JP4282940B2 - Inkjet recording method using aqueous ink composition - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
In the present invention, in ink jet recording, at least a part of a member in contact with ink is silicon, glass, or a film provided with any of oxide, nitride, metal, and organic compound (silicon is monocrystalline silicon, polysilicon) Or the glass is one of borosilicate glass, photosensitive glass, quartz glass and soda lime glass, or the film provided on either silicon or glass is silicon oxide, titanium oxide or chromium oxide. , Titanium nitride, silicon nitride, zirconium, and polyimide.) And an ink jet recording method.
[0002]
[Prior art]
In recent years, inkjet recording systems have become rapidly popular due to their small size, low price, low running cost, and low noise. Electrophotographic transfer paper, printing paper, typewriter paper, wire dot printer paper, word processor Inkjet printers capable of printing on various non-coated plain papers such as paper, letter paper, report paper, etc. are also on the market. Among these ink jet printers, there is an ink jet printer of a type using glass or silicon or silicon oxide because of ease of microfabrication, processing accuracy, process, and the like.
[0003]
The ink used in such an ink jet printer is generally composed of a colorant and a wetting agent (polyhydric alcohol or ethers thereof) dispersed or dissolved in a solvent and a solvent, and if necessary, a penetrating agent and an antifungal agent. , Containing preservatives, dispersants, etc., but if the ink is filled in an ink jet printer using the above glass or further silicon or silicon oxide and used or left for a long time, the glass or further silicon in contact with the ink, Silicon oxide is eluted. For this reason, the design accuracy of the ink jet printer is lowered, so that the size of the ink droplets and the ejection speed of the ink droplets are changed to deteriorate the image quality, or in the worst case, ejection failure occurs. In addition, since the bonding strength is reduced due to the elution of glass or further silicon or silicon oxide at the bonding portion, the bonding portion peels off and breaks down in the worst case.
[0004]
In particular, in an ink jet printer in which the liquid chamber member is made of glass, silicon, or silicon oxide, the dimensional accuracy of the liquid chamber that requires precision is lowered, and thus the above-described problem is remarkably generated.
[0005]
In addition, in an inkjet printer in which the fluid resistance portion is made of glass, silicon, or silicon oxide, the fluid resistance changes due to the elution of glass, silicon, or silicon oxide, and the ink droplet size or ink droplet ejection speed is reduced. The change is remarkable and the image quality is lowered, or in the worst case, ejection failure occurs.
[0006]
In addition, in an inkjet printer in which the diaphragm is made of glass, silicon, or silicon oxide, the thickness of the diaphragm is reduced, so the size of ink droplets or the ejection speed of ink droplets changes or ejection failure occurs. The quality deteriorates and eventually the diaphragm becomes thin, so it cannot withstand vibration and breaks.
[0007]
Inkjet printers with nozzles made of glass, silicon, or silicon oxide have large nozzle diameters, which can change the size of ink droplets or the ejection speed of ink droplets or cause ejection defects. Reduce.
[0008]
In addition, in the ink from which glass, silicon, or silicon oxide has been eluted, the dissolution or dispersion stability of the colorant is lowered, and the colorant is precipitated to cause clogging. Further, the eluted glass, silicon, or silicon oxide itself becomes supersaturated by evaporation of a solvent such as water and precipitates on the nozzle surface and causes clogging.
[0009]
At present, these problems have not been solved. For example, when the pre-filled ink runs out, the head can be replaced with it for a relatively short period of time. In order to solve these problems, as an ink jet printer, as disclosed in JP-A-5-1555023, WO98-42513, etc., inorganic or organic substances such as SiN, TiN, and TiO on glass or further silicon and silicon oxide. There is a method for preventing this by providing a layer. This has the effect of preventing the elution of glass, silicon, or silicon oxide. However, since the number of steps is increased in manufacturing, a great cost is required and the ink jet printer becomes very expensive. Also, these films are prone to pinholes and are difficult to form uniformly and often have defects in the films. Depending on the type and structure of the head, the film formation itself may not be incorporated into the process. Furthermore, in recent experiments, it has become clear that certain layers of black dyes cannot prevent elution even if these layers are provided. Has been confirmed.
[0010]
As an ink, Japanese Patent Application Laid-Open No. 9-123437 proposes a method for preventing precipitation by adding urea to the ink so that the glass, silicon, or silicon oxide dissolves stably even in the case of elution. However, since there is no effect of preventing the elution of glass, silicon, or silicon oxide itself, it is not possible to use glass, silicon, or silicon oxide in a portion where accuracy is required. For this reason, glass, silicon, silicon oxide that can be formed relatively easily by thermal oxidation, etc., and even silicon, silicon oxide, and other substrates provided with inorganic or organic layers such as SiN, TiN, TiO do not elute Ink is required.
[0011]
Japanese Examined Patent Publication No. 7-51687 discloses an ink in which the content of sodium ions is defined. Japanese Patent Laid-Open No. 5-331391 defines the contents of sodium and potassium. Similarly, Japanese Patent Laid-Open Nos. 8-333542 and 9-25441 define the contents of sodium and potassium, respectively. There is ink.
[0012]
The present applicant has proposed an ink containing quaternary ammonium as a specific dye and its counter ion in Japanese Patent No. 16777642, and Japanese Patent No. 2085163 discloses a dye and quaternary in the ink. An ink containing phosphonium ions has been proposed. These have solved problems such as clogging, kogation, and storage stability. After that, the phenomenon of elution of the substrate became known by providing an inorganic or organic layer such as SiN, TiN or TiO on glass or silicon, silicon oxide, or silicon or silicon oxide in contact with the ink. . Accordingly, when the proposed ink was examined again, it was found that the substrate elution was not sufficiently solved.
[0013]
[Problems to be solved by 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 the ink is silicon, glass, or a film provided with any of oxide, nitride, metal, and organic compound ( Silicon is either single crystal silicon or polysilicon, or glass is any of borosilicate glass, photosensitive glass, quartz glass, soda lime glass, or a film provided on either silicon or glass. As an ink for ink jet recording used in an ink jet printer formed of any one of silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, and polyimide), glass, silicon, silicon oxide in contact with the ink By preventing the elution of objects etc., the size of ink droplets and the ejection speed of ink droplets Changes in, to prevent ejection defects, and an object thereof to provide an excellent ink jet recording ink of the dispersion or dissolution stability of the ink.
[0014]
[Means for Solving the Problems]
As a result of diligent research, the inventors have reduced the content of specific elements such as sodium and potassium, and even if they are effective for clogging, kogation, etc., glass, silicon, silicon oxide in contact with ink The elution of things etc. cannot be prevented,
(1) At least a part of each member of the liquid chamber member, the fluid resistance portion, the diaphragm or the nozzle in contact with the ink is provided with silicon, glass, or an oxide, nitride, metal, or organic compound. An ink jet printer formed of any one of the formed films, and a water-based ink composition mainly composed of a coloring material and water, and having a pH of 6.5 to 11.5, the member in contact with the ink and the ink An ink jet recording method, wherein recording is performed using an ink for ink jet recording having a zeta potential of 0 to -50 mV,
(2) At least a part of each member of the liquid chamber member, the fluid resistance portion, the diaphragm, or the nozzle in contact with the ink is provided with silicon, glass, or an oxide, nitride, metal, or organic compound. An ink jet printer formed of any of the films formed, a water-based ink composition mainly composed of a pigment and water, and having a zeta potential of −20 mV or less at a pH of 6.5 to 11.5, and An ink jet recording method, wherein recording is performed using a member in contact with the ink and an ink for ink jet recording having a zeta potential between 0 and −50 mV,
(3) In the member according to any one of (1) and (2), silicon is either single crystal silicon or polysilicon, or glass is borosilicate glass, photosensitive glass, quartz glass, or soda lime. Inkjet recording characterized in that it is either 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. It has been found that the method can prevent elution of glass, silicon, silicon oxide and the like in contact with ink, and can solve all the above problems.
[0048]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in further detail below.
In the present invention, the color material, the water-soluble organic solvent, and the surfactant are selected so that the zeta potential of the water-based ink composition containing the color material and water as main components becomes the above value. Alternatively, even if the water-based ink composition exceeds the value, the ink is designed to have the above value by adding a corrosion inhibitor.
[0049]
It has become clear that corrosion of glass, silicon, silicon oxide, etc. is caused by all alkali metals contained in the ink. The total content is about 800 ppm from the measurement result of ICP, but it is 0.05% to 5.0%, preferably 0.1% to 2.0%, more preferably 0.00% with respect to the total ink. By containing 2 to 0.8% of a corrosion inhibitor, the zeta potential and the oxidation / reduction current value can be lowered, and elution of glass, silicon, silicon oxide, etc. in contact with the ink can be prevented.
[0050]
As used herein, the term “corrosion inhibitor” refers to phosphonium ions, acetylene compounds, cationic resins, cationic surfactants, cationic colorants, sulfonium ions, arsonium ions, boron compounds, beryllium ions (Be²⁺), Aluminum ions (Al³⁺), Zinc ion (Zn²⁺), Titanium ions (Ti⁴⁺), Zirconium ions (Zr⁴⁺), Silicate ions (Si²⁺) Etc. The alkali metal here is a metal belonging to Group 1 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, and francium, but the actual ink has the most sodium. In addition, in the calculation, there are only a few hundred grams of francium on the earth's crust 20km, and there is very little on the earth, so it can be considered to be almost zero, so in fact alkali metals excluding francium What is necessary is just to manage the total content of.
[0051]
The glass used in the present invention may be any ordinary glass, but borosilicate glass, quartz glass, low alkali glass, non-alkali glass, and soft glass (blue plate glass) are preferred. In the case of using a head composed of other materials, it is preferable to use a glass whose linear expansion coefficient approximates. For example, if the head is composed of silicon, heat resistant glass # 7740, Corning coat 7913, Corning coat 7052, Corning coat 7056 etc. are mentioned. As the most preferable glass for anodic bonding, non-alkali glass substrates OA-2 and OA-10, low alkali glass substrate BLC (manufactured by Nippon Electric Glass Co., Ltd.), blue glass (soft glass) SL, NA (manufactured by HOYA) and the like can be mentioned. It is done. These glasses can also be bonded to silicon. Photosensitive glass can also be used. A 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.
[0052]
The alkali metal in the ink is considered to have a function of continuing to elute glass, silicon and the like because it enters and diffuses into the glass, silicon, silicon oxide and the like in contact with the ink.
Such elution of glass, silicon and silicon oxide can also be suppressed by setting the total content of alkali metals in the ink to 700 ppm or less, preferably 150 ppm or less, more preferably 50 ppm or less. By including a corrosion inhibitor such as a phosphonium ion represented by the formula (1), it can be suppressed to a level that does not cause a problem even if the content of alkali metal is not reduced. The reason for this is that the corrosion inhibitor remains adsorbed on the surface of glass, silicon, silicon oxide, etc. that come into contact with the ink, so continuous elution of glass or silicon is not performed, even if the alkali metal content is high. It is thought that it works to prevent elution of silicon and silicon.
[0053]
By examining the electric double layer with the addition of the corrosion inhibitor, it can be confirmed that the zeta potential is different compared to the case where the corrosion inhibitor is not added, and that it remains adsorbed on the glass or silicon surface. . A high zeta potential of the substrate means that the hydrophilicity, ionicity, and reactivity are high and unstable. On the other hand, a low zeta potential means that the water repellency, nonionicity, and reactivity are low. When the following cationic compound is adsorbed on a substrate at a negative high potential, the potential decreases and goes toward stabilization. At this time, the ease of flow of the oxidation / reduction current is less likely to flow when the zeta potential is lower (lower ionicity), and conversely when the zeta potential is high. From the above, by measuring the zeta potential and oxidation / reduction current between the substrate and the ink and the zeta potential of the ink itself, it is possible to quantitatively grasp the ease and difficulty of corrosion.
[0054]
The ions used in the present invention need not all be one kind of compound, and can be used by mixing with other ions or compounds. As ions, sulfonium ion, ammonium ion, phosphonium ion, arsonium ion, beryllium ion (Be²⁺), Aluminum ions (Al³⁺), Zinc ion (Zn²⁺), Titanium ions (Ti⁴⁺), Zirconium ions (Zr⁴⁺), Silicide ions (Si²⁺And the like, and examples of the compound include a cationic resin, a boron compound, and an acetylene compound.
[0055]
Among the phosphonium ions represented by the general formula (1), the following No. 1, no. 2, no. 3, no. The compound represented by 4 has a particularly high elution preventing effect for glass, silicon, silicon oxide and the like, is excellent in dispersion or dissolution stability of the colorant, and satisfies other qualities required for inks for ink jet recording. .
[0056]
[Table 1]
[0057]
No. above. 1-No. In addition to the compound represented by No. 4, as the phosphonium ion represented by the general formula (1), specifically, No. 4 shown below. 5-No. The thing shown to 26 can be mention | raise | lifted.
[Table 2]
[0058]
Among the sulfonium ions represented by the general formula (3), the following No. 27, no. 28, no. 29, no. The compound represented by 30 has a particularly high elution preventing effect for glass, silicon, silicon oxide, etc., is excellent in colorant dispersion or dissolution stability, and satisfies other qualities required for ink jet recording inks. .
[Table 3]
[0059]
No. above. 27, no. 28, no. 29, no. In addition to the compound represented by No. 30, as the sulfonium ion represented by the general formula (3), specifically, No. 1 shown below. 31-No. 50 can be mentioned.
[Table 4]
[0060]
Furthermore, among the arsonium ions represented by the general formula (4), the following No. 51, no. 52, no. 53, no. The compound represented by 54 is more preferable because it has a particularly high elution preventing effect on silicon and silicon oxide, is excellent in dispersion or dissolution stability of the colorant, and satisfies other qualities required for inks for ink jet recording.
[Table 5]
[0061]
No. above. 51-No. In addition to the compound represented by No. 54, as the arsonium ion represented by the general formula (4), specifically, the following No. 55-No. The thing shown to 76 can be mention | raise | lifted.
[Table 6]
[0062]
Of course, the ions represented by the general formulas (1), (3), and (4) are not limited to these. Among these, one or a plurality of them can be added as long as they satisfy other qualities required for the ink for ink jet recording and have no side effects such as toxicity. Especially, it is preferable that the carbon number in 1 molecular ion is 4-12. When the number of carbon atoms exceeds 12, the solubility in a solvent such as water decreases, and the tendency to clog during printing pause or continuous printing, or to cause separation or precipitation of ink during storage of the ink is increased. Increased tendency to cause side effects.
[0063]
Although the present invention prevents corrosion even when the content of alkali metal is large as described above, anionic compounds such as colorants, penetrants, dispersants, and surfactants added to the ink are sodium salts or When obtained in the form of an alkali metal salt such as a potassium salt, depending on the amount added, the alkali metal content may exceed 800 ppm and become a considerable amount if used as it is.
[0064]
In this case, the alkali metal content may be reduced by changing at least part of the counter ions of the anionic compound to ions other than the alkali metal salt. As the method, an ion exchange resin method, a solution of an alkali metal salt such as sodium contains a desired ion, preferably an onium ion represented by general formula (1), general formula (3), or general formula (4). A salting-out method in which a salt is added and precipitated is a method for directly exchanging ions. Once the alkali metal salt such as sodium is used as a free acid, in addition to the method of treating with an ion exchange resin, a strong acid is added to an anionic compound or a solution thereof, and the residue is subjected to solvent extraction to obtain the remaining one. The method of filtering and isolate | separating is mentioned. When the anionic compound is obtained in a form other than the alkali metal, it may be used as it is. Further, at least a part of the ions may be used instead of the onium ions represented by the general formulas (1), (3), and (4) by the method described above. 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 an alkali metal, preferably general formulas (1), (3), ( The ink of the present invention can also be obtained by adding the onium ion shown in 4).
[0065]
Specifically, there are the following methods for adding onium ions to the ink composition.
(I) Method of adding as a pH adjuster:
By adding onium hydroxide, onium carbonate, or the like as a pH value adjusting agent, onium ions can be added to the ink composition. That is, onium hydroxide, onium carbonate, etc. have acid-base dissociation constants that are approximately equivalent to sodium hydroxide, sodium carbonate, etc., and conventionally, the pH of the ink is adjusted using sodium hydroxide, sodium carbonate, etc. It can be performed using onium in the same way as it was.
[0066]
(Ii) Method of adding as a dye counter ion:
-SO_ThreeThere are the following methods for adding as a counter ion of a dye having an acidic group such as H, —COOH, and —OH.
[0067]
(A) Acid precipitation method
It can be used when the dye precipitates when the pH value of the solution is lowered. Cations 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 the free acid type dye.
D^-M⁺+ H + X^-  → DH ↓ + M⁺X^-
(D is dye ion, M is Na, NH_Four, K and other cations, X^-Is Cl^-, NO^3-, SO₂ ^Four-, CH_ThreeCOO^-Anion. )
The precipitate is filtered, washed, and M as an impurity.⁺X^-except for. The dye thus obtained is dissolved in onium hydroxide and used in ink.
DH + [R₁R₂R_ThreeR_FourP] + OH^-  → D^-[R₁R₂R_ThreeR_FourP]⁺+ H₂O
[0068]
(B) Salting out method
Dissolve the dye in water, water-ethanol mixed solvent, water-methanol mixed solvent, water-acetone mixed solvent, add onium salts such as onium chloride, onium acetate, onium sulfate, etc. Allow to settle.
D^-M⁺+ [R₁R₂R_ThreeR_FourP] + X^-  → D [R₁R₂R_ThreeR_FourP] ↓ + M⁺X^-
The resulting precipitate is filtered, washed with the above solvent, etc.⁺X^-except for. This dye can be used in ink as it is.
[0069]
(C) Ion exchange method
Using a resin or membrane having a cation exchange capacity, the dye solution is directly converted into an onium salt by passing through the resin or membrane, or once converted into a free acid form as in the acid precipitation method of (a), and then onium hydroxide is used. To obtain the onium salt of the dye.
(A) The ion of the ion exchange group is converted into an onium type and allowed to pass through the dye solution.
R^-[R₁R₂R_ThreeR_FourP]⁺+ D^-M⁺  → R^-M⁺+ D^-[R₁R₂R_ThreeR_FourP]⁺
(R^-Is an ion exchange resin or membrane ion exchange group)
(B) The ion exchange group is H⁺Mold and pass dye solution through. In this case, it is particularly suitable for ion exchange of an acid dye having high solubility of a free acid type dye.
R^-H⁺+ D^-M⁺  → D^-H⁺+ R^-M⁺
[0070]
(D) Onium salt addition method in the synthesis stage
An onium salt is used as a material for synthesizing the dye. For example, when an acidic compound in a raw material is dissolved and added, a conventional method of dissolving using NaOH is dissolved using onium hydroxide. NaNO used for diazotization₂Instead of [R₁R₂R_ThreeR_FourP] + NO₂Is used. In order to perform alkali coupling, NaOH, Na₂CO_ThreeHowever, instead of this, a method of adding an onium salt can be mentioned.
[0071]
(E) Extraction method
D^-M⁺And D^-[R₁R₂R_ThreeR_FourP]⁺Or D^-H⁺D obtained by utilizing the difference in solubility in a specific solvent^-[R₁R₂R_ThreeR_FourP]⁺Is used for ink. For example, D^-M⁺After dissolving the dye, onium salt is added, the solvent in the solution is evaporated to dryness, and the onium salt of the dye and M⁺After obtaining a mixture with a salt, Soxhlet extraction is performed with an organic solvent such as methanol to obtain an onium salt of a dye having high solubility in methanol.
[0072]
(Iii) A method of adding as a counter ion of additives to inks other than dyes:
(A) Electrical conductivity regulator: Conventional NaCl, LiCl, Na₂SO_Four, NaNO_ThreeEtc. are used, but onium salts can be used instead.
(B) Preservatives: dehydroacetic acid soda, sodium benzoate, 2-pyridinethiol oxide sodium salt, 1,2-benzisothiazolin-3-one sodium salt, etc. are used. Use onium salts instead.
(C) Surfactant: Onium is used in place of sodium, which is an anionic surfactant such as dodecylbenzenesulfonic acid / sodium salt.
(D) Chelating agent: An onium salt is used in place of the EDTA trisodium salt.
[0073]
In order to add onium ions to the ink composition, it is added as onium hydroxide or onium carbonate as a pH value adjusting agent, or as a counter ion of a dye containing an acidic group such as sulfonic acid or carboxylic acid. Most preferred. Whether used as a pH adjuster or as a counter ion for ink raw materials such as other dyes, most of the onium ions are dissociated in the ink [R₁R₂R_ThreeR_FourP]⁺However, the cation in the ink is usually the most present as the counter ion of the dye in terms of quantity. Na other than onium contained in the ink⁺, K⁺, NH_Four ⁺Since the effect of the present invention is greater when the number of ions such as the number is as small as possible, it is preferable to change the counter ion (cation) of the dye to onium according to any of the above or other methods.
[0074]
Thus, when the anionic compound is available in free acid form, it is not necessary to replace the free acid type compound with a salt other than alkali metal at the time of ink preparation, and more than 30% with respect to the equivalent amount of the anionic compound. Preferably, the anionic compound having the counter cation is contained in the ink by adding 50% 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. As a result, the work required to manufacture the ink is simplified, the resulting ink can be made inexpensive, and the elution of glass, silicon, silicon oxide, etc. can be prevented very easily. preferable.
[0075]
When the counter ion is an onium ion represented by the general formulas (1), (3), and (4), it has a substituted or substituted alkyl group, and the number of carbon atoms in one molecular ion is 4 to 12 Preferably there is. When the number of carbon atoms exceeds 12, the solubility in a solvent such as water decreases, and the tendency to clog during printing pause or continuous printing, or to cause separation or precipitation of ink during storage of the ink is increased. Increased tendency to cause side effects.
[0076]
Counter ion of onium salt represented by general formula (1), (3), (4): X^-Is an inorganic anion such as halogen ion, nitrate ion, nitrite ion, acetate ion, phosphate ion, sulfate ion and organic such as formic acid, acetic acid, propionic acid, tangle acid, valeric acid, glycolic acid, gluconic acid, lactic acid Any organic anion derived from an acid may be used, but it is preferably ionically dissociated at a high rate in the ink. Therefore, one selected from a halogen ion, a nitrate ion, a nitrite ion, and an acetate ion. Valent anions are preferred, with hydroxyl ions being particularly preferred.
[0077]
As shown in the following reaction formula, a sulfonium salt can be synthesized by reacting a sulfur compound and a halogenated alkyl compound while heating in a solvent, and then a sulfonium salt can be synthesized and then subjected to a salt exchange reaction with a desired counter ion. Can be synthesized. For example, when dimethyl sulfide and chlorobenzene are reacted in acetonitrile, 50 can be synthesized, followed by salt exchange with sodium hydroxide to produce a sulfonium salt of hydroxyl ion.
In addition, the synthesis | combination of a phosphonium salt and an arsonium salt can be manufactured by using a phosphorus compound or an arsenic compound instead of a sulfur compound in the following reaction formula.
[Chemical 9]
(X^-Is the same as above, Y^-Is X^-Is a counter ion after salt exchange. )
[0078]
Further, as X goes to the left, the influence of the electron-withdrawing group is higher, the cationicity becomes stronger, the adhesion to the silicon substrate increases, and the corrosion prevention effect is expected to increase.
[0079]
In addition to these onium ions, a normal cationic resin such as polyallylamine and polyethyleneimine can be obtained with the same effect when added in an amount of about 1%. In addition, the acetylene surfactants orphine B, P, surfinol 61 and the like having a triple-bonded cylindrical electron cloud (pi-electrons) and an active hydrogen atom of the adjacent OH group are oriented or complexed on the glass or silicon surface. It is easily generated and shows the same effect as onium ions. In addition, cationic dyes, which are cationic coloring materials, cationic carbon black, cationic pigments, and boron compounds are also oriented on the surface of glass or silicon and exhibit the same effect as onium ions.
[0080]
Specific examples of cationic compounds include dicyandiamide / formalin polycondensate, dicyandiamide / diethylenetriamine polycondensate, epichlorohydrin / dimethylamine addition polymer, dimethyldiallylammonium chloride / SO2 copolymer, dimethyldiallylammonium chloride. Polymer, allylamine salt polymer, dialkylaminoethyl (meth) acrylate quaternary salt polymer, polyallylamine, cationic epoxy resin, polyethyleneimine, polyacrylamide, poly (meth) acrylic acid ester, polyvinylformamide, aminoacetalized polyvinyl Examples include alcohol, polyvinyl pyridine, polyvinyl benzylonium, and cationic emulsion.
[0081]
Commercially available cationic compounds can be used. Specifically, Sunstat E-818, Sunfix 70, Sunfix 555C, Sunfix LC-55, Sanfux PAC-700 Conch, Sanyo Elion A -3, Sunfix 414, Sunfix 555, Sunfix PRO-100, Sunfix 555US, Cellophor YM-500 (above, manufactured by Sanyo Chemical Industries), # 675, # FR-2P, # 1001 (above, Sumitomo Chemical) Industrial Products), LUPASOL SC61B (BASF) and the like. Moreover, ZP-700 (vinyl formamide type), MP-184 (polyacrylic acid ester type), MP-173H (polymethacrylic acid ester type), MP-180 (polymethacrylic acid ester type), MX-0210 (polymethacrylic acid type) Acid ester), MX-8130 (polyacrylate ester), E-395 (polyacrylate ester), E-305 (polyacrylate ester), Q-105H (dicyandiamide), Neo-600 ( (Polyacrylamide) (above, manufactured by Hymo), Super Flock 2490 (Polyacrylate), Super Flock 3180, 3380, 3580, 3880, 3390, 3590, 3500, SD2081 (Polyacrylamide), Acofloc C498T, C498Y ( Polyacrylic acid S Super Flock 1500, 1600, Acofloc C481, C483, C485, C488, C480 (polymethacrylate) (above, made by Mitsui Cytec), PAS-A-1, PAS-A-5, PAS -A-120L, PAS-A-120S, PSA-J-81, PAS-880, PAS-92 (diallyldimethylammonium salt copolymer), PAS-H-5L, PAS-H-10L, PAS-M -1 (diallyldimethylammonium salt polymer) (above, manufactured by Nitto Boseki Co., Ltd.), PAA-HCl-3L, PAA-HCl-10L (polyallylamine hydrochloride), PAA-10C (polyallylamine) (above, Nittobo Q-101 (polyamine type), Q-311 (polyamine type), Q-501 (polyamine type) On, manufactured by Hymo Co., Ltd.), Akofurokku C567, C573, C577, C581 (polyamine-based) (or include Mitsui Cytec Co., Ltd.).
[0082]
Examples of the cationic emulsion include Acryt UW319-SX, Acryt RKW-460, Acryt RKW-400SX, Acryt RKW-450SX, Acryt RKW-450 (manufactured by Taisei Corporation).
[0083]
These cationic resins and cationic emulsions may be used alone or in combination of two or more.
[0084]
Specifically, the types of acetylene compounds include Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104PA, Surfinol 104S, Surfinol 420, Surfinol manufactured by Nissin Chemical Industry Co., Ltd. 440, Surfinol 465, Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 504, Surfinol DF110D, Surfinol DF110L, Surfinol DF37, Surfinol DF58, Surfinol DF75, Surfinol DF210, Surfinol CT111, Surfinol CT121, Surfinol CT131, Surfinol CT151, Surfinol TG, Surfinol GA, Finoru 61, Olfine B, OLFINE P, OLFINE Y, OLFINE A, Olfine STG, Olfine SPC, Olfine E1004, Olfine E1010, and the like OLFINE AK-02.
[0085]
The water-based ink composition of the present invention can reduce elution of glass and silicon by including a color material with a resin or containing colored resin fine particles colored with a color material. The reason for this is that in the case of carbon black, impurities in the colorant, especially in the case of carbon black, it is considered that the acidic component contained in the carbon black dissolves glass and silicon. It is thought that the action of can be reduced. Specifically, microencapsulated carbon black and microencapsulated color pigment manufactured by Dainippon Ink and Chemicals, Inc., microencapsulated carbon black manufactured by Toyo Ink, resin fine particles manufactured by Toyobo, dyes manufactured by Kao Examples include pigment emulsion inks.
[0086]
Specific examples of boron compounds preferably contained in the water-based ink composition include triisopropyl borate, triethyloxonium tetrafluoroborate, triethyl borate, tributyl borate, tri-tert-butyl borate, tri- There are iso-propyl borate, trimethyl borate and the like. Examples of the surfactant include boron surfactant Emalbon (manufactured by Toho Chemical Industry Co., Ltd.) and diglycerin borate (manufactured by Boron International Co., Ltd.) (compounds No. 77 and No. 78, respectively). These semipolar boron compounds are compounds having positive (+) and negative (−) polarities in the molecule in the organic boron compound. An organic boron compound having a B—O bond usually forms a plane bond with a bond angle of 120 degrees because boron has a coordination number of 3, but the semipolar boron compound has an electron donating group attracted to the boron bond. It has a tetrahedral structure.
It is considered that the surface of the glass or silicon substrate has a negative (−) charge, and the boron compound forms a negative (−) repulsive layer to prevent the elution of the glass or silicon.
[0087]
[Chemical Formula 10]
Embedded image
[0088]
Further, beryllium ions (Be) preferably contained in the water-based ink composition.²⁺), Aluminum ions (Al³⁺), Zinc ion (Zn²⁺), Titanium ions (Ti⁴⁺), Zirconium ions (Zr⁴⁺), Silicate ions (Si²⁺As for ()), the following can be exemplified, but the invention is not limited to these, and those other than these can be widely used.
[0089]
About beryllium ion:
Beryllium oxide, beryllium hydroxide, beryllium sulfate tetrahydrate, etc.
[0090]
About aluminum ions:
Aluminum acetyl acetate, aluminum isopropylate, aluminum isopropoxide, aluminum ethylate, aluminum ethoxide, aluminum triisopropoxide, aluminum triethoxide, aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-tert -Butoxide, aluminum trimethoxide, aluminum n-butyrate, aluminum sec-butyrate, aluminum-n-butoxide, aluminum-sec-butoxide, aluminum-tert-butoxide, aluminum-iso-propyrate, aluminum-iso-propoxide, aluminum Methylate, aluminum ethoxide, etc.
[0091]
About zinc ion:
Zinc chloride, ammonium zinc chloride, zinc chloride diethyl ether complex, zinc zinc chloride, zinc oleate, zinc formate dihydrate, zinc citrate, zinc acetate dihydrate, zinc salicylate trihydrate, zinc oxalate dihydrate Hydrates, zinc tartrate, zinc nitrate hexahydrate, zinc trifluoromethanesulfonate, etc.
[0092]
About titanium ions:
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.
[0093]
About zirconium ions:
Zirconium acetyl acetate, zirconium isopropoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium propirate, zirconium iso-propylate, zirconium iso-propoxide and the like.
[0094]
About silicide ions:
Tetramethylammonium silicide, ethyl silicide, tetraethyl orthosilicide, tetraethyl silicide, ammonium hexafluorosilicide, etc.
[0095]
The pH of the ink to which these additives are added is preferably 7 to 10, and if it is within this range, the glass or silicon substrate is not eluted. For elution of glass or silicon substrate, the lower the pH, the more preferable, 7 to 9 is more preferable, and 7 to 8 is most preferable.
[0096]
As a solvent of the ink recording liquid of the present invention, water is often used as a main component. However, in order to make the ink have desired physical properties, to prevent the ink from drying, and to improve the dissolution stability of the ink. Therefore, a water-soluble organic solvent can be used for the purpose.
[0097]
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-hexanetriol, Polyhydric alcohols such as 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether Polyhydric alcohol alkyl ethers such as tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether, ethylene glycol Polyhydric alcohol aryl ethers such as ethylene monophenyl ether, 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, N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine and triethylamine Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol, propylene carbonate, ethylene carbonate, γ-butyrolactone, and the like can be used. These solvents can be used alone or in combination with water.
[0098]
Among 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 by using these, clogging due to drying of ink, that is, jetting characteristics due to water evaporation Excellent effects can be obtained in preventing defects and improving the dissolution stability of the ink of the present invention.
[0099]
As the colorant used in the present invention, any colorant may be used as long as it satisfies the alkali metal content (about 1000 ppm) in the ink shown in the present invention by reducing the alkali metal by the above-described method or the like. it can.
[0100]
As the water-soluble dye, dyes classified in the color index into acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes, preferably those having excellent water resistance and light resistance are used.
[0101]
If these dyes are specifically mentioned, as acid dyes and food dyes,
C. I. Acid Yellow 17, 23, 42, 44, 79, 142
C. I. Acid Red 1,8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 289
C. I. Acid Blue 9, 29, 45, 92, 249
C. I. Acid Black 1, 2, 7, 24, 26, 94
C. I. Food yellow 3, 4
C. I. Food Red 7, 9, 14
C. I. Food black 1, 2
[0102]
As direct dye,
C. I. Direct yellow 1,12,24,26,33,44,50,86,120,132,142,144
C. I. Direct Red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227
C. I. Direct orange 26, 29, 62, 102
C. I. Direct Blue 1,2,6,15,22,25,71,76,79,86,87,90,98,163,165,199,202
C. I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171
[0103]
As a basic dye,
C. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91
C. I. Basic Red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70, 73, 78, 82, 102, 104, 109, 112
C. I. Basic blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155
C. I. Basic black 2,8
[0104]
As a reactive dye,
C. I. Reactive Black 3, 4, 7, 11, 12, 17
C. I. Reactive Yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67
C. I. Reactive Red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97
C. I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, etc. can be used. In particular, acid dyes and direct dyes can be preferably used.
[0105]
Of course, a newly developed dye for inkjet can also be used. Examples include Projet Fast B1ack2, Projet Fast Magenta2, Projet Fast Yel1ow2, and Projet Fast Cyan2 (registered product name) manufactured by Abyssia.
[0106]
As pigments, inorganic pigments are manufactured by known methods such as contact method, furnace method, thermal method in addition to titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow. Carbon black can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acid dye chelates), nitro pigments, nitroso pigments, aniline black, etc. .
[0107]
Of these pigments, those having good affinity with the solvent are preferably used. The amount of pigment added as a colorant in the ink composition is preferably about 0.5 to 25% by weight, more preferably about 2 to 15% by weight.
[0108]
Specific examples of pigments preferably used in the present invention include black for carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, or copper, iron (C.I. CI pigment black 11), metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1). Further, for color use, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 81, 83, 95, 97, 98, 100, 101, 104, 408 109, 110, 117, 120, 138, 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 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like.
[0109]
In addition, the surface of pigment (for example, carbon) can be dispersed in water by adding a functional group such as a sulfone group or a carboxyl group to the surface of the pigment (for example, carbon) that has been treated with resin to disperse in water. The processed pigment etc. which were made can be used. Further, the pigment may be included in the microcapsule so that the pigment can be dispersed in water.
[0110]
According to a preferred embodiment of the present invention, the pigment in the ink preferably has an average particle size in the range of 50 nm to 200 nm. The average particle diameter here refers to a value of 50% volume cumulative percentage. In order to measure the volume cumulative percentage of 50%, for example, laser light is irradiated to particles that perform Brownian motion in ink, and the frequency (light frequency) of light returning from the particles (backscattered light) is measured. ) Can be used as a dynamic light scattering method (Doppler scattered light analysis) for obtaining the particle diameter from the change amount.
[0111]
Any pigment dispersant can be used as long as it satisfies the alkali metal content in the ink shown in the present invention by reducing the alkali metal as it is or by the method described above.
[0112]
The pigment is preferably added to the recording liquid as a pigment dispersion obtained by dispersing the pigment in an aqueous medium with a dispersant. As a preferable dispersing agent, a known dispersing agent used for preparing a conventionally known pigment dispersion can be used.
[0113]
Examples of the polymer dispersant include the following.
As a hydrophilic polymer, naturally occurring gum arabic, tragan gum, guar gum, karaya gum, low-strength bean gum, arabinogalactone, pectin, quince seed starch and other seaweed polymers, alginic acid, carrageenan, agar, etc. Animal polymers such as gelatin, casein, albumin and collagen, microbial polymers such as xanthene gum and dextran, and fibrin polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose in the semi-synthetic system, Starch polymers such as sodium starch glycolate and sodium starch phosphate, seaweed polymers such as sodium alginate and propylene glycol alginate, Phosphoric 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 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-acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate- Maleate copolymer, vinyl acetate-croton Copolymers, vinyl acetate - acrylic acid copolymer and the like.
[0114]
These copolymers preferably have a weight average molecular weight (Mw) of 3,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 15,000. The ratio (Mw / Mn) of Mw to number average molecular weight (Mw) is preferably 0.8 to 1.3, more preferably 0.9 to 1.1.
[0115]
The addition amount of the polymer dispersant may be appropriately added singly or in combination as long as the pigment is stably dispersed and the other effects of the present invention are not lost. The ratio of pigment to dispersant is preferably in the range of 1: 0.06 to 1: 3, more preferably in the range of 1: 0.125 to 1: 3.
[0116]
It is also possible to use a water-soluble surfactant as a pigment dispersant. In this case, the increase in the ink viscosity with respect to the amount used is smaller than when the polymer dispersant is used, and it is easy to obtain a pigment ink having good ejection characteristics when used in the ink jet recording method.
[0117]
Specific examples of water-soluble surfactants used as pigment dispersants include, for example, anionic surfactants such as alkyl aryl sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkyl sulfosuccinates. Acid salt, 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 sulfonate, Alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl ether sulfate ester, ether carboxylate, sulfosuccinate, α-sulfo fat Esters, fatty acid salts, condensates of higher fatty acid and an amino acid, a naphthenic acid salt or the like.
[0118]
Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts, onium salts and the like.
[0119]
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol ester, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid ester, polyoxyethylene polyoxy Propylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, fatty acid alkanolamide, amine oxide, polyoxyethylene alkylamine, Glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fat Esters, polyoxyethylene sorbitol fatty acid esters, alkyl (poly) Gurikokishido like.
[0120]
Examples of amphoteric surfactants include imidazoline derivatives such as imidazolinium betaine, dimethylalkyl lauryl betaine, alkyl glycine, and alkyldi (aminoethyl) glycine.
[0121]
The amount of the surfactant added as the dispersant may be suitably added singly or in combination as long as the pigment is stably dispersed and the other effects of the present invention are not lost.
[0122]
In addition to the above colorant and solvent, conventionally known additives can be added to the ink of the present invention. Any of these may be used as long as they satisfy the alkali metal content in the ink shown in the present invention by reducing the alkali metal by the above-described method or the like.
[0123]
For example, a penetrant can be added for the purpose of adjusting the surface tension of the ink. Examples of such penetrant include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3. -Polyhydric alcohols such as 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, tetraethylene glycol chlorophenyl ether, etc. Alkyl and aryl ethers of polyhydric alcohols, polyoxyethylene polyoxypropylene block copolymers, fluorosurfactants, lower alcohols such as ethanol and 2-propanol Kind, and the like.
[0124]
Furthermore, the surface tension of the recording liquid is adjusted to improve the permeability to the recording material, and the recording liquid discharge stability is improved by improving the wettability of the recording liquid to the head member of the ink jet printer. A surfactant can be added for the purpose.
[0125]
For example, as anionic surfactant, alkyl allyl, alkyl phosphate, alkyl sulfate, alkyl sulfonate, alkyl ether sulfate, 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 sulfonate, alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl Ether sulfate ester salt, ether carboxylate, sulfosuccinate, α-sulfo fatty acid ester, fatty acid salt, higher fatty acid and amino acid condensate, naphthenate, etc. .
[0126]
Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts, onium salts and the like.
[0127]
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol ester, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid ester, polyoxyethylene polyoxy Propylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, fatty acid alkanolamide, amine oxide, polyoxyethylene alkylamine, Glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fat Esters, polyoxyethylene sorbitol fatty acid esters, alkyl (poly) Gurikokishido like.
[0128]
Examples of amphoteric surfactants include imidazoline derivatives such as imidazolinium betaine, dimethylalkyl lauryl betaine, alkyl glycine, and alkyldi (aminoethyl) glycine.
[0129]
The addition amount of these surfactants in the ink composition is 0.01 wt% to 5.0 wt%, preferably 0.5 wt% to 3 wt%. If it is less than 0.01% by weight, there is no effect, and if it is more than 5.0% by weight, the permeability to the recording medium is unnecessarily high, and there is a problem in that the image density is lowered and the back-through occurs. In addition, the said surfactant can be used individually or in mixture of 2 or more types.
[0130]
Examples of antiseptic / antifungal agents include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, etc., among which the alkali metal content of the present invention is achieved. For this purpose, it is particularly preferable to use 1,2-dibenzylisothiazolin-3-one (Proxel CRL, Proxel LV, Proxel BDN, Proxel GXL, Sunpack AP manufactured by Sanai Oil Co., Ltd., manufactured by Avicia).
[0131]
As the pH adjuster, 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 alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate. Of these, amines such as diethanolamine and triethanolamine, ammonium hydroxide, quaternary ammonium hydroxide, quaternary onium hydroxide and the like may be used to achieve the alkali metal content of the present invention. Particularly preferred.
[0132]
In addition, a rust preventive agent, a water-soluble ultraviolet absorber, a water-soluble infrared absorber and the like can be added according to the purpose.
[0133]
An ink jet recording apparatus including a recording unit having a recording liquid storage portion storing the recording liquid of the present invention and a recording head for discharging recording droplets will be described with reference to the accompanying drawings. It is only one of them and does not limit the present invention.
[0134]
FIG. 1 is a schematic front view of a mechanism portion of a serial type ink jet recording apparatus equipped with an ink cartridge equipped with a recording liquid storage portion storing a recording liquid of the present invention. The mechanism portion of this ink jet recording apparatus lays the main support guide rod 3 and the sub support guide rod 4 between the side plates 1 and 2 on both sides in a substantially horizontal positional relationship, and the main support guide rod 3 and the sub support guide. The carriage 4 is supported by the rod 4 so as to be slidable in the main scanning direction. The carriage unit 5 has four heads 6 for ejecting yellow (Y) ink, magenta (M) ink, cyan (C) ink, and black (Bk) ink, respectively, and an ejection surface (nozzle surface) 6a. The four ink cartridges 7y, 7m, 7c, and 7k, which are ink supply bodies for each color, are mounted downward and are supplied to the four heads 6 on the upper side of the heads 6 of the carriage unit 5. Is installed in a replaceable manner.
[0135]
The carriage unit 5 is connected to a timing belt 11 stretched between a drive pulley (drive timing pulley) 9 and a driven pulley (idler pulley) 10 that are rotated by the main scan motor 8, and the main scan motor 8 is connected to the carriage unit 5. By controlling the driving, the carriage 5, that is, the four heads 6 are moved in the main scanning direction.
[0136]
Further, sub frames 13 and 14 are erected on the bottom plate 12 connecting the side plates 1 and 2, and a conveying roller 15 for feeding the paper 16 in the sub scanning direction orthogonal to the main scanning direction is provided between the sub frames 13 and 14. Holds freely. A sub-scanning motor 17 is disposed on the side of the sub-frame 14, and a gear 18 fixed to the rotation shaft of the sub-scanning motor 17 and the transporting roller 15 in order to transmit the rotation of the sub-scanning motor 17 to the transporting roller 15. And a gear 19 fixed to the shaft.
[0137]
Further, a reliability maintenance / recovery mechanism (hereinafter referred to as “subsystem”) 21 of the head 6 is disposed between the side plate 1 and the subframe 12. The sub-system 21 holds four cap means 22 for capping the ejection surface of each head 6 by a holder 23, and this holder 23 is held by a link member 24 so as to be swingable so that the carriage unit 5 can move in the main scanning direction. When the carriage unit 5 comes into contact with the engaging portion 25 provided on the holder 23 by the movement of the holder 23, the holder 23 is lifted up according to the movement of the carriage unit 5 and the ejection surface 6a of the inkjet head 6 is capped by the cap means 22, As the carriage unit 5 moves to the printing region side, the holder 23 is lifted down as the carriage unit 5 moves, so that the cap means 22 moves away from the ejection surface 6 a of the inkjet head 6.
[0138]
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. The suction pump 27 discharges the sucked waste liquid to a waste liquid storage tank (not shown) through a drain tube or the like.
[0139]
Further, on the side of the holder 23, a wiper blade 28, which is a wiping means made of an elastic member such as a fiber member, a foam member, or rubber, for wiping the discharge surface 6a of the inkjet head 6 is attached to a blade arm 29. Reference numeral 29 is pivotally supported so that it can be swung by rotation of a cam that is rotated by a driving means (not shown).
[0140]
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 into the recording apparatus, and FIG. 3 is a front sectional view of the ink cartridge.
As shown in FIG. 3, the ink cartridge 7 includes an ink absorber 42 that absorbs ink of a required color in a cartridge main body 41. The cartridge body 41 is formed by adhering or welding an upper lid member 44 to an upper opening of a case 43 having a wide opening at the upper portion, 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, and after being compressed and inserted into the cartridge body 41, the ink is absorbed.
[0141]
An ink supply port for supplying ink to the recording head 6 is formed at the bottom of the case 43 of the cartridge main body 41. The ink supply port is pressed by a pressing member 45, and is formed on the inner peripheral surface of the pressing member 45 of the ink supply port. Is fitted with a seal ring 46. The upper lid member 44 has an air opening 47 formed therein.
In the cartridge main body 41, the case 43 is compressed and deformed by the pressure applied to the wide side wall when the ink supply port is closed and the cartridge is handled during loading and transportation, or during vacuum packaging. In order to prevent internal ink from leaking, a cap member 50 is attached.
[0142]
Further, as shown in FIG. 2, the air opening 47 has an oxygen permeability of 100 ml / m.²The film-like sealing member 55 described above is adhered to the upper lid member 44 for sealing. The seal member 55 is sized to seal the plurality of grooves 48 formed around the air release port 47 as well as the atmosphere. By thus sealing the air opening 47 with the sealing member 55 having an oxygen permeability of 100 ml / m 2 or more, the ink cartridge 7 is packaged under reduced pressure using a packaging member such as a non-permeable aluminum laminate film. Therefore, even when the gas is dissolved in the ink due to the atmosphere in the space A (see FIG. 3) generated between the ink absorber 42 and the cartridge main body 41 during ink filling, The air is discharged into a space between the packaging body outside the cartridge main body 41 having a high degree of vacuum, and the degree of deaeration of the ink is improved.
[0143]
FIG. 4 shows and describes a configuration example of a recording unit including a recording liquid storage unit that stores the recording liquid of the present invention and a head unit for discharging recording droplets.
That is, the recording unit 30 is of a serial type, and is mainly composed of an inkjet head 6, an ink tank 41 that stores a recording liquid supplied to the inkjet head 6, and a lid member that seals the inside of the ink tank 41. The part is composed. The inkjet head 6 is formed with a large number of nozzles 32 for discharging a recording liquid. The recording liquid is guided from the ink tank 41 to a common liquid chamber (not shown) through an ink supply pipe (not shown), and is discharged from the nozzle 32 in accordance with an electrical signal from the recording apparatus main body input from the electrode 31. The Such a type of recording unit has a structure that is often used for a head of a type that can be manufactured at low cost, that is, a so-called thermal system or a head that uses thermal energy as a driving power source.
[0144]
A configuration example of the head unit for ejecting ink droplets will be described with reference to FIG. FIG. 5 is a cross-sectional side view of the entire electrostatic head unit.
The head of this configuration example has a laminated structure in which three silicon single crystal substrates 101, 102 (102a and 102b), 103 are stacked and bonded. The use of a silicon single crystal substrate is suitable for processing when a thin diaphragm (thickness of about several μm) for discharging ink is produced by etching, and a gap of about several μm is highly accurate. It is also a convenient material when forming by anodic bonding described later. Furthermore, when the diaphragm is vibrated by applying an electrostatic force, it is necessary to apply a voltage to the electrode to generate the electrostatic force, but since silicon is a semiconductor and can have a low resistance, The electrode on the diaphragm side can be substituted, and there is an advantage that it is not necessary to provide an electrode separately on the diaphragm side.
[0145]
The intermediate first substrate 101 includes a recess that forms a liquid chamber 106 having a bottom wall as a vibration plate 105, a narrow groove for an ink inflow port that forms a fluid resistance portion 107 provided at the rear of the recess, It has a recess that constitutes a common ink cavity 108 for supplying ink to the liquid chamber 106.
[0146]
Next, the lower second substrate 102 bonded to the lower surface of the first substrate 101 is obtained by providing a silicon oxide film 102a on a single crystal silicon substrate 102b. 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. In addition to silicon, the second substrate is also known using, for example, heat-resistant glass.
[0147]
Next, the upper third substrate 103 bonded to the upper surface of the first substrate 101 constitutes the nozzle hole 104, the ink discharge chamber 106, the fluid resistance portion 107 (member that regulates the flow of ink), and the ink cavity 108. The The substrate 103 is provided with an ink supply port 131 communicating with the ink cavity 108. The ink supply port 131 is connected to an ink cartridge (not shown) via a connection pipe and a tube (not shown). In addition to silicon, the third substrate is also known using, for example, glass, nickel, plastic, stainless steel, or the like.
[0148]
In the inkjet head of the configuration example using the electrostatic force configured as described above, when a positive pulse voltage is applied to the electrode 121 from the oscillation circuit 142, the surface of the electrode 121 is charged to a positive potential, and the corresponding diaphragm The lower surface of 105 is charged to a negative potential, and the vibration plate 105 bends downward due to electrostatic attraction.
[0149]
Next, when the application of the pulse voltage to the electrode 121 is turned off, the deflected diaphragm 105 is restored, so that the pressure in the liquid chamber 106 increases rapidly, and ink droplets 141 are formed from the nozzle holes 104. Ink is ejected toward an image receiver (not shown). Further, when the vibration plate 105 is bent downward again, ink is supplied 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. In recording, an electric pulse to be applied to the electrode 121 of each nozzle hole 104 is controlled.
[0150]
The ink of the present invention can suppress the elution of silicon and silicon oxide used in the printer as in the above configuration example, and the image quality is deteriorated due to the change of the ink droplet size and the discharge speed due to the decrease in the printer design accuracy In addition, it is possible to prevent problems such as occurrence of ejection failure and failure due to decrease in bonding strength of the joint, and clogging due to silicon elution into the ink can be prevented.
[0151]
【Example】
Examples of the present invention and comparative examples are shown below. Unless otherwise stated, the addition ratio refers to the weight percent of the active ingredient.
[0152]
(Synthesis method of sulfonium salt)
A 1-liter four-necked flask equipped with a sulfonium salt synthesis stirrer, reflux condenser, and thermometer was purged with nitrogen, and then 12.4 g (0.2 mol) of dimethyl sulfide and 200 ml of acetonitrile were added and mixed to dissolve. Then, 22.5 g (0.2 mol) of chlorobenzene dissolved in 100 ml of acetonitrile was added dropwise over 1 hour under stirring under heating and refluxing conditions, and the reaction was continued under heating and refluxing conditions while stirring for another 5 hours. A white crystal was precipitated.
Subsequently, the mixture was cooled to room temperature, and the precipitated crystals were separated by filtration and dried to obtain 30.2 g (yield 86.7%) of phenyldimethylsulfonium chloride. (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 with stirring, precipitation occurred and the mixture became cloudy and became a slurry. (Reaction Formula 2)
After completion of the dropwise addition, stirring was continued at room temperature for 1 hour, and then the crystals were filtered off and recrystallized from methanol to obtain 6.5 g (yield 83.0%) of phenyldimethylsulfonium hydroxide.
Elemental analysis of the phenyldimethylsulfonium hydroxide was performed. The results are shown in Table 7.
[0153]
(Schemes 1 and 2)
Embedded image
[0154]
[Table 7]
[0155]
Compound Nos. 27 to No. 50 sulfonium salts were synthesized in the same manner as described above.
However, when reacting a gaseous compound at room temperature, it was cooled with liquid nitrogen or the like and liquefied, or pressurized and reacted in an autoclave.
[0156]
[Table 8]
[0157]
Example 1
Black dye of the following formula: 3% by weight
Embedded image
Glycerin 5% by weight
20% ethylene glycol
Polyoxyethylene (3) tridecyl ether sodium acetate
(Nikko Chemicals, anionic surfactant) 1.0% by weight
Sunpack AP (manufactured by Sanai Oil Co., Ltd., fungicides) 0.4% by weight
Tetrabutylphosphonium hydroxide
(Aldrich reagent: corrosion inhibitor) 1.0% by weight
Remaining amount of ion exchange water
The mixture of the above formulation was continuously stirred at 50 ° C. for 4 hours, and after cooling, filtered through a filter having a pore size of 0.1 μm.
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 814 ppm. The pH value was 9.5.
[0158]
This ink is composed of a surface on which a silicon oxide film of 1000 mm is provided by thermal oxidation treatment on the surface of the vibration plate 110, a liquid chamber composed of heat-resistant glass # 7740, 100 surface, 110 surface, 111 surface silicon, 100 surface And an ink jet printer of a type in which the diaphragm is deformed and discharged by electrostatic force consisting of a nozzle and a fluid resistance, and subjected to a discharge test under the following conditions.
Drive frequency: 12KHz
Drive voltage: 23V
Nozzle diameter: 30 μm
Droplet volume: 30 pl / dot
Number of nozzles: 48 nozzles
Dot density: 600 dpi
[0159]
Test 1 (T1) Initial printing test
Printing was performed on three types of commercially available copy paper and three types of bond paper, and the characteristics of the images were examined.
[0160]
Test 2 (T2) Reliability test (printing test after printing pause, wettability)
After the printer was left in an environment of 50 ° C. and 60% RH for 1 month with ink filled, 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 the oxide film were measured. The thickness change amount of the glass and silicon was obtained by analyzing the ink after contact with the liquid by the liquid crystal emission spectroscopic analysis and converting it from the silicon concentration in the ink and the density of each material.
[0161]
In the initial printing test, a clear image having an image density of 1.3 or more was obtained on any paper. Even after printing was stopped, normal printing was possible without using any recovery means. As for wettability, the heat resistance glass # 7740 (trade name: Pyrex # 7740, manufactured by Corning Glrss Works, USA) has a thickness change of 0.18 μm, and the silicon thickness change amount is about 0.16 μm on the 100 side, 110 side Was about 0.06 μm, and the 111 surface was about 0.04 μm, which was a change in thickness with no problem as a liquid chamber, fluid resistance, or nozzle. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0162]
(Example 2)
The test was conducted in the same manner as in Example 1 except that 1.0% by weight of tributylsulfonium hydroxide (Compound No. 29 corrosion inhibitor) was used instead of tetrabutylphosphonium hydroxide in Example 1.
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. Even after printing was stopped, normal printing was possible without using any recovery means. As for wettability, the heat resistance glass # 7740 has a thickness change of 0.18 μm, and the silicon thickness change amount is about 0.16 μm on the 100 side, about 0.06 μm on the 110 side, and about 0.04 μm on the 111 side. The amount of change in the thickness was satisfactory for the liquid chamber, fluid resistance, and nozzle. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0163]
(Example 3)
Cyan dye of the following formula: 3% by weight
Embedded image
Glycerin 10% by weight
Diethylene glycol 10% by weight
Surfynol 465 (for acetylene alcohol)
Ethylene oxide additive; Air Products and Chemicals Inc.
Nonionic surfactant) 1.0% by weight
Diethylene glycol monobutyl ether 3% by weight
Proxel CRL (manufactured by Avicia, fungicides) 0.4% by weight
Tetrabutylphosphonium hydroxide
(Aldrich reagent: corrosion inhibitor) 0.5% by weight
Remaining amount of ion exchange water
While stirring the mixture of the above formulation at 50 ° C., stirring was continued for 4 hours. After cooling, the mixture was 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 alkali metal in the ink was 913 ppm. The pH value was 9.2.
[0164]
A printing test was performed on the ink using a printer equipped with the head having the configuration shown in FIG. 5, and a reliability test was performed. The head having the configuration shown in FIG. 5 was prepared under the following conditions.
The first substrate 101 comprises a (110) -oriented p-type single crystal silicon wafer polished on both sides, and the second substrate comprises a (100) -oriented p-type single crystal silicon wafer 102b polished on both sides and a thermal oxide film 102a. These substrates are subjected to anisotropic etching with a mask and an alkaline solution to form respective recesses corresponding to the liquid chamber 106, the fluid resistance portion 107, the ink cavity 108, etc., as shown in FIG. An electrode lead portion, an electrode terminal 123, and an insulating film 122 were formed. The thickness of the diaphragm 105 is 20 μm, and a silicon oxide film of 1000 mm is provided by thermal oxidation treatment.
Further, as shown in FIG. 5, a nozzle hole 104, an ink supply port 131, and the like are formed on the upper surface of the first substrate 101 by anisotropic dry etching on a (100) -oriented n-type single crystal silicon wafer polished on both sides. Then, the third substrate 103 was bonded, the oscillation circuit 142 and the like were connected as shown in the figure, and a positive pulse voltage was applied to the electrode terminal 123 for printing.
Therefore, the surface in contact with the ink is the surface on which the vibration plate is formed on the 110th surface by 1000 mm of silicon oxide film by thermal oxidation treatment, the liquid chamber is 100th surface, the 110th surface, the 111th surface silicon, the nozzle is 100th surface, The silicon of the isotropic dry etching surface and the silicon of the fluid resistance portion are 100 surfaces and 110 surfaces.
[0165]
The printer printing conditions were as follows.
Drive frequency: 12KHz
Drive voltage: 23V
Nozzle diameter: 30 μm
Droplet volume: 30 pl / dot
Number of nozzles: 48 nozzles
Dot density: 600 dpi
[0166]
Test 1 (T1) Initial printing test
Printing was performed on three types of commercially available copy paper and three types of bond paper, and the characteristics of the images were examined.
[0167]
Test 2 (T2) Printing test after printing pause, silicon wettability
After the printer was left in an environment of 50 ° C. and 60% RH for 1 month with ink filled, printing was performed to test whether normal printing was possible. Further, the amount of change in the thickness of the silicon and the amount of change in the thickness of the oxide film were measured.
[0168]
In the initial printing test, a clear image having an image density of 1.3 or more was obtained on any paper. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the amount of change in the thickness of silicon is about 0.15 μm on the 100 side, about 0.06 μm on the 110 side, and about 0.04 μm on the 111 side. There was no change in thickness. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0169]
(Example 4)
The test was conducted in the same manner as in 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.
[0170]
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. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the amount of change in the thickness of silicon is about 0.15 μm on the 100 side, about 0.06 μm on the 110 side, and about 0.04 μm on the 111 side. There was no change in thickness. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0171]
(Example 5)
Yellow dye of the following formula: 2% by weight
Embedded image
Glycerin 3% by weight
10% by weight of triethylene glycol
Embedded image
Dialkylsulfosuccinates of the above formula
(Anionic surfactant) 1.0% by weight
2-ethyl-1,3-hexanediol 2% by weight
Proxel BND (Abyssia fungicide) 0.4% by weight
Remaining amount of ion exchange water
While stirring the mixture of the above formulation at 50 ° C., the hydroxide of the phosphonium compound of Chemical Formula 1 is 40% relative to the equivalent of the anionic compound in the ink, and the hydroxide of the phosphonium compound of Chemical Formula 3 is the anion in the ink. 40% of the equivalent amount of the active compound was added. Stirring was continued for 4 hours as it was, 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 spectroscopic analysis, the content of alkali metal in the ink was 29 ppm. The pH value was 9.7.
[0172]
When the above ink was tested in the same manner as in Example 1 (using an alkali-free glass substrate instead of the heat-resistant glass # 7740), the initial print test showed a clear image density of 0.9 or higher on any paper. A good image was obtained. Even after printing was stopped, normal printing was possible without using any recovery means. As for wettability, the non-alkali glass substrate (OA-2 manufactured by Nippon Electric Glass Co., Ltd.) has a thickness change of 0.19 μm, and the silicon thickness change amount is about 0.15 μm on the 100 side and about 0.07 μm on the 110 side. , 111 surface was about 0.05 μm, and the amount of change in thickness was satisfactory as a liquid chamber, a fluid resistance portion, and a nozzle. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0173]
(Example 6)
In Example 5, compound no. 1 to 40% of the equivalent of the anionic compound in the ink. Instead of adding 40% of the phosphonium compound hydroxide to the equivalent of the anionic compound in the ink, compound no. Except that 27% of the sulfonium compound hydroxide was added to 40% of the anionic compound equivalent in the ink and 40% of the sulfonium compound hydroxide of the chemical formula 29 was added to the equivalent of the anionic compound in the ink. The test was conducted in the same manner as in No. 5.
[0174]
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. Even after printing was stopped, normal printing was possible without using any recovery means. As for wettability, the non-alkali glass substrate (OA-2 manufactured by Nippon Electric Glass Co., Ltd.) has a thickness change of 0.19 μm, and the silicon thickness change amount is about 0.15 μm on the 100 side and about 0.07 μm on the 110 side. , 111 surface was about 0.05 μm, and the amount of change in thickness was satisfactory as a liquid chamber, a fluid resistance portion, and a nozzle. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0175]
(Example 7)
Magenta dye of the following formula: 2.5% by weight
Embedded image
Diethylene glycol 20% by weight
Polyoxyethylene (6) tridecyl ether sodium acetate
(Nikko Chemicals, anionic surfactant) 0.3% by weight
2-pyrrolidone 2% by weight
Proxel GXL (manufactured by Avicia, fungicides) 0.4% by weight
Surfinol 61
(3,5-dimethyl-1-hexyn-3-ol) 0.9% by weight
Remaining amount of ion exchange water
The mixture having the above formulation was continuously stirred at 50 ° C. for 4 hours. After cooling, the mixture was filtered with a filter having a pore size of 0.1 μm.
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 460 ppm. The pH value was 10.1.
[0176]
When the above ink was tested in the same manner as in Example 4, a clear image with an image density of 1.1 or more was obtained on any paper in the initial printing test. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettedness, the change in thickness of silicon is about 0.32 μm on the 100 side, about 0.10 μm on the 110 side, and about 0.08 μm on the 111 side, which is problematic as a liquid chamber, fluid resistance part, and nozzle. There was no change in thickness. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0177]
(Example 8)
Except that 0.9% by weight of beryllium hydroxide (corrosion inhibitor) was used instead of Surfynol 61 (3,5-dimethyl-1-hexyn-3-ol) in Example 7, the same procedure as in Example 7 was performed. A test was conducted.
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. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettedness, the change in thickness of silicon is about 0.32 μm on the 100 side, about 0.10 μm on the 110 side, and about 0.08 μm on the 111 side, which is problematic as a liquid chamber, fluid resistance part, and nozzle. There was no change in thickness. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0178]
Example 9
Carboxyl group-bonded carbon black dispersion
(Average particle size 128 nm) 5% by weight
Glycerin 10% by weight
Diethylene glycol 10% by weight
Polyoxyethylene (3) tridecyl ether sodium acetate
(Nikko Chemicals, anionic surfactant) 1.0% by weight
2-pyrrolidone 2% by weight
2-ethyl-1,3-hexanediol 2% by weight
Sunpack AP (manufactured by Sanai Oil, fungicides) 0.4% by weight
Orphin B (3-methyl-1-butyne-3-
All Nissin Chemical Industry Co., Ltd .: corrosion inhibitor) 0.5% by weight
Remaining amount of ion exchange water
While stirring the mixture of the above formulation at 50 ° C., stirring was continued for 4 hours. After cooling, the mixture was filtered with a filter having a pore size of 0.8 μm.
When this ink was analyzed by plasma emission spectrometry, the content of alkali metal in the ink was 1020 ppm. The pH value was 8.3.
[0179]
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. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the amount of change in the thickness of silicon is about 0.20 μm on the 100 side, about 0.07 μm on the 110 side, and about 0.04 μm on the 111 side. There was no change in thickness. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0180]
(Example 10)
Orphine B of Example 9 (similar to Example 9 except that 0.5% by weight of aluminum ethylate (corrosion inhibitor) was used in place of 3-methyl-1-butyn-3-ol. The test was conducted.
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. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the amount of change in the thickness of silicon is about 0.20 μm on the 100 side, about 0.07 μm on the 110 side, and about 0.04 μm on the 111 side. There was no change in thickness. Further, the film thickness change amount of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0181]
(Example 11)
Instead of the black dye of Example 1, 5% of a dispersion of cationic carbon black (manufactured by Cabot Specialty Chemicals Inc.) was added in solid content, and an ink having the following formulation except for tetrabutylphosphonium hydroxide was used. In the same manner as in Example 1, the mixture was continuously stirred at 50 ° C. for 4 hours, and after cooling, filtered through a filter having a pore size of 0.8 μm.
Cationic carbon black dispersion 5% by weight
Glycerin 5% by weight
20% ethylene glycol
Olfine E1010 1.0% by weight
Sunpack AP (manufactured by Sanai Oil, fungicides) 0.4% by weight
Remaining amount of ion exchange water
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 932 ppm. The pH value was 9.8.
[0182]
When the above ink was tested in the same manner as in Example 1 (using an alkali-free glass substrate instead of the heat-resistant glass # 7740), the initial print test showed a clear image density of 1.2 or higher on any paper. A good image was obtained. Even after printing was stopped, normal printing was possible without using any recovery means. In the liquid contact property, the thickness change of the alkali-free glass substrate (OA-10 manufactured by Nippon Electric Glass Co., Ltd.) is 0.31 μm, and the silicon thickness change amount is about 0.18 μm on the 100 side, about 0.08 μm on the 110 side, The 111 surface was about 0.05 μm, and the amount of change in thickness was satisfactory for the liquid chamber, fluid resistance portion, and nozzle. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 4 mm, which was a film thickness change that had no problem as a diaphragm.
[0183]
Example 12
A mixture of the same formulation as in Example 1 was stirred at 50 ° C. for 4 hours, except that 15% of the following dispersion was added as a cyan pigment instead of the black dye of Example 1 and the following compound was used as a corrosion inhibitor. Then, after cooling, it was filtered with a filter having a pore diameter of 0.8 μm.
[0184]
<Dispersion>
C. 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 wt%
Ethylene glycol 30% by weight
Residual amount of water
<Corrosion inhibitor>
Tributyl borate (Reagent manufactured by Kanto Chemical Co.) 0.1% by weight
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 932 ppm. The pH value was 9.8.
[0185]
When the above ink was tested in the same manner as in Example 1, a clear image with an image density of 1.3 or more was obtained on any paper in the initial printing test. Even after printing suspension, normal printing was possible without using any recovery means. As for wettability, the heat resistance glass # 7740 has a thickness change of 0.15 μm, and the silicon thickness change amount is about 0.18 μm on the 100 side, about 0.03 μm on the 110 side, and about 0.05 μm on the 111 side. The amount of change in the thickness of the liquid chamber, the fluid resistance, and the nozzle was satisfactory. Further, the change in film thickness of the silicon oxide film on the 110th surface was about 3 mm, which was a film thickness change that was not a problem as a diaphragm.
[0186]
(Example 13)
Instead of the cyan dye of Example 3, 20% by weight of the following dispersion was added as a yellow pigment, and a mixture having the same formulation as in Example 2 was used at 50 ° C., except that the following cationic compound was used as a corrosion inhibitor. Stirring was continued for a period of time, and after cooling, filtration was performed with a filter having a pore diameter of 0.8 μm.
<Dispersion>
C. 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 wt%
25% by weight of ethylene glycol
Residual amount of water
<Corrosion inhibitor>
Cationic polymer (Nippon Shokubai Co., Ltd.) 1.0% by weight
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 886 ppm. The pH value was 9.1.
[0187]
When the above ink was tested in the same manner as in Example 1, a clear image having an image density of 0.9 or more was obtained on any paper in the initial printing test. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the amount of change in the thickness of silicon is about 0.29 μm on the 100 side, about 0.13 μm on the 110 side, and about 0.10 μm on the 111 side, which is problematic as a liquid chamber, fluid resistance part, and nozzle. There was no change in thickness. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0188]
(Example 14)
The test was conducted in the same manner as in Example 13 except that 1.0% by weight of zinc chloride (corrosion inhibitor) was used instead of the cationic polymer of Example 13. 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. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the amount of change in the thickness of silicon is about 0.29 μm on the 100 side, about 0.13 μm on the 110 side, and about 0.10 μm on the 111 side, which is problematic as a liquid chamber, fluid resistance part, and nozzle. There was no change in thickness. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0189]
(Example 15)
The following colorant was used as a cationic yellow dye instead of the black dye of Example 1, and the ink having the following formulation except for tetrabutylphosphonium hydroxide was used. Stirring was continued for 4 hours, and after cooling, filtration was performed with a filter having a pore size of 0.3 μm.
[0190]
Cationic yellow dye Kayacrill ED (Nippon Kayaku Co., Ltd.) 3% by weight
Glycerin 5% by weight
20% ethylene glycol
2-ethyl-1,3-hexanediol 2.0% by weight
Sunpack AP (manufactured by Sanai Oil, fungicides) 0.4% by weight
Remaining amount of ion exchange water
<Corrosion inhibitor>
Cationic surfactant cation G-50
(Benzalkonium chloride manufactured by Sanyo Chemical Industries, Ltd.) 1.0% by weight
When this ink was analyzed by plasma emission spectral 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, in the initial printing test, a clear image having an image density of 1.2 or more was obtained on any paper. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the heat-resistant glass # 7740 has a thickness change of 0.15 μm, and the silicon thickness change is about 0.19 μm on the 100 side, about 0.11 μm on the 110 side, and about 0.12 μm on the 111 side. Yes, it was the amount of change in thickness with no problem as a liquid chamber, a fluid resistance portion, or a nozzle. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0191]
(Example 16)
A mixture having the same formulation as in Example 2 was stirred at 50 ° C. for 4 hours, except that 20% of the following dispersion was added as a yellow pigment in place of the cyan dye of Example 3 and the following compound was used as a corrosion inhibitor. Then, after cooling, it was filtered with a filter having a pore diameter of 0.8 μm.
<Dispersion>
C. 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 wt%
25% by weight of ethylene glycol
Residual amount of water
<Corrosion inhibitor>
Titanium ethylate 1.0% by weight
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 886 ppm. The pH value was 9.1.
[0192]
When the above ink was tested in the same manner as in Example 1, in the initial printing test, a clear image having an image density of 1.2 or more was obtained on any paper. Even after printing was stopped, normal printing was possible without using any recovery means. In silicon wettability, the change in thickness of silicon is about 0.19 μm on the 100 side, about 0.11 μm on the 110 side, and about 0.12 μm on the 111 side, which is problematic as a liquid chamber, fluid resistance part, and nozzle. There was no change in thickness. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0193]
(Example 17)
The following coloring material was used as a cationic magenta dye instead of the black dye of Example 1, and the ink having the following formulation except for tetrabutylphosphonium hydroxide was used. Stirring was continued for 4 hours, and after cooling, filtration was performed with a filter having a pore size of 0.3 μm.
[0194]
Cationic magenta dye Kayacrile ED (Nippon Kayaku Co., Ltd.) 3% by weight
Glycerin 5% by weight
20% ethylene glycol
Olfine E1010 1.0% by weight
Sunpack AP (manufactured by Sanai Oil, fungicides) 0.4% by weight
Remaining amount of ion exchange water
When this ink was analyzed by plasma emission spectrometry, the content of alkali metal in the ink was 958 ppm. The pH value was 9.7.
[0195]
When the above ink was tested in the same manner as in Example 1 (using blue plate glass instead of heat-resistant glass # 7740), in the initial printing test, a clear image having an image density of 1.1 or more was observed on any paper. was gotten. Even after printing was stopped, normal printing was possible without using any recovery means. In liquid contact, blue plate glass (soft glass manufactured by HOYA) has a thickness change of 0.21 μm, and silicon has a thickness change of about 0.25 μm for 100 surfaces, about 0.11 μm for 110 surfaces, and about 0.11 μm for 111 surfaces. The thickness change amount was 0.08 μm, and there was no problem with the thickness of the liquid chamber, the fluid resistance portion, and the nozzle. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0196]
(Example 18)
12% of the following dispersion was added as a magenta pigment in place of the yellow dye of Example 6, and a mixture having the same formulation as Example 6 was stirred at 50 ° C. for 4 hours, except that the following compound was used as a corrosion inhibitor. Then, after cooling, it was filtered with a filter having a pore diameter of 0.8 μm.
[0197]
<Dispersion>
C. I. Pigment Red 122 (average particle size 120 nm) 33% by weight
Dispersant (dipolyoxyethylene
Nonylphenyl ether phosphate) 17.5% by weight
No. 13 compounds 1.5% by weight
25% by weight of ethylene glycol
Residual amount of water
[0198]
<Corrosion inhibitor>
Zirconium isopropoxide 1.0% by weight
When this ink was analyzed by plasma emission spectrometry, the content of alkali metal in the ink was 958 ppm. The pH value was 9.7.
[0199]
When the above ink was tested in the same manner as in Example 1 (using blue plate glass instead of heat-resistant glass # 7740), in the initial printing test, a clear image having an image density of 1.1 or more was observed on any paper. was gotten. Even after printing was stopped, normal printing was possible without using any recovery means. As for wettability, the thickness change of blue plate glass (soft glass, manufactured by HOYA) is 0.21 μm, and the thickness change amount of silicon is about 0.25 μm for 100 surfaces, about 0.11 μm for 110 surfaces, and about 111 surfaces for 111 surfaces. The thickness change was about 0.08 μm, and there was no problem with the thickness of the liquid chamber, the fluid resistance portion, and the nozzle. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0200]
Example 19
The following coloring material was used as the microencapsulated carbon black instead of the black dye of Example 1, and the ink having the following formulation except for tetrabutylphosphonium hydroxide was used. Stirring was continued for 4 hours, and after cooling, filtration was performed with a filter having a pore size of 0.3 μm.
[0201]
Microencapsulated carbon black (average particle size 110nm)
(Dainippon Ink Chemical Co., Ltd.) 5% by weight
Glycerin 5% by weight
20% ethylene glycol
Olfine E1010 1.0% by weight
Sunpack AP (manufactured by Sanai Oil, fungicides) 0.4% by weight
Remaining amount of ion exchange water
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 156 ppm. The pH value was 9.7.
[0202]
When the above ink was tested in the same manner as in Example 1 (using photosensitive glass (manufactured by HOYA) instead of heat resistant glass # 7740), the initial print test showed an image density of 1.0 on any paper. The above clear image was obtained. Even after printing was stopped, normal printing was possible without using any recovery means. In liquid contact, the thickness change of photosensitive glass (manufactured by HOYA) is 0.21 μm, and the thickness change amount of silicon is about 0.26 μm for 100 surfaces, about 0.10 μm for 110 surfaces, and about 0 for 111 surfaces. It was 0.06 μm, and the amount of change in thickness was satisfactory as a liquid chamber, a fluid resistance portion, and a nozzle. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 4 mm, which was a film thickness change that had no problem as a diaphragm.
[0203]
(Example 20)
12% of the following dispersion was added as a magenta pigment in place of the yellow dye of Example 6, and a mixture having the same formulation as Example 6 was stirred at 50 ° C. for 4 hours, except that the following compound was used as a corrosion inhibitor. Then, after cooling, it was filtered with a filter having a pore diameter of 0.8 μm.
<Dispersion>
C. I. Pigment Red 122 (average particle size 120 nm) 33% by weight
Dispersant (dipolyoxyethylene nonyl
Phenyl ether phosphoric acid) 17.5% by weight
No. 13 compounds 1.5% by weight
25% by weight of ethylene glycol
Residual amount of water
<Corrosion inhibitor>
Tetramethylammonium silicate 1.0% by weight
When this ink was analyzed by plasma emission spectrometry, the content of alkali metal in the ink was 958 ppm. The pH value was 9.7.
[0204]
When the above ink was tested in the same manner as in Example 1 (photosensitive glass (manufactured by HOYA) was used instead of heat resistant glass # 7740), the initial print test showed an image density of 1. One or more clear images were obtained. Even after printing was stopped, normal printing was possible without using any recovery means. In liquid contact, the thickness change of photosensitive glass (manufactured by HOYA) is 0.21 μm, and the thickness change amount of silicon is about 0.25 μm on 100 side, about 0.11 μm on 110 side, and about 0 on 111 side. It was 0.08 μm, and the amount of change in thickness was satisfactory as a liquid chamber, a fluid resistance portion, and a nozzle. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 5 mm, which was a film thickness change that had no problem as a diaphragm.
[0205]
(Example 21)
As a yellow dye instead of the black dye of Example 1, Projet Fast Yellow 2 (manufactured by Avicia) was once converted into a free acid by using an ion exchange resin, and then compound No. 1 was obtained. A mixture having the same formulation as in Example 1 except that 3% of a dye partially substituted with a hydroxide of phosphonium compound 3 was added and stirred for 4 hours at 50 ° C. After cooling, a filter having a pore size of 0.8 μm I made a filter.
When this ink was analyzed by plasma emission spectrometry, the content of alkali metal in the ink was 630 ppm. The pH value was 9.6.
[0206]
When the above ink was tested in the same manner as in Example 1 (using a low alkali glass substrate instead of heat resistant glass # 7740), the initial printing test showed a clear image density of 0.9 or more on any paper. A good image was obtained. Even after printing was stopped, normal printing was possible without using any recovery means. In the liquid contact property, the thickness change of the low alkali glass substrate (manufactured by BLC Nippon Electric Glass Co., Ltd.) is 0.21 μm, and the silicon thickness change amount is about 0.40 μm on the 100 side, about 0.15 μm on the 110 side, 111 The surface was about 0.13 μm, and it was a change in thickness with 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 110th surface was about 6 mm, which was a film thickness change amount causing no problem as a diaphragm.
[0207]
(Example 22)
Compound 21 of Example 21 3 instead of the phosphonium compound hydroxide. The test was performed in the same manner as in Example 21 except that the hydroxide of 29 sulfonium compound 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. Even after printing was stopped, normal printing was possible without using any recovery means. In the liquid contact property, the thickness change of the low alkali glass substrate (manufactured by BLC Nippon Electric Glass Co., Ltd.) is 0.21 μm, and the silicon thickness change amount is about 0.40 μm on the 100 side, about 0.15 μm on the 110 side, 111 The surface was about 0.13 μm, and it was a change in thickness with no problem as a liquid chamber, a fluid resistance portion, or a nozzle. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 6 mm, which was a film thickness change that had no problem as a diaphragm.
[0208]
(Example 23)
Example 1 was used except that 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 instead of the tetrabutylphosphonium hydroxide of Example 1. A similar test was conducted. 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. Even after printing suspension, normal printing was possible without using any recovery means. As for wettability, the thickness change of heat-resistant glass # 7740 is 0.1 μm, and the silicon thickness change amount is about 0.15 μm on the 100 side, about 0.04 μm on the 110 side, and about 0.03 μm on the 111 side. The thickness of the liquid chamber, current resistance, and nozzle were satisfactory. In addition, the change in film thickness of the silicon oxide film on the 110th surface was about 3 A, which was a film thickness change that had no problem as a diaphragm.
[0209]
(Comparative Example 1)
In the ink formulation of Example 1, the pH was adjusted by adding lithium hydroxide instead of tetrabutylphosphonium hydroxide. After stirring for 4 hours at 50 ° C., the mixture was filtered with a filter having a pore size of 0.1 μm.
Embedded image
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 940 ppm. The pH value was 9.8.
This ink was filled into a printer in the same manner as in Example 1, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 1 was obtained. However, in the ejection response test after the printing pause, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 8/48 nozzles. A defect occurred.
As for wettability, the heat resistance glass # 7740 has a thickness change of 11.2 μm, and the silicon thickness change amount is about 6.0 μm on the 100 side, about 3.5 μm on the 110 side, and about 0.60 μm on the 111 side. The amount of change that causes a problem of accuracy as a liquid chamber, a fluid resistance portion, and a nozzle, and the silicon oxide film on the 110th surface is all eluted, and the amount of change that causes a problem as a diaphragm.
[0210]
(Comparative Example 2)
In the ink formulation of Example 2, the pH was adjusted by adding sodium hydroxide instead of tributylsulfonium hydroxide. After stirring for 4 hours at 50 ° C., the mixture was filtered with a filter having a pore size of 0.1 μm.
Embedded image
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 940 ppm. The pH value was 9.8.
This ink was filled into a printer in the same manner as in Example 1, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 1 was obtained. However, in the ejection response test after the printing pause, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 8/48 nozzles. A defect occurred.
As for wettability, the heat resistance glass # 7740 has a thickness change of 11.2 μm, and the silicon thickness change amount is about 6.0 μm on the 100 side, about 3.5 μm on the 110 side, and about 0.60 μm on the 111 side. The amount of change that causes a problem of accuracy as a liquid chamber, a fluid resistance portion, and a nozzle, and the silicon oxide film on the 110th surface is all eluted, and the amount of change that causes a problem as a diaphragm.
[0211]
(Comparative Example 3)
In the ink formulation of Example 3, the pH was adjusted by adding sodium hydroxide instead of tetrabutylphosphonium hydroxide. Stirring was continued at 50 ° C. for 4 hours, and after cooling, the mixture 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 1280 ppm. The pH value was 10.3.
This ink was filled into a printer in the same manner as in Example 3, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 2 was obtained. However, in the ejection responsiveness test after the printing pause, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 28/48 nozzles. A defect occurred.
In silicon wettability, the amount of change in the thickness of silicon is about 8.2 μm on the 100 side, about 4.7 μm on the 110 side, and about 0.80 μm on the 111 side. The amount of change that causes a problem was observed, and all of the silicon oxide film on the 110th surface was eluted, and the 8/48 diaphragm was too thin to withstand vibration and was damaged.
[0212]
(Comparative Example 4)
In the ink formulation of Example 4, the pH was adjusted by adding potassium hydroxide instead of tetrabutylarsonium hydroxide. Stirring was continued at 50 ° C. for 4 hours, and after cooling, the mixture 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 1280 ppm. The pH value was 10.3.
This ink was filled into a printer in the same manner as in Example 3, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 2 was obtained. However, in the ejection responsiveness test after the printing pause, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 28/48 nozzles. A defect occurred.
In silicon wettability, the amount of change in the thickness of silicon is about 8.2 μm on the 100 side, about 4.7 μm on the 110 side, and about 0.80 μm on the 111 side. The amount of change that causes a problem was observed, and all of the silicon oxide film on the 110th surface was eluted, and the 8/48 diaphragm was too thin to withstand vibration and was damaged.
[0213]
(Comparative Example 5)
In the ink formulation of Example 5, in place of the compounds of Chemical Formulas 1 and 3, potassium hydroxide was 40% with respect to the equivalent amount of the anionic compound in the ink, and lithium hydroxide was 40 percent with respect to the equivalent amount of the anionic compound in the ink. % Was added. Stirring was continued for 4 hours as it was, 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 spectroscopic analysis, the content of alkali metal in the ink was 970 ppm. The pH value was 9.6.
This ink was filled into a printer in the same manner as in Example 3, and printing and storage tests were conducted.
With this ink, an initial image equivalent to that in Example 3 was obtained. However, in the ejection responsiveness test after the suspension of printing, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 12/48 nozzles. A defect 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 silicon thickness change amount is about 6.2 μm on the 100 side, 110 The surface is about 3.6μm and the 111th surface is about 0.60μm, which is the amount of change that causes accuracy problems as the liquid chamber, fluid resistance, and nozzle, and the silicon oxide film on the 110th surface is all eluted. The amount of change was a problem as a diaphragm.
[0214]
(Comparative Example 6)
In the ink formulation of Example 6, no. 27, no. Instead of 29 compounds, sodium hydroxide was added at 40% with respect to the equivalent of the anionic compound in the ink, and lithium hydroxide was added at 40% with respect to the equivalent of the anionic compound in the ink. Stirring was continued for 4 hours as it was, 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 spectroscopic analysis, the content of alkali metal in the ink was 970 ppm. The pH value was 9.6.
This ink was filled into a printer in the same manner as in Example 3, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 3 was obtained. However, in the ejection responsiveness test after the suspension of printing, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 12/48 nozzles. A defect 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 silicon thickness change amount is about 6.2 μm on the 100 side, 110 The surface is about 3.6μm and the 111th surface is about 0.60μm, which is the amount of change that causes accuracy problems as the liquid chamber, fluid resistance, and nozzle, and the silicon oxide film on the 110th surface is all eluted. The amount of change was a problem as a diaphragm.
[0215]
(Comparative Example 7)
In the ink formulation of Example 7, the pH was adjusted by adding potassium hydroxide instead of the 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 0.1 μm.
When this ink was analyzed by plasma emission spectroscopic analysis, the content of alkali metal in the ink was 810 ppm. The pH value was 10.1.
This ink was filled into a printer in the same manner as in Example 4, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 4 was obtained. However, in the ejection responsiveness test after the printing pause, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to the 4/48 nozzle. A defect occurred.
In silicon wettability, the amount of change in the thickness of silicon is about 5.3 μm on the 100 side, about 3.1 μm on the 110 side, and about 0.50 μm on the 111 side. The amount of change that causes a problem, and all of the silicon oxide film on the 110th surface was eluted, and the amount of change was a problem as a diaphragm.
[0216]
(Comparative Example 8)
In the ink formulation of Example 8, the pH was adjusted by adding sodium hydroxide instead of the 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 0.1 μm.
When this ink was analyzed by plasma emission spectroscopic analysis, the content of alkali metal in the ink was 810 ppm. The pH value was 10.1.
This ink was filled into a printer in the same manner as in Example 4, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 4 was obtained. However, in the ejection responsiveness test after the printing pause, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to the 4/48 nozzle. A defect occurred.
In silicon wettability, the amount of change in the thickness of silicon is about 5.3 μm on the 100 side, about 3.1 μm on the 110 side, and about 0.50 μm on the 111 side. The amount of change that causes a problem, and all of the silicon oxide film on the 110th surface was eluted, and the amount of change was a problem as a diaphragm.
[0217]
(Comparative Example 9)
In the ink formulation of Example 9, the pH was adjusted by adding sodium hydroxide instead of the corrosion inhibitor. Stirring was continued at 50 ° C. for 4 hours, and after cooling, the mixture was filtered with a filter having a pore size of 0.1 μm.
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 870 ppm. The pH value was 8.3.
This ink was filled into a printer in the same manner as in Example 9, and printing and storage tests were conducted. With this ink, an initial image equivalent to that in Example 5 was obtained. However, in the ejection responsiveness test after the suspension of printing, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 7/48 nozzles. A defect occurred.
In silicon wettability, the change in thickness of silicon is about 5.8 μm on the 100 side, about 3.4 μm on the 110 side, and about 0.60 μm on the 111 side. The amount of change that causes a problem, and all of the silicon oxide film on the 110th surface was eluted, and the amount of change was a problem as a diaphragm.
[0218]
(Comparative Example 10)
In the ink formulation of Example 12, the pH was adjusted by adding lithium hydroxide instead of tributyl borate (corrosion inhibitor). Stirring was continued at 50 ° C. for 4 hours, and after cooling, the mixture was filtered with a filter having a pore size of 0.1 μm.
When this ink was analyzed by plasma emission spectral analysis, the content of alkali metal in the ink was 870 ppm. The pH value was 8.3.
This ink was filled into a printer in the same manner as in Example 5 to perform printing and storage tests. With this ink, an initial image equivalent to that in Example 5 was obtained. However, in the ejection responsiveness test after the suspension of printing, since the dissolution stability of the dye deteriorated due to the dissolution of silicon into the ink, the ink was discharged to 7/48 nozzles. A defect occurred.
In silicon wettability, the amount of change in the thickness of silicon is about 5.5 μm on the 100 side, about 3.3 μm on the 110 side, and about 0.55 μm on the 111 side. The amount of change that causes a problem, and all of the silicon oxide film on the 110th surface was eluted, and the amount of change was a problem as a diaphragm.
[0219]
(Measurement of zeta potential) Example9-14, 16 and 18-20And the zeta potential of the inks of Comparative Examples 1 to 10, the substrate (silicon substrate, glass substrate, silicon substrate having an oxide film, etc., which are members used for the head)inkThe zeta potential between them was measured. The zeta potential was measured using an electrophoresis apparatus using a laser Doppler method. The apparatus used was LES-8000 manufactured by Otsuka Electronics. The zeta potential was determined for the dye ink at pH 10.5 and the pigment ink at pH 10.6. When the color material is a pigment, the measurement can be performed with the ink itself, but when the color material is a dye, the measurement is performed using monitor particles.
[0220]
(Measurement of oxidation / reduction current value)
Moreover, the potential versus oxidation / reduction current was measured by cyclic voltammetry between the substrate and the ink. The apparatus used was POTENTISTAT / GALVANOSTAT HA-501G (ARBITRARY FUNCTION GENERATOR HB-105) manufactured by HOKUTO DENKO Ltd. A saturated calomel electrode (SCE) was used as a reference electrode (reference electrode). The potential is -3.0 to 5.0 V vs. SCE, and 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. Tables 9 and 10 show the values of the respective examples and comparative examples.
[0221]
[Table 9]
[0222]
From the above results, when the pH of the water-based ink composition is 6.5 to 11.5, the zeta potential is −20 mV or less, and the zeta potential between the member and the coloring material is 0 to −50 mV. It became clear that elution into the ink of silicon, silicon oxide film, etc. was suppressed. Further, the oxidation / reduction current value between the member and the ink at this time is 0 to 1.0 μA / cm for the oxidation / reduction current value with respect to the potential range of −2.0 to 5.0 V vs. SCE (vs. saturated calomel electrode).²(Pt.) Was also revealed. On the other hand, it is also clear that the water-based ink composition not in this range shown in the comparative example has a remarkable elution into the ink of glass, silicon, silicon oxide film or the like.
[0223]
【The invention's effect】
According to the present invention, a printerCan prevent the elution of silicon, glass, or films formed with oxides, nitrides, metals, or organic compounds, etc., and the size and discharge speed of ink droplets due to a decrease in printer design accuracy This prevents problems such as image quality degradation due to changes in ink quality, ejection failure, and failure due to joint strength degradation, and clogging due to elution of glass and silicon into the ink.Inkjet recording methodCan be provided.
[Brief description of the 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 an ink cartridge before being loaded into a recording apparatus.
FIG. 3 is a front sectional view of the ink cartridge.
FIG. 4 is an external perspective view of a recording unit integrated with a recording head.
FIG. 5 is a cross-sectional side view of the entire head unit.
[Explanation of symbols]
1 Side plate
2 Side plate
3 Main support guide rod
4 Sub-support guide rod
5 Carriage unit
6 heads
6a Head ejection surface
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 Transport roller
16 paper
17 Sub-scanning motor
18 gear
19 Gear
21 Subsystem
22 Cap means
23 Holder
24 Link member
25 engaging 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 Opening to the atmosphere
48 grooves
50 Cap member
51 Holding member for ink supply port of cartridge
53 For the holding part of the cartridge
55 Sealing member
71 Protrusion for each color of cartridge
81 Upper space of cartridge
For 81a
82 Dents
101, 102, 103 Silicon single crystal substrate
104 Nozzle hole
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 droplet
142 Power supply (voltage applied)

Claims (3)

A film in which at least a part of each member of a liquid chamber member, a fluid resistance portion, a diaphragm, or a nozzle in contact with ink is provided with silicon, glass, or an oxide, nitride, metal, or organic compound. A zeta potential between the ink-contacting member and an ink-jet printer formed of any of the above, a water-based ink composition mainly composed of a colorant and water, and having a pH of 6.5 to 11.5 An ink jet recording method, wherein recording is performed using an ink for ink jet recording having a 0 to -50 mV . A film in which at least a part of each member of the liquid chamber member, the fluid resistance portion, the diaphragm or the nozzle in contact with the ink is provided with silicon, glass, or an oxide, nitride, metal, or organic compound. An aqueous ink composition mainly composed of a pigment and water, having a zeta potential of -20 mV or less at a pH of 6.5 to 11.5 and in contact with the ink An ink jet recording method, wherein recording is performed using an ink for ink jet recording having a zeta potential between 0 and -50 mV between the member and the ink. The member according to any one of claims 1-2, wherein the silicon is any one of single crystal silicon and polysilicon, or the glass is any one of borosilicate glass, photosensitive glass, quartz glass, and soda lime glass. Or an ink jet recording method, wherein the film provided on one of silicon and glass is any one of silicon oxide, titanium oxide, chromium oxide, titanium nitride, silicon nitride, zirconium, and polyimide.