ink composition as described in any of (1) to (3) above, which contains zinc ions (Zn ²⁺ ).

(15) The aqueous ink composition as described in any of (1) to (3) above, which contains titanium ion (Ti ⁴⁺ ).

(16) The aqueous ink composition as described in any of (1) to (3) above, which contains zirconium ions (Zr ⁴⁺ ).

(17) The aqueous ink composition as described in any of (1) to (3) above, which contains a silicate ion (Si ²⁺ ).

(18) The above cationic ion, cation
Compounds, phosphonium represented by the general formula (1),
An acetylene compound represented by general formula (2), a general formula
The sulfonium ion represented by (3), in the general formula (4)
Arsonium ions represented, boron compounds, beryliu
Muion (Be²⁺), Aluminum ion, (A
l³⁺), Zinc ion (Zn²⁺), Titanium ion (T
i⁴⁺), Zirconium ion (Zr ⁴⁺), Silicate toy
On (Si²⁺) At least two of
Water according to any one of (1) to (3) above
Ink composition.

(19) The aqueous ink composition as described in any of (1) to (18) above, wherein the pH of the ink is in the range of 7 to 10.

(20) The aqueous ink composition according to any one of (1) to (19), which is a member of a liquid chamber member,
At least a part of each of the fluid resistance portion or the vibration plate is used for an ink jet printer in which silicon, glass, or a film provided with any of oxide, nitride, metal, and organic compound is formed on these materials. An inkjet recording ink characterized by the above.

(21) The water-based ink composition according to any one of (1) to (19), wherein at least a part of the nozzle member is made of silicon, glass, or an oxide or nitride thereof. An ink for inkjet recording, which is used in an inkjet printer formed of a film provided with either a metal or an organic compound.

(22) In the aqueous ink composition according to any one of (1) to (19) above, the silicon in the member is either single crystal silicon or polysilicon, or the glass is borosilicate. Any of glass, photosensitive glass, quartz glass, soda lime glass, or a film provided on any of silicon and glass is made of silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, or polyimide. The inkjet recording ink according to any one of (20) and (21) above, which is any one of the above.

(23) An ink jet printer in which at least a part of the member that comes into contact with the ink is formed of silicon, glass, or a film formed of any of oxides, nitrides, metals, and organic compounds on these. And an inkjet recording ink according to any one of (20) to (22) above for recording.

(24) An ink jet in which at least a part of the member of the liquid chamber member is formed of silicon, glass, or a film provided with any of oxide, nitride, metal, and organic compound. Printer and above (2
0) An ink jet recording method characterized by performing recording using the ink for ink jet recording described in 0).

(25) An ink jet in which at least a part of the member of the fluid resistance portion is formed of silicon, glass, or a film provided with any of oxide, nitride, metal, and organic compound. Printer and above (2
0) An ink jet recording method characterized by performing recording using the ink for ink jet recording described in 0).

(26) Inkjet printer in which at least a part of the member of the diaphragm is formed of silicon, glass, or a film provided with any of these oxides, nitrides, metals, and organic compounds. And the above (2
0) An ink jet recording method characterized by performing recording using the ink for ink jet recording described in 0).

(27) An ink jet printer in which at least a part of the member of the nozzle is formed of silicon, glass, or a film provided with any of these oxides, nitrides, metals, and organic compounds. , Above (2
An ink jet recording method, which comprises performing recording using the ink for ink jet recording described in 1).

(28) In the member described in any of (23) to (27), the silicon is single crystal silicon.
Any of polysilicon, or glass is borosilicate glass, photosensitive glass, quartz glass, soda lime glass, or silicon, the film provided on any of the silicon oxide, titanium oxide, An ink jet recording method, which is one of chromium oxide, titanium nitride, silicon nitride, zirconium, and polyimide.

(29) Liquid chamber member, fluid resistance portion, diaphragm,
The inkjet recording ink and inkjet recording method according to any one of (19) to (28) above, wherein the groove is formed by subjecting the nozzle to etching, sandblasting, excimer laser processing, and drilling.

(30) In a recording liquid cartridge provided with a recording liquid storage section for storing a recording liquid, the recording liquid is the ink for ink jet recording according to any one of the above (20) to (22). Recording liquid cartridge.

(31) In a recording liquid cartridge provided with a recording liquid containing portion containing a recording liquid and a head portion for ejecting recording liquid droplets, the recording liquid is the above (20) to
A recording liquid cartridge comprising the ink for inkjet recording according to any one of (22).

(32) In an ink jet recording apparatus provided with a recording liquid cartridge having a recording liquid container for containing a recording liquid and a recording head for ejecting recording liquid droplets, the recording liquid is the above (20) to An inkjet recording apparatus comprising the inkjet recording ink according to any one of (22).

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. In the present invention, the coloring material, the water-soluble organic solvent, and the surfactant are selected so that the zeta potential of the aqueous ink composition containing the coloring material and water as the main components has the above values. Alternatively, even if the water-based ink composition exceeds the value, a corrosion inhibitor is added to design the ink so that the above value is obtained.

It has been clarified that the corrosion of glass, silicon, silicon oxide, etc. is caused by all the alkali metals contained in the ink. The total content is I
From the CP measurement result, it is about 800 ppm, but 0.05% to 5.0%, preferably 0.1% to 2.0%, and more preferably 0.2% to the total ink.
By containing 0.8% of the corrosion inhibitor, the zeta potential and the oxidation / reduction current value can be lowered, and the elution of glass, silicon, silicon oxide or the like in contact with the ink can be prevented.

The term "corrosion inhibitor" as used herein means phosphonium ion, acetylene compound, cationic resin, cationic surfactant, cationic coloring material, sulfonium ion, arsonium ion, boron compound, beryllium ion (Be ^{2 +} ), Aluminum ion (Al ³⁺ ), zinc ion (Zn ²⁺ ), titanium ion (Ti ⁴⁺ ), zirconium ion (Zr ⁴⁺ ), silicate ion (S
i ²⁺ ) etc. The alkali metal referred to here is a metal of Group 1 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, and francium, but sodium is the most abundant in the actual ink. Francium is calculated to be 20 km on the earth's crust.
There is only a few hundred grams in the whole and there is only a very small amount on the earth, so it can be considered that it is almost zero, so in practice it is sufficient to manage the total content of alkali metals excluding francium.

As the glass used in the present invention, any ordinary glass may be used, but borosilicate glass, quartz glass, low alkali glass, non-alkali glass and soft glass (blue plate glass) are preferable. When used in a head composed of another material, it is preferable to use glass having a linear expansion coefficient close to that of the other material. For example, in the case of a head composed of silicon, heat-resistant glass # 7740, Corning coat 7
913, Corning coat 7052, Corning coat 7056 and the like. The most preferable glass for anodic bonding is a non-alkali glass substrate OA-2, OA-1.
0, low-alkali glass substrate BLC (manufactured by Nippon Electric Glass Co., Ltd.), blue plate glass (soft glass) SL, NA (HOYA)
Manufactured by the company) and the like. These glasses can also be bonded to silicon. Further, photosensitive glass can also be used. Photosensitive glass capable of anisotropic etching is more preferable. Specifically, there are HOYA photosensitive glass PEG3 manufactured by HOYA and photosensitive glass capable of anisotropic etching manufactured by Nippon Electric Glass.

It is considered that the alkali metal in the ink enters the glass, silicon, silicon oxide or the like that is in contact with the ink and diffuses so that the glass, silicon and the like continue to be eluted. The elution of such glass, silicon, and silicon oxide is such that the total content of alkali metals in the ink is 700 ppm or less, preferably 15
It can be suppressed by setting it to 0 ppm or less, more preferably 50 ppm or less, but by including a corrosion inhibitor such as phosphonium ion represented by the general formula (1), it is not a problem even if the content of alkali metal is not reduced. It can be suppressed to a level where The reason is that the corrosion inhibitor is
Since it is adsorbed and stays on the surface of glass, silicon, silicon oxide, etc. in contact with ink, continuous elution of glass and silicon is not performed, and even if the content of alkali metal is large, it works to prevent elution of glass and silicon. It is believed that there is.

This means that, when the electric double layer with the corrosion inhibitor added was examined, a difference in zeta potential was confirmed as compared with the case where the corrosion inhibitor was not added, and it was adsorbed and remained on the glass or silicon surface. Can be confirmed. The high zeta potential of the substrate means that it has high hydrophilicity, ionicity and reactivity and is unstable. On the other hand, a low zeta potential means low water repellency, nonionicity, and low reactivity. When the following cationic compounds are adsorbed on the substrate at a high negative potential, the potential decreases and the stability goes toward stabilization. At this time, the easiness of the flow of the oxidation / reduction current is more likely to flow when the zeta potential is lower (lower in ionicity), and conversely when the zeta potential is higher. From the above, by measuring the zeta potential between the substrate and the ink, the oxidation / reduction current, and the zeta potential of the ink itself, it is possible to quantitatively grasp the easiness or difficulty of corrosion.

It is not necessary that all the ions used in the present invention be one type of compound, and they can be used as a mixture with other ions or compounds. As ions, sulfonium ion, ammonium ion, phosphonium ion,
Arsonium ion, beryllium ion (Be ²⁺ ), aluminum ion (Al ³⁺ ), zinc ion (Zn ²⁺ ),
Titanium ion (Ti ⁴⁺ ), zirconium ion (Z
r ⁴⁺ ), silicide ions (Si
²⁺ ) and the like, and examples of the compound include a cationic resin, a boron compound, an acetylene compound and the like.

Among the phosphonium ions represented by the general formula (1), the following No. 1, No. 2, No. 3, N
o. The compound represented by 4 is particularly preferable because it has a particularly high effect of preventing elution of glass, silicon, silicon oxide and the like, is excellent in dispersion or dissolution stability of the colorant, and satisfies other qualities required for an inkjet recording ink. .

[0056]

[Table 1]

The above No. 1-No. In addition to the compound represented by No. 4, as the phosphonium ion represented by the general formula (1), specifically, No. 5 to No. The items shown in 26 can be given.

[Table 2]

Further, among the sulfonium ions represented by the general formula (3), the following No. 27, No. 28, N
o. 29, No. The compound represented by 30 is particularly preferable because it has a particularly high effect of preventing elution of glass, silicon, silicon oxide and the like, has excellent dispersion or dissolution stability of the colorant, and satisfies other qualities required for an inkjet recording ink. .

[Table 3]

The above No. 27, No. 28, No. Two
9, No. In addition to the compound represented by 30, a compound represented by the general formula (3)
Specific examples of the sulfonium ion represented by No. 31-No. The items shown in 50 can be mentioned.

[Table 4]

Further, among the arsonium ions represented by the general formula (4), the following No. 51, No. 52, N
o. 53, No. The compound represented by 54 is particularly preferable because it has a particularly high effect of preventing elution of silicon and silicon oxide, is excellent in dispersion or dissolution stability of the colorant, and satisfies other qualities required for the inkjet recording ink.

[Table 5]

The above No. 51-No. Other than the compound represented by No. 54, as the arsonium ion represented by the general formula (4), specifically, No. 55-No. 7
The items shown in 6 can be given.

[Table 6]

Of course, the ions represented by the general formulas (1), (3) and (4) are not limited to these. From these, if the other quality required for the ink jet recording ink is satisfied and there is no side effect such as toxicity,
One or more can be added. Among them, it is preferable that the number of carbon atoms in one molecular ion is 4 to 12. When the carbon number is more than 12, solubility in a solvent such as water decreases, clogging occurs during printing pauses or continuous printing, and ink tends to separate and precipitate during storage. The side effects are more likely to occur.

As described above, the present invention prevents corrosion even if the content of alkali metal is large. However, when an anionic compound such as a colorant, a penetrant, a dispersant, or a surfactant added to the ink is used. When it is obtained in the form of an alkali metal salt such as sodium salt or potassium salt, the content of the alkali metal may exceed 800 ppm and become a considerable amount depending on the addition amount.

At this time, the content of the alkali metal may be reduced by at least partially replacing the counter ion of the anionic compound with an ion other than the alkali metal salt. As the method, a method using an ion exchange resin, a desired ion in a solution of an alkali metal salt such as sodium,
Preferably, the general formula (1), the general formula (3) and the general formula (4)
A salting out method in which a salt containing an onium ion represented by is added and precipitated is mentioned as a method for directly exchanging ions. The method of once converting the salt of an alkali metal such as sodium into the free acid is not limited to the method of treating with an ion exchange resin, but a strong acid is added to the anionic compound or a solution thereof, and the residue is subjected to solvent extraction to obtain the remaining one. The method of filtering and separating is mentioned. When the anionic compound is obtained in a type other than the alkali metal, it may be used as it is. In addition, at least a part of the ions is expressed by the general formula (1) by the method described above,
It is also possible to use in place of the onium ions represented by (3) and (4). When the anionic compound is obtained in the form of a free acid, at least a part of the anionic compound of the free acid or a solution thereof is an ion other than alkali metal,
The ink of the present invention can also be obtained by adding onium ions preferably represented by the general formulas (1), (3) and (4).

Specifically, there are the following methods for adding onium ions to the ink composition. (I) Method of adding as a pH adjuster: Onium ions can be added to the ink composition by adding as onium hydroxide, onium carbonate or the like as a pH adjuster. That is, onium hydroxide, onium carbonate, and the like have an acid-base dissociation constant approximately equal to that of sodium hydroxide, sodium carbonate, etc., and conventionally, pH of the ink is adjusted using sodium hydroxide, sodium carbonate, etc. It can be done with onium as before.

(Ii) Method for adding as counter ion of dye: The following method is available for adding as counter ion of dye having an acidic group such as --SO ₃ H, --COOH, --OH.

(A) Acid precipitation method It can be used when the dye precipitates when the pH value of the solution is lowered. Dye [DM], which is a salt of a cation other than onium (generally Na ⁺ ), is dissolved in a solvent, and an acid such as hydrochloric acid, sulfuric acid, acetic acid or nitric acid is added to precipitate a free acid type dye. D ⁻ M ⁺ + H + X ⁻ → DH ↓ + M ⁺ X ⁻ (D is a dye ion, M is a cation such as Na, NH ₄ , K, X ⁻ is Cl ⁻ , NO ^{3 −} , SO ₂ ⁴⁻ , CH ₃ COO ^-. it is an anion such as a) precipitate filtration, washed, M ⁺ X as an impurity ^- excluding. The dye thus obtained is dissolved in onium hydroxide and used in the ink. DH + _{[R 1 R 2 R 3 R 4} P ] + OH ^- → D ^- [R ₁ R ₂ R
₃ R ₄ P] ⁺ + H ₂ O

(B) Salting-out method The dye is dissolved in water, a water-ethanol mixed solvent, a water-methanol mixed solvent, a water-acetone mixed solvent, and an onium salt such as onium chloride, onium acetate or onium sulfate is added. And the dye is precipitated as an onium salt. D ^- M ⁺ + [R ₁ R ₂ R ₃ R ₄ P] + X ^- → D [R ₁ R ₂ R ₃ R
₄ P] ↓ + M ⁺ X ^{− The} obtained precipitate was filtered and washed with the above-mentioned solvent, etc., and M ⁺ X ⁻
except for. This dye can be used as it is in ink.

(C) Ion exchange method Using a resin or membrane having a cation exchange ability, the dye solution is passed through the resin or membrane to directly form an onium salt, or once released as in the acid precipitation method of (a). After acidification, onium hydroxide gives the onium salt of the dye. (A) The ion of the ion exchange group is converted to an onium type, and the dye solution is passed through. R ^- _{[R 1 R 2 R 3 R 4} P ] ^{+ + D - M + → R} - M + + D
^- [R ₁ R ₂ R ₃ R ₄ P] ⁺ (R ⁻ is an ion exchange group of the ion exchange resin or membrane) (b) The ion exchange group is made into H ⁺ type and the dye solution is passed through. In this case, it is particularly suitable for ion exchange of acid dyes having high solubility of free acid type dyes. R ^- H ⁺ + D ^- M ⁺ → D ^- H ⁺ + R ^- M ⁺

(D) Onium salt addition method in the synthesis stage An onium salt is used as a material for synthesizing a dye. For example, when the acidic compound in the raw material is dissolved and added, it is a method of using onium hydroxide to dissolve what was conventionally dissolved using NaOH. N used for diazotization
[R ₁ R ₂ R ₃ R ₄ P] + NO ₂ is used instead of aNO ₂ . Conventionally, NaOH and Na ₂ CO ₃ have been added to the reaction solution for carrying out the alkali coupling, but a method of adding an onium salt instead of this, and the like can be mentioned.

[0071] (e) extraction method D ^- M ⁺ and D ^- _{[R 1 R 2 R 3 R 4} P ] ⁺ or D ^- H ⁺ D obtained by utilizing the difference in solubility for a particular solvent ^- [R ₁ R ₂ R ₃
R ₄ P] ⁺ is used in the ink. For example, D ^-
After dissolving the M ⁺ dye, the onium salt was added, and the solvent in the solution was evaporated to dryness to obtain a mixture of the onium salt of the dye and the M ⁺ salt, and Soxhlet extraction was performed with an organic solvent such as methanol. A method of obtaining an onium salt of a dye having a high solubility in methanol.

(Iii) Method of adding additives other than dyes to ink as counter ions: (a) Electrical conductivity modifier ... Conventional NaCl, LiCl, N
Although a ₂ SO ₄ , NaNO _{3 and the} like are used, an onium salt can be used in place of them. (B) Preservatives: sodium dehydroacetate, sodium benzoate,
2-Pyridinethiol oxide sodium salt, 1,
Although 2-benzisothiazalin-3-one sodium salt and the like are used, an onium salt is used instead of these sodium salts. (C) Surfactant: Onium is used instead of sodium as an anionic surfactant such as dodecylbenzenesulphonic acid / sodium salt. (D) Chelating agent: An onium salt is used instead of the EDTA trisodium salt.

Add onium ion to ink composition
Contains onium hydroxide or carbonic acid as a pH adjuster.
Added as onium or sulfonic acid, calcium
As a counter ion for dyes containing acidic groups such as boric acid
Most preferably, it is added. Used as a pH adjuster
Also, as a counter ion for ink materials such as other dyes
Most of the onium ions dissociate in the ink even when used
Then [R₁R₂R₃R_FourP] ⁺To be present as
In general, the cations in ink are dyes
Most exist as counter ions of. I
Na other than onium contained in the ink⁺, K⁺, NH_Four ⁺etc
The effect of the present invention is greater when the number of ions is smaller as much as possible.
Therefore, use one of the above or other methods depending on the purpose.
Change the counter ion (cation) of the dye to onium
It is preferable to use it.

When the anionic compound is available in the form of free acid as described above, it is not necessary to replace the compound of free acid type with a salt other than the alkali metal at the time of ink preparation, and the amount is 30 with respect to the equivalent amount of the anionic compound. % Or more, more preferably 5
By adding 0% or more of the onium ion represented by the general formula (1) and adjusting the pH value of the ink to 6.5 to 11.5, the anionic compound having the above counter cation is contained in the ink. In particular, the work required until the ink is manufactured is simplified, the obtained ink can be made inexpensive, and the elution of glass, silicon, silicon oxide, etc. can be prevented very easily, which is preferable.

The counter ion has the general formula (1),
In the case of the onium ion represented by (3) or (4), it preferably has a substituted or substituted alkyl group and the number of carbon atoms in one molecular ion is 4 to 12. When the carbon number is more than 12, solubility in a solvent such as water decreases, clogging occurs during printing pauses or continuous printing, and ink tends to separate and precipitate during storage. The side effects are more likely to occur.

The counter ion of the onium salt represented by the general formula (1), (3) or (4): X ⁻ is an inorganic substance such as a halogen ion, a nitrate ion, a nitrite ion, an acetate ion, a phosphate ion or a sulfate ion. Any type of anion such as organic anions and organic anions derived from organic acids such as formic acid, acetic acid, propionic acid, valeric acid, valeric acid, glycolic acid, gluconic acid, lactic acid, etc. can be used. Is preferably dissociated into, therefore, halogen ions, nitrate ions,
A monovalent anion selected from nitrite ion and acetate ion is preferable, and hydroxyl ion is particularly preferable.

As shown in the following reaction formula, the sulfonium salt can be synthesized by reacting a sulfur compound with an alkyl halide compound while heating in a solvent to synthesize a sulfonium salt. It can be synthesized by an exchange reaction. For example, when dimethyl sulfide and chlorobenzene are reacted in acetonitrile,
The No. 50 can be synthesized and then salt-exchanged with sodium hydroxide to give a sulfonium salt of the hydroxyl ion. The phosphonium salt and the arsonium salt can be synthesized by using a phosphorus compound or an arsenic compound instead of the sulfur compound in the following reaction formula.

[Chemical 9] (X ⁻ is the same as above, Y ⁻ is the counter ion after salt exchange from X ⁻ .)

Further, it is expected that as X goes to the left, the influence of the electron-withdrawing group is higher, the cationicity is stronger, the adhesion to the silicon substrate is increased, and the corrosion prevention effect is increased.

In addition to these onium ions, ordinary cationic resins such as polyallylamine and polyethyleneimine exhibit similar effects when added at about 1%. Further, acetylene-based surfactants such as Olfine B, P and Surfynol 61 having a triple-bonded cylindrical electron cloud (pi-electron) and an active hydrogen atom of an adjacent OH group may cause orientation or complex formation on the glass or silicon surface. It is easily generated and exhibits the same effect as onium ions. Further, cationic dyes, cationic carbon blacks, cationic pigments and boron compounds, which are cationic coloring materials, are also oriented on the surface of glass or silicon and exhibit the same effect as onium ions.

Specific examples of the cationic compound include dicyandiamide / formalin polycondensate, dicyandiamide / diethylenetriamine polycondensate, epichlorohydrin / dimethylamine addition polymer, dimethyldiallylammonium chloride / SO2 copolymer, dimethyldiallyl. Ammonium chloride polymer, polymer of allylamine salt, quaternary salt of dialkylaminoethyl (meth) acrylate, polyallylamine, cationic epoxy resin, polyethyleneimine, polyacrylamide, poly (meth) acrylic acid ester, polyvinylformamide, amino Acetalized polyvinyl alcohol,
Examples thereof include polyvinyl pyridine, polyvinyl benzyl onium, and cationic emulsion.

Commercially available compounds can be used as these cationic compounds. Specifically, Sunstat E-81 is used.
8, Sunfix 70, Sunfix 555C, Sunfix LC-55, Sunhooks PAC-700
Conch, Sanyo Elion A-3, Sunfix 41
4, Sunfix 555, Sunfix PRO-1
00, Sunfix 555US, Cellopol YM-5
00 (above, Sanyo Chemical Industry Co., Ltd.), # 675, # FR-
2P, # 1001 (above, Sumitomo Chemical Co., Ltd.), LUP
Examples include ASOL SC61B (manufactured by BASF). In addition, ZP-700 (vinyl formamide type), M
P-184 (Polyacrylic ester type), MP-17
3H (polymethacrylic acid ester type), MP-180
(Polymethacrylic acid ester type), MX-0210 (Polymethacrylic acid ester type), MX-8130 (Polyacrylic acid ester type), E-395 (Polyacrylic acid ester type), E-305 (Polyacrylic acid ester type) ), Q-105H (dicyandiamide type), Neo-
600 (polyacrylamide type) (above, manufactured by Hymo Co., Ltd.), Super Flock 2490 (polyacrylate type), Super Flock 3180, 3380, 358.
0, 3880, 3390, 3590, 3500, SD2
081 (Polyacrylamide), Acofloc C498
T, C498Y (polyacrylic ester type), Super Flock 1500, 1600, Acofloc C48
1, C483, C485, C488, C480 (polymethacrylic acid ester), (above, Mitsui Cytec Co., Ltd.), PAS-A-1, PAS-A-5, PAS-A-.
120L, PAS-A-120S, PSA-J-81,
PAS-880, PAS-92 (diallyldimethylammonium salt-based copolymer), PAS-H-5L, PAS-
H-10L, PAS-M-1 (diallyldimethylammonium salt-based polymer) (above, Nitto Boseki Co., Ltd.), PAA-
HCl-3L, PAA-HCl-10L (polyallylamine hydrochloride), PAA-10C (polyallylamine)
(Nitto Boseki Co., Ltd.) Q-101 (polyamine type),
Q-311 (polyamine type), Q-501 (polyamine type) (above, manufactured by Hymo Co., Ltd.), Acofloc C567, C
573, C577, C581 (polyamine type) (above,
Mitsui Cytec Co., Ltd.) and the like.

Examples of the cationic emulsion include Akrit UW319-SX, Akrit RKW-460, Akrit RKW-400SX, Akrit RKW-450.
SX, ACRYT RKW-450 (above, Taisei Kako Co., Ltd.), etc.

These cationic resins and cationic emulsions may be used alone or in combination of two or more.

Further, specifically, as a kind of the acetylene compound, Surfynol 104 manufactured by Nisshin Chemical Industry Co., Ltd.
E, Surfynol 104H, Surfynol 104
A, Surfynol 104BC, Surfynol 104
PA, Surfynol 104S, Surfynol 42
0, Surfynol 440, Surfynol 465, Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 504, Surfinol DF110D, Surfinol DF110L, Surfinol DF37, Surfinol DF58, Surfinol DF75, Surfinol DF210, Surfynol CT111, Surfynol CT121, Surfynol CT131, Surfynol CT151, Surfynol TG, Surfynol GA, Surfynol 6
1, olphin B, olphin P, olphin Y, olphin A, olfin STG, olphin SPC, olphin E1004, olphin E1010, olphin AK-02 and the like.

When the water-based ink composition of the present invention contains a coloring material with a resin or contains colored resin fine particles colored with the coloring material, the elution of glass or silicon can be reduced. The reason for this is that, in the case of impurities in the coloring material, particularly carbon black, it is considered that the acidic component contained in the carbon black dissolves glass and silicon. It is considered that the action of can be reduced. Specifically, micro-encapsulated carbon black and micro-encapsulated color pigment manufactured by Dainippon Ink and Chemicals Inc., micro-encapsulated carbon black manufactured by Toyo Ink Co., resin fine particles manufactured by Toyobo Co., Ltd., dyes manufactured by Kao Corporation, and There are pigment emulsion inks and the like.

Specific examples of the boron compound preferably contained in the aqueous ink composition include triisopropyl borate, triethyloxonium tetrafluoroborate, triethyl borate, tributyl borate and tri-tert-butyl borate. , Tori-iso-
Examples include propyl borate and trimethyl borate. Examples of the surfactant include boron surfactant Emulbon (manufactured by Toho Chemical Industry Co., Ltd.) and diglycerin borate (manufactured by Boron International Co., Ltd.) (Compound No. 77, No. 77 of the following formulas, respectively).
78) and the like. These semipolar boron compounds have an intramolecular plus (+) in the organic boron compound.
And a compound having a minus (-) polarity. An organoboron compound having a B—O bond usually forms a planar bond with a bond angle of 120 degrees because boron has a coordination number of 3, but in the above semipolar boron compound, an electron-donating group is attracted to the boron bond. It has a tetrahedral structure. The surface of the glass or silicon substrate has a negative (-) charge, and the boron compound forms a negative (-) repulsive layer against this.
It is thought to prevent the elution of glass and silicon.

[0087]

[Chemical 10]

[Chemical 11]

Further, beryllium ion (Be ²⁺ ), aluminum ion (Al ³⁺ ), zinc ion (Zn ²⁺ ), titanium ion (Ti ⁴⁺ ), zirconium ion (Zr) which are preferably contained in the aqueous ink composition. Examples of ⁴⁺ ) and silicate ions (Si ²⁺ ) include the following, but the present invention is not limited to these and various other effective ones can be widely used.

Beryllium Ion: Beryllium oxide, beryllium hydroxide, beryllium sulfate tetrahydrate, etc.

Regarding aluminum ion: Aluminum acetyl acetate, aluminum isopropylate, aluminum isopropyloxide, aluminum ethylate, aluminum ethoxide, aluminum triisopropoxide, aluminum triethoxide, aluminum tri-n-butoxide, aluminum tri-se.
c-butoxide, aluminum tri-tert-butoxide, aluminum trimethoxide, aluminum n-
Butyrate, aluminum sec-butyrate, aluminum-n-butoxide, aluminum-sec-butoxide, aluminum-tert-butoxide, aluminum-iso-propylate, aluminum-iso.
-Propoxide, aluminum methylate, aluminum ethoxide and the like.

Regarding zinc ion: zinc chloride, zinc ammonium chloride, zinc chloride diethyl ether complex, zinc ammonium chloride, zinc oleate, zinc formate dihydrate,
Zinc citrate, zinc acetate dihydrate, zinc salicylate trihydrate, zinc oxalate dihydrate, zinc tartrate, zinc nitrate hexahydrate, zinc trifluoromethanesulfonate, etc.

Regarding titanium ion: cyclopentadiethyltitanium trichloride, dicyclopentadiethyltitanium, titanium isopropylate, titanium isopropoxide, titanium ethylate, titanium tetraisopropoxide, titanium tetraethoxide,
Titanium tetra-n-butoxide, titanium tetrapropoxide, titanium n-butyrate, titanium n-butoxide, titanium iso-propylate, titanium iso-propoxide and the like.

Regarding zirconium ion: zirconium acetyl acetate, zirconium isopropoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium propylate, zirconium iso-propylate, zirconium iso-propoxide and the like.

Regarding silicide ions: Tetramethylammonium silicide, ethyl silicide, tetraethylorthosilicide, tetraethylsilicide, ammonium hexafluorosilicide, etc.

PH of the ink containing these additives
Is preferably from 7 to 10, and if it is within this range, the glass or silicon substrate will not be eluted. For elution of the glass or silicon substrate, the lower the pH, the more preferable, 7-9 is more preferable, and 7-8 is most preferable.

As the solvent of the ink recording liquid of the present invention, water is often used as a main component, but in order to make the ink have desired physical properties, to prevent the ink from drying, and to stabilize the dissolution of the ink. A water-soluble organic solvent can be used for the purpose of improving

That is, as the water-soluble organic solvent, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5 pentanediol, 1,6 hexanediol, glycerin, 1,2,6- Polyhydric alcohols such as xanthotriol, 1,2,4-butanetriol, 1,2,3-butanetriol and petriol;
Polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, Polyhydric alcohol aryl ethers such as ethylene glycol monobenzyl ether, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2
-Pyrrolidone, 1,3-dimethylimidazolidinone, ε
-Nitrogen-containing heterocyclic compounds such as caprolactam, amides such as formamide, N-methylformamide and N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine and triethylamine ,
Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, γ-butyrolactone and the like can be used. These solvents may be used alone or in combination with water together with water.

Of these, particularly preferred are diethylene glycol, thiodiethanol, polyethylene glycol 200 to 600, triethylene glycol, glycerin, 1,2,6-hexanetriol, 1,2,4-.
Butanetriol, petriol, 1,5-pentanediol, N-methyl-2-pyrrolidone, N-hydroxyethylpyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, and drying of the ink by using these It is possible to obtain excellent effects in preventing clogging caused by the above, that is, in ejection characteristic failure due to water evaporation, and improving the dissolution stability of the ink of the present invention.

As the coloring material used in the present invention, the content of the alkali metal in the ink shown in the present invention (about 1) may be used as it is or by reducing the alkali metal by the method described above.
000 ppm) can be used.

The water-soluble dye is a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye, and an edible dye in the color index, and those having excellent water resistance and light resistance are preferably used.

Specific examples of these dyes include acid dyes and food dyes such as C.I. I. Acid Yellow 17,23,42,44,
79, 142 C.I. I. Acid Red 1,8,13,14,18,
26, 27, 35, 37, 42, 52, 82, 87, 8
9, 92, 97, 106, 111, 114, 115, 1
34, 186, 249, 254, 289 C.I. I. Acid Blue 9,29,45,92,24
9 C. I. Acid Black 1, 2, 7, 24, 26,
94 C.I. I. Food Yellow 3,4 C.I. I. Hood Red 7, 9, 14 C.I. I. Hood black 1,2

As the direct dye, C.I. I. Direct Yellow 1, 12, 24, 26,
33, 44, 50, 86, 120, 132, 142, 1
44 C.I. I. Direct Red 1, 4, 9, 13, 17,
20, 28, 31, 39, 80, 81, 83, 89, 2
25,227 C.I. I. Direct Orange 26, 29, 62, 10
2 C. I. Direct Blue 1, 2, 6, 15, 2
2, 25, 71, 76, 79, 86, 87, 90, 9
8, 163, 165, 199, 202 C.I. I. Direct Black 19,22,32,3
8, 51, 56, 71, 74, 75, 77, 154, 1
68,171

As the basic dye, C.I. I. Basic Yellow 1,2,11,13,1
4,15,19,21,23,24,25,28,2
9, 32, 36, 40, 41, 45, 49, 51, 5
3, 63, 64, 65, 67, 70, 73, 77, 8
7,91 C.I. I. Basic Red 2,12,13,14,1
5,18,22,23,24,27,29,35,3
6,38,39,46,49,51,52,54,5
9,68,69,70,73,78,82,102,1
04, 109, 112 C.I. I. Basic Blue 1,3,5,7,9,2
1, 22, 26, 35, 41, 45, 47, 54, 6
2,65,66,67,69,75,77,78,8
9, 92, 93, 105, 117, 120, 122, 1
24, 129, 137, 141, 147, 155 C.I. I. Basic Black 2,8

As the reactive dye, C.I. I. Reactive Black 3,4,7,11,1
2,17 C.I. I. Reactive Yellow 1, 5, 11, 13,
14, 20, 21, 22, 25, 40, 47, 51, 5
5,65,67 C.I. I. Reactive Red 1,14,17,25,
26, 32, 37, 44, 46, 55, 60, 66, 7
4, 79, 96, 97 C.I. I. Reactive blue 1,2,7,14,1
5,23,32,35,38,41,63,80,95
Etc. can be used. Particularly, acid dyes and direct dyes can be preferably used.

Of course, a newly developed dye for ink jet can also be used. For example, Avicia Projet Fast B1ack2, Projet Fast Magenta2, Proj
Examples include et Fast Yel1ow2 and Projet Fast Cyan2 (registered product name).

As the pigments, inorganic pigments such as titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red,
In addition to chrome yellow, contact method, furnace method,
Carbon black produced by a known method such as a thermal method can be used. The organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofuraron pigments), dye chelates (for example, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used. .

Of these pigments, those having a good affinity for the solvent are preferably used. The addition amount of the pigment as the colorant in the ink composition is preferably about 0.5 to 25% by weight, more preferably about 2 to 15% by weight.

Specific examples of the pigments preferably used in the invention include furnace black for black, and furnace black,
Lamp black, acetylene black, channel black and other carbon blacks (CI Pigment Black 7), copper, iron (CI Pigment Black 11), titanium oxide and other metals, and aniline black (CI). Pigment Black 1) and other organic pigments. Further, for color, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 3
4, 35, 37, 42 (yellow iron oxide), 53, 55, 8
1, 83, 95, 97, 98, 100, 101, 10
4, 408, 109, 110, 117, 120, 13
8, 150, 153, C.I. I. Pigment Orange 5,
13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31,
38, 48: 1, 48: 2 (Permanent Red 2B
(Ca)), 48: 3, 48: 4, 49: 1, 52:
2,53: 1, 57: 1 (Brilliant Carmine 6
B), 60: 1, 63: 1, 63: 2, 64: 1, 8
1, 83, 88, 101 (Bengara), 104, 10
5, 106, 108 (Cadmium Red), 112, 1
14, 122 (quinacridone magenta), 123, 14
6, 149, 166, 168, 170, 172, 17
7, 178, 179, 185, 190, 193, 20
9, 219, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 3
8, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 6
3, C.I. I. Pigment Green 1, 4, 7, 8, 1
0, 17, 18, 36, etc.

In addition, a surface of a pigment (for example, carbon) is treated with a resin or the like to make it dispersible in water, or a functional group such as a sulfonic group or a carboxyl group is added to the surface of a pigment (for example, carbon) to add water. It is possible to use a processed pigment that can be dispersed in Alternatively, the pigment may be contained in microcapsules so that the pigment can be dispersed in water.

According to a preferred embodiment of the present invention, the pigment in the ink preferably has an average particle size of 50 nm to 200 nm. The average particle diameter as used herein refers to a value of 50% of cumulative volume. Volume cumulative percentage 50%
To measure the value of, for example, irradiate the particles in the ink that undergo Brownian motion with laser light, and calculate the change in the frequency (light frequency) of the light (backscattered light) returning from the particles. A method called a dynamic light scattering method (Doppler scattered light analysis) for determining the particle size can be used.

As the pigment dispersant, any pigment dispersant can be used as it is or as long as the content of the alkali metal in the ink shown in the present invention is satisfied by reducing the alkali metal by the method described above.

The pigment is preferably added to the recording liquid as a pigment dispersion obtained by dispersing it in an aqueous medium with a dispersant. As a preferable dispersant, a known dispersant used for preparing a conventionally known pigment dispersion liquid can be used.

Examples of the polymer dispersant include the following. As a hydrophilic polymer, natural gum arabic, traggan gum, guar gum, karaya gum, roasted bean gum, arabinogalactolactone, pectin, quince seed starch and other plant macromolecules, alginic acid, carrageenan, seaweed macromolecules such as agar, Gelatin, casein, albumin, animal-based polymers such as collagen, xanthene gum, microbial-based polymers such as dextran, in semi-synthetic systems methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, fibrin-based polymers such as carboxymethyl cellulose, Starch-based polymers such as sodium starch glycolate and starch phosphate sodium, seaweed-based polymers such as sodium alginate and propylene glycol alginate, and polyacetals in pure synthetic systems. Acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer Coal, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid Copolymer-alkyl acrylate copolymer,
Styrene-maleic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid Examples thereof include copolymers and vinyl acetate-acrylic acid copolymers.

These copolymers have a weight average molecular weight (M
w) is preferably 3,000 to 50,000,
It is more preferably 5,000 to 30,000, and most preferably 7,000 to 15,000. The ratio (Mw / Mn) of Mw and the number average molecular weight (Mw) is preferably 0.8 to 1.3, more preferably 0.9 to 1.1.

The polymer dispersant may be added alone or in combination of two or more kinds as long as the pigment is stably dispersed and the other effects of the present invention are not lost. The ratio of the pigment to the dispersant is preferably in the range of 1: 0.06 to 1: 3, more preferably 1: 0.125 to 1: 3.

It is also possible to use a water-soluble surfactant as a pigment dispersant. In this case, the increase in ink viscosity with respect to the amount used is smaller than that when a polymer dispersant is used, and it is easy to obtain a pigment ink having good ejection characteristics when used in an inkjet recording method.

Specific examples of the water-soluble surfactant used as a pigment dispersant include, for example, anionic surfactants such as alkylaryl sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfonates, and alkyl ether sulfates. , Alkyl sulfosuccinate, alkyl naphthalene sulfonate, alkyl ester sulfate, alkyl benzene sulfonate, alkyl diphenyl ether disulfonate, alkyl aryl ether phosphate, alkyl aryl ether sulfate, alkyl aryl ether ester sulfate, olefin sulfone Acid salt, alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl ether sulfate ester salt, ether carboxylate, sulfosuccinate, α Sulfo fatty acid esters, fatty acid salts,
There are condensates of higher fatty acids and amino acids, naphthenates and the like.

Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts and onium salts. .

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol ester,
Polyoxyethylene fatty acid amide, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester poly There are oxyethylene ether, fatty acid alkanolamide, amine oxide, polyoxyethylene alkylamine, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, alkyl (poly) glycoxide and the like.

Examples of the amphoteric surfactant include imidazoline derivatives such as imidazolinium betaine, dimethylalkyllauryl betaine, alkylglycine and alkyldi (aminoethyl) glycine.

The surfactant as a dispersant may be added singly or in combination of two or more as long as the pigment is stably dispersed and the other effects of the present invention are not lost.

To the ink of the present invention, conventionally known additives can be added in addition to the above colorant and solvent. Any of these may be used as they are or as long as the content of the alkali metal in the ink shown in the present invention is satisfied by reducing the alkali metal by the method described above.

For example, a penetrant can be added for the purpose of adjusting the surface tension of the ink. Examples of such penetrants include 2-ethyl-1,3-hexanediol, 2,
Polyhydric alcohols such as 2,4-trimethyl-1,3-pentanediol, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether , Alkyl and aryl ethers of polyhydric alcohols such as tetraethylene glycol chlorophenyl ether, polyoxyethylene polyoxypropylene block copolymers, fluorine-based surfactants, ethanol,
Lower alcohols such as 2-propanol may be mentioned.

Further, the ejection stability of the recording liquid is improved by adjusting the surface tension of the recording liquid in the ink to improve the permeability of the recording material and the wettability of the recording liquid to the head member of the ink jet printer. A surfactant can be added for the purpose of improving

For example, as the anionic surfactant, alkyl allyl, alkyl phosphate, alkyl sulfate, alkyl sulfonate, alkyl ether sulfate, alkyl sulfosuccinate, alkyl naphthalene sulfonate, alkyl ester sulfate, alkyl benzene sulfone is used. Acid salt, alkyl diphenyl ether disulfonate, alkyl aryl ether phosphate, alkyl aryl ether sulfate, alkyl aryl ether ester sulfate, olefin sulfonate, alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, poly Oxyethylene alkyl ether sulfate ester salt, ether carboxylate, sulfosuccinate, α
-Sulfo fatty acid ester, fatty acid salt, condensate of higher fatty acid and amino acid, naphthenate and the like.

Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts and onium salts. .

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol ester,
Polyoxyethylene fatty acid amide, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester poly There are oxyethylene ether, fatty acid alkanolamide, amine oxide, polyoxyethylene alkylamine, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, alkyl (poly) glycoxide and the like.

Examples of the amphoteric surfactant include imidazoline derivatives such as imidazolinium betaine, dimethylalkyllauryl betaine, alkylglycine and alkyldi (aminoethyl) glycine.

The addition amount of these surfactants in the ink composition is 0.01% by weight to 5.0% by weight, preferably 0.5% by weight to 3% by weight. If it is less than 0.01% by weight, the effect is not obtained, and if it is more than 5.0% by weight, the permeability to the recording medium becomes unnecessarily high, and there is a problem that the image density is lowered or strikethrough occurs. In addition, the said surfactant can be used individually or in mixture of 2 or more types.

As an antiseptic / antifungal agent, sodium benzoate,
There are sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate and the like. Among them, 1,2-dibenzylisothiazoline is used to achieve the content of the alkali metal of the present invention. -3-one (Proxel CRL, Proxel LV, Proxel BDN, manufactured by Abyssia)
It is particularly preferable to use Proxel GXL, Sunpack AP manufactured by San-ai Oil Co., Ltd.

As the pH adjustor, any substance can be used as long as it can adjust the pH to a desired value without adversely affecting the ink to be prepared. Examples thereof include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate. Among them, amines such as diethanolamine and triethanolamine, ammonium hydroxide, quaternary ammonium hydroxide, quaternary onium hydroxide and the like are used to achieve the alkali metal content of the present invention. Particularly preferred.

In addition, a rust preventive agent, a water-soluble ultraviolet absorber, a water-soluble infrared absorber and the like can be added depending on the purpose.

An ink jet recording apparatus having a recording unit having a recording liquid container of the present invention containing a recording liquid and a recording head for ejecting recording liquid droplets will be described with reference to the accompanying drawings. Is only one of the configuration examples and does not limit the present invention.

FIG. 1 is a schematic front view of a mechanical portion of a serial type ink jet recording apparatus equipped with an ink cartridge having a recording liquid storage portion for storing the recording liquid of the present invention.
The mechanism portion of this ink jet recording apparatus has a main support guide rod 3 and a sub-support guide rod 4 which are laterally bridged between the side plates 1 and 2 on both sides in a substantially horizontal positional relationship. The rod 4 supports the carriage unit 5 slidably in the main scanning direction. The carriage unit 5 has yellow (Y) ink,
Four heads 6 for ejecting magenta (M) ink, cyan (C) ink, and black (Bk) ink,
The ejection surface (nozzle surface) 6a is mounted downward, and the four heads 6 of the carriage unit 5 are provided on the upper side of the heads 6 with four ink supply members of each color. Ink cartridges 7y, 7m, 7c,
It has a 7k that can be replaced.

The carriage unit 5 is connected to a timing belt 11 stretched between a drive pulley (drive timing pulley) 9 rotated by a main scanning motor 8 and a driven pulley (idler pulley) 10 for main scanning. By controlling the drive of the motor 8, the carriage 5, that is, the four heads 6 are moved in the main scanning direction.

Subframes 13 and 14 are erected on the bottom plate 12 that connects the side plates 1 and 2.
A conveyance roller 15 for feeding the sheet 16 in the sub-scanning direction orthogonal to the main scanning direction is rotatably held between the sheets 3 and 14. Then, the sub scanning motor 17 is provided on the side of the sub frame 14.
And the rotation of the sub-scanning motor 17 is controlled by the conveyance roller 1
5, the gear 18 fixed to the rotary shaft of the sub-scanning motor 17 and the gear 19 fixed to the shaft of the transport roller 15 are transmitted.
It has and.

Further, a reliability maintaining / restoring mechanism (hereinafter referred to as “subsystem”) 21 for the head 6 is arranged between the side plate 1 and the subframe 12. The subsystem 21 holds four cap means 22 for capping the ejection surface of each head 6 with a holder 23.
3 is swingably held by the link member 24, and the carriage unit 5 comes into contact with the engaging portion 25 provided on the holder 23 by the movement of the carriage unit 5 in the main scanning direction. 23 is lifted up and the ink jet head 6 is moved by the cap means 22.
The ejection surface 6a of the carriage unit 5 is capped.
Is moved to the printing area side, the carriage unit 5
The holder 23 is lifted down in accordance with the movement of, and the cap means 22 is separated from the ejection surface 6a of the inkjet head 6.

The cap means 22 is connected to the suction pump 27 via the suction tube 26, forms an atmosphere opening port, and communicates with the atmosphere via the atmosphere opening tube and the atmosphere opening valve. Further, the suction pump 27 discharges the sucked waste liquid to a waste liquid storage tank (not shown) via a drain tube or the like.

Further, on the side of the holder 23, a wiper blade 28, which is a wiping means made of a fiber member for wiping the ejection surface 6a of the ink jet head 6, a foam member or an elastic member such as rubber, is provided as a blade arm 29.
The blade arm 29 is pivotally supported so that it can be pivoted by the rotation of a cam which is pivoted by a driving means (not shown).

Next, the ink cartridge 7 will be described with reference to FIGS. Here, FIG. 2 is an external perspective view of the ink cartridge before being loaded in the recording apparatus, and FIG.
FIG. 3 is a front sectional view of an ink cartridge. The ink cartridge 7 has a cartridge body 41 as shown in FIG.
An ink absorber 42, which absorbs ink of a desired color, is housed therein. The cartridge body 41 is formed by adhering or welding an upper lid member 44 to the upper opening of a case 43 having a wide opening at the top, and is made of, for example, a resin molded product. The ink absorber 42 is made of a porous material such as a urethane foam body and absorbs ink after being compressed and inserted into the cartridge body 41.

An ink supply port for supplying ink to the recording head 6 is formed at the bottom of the case 43 of the cartridge body 41, and this ink supply port is pressed by a pressing member 45, and inside the pressing member 45 of this ink supply port. A seal ring 46 is fitted on the peripheral surface. Further, the upper lid member 44 is formed with an atmosphere opening port 47. In the cartridge main body 41, the case 43 is compressed and deformed by the pressure applied to the wide side wall at the time of loading the cartridge, handling the cartridge at the time of loading, transporting, or vacuum packaging before loading. A cap member 50 is attached to prevent the ink inside from leaking.

Further, as shown in FIG. 2, the atmosphere opening port 47 is sealed by sticking a film-like sealing member 55 having an oxygen permeability of 100 ml / m ² or more to the upper lid member 44. The sealing member 55 is sized to seal not only the atmosphere opening port 47 but also a plurality of grooves 48 formed around it. In this way, the atmosphere opening 47 has an oxygen permeability of 10
By sealing with a sealing member 55 of 0 ml / m 2 or more, the ink cartridge 7 is packaged in a reduced pressure state using a packaging member such as an aluminum laminated film that does not have air permeability. Even when a gas is dissolved in the ink due to the atmosphere in the space A (see FIG. 3) generated between the ink and the main body 41, the air in the ink is exposed to the outside of the cartridge main body 41 having a high degree of vacuum through the seal member 55. The ink is discharged into the space between the packaging member and the degree of deaeration of the ink is improved.

Further, FIG. 4 shows an example of the structure of a recording unit having a recording liquid accommodating portion for accommodating the recording liquid of the present invention and a head portion for ejecting recording droplets. That is, the recording unit 30 is of a serial type, and includes the inkjet head 6 and the ink tank 4 that stores the recording liquid supplied to the inkjet head 6.
1 and a lid member that seals the inside of the ink tank 41 constitute a main part. A large number of nozzles 32 for ejecting the recording liquid are formed in the inkjet head 6. The recording liquid is guided from an ink tank 41 to a common liquid chamber (not shown) through an ink supply pipe (not shown), and is ejected from a nozzle 32 in response to an electric signal from the recording apparatus main body input from an electrode 31. It This type of recording unit has a structure that is often used for a head of a type that can be manufactured at a low cost, that is, a so-called thermal type or bubble type head that uses thermal energy as a driving power source.

A head portion for ejecting ink droplets will be described with reference to the configuration example shown in FIG. FIG. 5 is a sectional side view of the entire electrostatic head unit. The head of this configuration example has three silicon single crystal substrates 101, 102 (102
a and 102b) and 103 are laminated and joined. The use of a silicon single crystal substrate is suitable for processing when a thin vibration plate (thickness of about several μm) for ejecting ink is produced by etching,
It is also a convenient material when forming a gap of about m with high accuracy by anodic bonding described later. Furthermore, when an electrostatic force is applied to vibrate the diaphragm, it is necessary to apply a voltage to the electrodes to generate an electrostatic force, but since silicon is a semiconductor and can have a low resistance, The electrodes on the diaphragm side can be substituted, and there is an advantage that there is no need to separately provide electrodes on the diaphragm side.

The first substrate 101 in the middle thereof has a recess for forming a liquid chamber 106 having a bottom wall as a vibrating plate 105 and a thin ink inlet for forming a fluid resistance portion 107 provided at the rear of the recess. It has a groove and a recess forming a common ink cavity 108 for supplying ink to the liquid chamber 106.

Next, the lower second substrate 102 joined to the lower surface of the first substrate 101 is a single crystal silicon substrate 102b on which a silicon oxide film 102a is provided. An electrode 121 having substantially the same shape as the diaphragm 105 is formed on the first substrate 102a. The electrode 121 has an (electrode) terminal portion 123, and the electrode 121 and the entire lead portion of the electrode are covered with an insulating film 122 except for the (electrode) terminal portion 123 of the electrode. As the second substrate, one using heat-resistant glass or the like other than silicon is known.

Next, by the upper third substrate 103 bonded to the upper surface of the first substrate 101, the nozzle hole 104, the ink ejection chamber 106, the fluid resistance portion 107 (member for regulating the flow of ink) and the ink cavity 108. Is configured. An ink supply port 131 communicating with the ink cavity 108 is formed in the substrate 103. Ink supply port 1
Reference numeral 31 is connected to an ink cartridge (not shown) via a connection pipe and a tube (not shown). As the third substrate, other than silicon, for example, glass, nickel, plastic, stainless steel, or the like is known.

In the ink jet head of the constitutional example utilizing the electrostatic force constructed as described above, the electrode 121
When a positive pulse voltage is applied from the oscillating circuit 142, the surface of the electrode 121 is charged to a positive potential and the lower surface of the corresponding vibrating plate 105 is charged to a negative potential, and the vibrating plate 105 is charged.
Bends downward due to the electrostatic attraction.

Next, when the application of the pulse voltage to the electrode 121 is turned off, the flexed vibrating plate 105 is restored, so that the pressure in the liquid chamber 106 rapidly rises, and the ink droplet 141 is ejected from the nozzle hole 104. The ink is formed and ink is ejected toward a not-shown image receiving body. And further, the diaphragm 10
When 5 is again bent downward, ink is replenished from the ink cavity 108 into the liquid chamber 106 through the fluid resistance portion 107. As the oscillation circuit 142, the one that turns ON / OFF the pulse voltage as described above, an AC power supply, or the like is used. The recording is performed by controlling the electric pulse to be applied to the electrode 121 of each nozzle hole 104.

The ink of the present invention can suppress the elution of silicon and silicon oxide used in the printer as in the above-mentioned configuration example, and the image due to the change of the ink droplet size and the ejection speed due to the deterioration of the printer design accuracy. It is possible to prevent problems such as deterioration in quality, occurrence of ejection failure, and failure due to decrease in joint strength of the joint portion, and to prevent clogging due to elution of silicon into the ink.

[0151]

EXAMPLES Examples and comparative examples of the present invention will be shown below.
Unless otherwise specified, the addition ratio is% by weight of the active ingredient.
Refers to.

(Sulfonium Salt Synthesis Method) A 1-liter 4-necked flask equipped with a sulfonium salt synthesis stirrer, reflux condenser and thermometer was replaced with nitrogen, and 12.4 g (0.2 Mol) and 200 ml of acetonitrile are mixed and dissolved, and 22.5 g (0.2 mol) of chlorobenzene dissolved in 100 ml of acetonitrile under heating and refluxing conditions while stirring is added to 1 mol.
The mixture was added dropwise over a period of time, and the reaction was continued under heating under reflux for 5 hours with stirring. As a result, white crystals were precipitated.
Then, it was cooled to room temperature, and the precipitated crystal was separated by filtration and dried to obtain phenyldimethylsulfonium chloride 3
0.2 g (yield 86.7%) was obtained. (Reaction formula 1) 8.7 g (0.05 mol) of phenyldimethylsulfonium chloride thus obtained was dissolved in 200 ml of methanol-water (1/1 (volume ratio)) and placed in a flask of the same volume, When 2.0 g (0.05 mol) of sodium hydroxide dissolved in 300 ml of water was added dropwise to the obtained solution while stirring, a precipitate was generated and the solution became cloudy and became a slurry. (Reaction scheme 2) After completion of the dropwise addition, stirring was continued at room temperature for 1 hour, and then the crystals were separated by filtration and then recrystallized from methanol. As a result, 6.5 g of phenyldimethylsulfonium hydroxide (yield 83.
0%) was obtained. Elemental analysis of this phenyldimethylsulfonium hydroxide was performed. The results are shown in Table 7.

(Scheme 1 and 2)

[Chemical 12]

[0154]

[Table 7]

Compound No. shown in Table 8 27 to No. 5
The sulfonium salt of 0 was synthesized in the same manner as above. However, when reacting a gaseous compound at room temperature, it was liquefied by cooling with liquid nitrogen or the like, or pressurized to react in an autoclave.

[0156]

[Table 8]

[0157] (Example 1)     Black dye of the following formula 3% by weight

[Chemical 13] Glycerin 5% by weight Ethylene glycol 20% by weight Polyoxyethylene (3) sodium tridecyl ether acetate (Nikko Chemicals, anionic surfactant) 1.0% by weight Sunpack AP (Sanai Petroleum, fungicide) 0.4 wt% tetrabutylphosphonium hydroxide (Aldrich reagent: corrosion inhibitor) 1.0 wt% ion-exchanged water Residual amount The mixture of the above formulation was continuously stirred at 50 ° C. for 4 hours, and after cooling, the pore size was adjusted to 0. It was filtered with a 1 μm filter. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 814 ppm. The pH value was 9.5.

This ink is composed of a surface of a vibrating plate on which a surface of silicon oxide of 1000 liters is formed by thermal oxidation on the surface of 110, and heat resistant glass # 7740, 100 surface and 110 surface.
Surface, liquid chamber made of silicon on 111 surface, 100 surface and 1
It was filled in an inkjet printer of a system in which a nozzle made up of 11 surfaces and a vibrating plate was deformed and discharged by an electrostatic force made up of fluid resistance, and the following printing test and reliability test were conducted under the following conditions. Driving frequency: 12 KHz Driving voltage: 23 V Nozzle diameter: 30 μm Droplet volume: 30 pl / dot Nozzle number: 48 Nozzle dot density: 600 dpi

Test 1 (T1) Initial printing test Printing was performed on three commercially available copy papers and three bond papers.
The characteristics of the image were examined.

Test 2 (T2) Reliability test (printing test after printing pause, liquid contact) 50 ° C., 60% R with ink filled in the printer
After leaving the printer in the H environment for 1 month, printing was performed to test whether normal printing was possible. Further, the amount of change in thickness of glass and silicon and the amount of change in film thickness of oxide film were measured. The amount of change in the thickness of glass and silicon was analyzed by plasma emission spectroscopy of the ink after contact with the liquid,
It was calculated by converting from the silicon concentration in the ink and the density of each material.

In the initial printing test, a clear image having an image density of 1.3 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. Heat resistant glass # 77 for liquid contact
40 (Brand name: Pyrex # 7740, Cornin, USA
g Glrss Works) has a thickness variation of 0.18 μm, and the silicon thickness variation is about 0.16 μm for 100 faces, 11
The 0-th surface was about 0.06 μm, and the 111-th surface was about 0.04 μm, which was the amount of change in thickness without any problem as a liquid chamber, fluid resistance, or nozzle. Further, the change amount of the thickness of the silicon oxide film on the 110th face was about 3Å, which was a problematic amount change of the diaphragm.

Example 2 In place of the tetrabutylphosphonium hydroxide of Example 1, tributylsulfonium hydroxide (Compound No. 29 corrosion inhibitor) was used.
The test was conducted in the same manner as in Example 1 except that 0% by weight was used.
As a result, in the initial printing test, a clear image having an image density of 1.3 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. Heat resistant glass # 774 for liquid contact
The thickness change of 0 is 0.18 μm, and the thickness change of silicon is about 0.16 μm on 100 side and about 0.06 μ on 110 side.
The m and 111 planes were about 0.04 μm, which was the amount of change in thickness without any problem as a liquid chamber, a fluid resistance, or a nozzle. Further, the change amount of the thickness of the silicon oxide film on the 110th face was about 3Å, which was a problematic amount change of the diaphragm.

[0163] (Example 3)     Cyan dye of the following formula 3% by weight

[Chemical 14] Glycerin 10% by weight Diethylene glycol 10% by weight Surfynol 465 (ethylene oxide additive of acetylene alcohol; nonionic surfactant manufactured by Air Products and Chemicals Inc.) 1.0% by weight diethylene glycol monobutyl ether 3% by weight Proxel CRL (manufactured by Avicia) Antifungal agent 0.4 wt% Tetrabutylphosphonium hydroxide (Aldrich's reagent: corrosion inhibitor) 0.5 wt% Ion-exchanged water Residual amount While stirring the mixture of the above formulation at 50 ° C. for 4 hours. Subsequently, after cooling, filtration was performed with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 9
It was 13 ppm. The pH value was 9.2.

A printing test was carried out on this ink using a printer equipped with the head having the structure shown in FIG. 5, and a reliability test was carried out. The head having the structure shown in FIG. 5 was prepared under the following conditions. The first substrate 101 is a double-sided polished p-type single crystal silicon wafer with a (110) plane orientation, and the second substrate 101 is a double-sided polished p-type single crystal silicon wafer 102b with a thermal oxide film 102a. By subjecting these substrates to anisotropic etching using a mask and an alkaline solution, as shown in FIG.
06, the fluid resistance portion 107, the respective concave portions corresponding to the ink cavities 108, etc. were formed, and further, the electrode 121, the electrode lead portion, the electrode terminal 123, and the insulating film 122 were formed. The thickness of the vibrating plate 105 was 20 μm, and a film of silicon oxide was provided by 1000 Å by thermal oxidation treatment. Further, as shown in FIG. 5, both sides were polished on the upper side of the first substrate 101 (100).
A nozzle hole 104, an ink supply port 131 and the like are formed on an n-type single crystal silicon wafer having a plane orientation by anisotropic dry etching, the third substrate 103 is joined, and an oscillation circuit 142 and the like are connected as shown in the figure. Printing was performed by applying a positive pulse voltage to the electrode terminal 123. Therefore, the surface that comes into contact with ink is the surface of the vibrating plate that has 1000 liters of silicon oxide film on the 110 surface by thermal oxidation, the liquid chamber that has 100 surfaces, the silicon of 110 and 111 surfaces, and the nozzle that has 100 surfaces. Silicon on the anisotropic dry-etched surface, 100 on the fluid resistance part,
It is made of silicon with 110 faces.

The printing conditions of the printer were as follows. Driving frequency: 12 KHz Driving voltage: 23 V Nozzle diameter: 30 μm Droplet volume: 30 pl / dot Nozzle number: 48 Nozzle dot density: 600 dpi

Test 1 (T1) Initial printing test Printing was performed on three commercially available copy papers and three bond papers.
The characteristics of the image were examined.

Test 2 (T2) Printing test after pause of printing, silicone liquid contact property With the above printer filled with ink, 50 ° C., 60% R
After leaving the printer in the H environment for 1 month, printing was performed to test whether normal printing was possible. In addition, the amount of change in thickness of silicon and the amount of change in film thickness of oxide film were measured.

In the initial printing test, a clear image having an image density of 1.3 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. In the case of silicon wettability, the amount of change in thickness of silicon is about 0.15 μm for surface 100, about 0.06 μm for surface 110, and about 0.04 μm for surface 111, which is a problem for the liquid chamber, fluid resistance portion, and nozzle. There was no change in thickness. Further, the change amount of the thickness of the silicon oxide film on the 110th face was about 3Å, which was a problematic amount change of the diaphragm.

Example 4 The same as Example 3 except that 0.5% by weight of tetrabutylarsonium hydroxide (Compound No. 74 corrosion inhibitor) was used in place of the tetrabutylphosphonium hydroxide of Example 3. Was tested.

As a result, in the initial print test, a clear image having an image density of 1.3 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. In the case of wetted silicon, the thickness change of silicon is about 0.15μ for 100 surfaces.
m, 110 surface is about 0.06 μm, 111 surface is about 0.04
The thickness change amount was μm, and there was no problem for the liquid chamber, the fluid resistance portion, and the nozzle. Further, the change amount of the thickness of the silicon oxide film on the 110th face was about 3Å, which was a problematic amount change of the diaphragm.

[0171] (Example 5)     2% by weight of yellow dye of the following formula

[Chemical 15] Glycerin 3% by weight Triethylene glycol 10% by weight

[Chemical 16] Dialkylsulfosuccinate of the above formula (anionic surfactant) 1.0% by weight 2-ethyl-1,3-hexanediol 2% by weight Proxel BND (antifungal agent manufactured by Avicia) 0.4% by weight ion-exchanged water Residual amount While stirring the mixture of the above formulation at 50 ° C., the hydroxide of the phosphonium compound of Chemical formula 1 was 40% with respect to the equivalent amount of the anionic compound in the ink, and the hydroxide of the phosphonium compound of Chemical formula 3 was in the ink. 4 to the equivalent amount of the anionic compound
0% was added. Continue stirring for 4 hours as it is, and after cooling,
It was filtered with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 29 ppm. The pH value was 9.7.

The above ink was tested in the same manner as in Example 1 (using a non-alkali glass substrate in place of the heat-resistant glass # 7740). In the initial print test, the image density was 0.9 on any paper. The above clear image was obtained. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the liquid contact property, the thickness change of the non-alkali glass substrate (OA-2 manufactured by Nippon Electric Glass Co., Ltd.) is 0.19 μm, and the thickness change amount of silicon is about 0.15 μm for 100 faces and about 0.07 μm for 110 faces. , 111
The surface had a thickness of about 0.05 μm, and there was no problem in changing the thickness of the liquid chamber, the fluid resistance portion, and the nozzle. Also, 110
The amount of change in film thickness of the silicon oxide film on the surface was about 3Å, which was a film thickness change that was not a problem for the diaphragm.

(Example 6) In Example 5, the compound N
o. The hydroxide of the phosphonium compound of No. 1 was 40% with respect to the equivalent amount of the anionic compound in the ink. Instead of adding 40% of the hydroxide of the phosphonium compound of 3 to the equivalent amount of the anionic compound in the ink, compound N
o. Example 27 except that the hydroxide of the sulfonium compound of No. 27 was added at 40% to the equivalent amount of the anionic compound in the ink, and the hydroxide of the sulfonium compound of Chemical formula 29 was added at 40% to the equivalent amount of the anionic compound in the ink. The test was conducted in the same manner as in No. 5.

As a result, in the initial print test, a clear image having an image density of 0.9 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the liquid contact property, the thickness change of the non-alkali glass substrate (OA-2 manufactured by Nippon Electric Glass Co., Ltd.) is 0.19 μm, and the thickness change amount of silicon is about 0.15 μm for 100 faces and about 0.07 μm for 110 faces. , 111 surface was about 0.05 μm, and the amount of change in thickness was satisfactory for the liquid chamber, the fluid resistance portion, and the nozzle. Further, the change amount of the thickness of the silicon oxide film on the 110th face was about 3Å, which was a problematic amount change of the diaphragm.

[0175] (Example 7)     Magenta dye of the formula below 2.5% by weight

[Chemical 17] Diethylene glycol 20% by weight Polyoxyethylene (6) sodium tridecyl ether acetate (manufactured by Nikko Chemicals, anionic surfactant) 0.3% by weight 2-pyrrolidone 2% by weight Proxel GXL (manufactured by Abyssia) 0 0.4 wt% Surfynol 61 (3,5-dimethyl-1-hexyn-3-ol) 0.9 wt% ion-exchanged water Residual amount The mixture of the above formulation was continuously stirred at 50 ° C. for 4 hours,
After cooling, filtration was performed with a filter having a pore size of 0.1 μm.
When this ink was analyzed by plasma emission spectroscopic analysis, the content of alkali metal in the ink was 460 ppm. The pH value was 10.1.

When the above ink was tested in the same manner as in Example 4, a clear image having an image density of 1.1 or more was obtained on any paper in the initial printing test. Normal printing was possible even after printing was stopped without using any recovery means. In the case of silicon wettability, the amount of change in thickness of silicon is about 0.32 μm for surface 100, about 0.10 μm for surface 110, and about 0.08 μm for surface 111, which is a problem for the liquid chamber, fluid resistance portion, and nozzle. There was no change in thickness. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

(Example 8) Surfynol 6 of Example 7
The test was performed in the same manner as in Example 7 except that beryllium hydroxide (corrosion inhibitor) was used in an amount of 0.9% by weight instead of 1 (3,5-dimethyl-1-hexyn-3-ol). As a result, in the initial printing test, a clear image having an image density of 1.1 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. In the case of silicon wettability, the amount of change in thickness of silicon is about 0.32 μm for surface 100, about 0.10 μm for surface 110, and about 0.08 μm for surface 111, which is a problem for the liquid chamber, fluid resistance portion, and nozzle. There was no change in thickness. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

Example 9 Carboxyl Group Bonding Carbon Black Dispersion (Average Particle Size 128 nm) 5% by Weight Glycerin 10% by Weight Diethylene Glycol 10% by Weight Polyoxyethylene (3) sodium tridecyl ether acetate (manufactured by Nikko Chemicals, Inc. Anionic surfactant) 1.0% by weight 2-pyrrolidone 2% by weight 2-ethyl-1,3-hexanediol 2% by weight Sunpack AP (manufactured by Sanai Petroleum Co., Ltd., antifungal agent) 0.4% by weight Olphine B ( 3-Methyl-1-butyne-3-all manufactured by Nisshin Chemical Industry Co., Ltd .: Corrosion inhibitor) 0.5 wt% ion-exchanged water Residual amount While stirring the mixture of the above formulation at 50 ° C., stirring for 4 hours is performed. Subsequently, after cooling, filtration was performed with a filter having a pore size of 0.8 μm. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 1
It was 020 ppm. The pH value was 8.3.

When the above ink was tested in the same manner as in Example 4, a clear image having an image density of 1.4 or more was obtained on any paper in the initial printing test. Normal printing was possible even after printing was stopped without using any recovery means. In the wettability with silicon, the amount of change in thickness of silicon is about 0.20 μm for surface 100, about 0.07 μm for surface 110, and about 0.04 μm for surface 111, which is a problem for the liquid chamber, fluid resistance portion, and nozzle. There was no change in thickness. Further, the change amount of the thickness of the silicon oxide film on the 110th face was about 3Å, which was a problematic amount change of the diaphragm.

(Example 10) Olfine B of Example 9
(Instead of 3-methyl-1-butyn-3-ol, 0.5% by weight of aluminum ethylate (corrosion inhibitor) was added in an amount of 0.
The test was conducted in the same manner as in Example 9 except that 5% by weight was used. As a result, in the initial printing test, a clear image having an image density of 1.4 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. With respect to silicon wettability, the amount of change in thickness of silicon is about 0.20 μm for 100 face, about 0.07 μm for 110 face, and about 0.04 μm for 111 face,
The amount of change in the thickness was such that there was no problem for the liquid chamber, the fluid resistance portion, and the nozzle. Further, the change amount of the thickness of the silicon oxide film on the 110th face was about 3Å, which was a problematic amount change of the diaphragm.

Example 11 A cationic carbon black dispersion (manufactured by Cabot Specialty Chemicals, Inc.) was added to the black dye of Example 1 at a solid content of 5% to remove tetrabutylphosphonium hydroxide. Using the ink having the following formulation, the mixture was continuously stirred at 50 ° C. for 4 hours in the same manner as in Example 1, and after cooling,
It was filtered with a filter having a pore size of 0.8 μm. Dispersion of cationic carbon black 5% by weight Glycerin 5% by weight Ethylene glycol 20% by weight Olfin E1010 1.0% by weight Sunpack AP (san-ai petroleum, fungicide) 0.4% by weight Ion-exchanged water Remaining amount of this ink Was analyzed by plasma emission spectroscopy, the content of the alkali metal in the ink was 932 ppm. The pH value was 9.8.

The above ink was tested in the same manner as in Example 1 (using a non-alkali glass substrate in place of the heat-resistant glass # 7740). In the initial printing test, the image density was 1.2 on any paper. The above clear image was obtained. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the liquid contact property, the thickness change of the non-alkali glass substrate (OA-10 made by Nippon Electric Glass Co., Ltd.) is 0.31 μm, and the thickness change amount of silicon is about 0.18 μm for 100 faces and about 0.08 μm for 110 faces. 111
The surface had a thickness of about 0.05 μm, and there was no problem in changing the thickness of the liquid chamber, the fluid resistance portion, and the nozzle. Also, 110
The amount of change in film thickness of the silicon oxide film on the surface was about 4Å, which was a problem of film thickness change as a diaphragm.

Example 12 15% of the following dispersion was added as a cyan pigment instead of the black dye of Example 1,
Example 1 except that the following compounds were used as corrosion inhibitors
Stir the mixture of the same formulation at 50 ° C. for 4 hours,
After cooling, it was filtered with a filter having a pore size of 0.8 μm.

<Dispersion> C.I. I. Pigment Blue 15: 3 (phthalocyanine blue) (average particle size 123 nm) 20% by weight Dispersant (styrene-acrylate-methacrylic acid diethanolamine salt copolymer) 4.5% by weight Ethylene glycol 30% by weight Water balance <corrosion inhibitor > Tributylborate (reagent manufactured by Kanto Chemical Co., Inc.) 0.1% by weight When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 932 ppm. The pH value was 9.8.

When the above ink was tested in the same manner as in Example 1, a clear image having an image density of 1.3 or more was obtained on any paper in the initial printing test. Even after the printing was stopped, normal printing was possible without using any recovery means. Heat resistant glass # 774 for liquid contact
The thickness change of 0 is 0.15 μm, and the thickness change of silicon is about 0.18 μm on 100 side and about 0.03 μ on 110 side.
The m and 111 planes were about 0.05 μm, which was the amount of change in thickness that does not pose a problem for the liquid chamber, the fluid resistance, and the nozzle. Further, the film thickness change amount of the silicon oxide film on the 110 surface was about 3Å, which was a film thickness change amount that was not a problem for the diaphragm.

Example 13 The same formulation as in Example 2 except that 20% by weight of the following dispersion was added as a yellow pigment instead of the cyan dye of Example 3 and the following cationic compound was used as a corrosion inhibitor. The mixture was stirred at 50 ° C. for 4 hours, cooled, and filtered with a filter having a pore size of 0.8 μm. <Dispersion> C.I. I. Pigment Yellow 138 (average particle size 96 nm) 25% by weight Dispersant (formalin condensate of naphthalene sulfonate) 8% by weight Ammonia water 1.3% by weight Ethylene glycol 25% by weight Water balance <corrosion inhibitor> Cationic polymer ( 1.0 wt% This ink was analyzed by plasma emission spectroscopy, and the content of alkali metal in the ink was 886 ppm. The pH value was 9.1.

When the above ink was tested in the same manner as in Example 1, a clear image with an image density of 0.9 or more was obtained on any paper in the initial printing test. Normal printing was possible even after printing was stopped without using any recovery means. With respect to silicon wettability, the amount of change in thickness of silicon is about 0.29 μm for surface 100, about 0.13 μm for surface 110, and about 0.10 μm for surface 111, which is a problem for the liquid chamber, fluid resistance portion, and nozzle. There was no change in thickness. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

Example 14 1.0% by weight of zinc chloride (corrosion inhibitor) was used in place of the cationic polymer of Example 13.
The test was performed in the same manner as in Example 13 except that the test was used. As a result, in the initial printing test, a clear image having an image density of 0.9 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. With respect to silicon wettability, the amount of change in thickness of silicon is about 0.29 μm for surface 100, about 0.13 μm for surface 110, and about 0.10 μm for surface 111, which is a problem for the liquid chamber, fluid resistance portion, and nozzle. There was no change in thickness. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

Example 15 Similar to Example 1, using the following coloring material as a cationic yellow dye instead of the black dye of Example 1 and using an ink having the following formulation except for tetrabutylphosphonium hydroxide: Then, the mixture was continuously stirred at 50 ° C. for 4 hours, and after cooling, the pore size was 0.3 μm.
It was filtered with the m filter.

Cationic yellow dye Kayacryl ED (manufactured by Nippon Kayaku Co., Ltd.) 3% by weight Glycerin 5% by weight Ethylene glycol 20% by weight 2-Ethyl-1,3-hexanediol 2.0% by weight Sunpack AP (manufactured by San-ai Petroleum) 0.4% by weight Ion-exchanged water Residual amount <Corrosion inhibitor> Cationic surfactant Cation G-50 (manufactured by Sanyo Chemical Industries, Benzalkonium chloride) 1.0% by weight Plasma emission spectroscopy of this ink As a result of analysis, the content of alkali metal in the ink was 886 ppm. The pH value was 9.1. When the above ink was tested in the same manner as in Example 1, a clear image having an image density of 1.2 or more was obtained on any paper in the initial printing test. Normal printing was possible even after printing was stopped without using any recovery means.
With respect to silicon wettability, the change in thickness of heat-resistant glass # 7740 is 0.15 μm, and the amount of change in thickness of silicon is about 0.19 μm for 100 faces, about 0.11 μm for 110 faces, and about 0.12 μm for 111 faces. Yes, there was no problem with the thickness of the liquid chamber, the fluid resistance portion, and the nozzle. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

Example 16 20% of the following dispersion was added as a yellow pigment in place of the cyan dye of Example 3,
Example 2 except that the following compounds were used as corrosion inhibitors
Stir the mixture of the same formulation at 50 ° C. for 4 hours,
After cooling, it was filtered with a filter having a pore size of 0.8 μm. <Dispersion> C.I. I. Pigment Yellow 138 (average particle size 96 nm) 25% by weight Dispersant (formalin condensate of naphthalene sulfonate) 8% by weight Ammonia water 1.3% by weight Ethylene glycol 25% by weight Water balance <corrosion inhibitor> Titanium ethylate 1.0% by weight When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 886 ppm. The pH value was 9.1.

When the above ink was tested in the same manner as in Example 1, a clear image with an image density of 1.2 or more was obtained on any paper in the initial printing test. Normal printing was possible even after printing was stopped without using any recovery means. In the wettability with silicon, the thickness variation of silicon is about 0.19 μm for 100 surface, about 0.11 μm for 110 surface, and about 0.12 μm for 111 surface, which is a problem for the liquid chamber, the fluid resistance portion, and the nozzle. There was no change in thickness. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

(Example 17) The same method as in Example 1 was carried out by using the following coloring material as a cationic magenta dye instead of the black dye of Example 1 and using an ink having the following formulation except for tetrabutylphosphonium hydroxide. Then, the mixture was continuously stirred at 50 ° C. for 4 hours, and after cooling, the pore size was 0.3 μm.
It was filtered with the m filter.

Cationic magenta dye Kayacryl ED (manufactured by Nippon Kayaku Co., Ltd.) 3% by weight Glycerin 5% by weight Ethylene glycol 20% by weight Olfine E1010 1.0% by weight Sunpack AP (Sanai Petroleum, fungicide) 0.4 Weight% ion-exchanged water residual amount When this ink was analyzed by plasma emission spectroscopic analysis, the content of alkali metal in the ink was 958 ppm. The pH value was 9.7.

The above ink was tested in the same manner as in Example 1 (using soda lime glass in place of heat resistant glass # 7740). In the initial printing test, the image density was 1.1 or more on any paper. A clear image was obtained. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the liquid contact property, the thickness change of soda lime glass (made by HOYA Soft Glass Co., Ltd.) was 0.21 μm, and the thickness change amount of silicon was about 0.25 μm for 100 planes, 11
The 0-th surface was about 0.11 μm, and the 111-th surface was about 0.08 μm, which was the amount of change in thickness that did not pose a problem for the liquid chamber, the fluid resistance portion, and the nozzle. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

Example 18 A mixture having the same formulation as in Example 6 except that 12% of the following dispersion liquid was added as a magenta pigment instead of the yellow dye of Example 6 and the following compound was used as a corrosion inhibitor: Stirring was continued at 50 ° C. for 4 hours, and after cooling, filtration was performed with a filter having a pore size of 0.8 μm.

[0197] <Dispersion>     C. I. Pigment Red 122 (average particle size 120 nm) 33% by weight     Dispersant (dipolyoxyethylene         Nonylphenyl ether phosphoric acid) 17.5% by weight     No. 13 compounds 1.5% by weight     25% by weight of ethylene glycol     Water balance

<Corrosion Inhibitor> Zirconium isopropoxide 1.0% by weight When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 958 ppm. The pH value was 9.7.

The above ink was tested in the same manner as in Example 1 (using soda lime glass in place of heat resistant glass # 7740). In the initial printing test, the image density was 1.1 or more on any paper. A clear image was obtained. Normal printing was possible even after printing was stopped without using any recovery means. In terms of liquid contact, the change in thickness of soda lime glass (soft glass, manufactured by HOYA) is 0.21 μm,
The thickness variation of silicon is about 0.25 μm for 100 planes, 1
The ten surfaces had a thickness of about 0.11 μm and the 111 surfaces had a thickness of about 0.08 μm. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

(Example 19) [0200] The following coloring material was used as the microencapsulated carbon black in place of the black dye of Example 1, and the ink of the following formulation except for tetrabutylphosphonium hydroxide was used. Then, the mixture was continuously stirred at 50 ° C. for 4 hours, and after cooling,
It was filtered with a filter having a pore size of 0.3 μm.

Microencapsulated carbon black (average particle size: 110 nm) (manufactured by Dainippon Ink and Chemicals, Inc.) 5% by weight glycerin 5% by weight ethylene glycol 20% by weight Olfine E1010 1.0% by weight Sunpack AP (manufactured by San-ai Petroleum, Antifungal agent) 0.4 wt% ion-exchanged water Residual amount When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 156 ppm. The pH value was 9.7.

The above ink was tested in the same manner as in Example 1 (a photosensitive glass (manufactured by HOYA) was used in place of the heat-resistant glass # 7740).
A clear image having an image density of 1.0 or more was obtained on any of the papers. Normal printing was possible even after printing was stopped without using any recovery means. With respect to liquid contact, the thickness change of the photosensitive glass (manufactured by HOYA) is 0.2.
1 μm, silicon thickness variation is about 0.26 per 100 faces
μm, 110 surface is about 0.10 μm, 111 surface is about 0.0
The thickness was 6 μm, and there was no problem in changing the thickness of the liquid chamber, the fluid resistance portion, and the nozzle. Further, the film thickness change amount of the silicon oxide film on the 110 surface was about 4Å, which was a film thickness change amount that was not a problem for the diaphragm.

Example 20 A mixture having the same formulation as in Example 6 except that 12% of the following dispersion was added as a magenta pigment instead of the yellow dye of Example 6 and the following compound was used as a corrosion inhibitor: Stirring was continued at 50 ° C. for 4 hours, and after cooling, filtration was performed with a filter having a pore size of 0.8 μm. <Dispersion> C.I. I. Pigment Red 122 (average particle size 120 nm) 33% by weight Dispersant (dipolyoxyethylene nonyl phenyl ether phosphoric acid) 17.5% by weight No. Compound of 13 1.5% by weight Ethylene glycol 25% by weight Water balance <Corrosion inhibitor> Tetramethylammonium silicate 1.0% by weight When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was found. Was 958 ppm. The pH value was 9.7.

The above ink was tested in the same manner as in Example 1 (a photosensitive glass (manufactured by HOYA) was used in place of the heat-resistant glass # 7740), and an image was printed on any paper in the initial printing test. A clear image having a density of 1.1 or more was obtained. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the liquid contact property, the thickness change of the photosensitive glass (manufactured by HOYA) is 0.21 μm, and the thickness change amount of silicon is about 0.25 μm for 100 side, about 0.11 μm for 110 side, and about 0 for 111 side. It was 0.08 μm, which was a change amount of the thickness which does not pose any problem as the liquid chamber, the fluid resistance portion and the nozzle. In addition, the film thickness change amount of the silicon oxide film on the 110 surface was about 5Å, which was a film thickness change amount that did not pose a problem as a diaphragm.

(Example 21) As a yellow dye instead of the black dye of Example 1, Projet Fast was used.
Yellow 2 (manufactured by Abyssia) was once converted into a free acid by using an ion exchange resin to partially convert the alkali metal, and then compound N
o. The mixture having the same formulation as in Example 1 was continuously stirred at 50 ° C. for 4 hours except that 3% of a partially substituted dye was added to the phosphonium compound hydroxide of 3, and after cooling, the pore size was 0.8 μm.
It was filtered with the m filter. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 630 ppm. Also pH
The value was 9.6.

The above ink was tested in the same manner as in Example 1 (using a low alkali glass substrate in place of the heat-resistant glass # 7740). In the initial printing test, the image density was 0.9 on any paper. The above clear image was obtained. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the wettability, the thickness change of the low-alkali glass substrate (BLC Nippon Electric Glass Co., Ltd.) is 0.21 μm, and the thickness change amount of silicon is about 0.40 μm for 100 side, about 0.15 μm for 110 side, 111 The surface was about 0.13 μm, and the amount of change in thickness had no problem as a liquid chamber, a fluid resistance portion, or a nozzle. Further, the film thickness change amount of the silicon oxide film on the 110 surface was about 6Å, which was a film thickness change amount with no problem as a diaphragm.

(Example 22) Compound No. of Example 21.
Compound N instead of hydroxide of phosphonium compound of 3
o. The test was conducted in the same manner as in Example 21 except that the hydroxide of 29 sulfonium compound was used. As a result, in the initial print test, the image density of 0.
A clear image of 9 or more was obtained. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the wettability, the thickness change of the low-alkali glass substrate (BLC Nippon Electric Glass Co., Ltd.) is 0.21 μm, and the thickness change amount of silicon is about 0.40 μm for 100 side, about 0.15 μm for 110 side, 111 The surface was about 0.13 μm, and the amount of change in thickness had no problem as a liquid chamber, a fluid resistance portion, or a nozzle. Further, the film thickness change amount of the silicon oxide film on the 110 surface was about 6Å, which was a film thickness change amount with no problem as a diaphragm.

Example 23 In place of the tetrabutylphosphonium hydroxide of Example 1, 1.0% by weight of a mixture of 0.5% by weight of tetrabutylphosphonium hydroxide and 0.5% by weight of tributylsulfonium hydroxide was used. The test was conducted in the same manner as in Example 1 except that it was used. As a result, in the initial printing test, a clear image having an image density of 1.3 or more was obtained on any paper. Normal printing was possible even after printing was stopped without using any recovery means. Regarding the liquid contact property, the thickness change of the heat resistant glass # 7740 is 0.1 μm, and the thickness change amount of silicon is about 0.15 μm for the 100 side, about 0.04 μm for the 110 side, and about 0.03 μm for the 111 side. There was no problem with the liquid chamber, the flow resistance, and the nozzle. Further, the amount of change in film thickness of the silicon oxide film on the 110th face was about 3 A, which was a problem that the film could be used as a diaphragm.

Comparative Example 1 In the ink formulation of Example 1, lithium hydroxide was added in place of tetrabutylphosphonium hydroxide to adjust the pH. After continuing stirring at 50 ° C. for 4 hours, filtration was performed with a filter having a pore size of 0.1 μm.

[Chemical 18] When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 940 ppm. The pH value was 9.8. A printer was filled with this ink in the same manner as in Example 1, and printing and storage tests were conducted. With this ink, an initial image equivalent to that of Example 1 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to 8/48 nozzles. A defect has occurred. With respect to liquid contact, the thickness change of heat-resistant glass # 7740 is 11.2μ.
m, the thickness change of silicon is about 6.0 μm for 100 planes,
The 110 surface is about 3.5 μm, the 111 surface is about 0.60 μm, which is the amount of change that causes accuracy problems in the liquid chamber, the fluid resistance portion, and the nozzle, and the silicon oxide film on the 110 surface is all eluted. The amount of change was a problem for the diaphragm.

Comparative Example 2 In the ink formulation of Example 2, sodium hydroxide was added in place of tributylsulfonium hydroxide to adjust the pH. After continuing stirring at 50 ° C. for 4 hours, filtration was performed with a filter having a pore size of 0.1 μm.

[Chemical 19] When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 940 ppm. The pH value was 9.8. A printer was filled with this ink in the same manner as in Example 1, and printing and storage tests were conducted. With this ink, an initial image equivalent to that of Example 1 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to 8/48 nozzles. A defect has occurred. With respect to liquid contact, the thickness change of heat-resistant glass # 7740 is 11.2μ.
m, the thickness change of silicon is about 6.0 μm for 100 planes,
The 110 surface is about 3.5 μm, the 111 surface is about 0.60 μm, which is the amount of change that causes accuracy problems in the liquid chamber, the fluid resistance portion, and the nozzle, and the silicon oxide film on the 110 surface is all eluted. The amount of change was a problem for the diaphragm.

Comparative Example 3 In the ink formulation of Example 3, sodium hydroxide was added in place of tetrabutylphosphonium hydroxide to adjust the pH. After continuing stirring at 50 ° C. for 4 hours, the mixture was cooled and then filtered with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopic analysis, the content of the alkali metal in the ink was 1280 ppm. The pH value was 10.3. A printer was filled with this ink in the same manner as in Example 3, and printing and storage tests were performed. With this ink, an initial image equivalent to that of Example 2 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore it was ejected to 28/48 nozzles. A defect has occurred. With respect to silicon wettability, the amount of change in thickness of silicon is about 8.2 μm for surface 100, about 4.7 μm for surface 110, and about 0.80 μm for surface 111. This is the amount of change that causes a problem, and the silicon oxide film on the 110th face was all eluted, and the 8/48 diaphragm was too thin to withstand vibration and was damaged.

Comparative Example 4 In the ink formulation of Example 4, potassium hydroxide was added instead of tetrabutylarsonium hydroxide to adjust the pH. 4 at 50 ° C
After continuing stirring for a time, after cooling, filtration was performed with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopic analysis, the content of the alkali metal in the ink was 1280 ppm. The pH value is 1
It was 0.3. A printer was filled with this ink in the same manner as in Example 3, and printing and storage tests were performed. With this ink, an initial image equivalent to that of Example 2 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore it was ejected to 28/48 nozzles. A defect has occurred. With respect to silicon wettability, the amount of change in thickness of silicon is about 8.2 μm for surface 100, about 4.7 μm for surface 110, and about 0.80 μm for surface 111. This is the amount of change that causes a problem, and the silicon oxide film on the 110th face was all eluted, and the 8/48 diaphragm was too thin to withstand vibration and was damaged.

(Comparative Example 5) In the ink formulation of Example 5, potassium hydroxide was used instead of the compounds of Chemical formulas 1 and 3 in an amount of 40% relative to the equivalent amount of the anionic compound in the ink, and lithium hydroxide in the ink. 4 to the equivalent of anionic compound
0% was added. Continue stirring for 4 hours as it is, and after cooling,
It was filtered with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 970 ppm. The pH value was 9.6. A printer was filled with this ink in the same manner as in Example 3, and printing and storage tests were performed. With this ink, an initial image equivalent to that of Example 3 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to the 12/48 nozzle. A defect has occurred. In the liquid contact property, the thickness change of the alkali-free glass substrate (OA-2 manufactured by Nippon Electric Glass Co., Ltd.) is 13.9 μm, and in the silicon liquid contact property,
The thickness variation of silicon is about 6.2 μm for 100 planes, 11
The 0-side is about 3.6 μm and the 111-side is about 0.60 μm, which is the amount of change that causes accuracy problems as the liquid chamber, the fluid resistance portion, and the nozzle. Also, the silicon oxide film on the 110-side is all eluted. The amount of change was a problem for the diaphragm.

Comparative Example 6 In the ink formulation of Example 6, No. 27, No. Instead of the compound of 29, sodium hydroxide was added in an amount of 40% relative to the equivalent amount of the anionic compound in the ink, and lithium hydroxide was added in an amount of 40% relative to the equivalent amount of the anionic compound in the ink. Stirring was continued for 4 hours as it was, and after cooling, filtration was performed with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 970 p.
It was pm. The pH value was 9.6. The printer was filled with this ink in the same manner as in Example 3, and printing was performed.
A storage test was conducted. With this ink, an initial image equivalent to that of Example 3 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to the 12/48 nozzle. A defect has occurred. In the liquid contact property, the thickness change of the non-alkali glass substrate (OA-2 manufactured by Nippon Electric Glass Co., Ltd.) is 13.9 μm, and in the liquid contact property of silicon, the thickness change amount of silicon is about 6.
2μm, 110 face is about 3.6μm, 111 face is about 0.6
The amount of change was 0 μm, which caused a problem of accuracy in the liquid chamber, the fluid resistance portion, and the nozzle, and the silicon oxide film on the 110th surface was all eluted, which was a problem of the diaphragm.

(Comparative Example 7) In the ink formulation of Example 7, potassium hydroxide was added instead of the corrosion inhibitor to obtain p.
H adjustment was performed. Stirring was continued at 50 ° C. for 4 hours, and after cooling, filtration was performed with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopy,
The content of alkali metal in the ink was 810 ppm. The pH value was 10.1. A printer was filled with this ink in the same manner as in Example 4, and printing and storage tests were conducted. With this ink, an initial image equivalent to that of Example 4 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to the 4/48 nozzle. A defect has occurred. With respect to silicon wettability, the amount of change in thickness of silicon is about 5.3 μm for surface 100, about 3.1 μm for surface 110, and about 0.50 μm for surface 111. This is a change amount that causes a problem, and the silicon oxide film on the 110th surface is all eluted, which is a change amount that causes a problem as a diaphragm.

Comparative Example 8 In the ink formulation of Example 8, sodium hydroxide was added instead of the corrosion inhibitor to adjust the pH. Stirring was continued at 50 ° C. for 4 hours, and after cooling, filtration was performed with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopy,
The content of alkali metal in the ink was 810 ppm. The pH value was 10.1. A printer was filled with this ink in the same manner as in Example 4, and printing and storage tests were conducted. With this ink, an initial image equivalent to that of Example 4 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to the 4/48 nozzle. A defect has occurred. With respect to silicon wettability, the amount of change in thickness of silicon is about 5.3 μm for surface 100, about 3.1 μm for surface 110, and about 0.50 μm for surface 111. This is a change amount that causes a problem, and the silicon oxide film on the 110th surface is all eluted, which is a change amount that causes a problem as a diaphragm.

Comparative Example 9 In the ink formulation of Example 9, sodium hydroxide was added in place of the corrosion inhibitor to adjust the pH. After continuing stirring at 50 ° C. for 4 hours,
After cooling, filtration was performed with a filter having a pore size of 0.1 μm.
When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 870 ppm. The pH value was 8.3. A printer was filled with this ink in the same manner as in Example 9, and printing and storage tests were conducted. With this ink, an initial image equivalent to that of Example 5 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to the 7/48 nozzle. A defect has occurred. With respect to silicon wettability, the amount of change in thickness of silicon is about 5.8 μm for surface 100, about 3.4 μm for surface 110, and about 0.60 μm for surface 111, which is accurate for the liquid chamber, fluid resistance portion, and nozzle. This is a change amount that causes a problem, and the silicon oxide film on the 110th surface is all eluted, which is a change amount that causes a problem as a diaphragm.

(Comparative Example 10) In the ink formulation of Example 12, lithium hydroxide was added in place of tributyl borate (corrosion inhibitor) to adjust the pH. After continuing stirring at 50 ° C. for 4 hours, the mixture was cooled and then filtered with a filter having a pore size of 0.1 μm. When this ink was analyzed by plasma emission spectroscopy, the content of alkali metal in the ink was 870 ppm. The pH value was 8.3. A printer was filled with this ink in the same manner as in Example 5, and printing and storage tests were conducted. With this ink, an initial image equivalent to that of Example 5 was obtained, but in the ejection response test after the pause of printing, the dissolution stability of the dye deteriorated due to the elution of silicon into the ink, and therefore the ink was ejected to the 7/48 nozzle. A defect has occurred. In the wettability with silicon, the thickness variation of silicon is about 5.5 μm for 100 surface, about 3.3 μm for 110 surface, and about 0.55 μm for 111 surface.
The fluid resistance portion and the nozzle were variations causing accuracy problems, and the silicon oxide film on the 110th surface was all eluted, which was a variation problematic as a diaphragm.

(Measurement of Zeta Potential) The zeta potentials of the inks of Examples 1 to 22 and Comparative Examples 1 to 10, the color of the substrate (silicon substrate, glass substrate, silicon substrate having an oxide film, etc. used for the head) and color. The zeta potential between the materials was measured. The zeta potential was measured using an electrophoresis device using the laser Doppler method. The device is LES made by Otsuka Electronics
-8000 was used. Zeta potential is the pH of dye ink
The value at 10.5 and the pigment ink at pH 10.6 were determined. When the coloring material is a pigment, the ink itself can be used for the measurement. When the coloring material is a dye, the measurement is performed using monitor particles.

(Measurement of Oxidation / Reduction Current Value) The potential vs. oxidation / reduction current was measured by cyclic voltammetry between the substrate and the ink. The device is HOKUTO D
ENKO Ltd's POTENTI STAT / G
ALVANOSTAT HA-501G (ARBITR
ARY FUNCTION GENERATION HB
(Use -105) was used. A saturated calomel electrode (SCE) was used as a reference electrode (standard electrode). Potential is -3.0
-5.0V vs SCE, the oxidation / reduction current value is-
1.5 to 2.0 μA / cm ² (Pt.) Was measured. As a result, the following measurement results were obtained. The values of each Example and Comparative Example are shown in Tables 9 and 10.

[0221]

[Table 9]

[Table 10]

From the above results, the pH of the aqueous ink composition
Has a zeta potential of -20 mV or less at 6.5 to 11.5, and a zeta potential between the member and the color material is 0 to -50 mV.
Therefore, it was revealed that elution of glass, silicon, silicon oxide film, etc. into the ink can be suppressed. At this time, the oxidation / reduction current value between the member and the ink is 0-1.0 with respect to the potential range of -2.0 to 5.0 V vs SCE (to the saturated calomel electrode).
It was also clarified that it was μA / cm ² (Pt.).
On the other hand, it is also clear that the water-based ink compositions shown in Comparative Examples, which do not fall within this range, cause remarkable dissolution of glass, silicon, silicon oxide film, etc. into the ink.

[0223]

According to the constitution described in claim 1, when the pH of the aqueous ink composition is 6.5 to 11.5 and the zeta potential between the member and the coloring material is 0 to -50 mV, It is possible to prevent the elution of silicon, glass used in printers, or films provided with any of these oxides, nitrides, metals, and organic compounds, and to reduce the size and ejection of ink droplets due to the reduction in printer design accuracy. It is possible to provide an ink that prevents problems such as deterioration of image quality due to a change in speed, occurrence of ejection failure, and failure due to a decrease in bonding strength of a joint portion, and also that clogging due to elution of glass or silicon into ink is prevented. .

According to the structure described in claim 2, the zeta potential at the pH of the aqueous ink composition of 6.5 to 11.5 is -20 mV or less, and the zeta potential between the member and the coloring material is 0. -50 mV, silicon, glass, or oxides, nitrides, metals, etc. used in printers
It is possible to prevent the elution of the film provided with any of the organic compounds, and to reduce the image quality due to the change in the ink droplet size and the ejection speed due to the decrease in the design accuracy of the printer, the occurrence of ejection failure, and the bonding strength of the joint part. It is possible to provide an ink that prevents problems such as breakdown due to deterioration and prevents clogging due to elution of glass or silicon into the ink.

According to the constitutions of claims 3 to 18, even if the potential and current values of the water-based ink composition do not satisfy the above values, cationic ions, cationic compounds and cationic substances are contained in the ink. , A cationic resin, a cationic surfactant, a cationic coloring material, a cationic dye, a cationic carbon black, a cationic pigment, a coloring material is contained in the resin, or colored resin fine particles colored with a coloring material, Phosphonium ion, acetylene compound, sulfonium ion, arsonium ion, boron compound, beryllium ion (Be ²⁺ ), aluminum ion (Al ³⁺ ), zinc ion (Zn ²⁺ ), titanium ion (Ti ⁴⁺ ), zirconium ions (Zr ^4+), by including silicate ions (Si ^2+), etc., silicon is used in the printer, moth Or adsorbs on the surface of a film provided with any of oxides, nitrides, metals, and organic compounds, and satisfies the above values. Oxide,
It is possible to prevent elution of a film provided with any of nitride, metal, or organic compound, and to reduce image quality due to changes in ink droplet size and ejection speed due to printer design accuracy deterioration, occurrence of ejection failure, and coupling. It is possible to provide an ink that prevents a problem such as a failure due to a decrease in the bonding strength of a portion and prevents clogging due to elution of glass or silicon into the ink.

According to the nineteenth aspect, when the pH of the water-based ink composition is in the range of 7 to 10, silicon, glass, or an oxide, a nitride, a metal, or an organic compound used in a printer can be used. It adheres to the surface of the film provided with any of the compounds and stays there, satisfying the above-mentioned values, so either silicon, glass used for printers, or oxides, nitrides, metals, or organic compounds It is possible to prevent elution of the provided film, etc., and to reduce problems such as image quality deterioration due to changes in ink droplet size and ejection speed due to printer design accuracy deterioration, ejection failure, and joint strength reduction at joints. It is possible to provide an ink that prevents the ink and also prevents clogging due to elution of glass or silicon into the ink.

According to the twentieth aspect, it is possible to suppress the elution of glass, silicon or the like of the liquid chamber member, the fluid resistance portion or the vibrating plate, which requires precision, without increasing the volume of the liquid chamber. Since it is possible to maintain a desired liquid chamber volume, it is possible to provide ink that prevents deterioration of image quality and occurrence of ejection failure due to changes in ink droplet size and ejection speed.

According to the twenty-first aspect, since it is possible to suppress elution of glass, silicon or the like of the nozzle which requires precision, it is possible to maintain a desired nozzle diameter without expanding the diameter of the nozzle. Therefore, it is possible to provide an ink that prevents deterioration of image quality and occurrence of ejection failure due to changes in ink droplet size and ejection speed.

According to the structure described in claim 22, in the member described in claims 1, 2, 19 and 20, the silicon is either single crystal silicon or polysilicon, or the glass is borosilicate glass. Photosensitive glass, quartz glass, soda-lime glass, or silicon, the film provided on either glass is silicon oxide,
Titanium oxide, chromium oxide, titanium nitride, silicon nitride,
Even if zirconium or polyimide is used, it is possible to prevent the elution of silicon, glass, or a film provided with any of these oxides, nitrides, metals, and organic compounds, which is used in printers, and Prevents problems such as image quality deterioration due to changes in ink droplet size and ejection speed due to reduced design accuracy, ejection failure, and failure due to reduced joint strength at the joints. Ink that can prevent clogging can be provided.

According to the twenty-third aspect, since it is possible to suppress elution of glass, silicon, or the like of the member that comes into contact with the ink that requires precision, the desired liquid chamber volume can be obtained without increasing the liquid chamber volume. Since this can be maintained, it is possible to provide an inkjet recording method that prevents deterioration of image quality and occurrence of ejection failure due to changes in ink droplet size and ejection speed.

According to the twenty-fourth aspect, the elution of glass, silicon or the like of the liquid chamber member requiring precision can be suppressed, so that the desired liquid chamber volume can be maintained without increasing the liquid chamber volume. Therefore, it is possible to provide an inkjet recording method that prevents deterioration of image quality and occurrence of ejection failure due to changes in ink droplet size and ejection speed.

According to the twenty-fifth aspect, since elution of glass, silicon or the like in the fluid resistance portion requiring precision can be suppressed, the desired fluid resistance can be maintained without changing the fluid resistance. Therefore, it is possible to provide an ink jet recording method that prevents deterioration of image quality and occurrence of ejection failure due to changes in ink droplet size and ejection speed.

According to the twenty-sixth aspect, since it is possible to suppress elution of glass, silicon or the like of the diaphragm requiring precision, it is possible to reduce the thickness of the diaphragm without decreasing the thickness of the diaphragm. Therefore, it is possible to provide an inkjet recording method that prevents deterioration of image quality, occurrence of ejection failure, and damage to the diaphragm due to changes in ink droplet size and ejection speed.

According to the twenty-seventh aspect, since it is possible to suppress elution of glass, silicon or the like of the nozzle which requires precision, it is possible to maintain a desired nozzle diameter without expanding the nozzle diameter. Therefore, it is possible to provide an inkjet recording method that prevents deterioration of image quality and occurrence of ejection failure due to changes in ink droplet size and ejection speed.

According to the method described in claim 28, in the member described in claims 23 to 27, the silicon is either single crystal silicon or polysilicon, or the glass is borosilicate glass, photosensitive glass, Either quartz glass or soda-lime glass, or if the film provided on either silicon or glass is silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, or polyimide Since it is possible to suppress elution of glass, silicon, etc. of a member that comes into contact with the ink that requires precision, it is possible to maintain a desired liquid chamber volume without increasing the liquid chamber volume. It is possible to provide an ink jet recording method that prevents the deterioration of image quality and the occurrence of ejection failure due to changes in the ink.

According to the method described in claim 29, the liquid chamber member, the fluid resistance portion, the vibrating plate and the nozzle, which require precision, are processed by etching, sandblasting, excimer laser processing and drilling. Therefore, it is possible to provide an ink jet recording method in which the image quality is not deteriorated and ejection failure does not occur.

According to the thirtieth to thirty-second aspects, the elution of glass, silicon, and silicon oxide used in the printer can be suppressed in this manner, and the size and ejection of the ink droplet due to the reduction in the design accuracy of the printer. A recording liquid cartridge containing ink that prevents problems such as image quality deterioration due to speed change, ejection failure, failure due to deterioration of joint strength at the joint part, and clogging due to silicon elution into ink, recording A unit and a recording device can be provided.

[Brief description of drawings]

FIG. 1 is a schematic front view showing a configuration example of a serial-type ink jet recording apparatus equipped with an ink cartridge containing a recording liquid to which the present invention is applied.

FIG. 2 is an external perspective view of the ink cartridge before being loaded in the recording apparatus.

FIG. 3 is a front sectional view of an ink cartridge.

FIG. 4 is an external perspective view of a recording unit integrated with a recording head.

FIG. 5 is a sectional side view of the entire head portion.

[Explanation of symbols]

1 side plate 2 side plates 3 Main support guide rod 4 Secondary support guide rod 5 Carriage unit 6 heads 6a ejection surface of head 7y, 7m, 7c, 7k ink cartridge 8 Main scanning motor 9 Drive pulley 10 Driven pulley 11 Timing belt 12 Bottom plate 13 subframes 14 subframes 15 Conveyor roller 16 sheets 17 Sub-scanning motor 18 gears 19 gears 21 subsystem 22 Cap means 23 Holder 24 Link member 25 Engagement part 26 Suction tube 27 Suction pump 28 Wiper blade 29 blade arm 30 recording units 31 electrodes 32 nozzles 41 Cartridge body 42 ink absorber 43 cases 44 Upper lid member 45 Holding member for ink supply port of cartridge 46 seal ring 47 Atmosphere opening 48 grooves 50 Cap member 51 Ink supply port holding member for cartridge 53 Taking out the holding part of the cartridge 55 Seal member 71 Projection for each color of cartridge 81 Upper space of cartridge 81a 82 dents 101, 102, 103 Single crystal substrate of silicon 104 nozzle holes 105 diaphragm 106 Liquid temperature 107 Liquid resistance part 108 ink cavity 121 electrodes 122 Passivation film (protective film) 123 Electrode terminal 131 Ink supply port 141 ink droplets 142 power supply (voltage application)

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuyo Nagai             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Keiji Murakami             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2C056 EA21 FA02 FC01 HA17                 2H086 BA02 BA55 BA59 BA60                 4J039 AD06 AD09 AD10 AD12 AE05                       AE13 BA04 BA15 BA16 BA20                       BA31 BA32 BA35 BA39 BC09                       BC27 BC54 BC56 BC58 BE01                       BE02 CA03 CA06 EA41 GA24

Claims (32)

[Claims] 1. An ink used in an ink jet printer, wherein at least a part of a member in contact with the ink is formed of silicon, glass, or a film in which any one of oxide, nitride, metal, and organic compound is provided. And a zeta potential between the member and the coloring material at a pH of 6.5 to 11.5 is 0 to -50 mV. 2. An ink used in an inkjet printer, wherein at least a part of a member in contact with the ink is formed of silicon, glass, or a film in which any one of oxide, nitride, metal, and organic compound is provided. And the zeta potential at pH 6.5 to 11.5 is −
A water-based ink composition, which has a zeta potential of 20 mV or less and a member-coloring material of 0 to -50 mV. 3. The aqueous ink composition according to claim 1, wherein the coloring material is contained in a resin or contains colored resin fine particles colored with the coloring material. 4. The aqueous ink composition according to any one of claims 1 to 3, which contains a cationic ion and / or a cationic compound. 5. The cationic compound is a cationic resin,
The aqueous ink composition according to claim 4, which is a cationic surfactant and / or a cationic coloring material. 6. The cationic coloring material is a cationic dye,
The aqueous ink composition according to claim 5, which is a cationic carbon black or a cationic pigment. 7. The aqueous ink composition according to any one of claims 1 to 3, which contains a phosphonium ion represented by the following general formula (1). General formula (1) (In the formula, Ra, Rb, Rc, and Rd represent a linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a halogenated alkyl group, a substituted or unsubstituted phenyl group, and X ⁻ Represents a counter ion.) 8. The aqueous ink composition according to claim 1, further comprising an acetylene compound represented by the following general formula (2). General formula (2) (However, R ^{1 to} R ⁶ are linear alkyl groups having 1 to 5 carbon atoms,
m and n represent the integer of 0-20. ) 9. The aqueous ink composition according to claim 1, further comprising a sulfonium ion represented by the following general formula (3). General formula (3) (In the formula, Ra, Rb and Rc are linear, branched, cyclic alkyl groups having 1 to 4 carbon atoms, hydroxyalkyl groups,
It represents a halogenated alkyl group or a substituted or unsubstituted phenyl group, and X ⁻ represents a counter ion. ) 10. The aqueous ink composition according to claim 1, further comprising an arsonium ion represented by the following general formula (4). General formula (4) (In the formula, Ra, Rb, Rc, and Rd represent a linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a halogenated alkyl group, a substituted or unsubstituted phenyl group, and X ⁻ Represents a counter ion.) 11. The water-based ink composition according to claim 1, which contains a boron compound. 12. The water-based ink composition according to claim 1, which contains beryllium ions (Be ²⁺ ). 13. The aqueous ink composition according to claim 1, which contains aluminum ions (Al ³⁺ ). 14. The aqueous ink composition according to claim 1, which contains zinc ions (Zn ²⁺ ). 15. The water-based ink composition according to claim 1, which contains titanium ions (Ti ⁴⁺ ). 16. The aqueous ink composition according to claim 1, which contains zirconium ions (Zr ⁴⁺ ). 17. The water-based ink composition according to claim 1, which contains silicate ions (Si ²⁺ ). 18. The cationic ion, the cationic compound, the cationic substance, the phosphonium represented by the general formula (1), the acetylene compound represented by the general formula (2) and the general formula (3). Sulfonium ion, arsonium ion represented by the general formula (4), boron compound, beryllium ion (Be ²⁺ ), aluminum ion, (Al ³⁺ ), zinc ion (Zn 2+), titanium ion (Ti ⁴⁺⁾ ), Zirconium ion (Zr ⁴⁺ ), and silicate ion (Si ²⁺ ), at least two kinds are contained, The aqueous ink composition in any one of Claims 1-3 characterized by the above-mentioned. 19. The aqueous ink composition according to claim 1, wherein the pH of the ink is in the range of 7 to 10. 20. The water-based ink composition according to claim 1, wherein at least a part of each of the liquid chamber member, the fluid resistance portion, and the vibration plate is made of silicon, glass, or these. An ink-jet recording ink, which is used in an ink-jet printer formed of any one of a film provided with any of oxide, nitride, metal, and organic compound. 21. The water-based ink composition according to claim 1, wherein at least a part of the nozzle member is silicon, glass, or an oxide, a nitride, a metal, or an organic compound thereof. An ink for inkjet recording, which is used for an inkjet printer formed of any one of the films provided in any one of 1. 22. The water-based ink composition according to any one of claims 1 to 19, wherein the silicon in the member is either single crystal silicon or polysilicon, or the glass is borosilicate glass or photosensitive. Glass, quartz glass,
Either soda-lime glass, or silicon,
22. The inkjet recording ink according to claim 20, wherein the film provided on any of the glasses is any one of silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, and polyimide. 23. An ink jet printer in which at least a part of a member in contact with ink is formed of silicon, glass, or a film provided with any of oxides, nitrides, metals, and organic compounds thereof. , Claim 2
23. An inkjet recording method, wherein recording is performed using the inkjet recording ink according to any one of 0 to 22. 24. At least a part of the member of the liquid chamber member,
An inkjet printer formed of silicon, glass, or any of oxides, nitrides, metals, and organic compounds formed thereon, and the inkjet recording ink according to claim 20. An ink jet recording method characterized by recording. 25. An ink jet printer in which at least a part of the member of the fluid resistance portion is formed of silicon, glass, or a film provided with any of oxides, nitrides, metals, and organic compounds thereof. And claim 2
The ink jet recording ink according to item 0 is used for recording. 26. An ink jet printer in which at least a part of a member of a diaphragm is formed of silicon, glass, or a film provided with any of oxides, nitrides, metals, and organic compounds thereof. An ink jet recording method, wherein recording is performed using the ink for ink jet recording according to claim 20. 27. An ink jet printer in which at least a part of a member of the nozzle is formed of silicon, glass, or a film provided with any of oxides, nitrides, metals, and organic compounds thereof. An ink jet recording method, wherein recording is performed using the ink for ink jet recording according to claim 21. 28. The member according to claim 23, wherein the silicon is either single crystal silicon or polysilicon, or the glass is borosilicate glass, photosensitive glass, quartz glass, soda lime glass. Or the film provided on either silicon or glass is any one of silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, and polyimide. . 29. The groove is formed by subjecting the liquid chamber member, the fluid resistance portion, the diaphragm, and the nozzle to etching, sandblasting, excimer laser processing, and drilling. Ink for inkjet recording and an inkjet recording method according to item 1. 30. A recording liquid cartridge comprising a recording liquid storage section for storing the recording liquid, wherein the recording liquid is the recording liquid cartridge.
23. A recording liquid cartridge, which is the inkjet recording ink according to any one of 0 to 22. 31. An ink jet recording apparatus according to any one of claims 20 to 22, wherein a recording liquid cartridge is provided with a recording liquid containing portion containing a recording liquid and a head portion for ejecting recording liquid droplets. A recording liquid cartridge characterized by being a recording ink. 32. An ink jet recording apparatus comprising a recording liquid cartridge having a recording liquid containing portion containing a recording liquid and a recording head for ejecting recording liquid droplets, wherein the recording liquid is according to any one of claims 20 to 22. An inkjet recording apparatus, which is the inkjet recording ink according to any one of claims 1.