JP5471957B2 - Cleaning and filling liquid for ink jet recording apparatus and ink cartridge, and cartridge containing the washing and filling liquid - Google Patents

Description

  The present invention relates to a cleaning / filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge, and a cartridge containing the cleaning / filling liquid.

In general, as an image forming apparatus that combines a printer, a fax machine, a copier, a plotter, or a plurality of these functions, for example, a recording head composed of a liquid ejection head that ejects ink droplets is provided, while conveying a medium, Some ink droplets are attached to a sheet to form an image. In such a liquid ejection type image forming apparatus, it is possible to form a pattern in a non-contact manner by ejecting liquid droplets from a number of pores called a number of nozzles of the liquid ejection head. The image can be formed by a single image forming process regardless of the type and shape.
This liquid discharge head includes a nozzle portion having a fine orifice having a diameter of 50 μm or less, a pressure generating portion connected to the nozzle portion, a liquid chamber portion for supplying liquid to the pressure generating portion, and a filter portion for filtering the liquid flowing into the liquid chamber Etc., and processed and formed with very high accuracy.
In addition, since the number of nozzles per head is enormous, from several tens to several thousand, the entire system operates normally before shipping as a product. It is necessary to make sure that there is no state in which the liquid droplets are not ejected and in which the ejected droplets cannot form a desired size.
In order to perform such an inspection, a defect is detected by filling the head with a detectable liquid and discharging the liquid from the head. In addition, it is necessary to wash out the ink in the ink jet recording apparatus so that the ink filled in the head and the ink supply system does not leak to the outside due to repair or the like, and the surroundings are not soiled.

Conventionally, water or an aqueous surfactant solution has been used as the cleaning liquid. However, these can ensure cleaning properties, but there are problems such as deterioration in filling properties at the time of refilling and occurrence of defective discharge. there were.
More recently, inks using pigments as colorants have been put into practical use from the viewpoint of water resistance and light resistance. Also, when using dyes, from the same viewpoint, there is a tendency to increase the dye concentration or use a low water solubility, and the above problem has become more prominent.
In particular, in the case of using a pigment or a resin, if even a small amount of ink in the head remains, the ink is fixed and the dischargeability is lowered. Therefore, for example, Patent Documents 1 and 2 propose adding a resin solvent to the maintenance liquid. In this case, the maintenance liquid has a function of dissolving and redispersing the residual solid content even when the ink is dried.
However, the solvents described in Patent Documents 1 and 2 have a risk of causing the adhesive surface to swell by giving solubility to the adhesive used in the head. For this reason, there is a problem in that the strength of the head is lowered, the desired rigidity cannot be obtained, and the intended ejection property cannot be obtained.
In consideration of the cleanability and storage stability of the apparatus, a cleaning liquid using an ethindiol nonionic surfactant as described in Patent Document 3 has also been proposed. However, the cleaning liquid has low foaming properties, but has lower detergency because of its lower solubility in water and lower ability to lower the surface tension than general alkyl alcohol nonionic surfactants.

In view of the cleanability in the apparatus, a method using a polyoxyalkylene secondary alcohol ether as described in Patent Document 4 has been proposed. By using such a surfactant, it is possible to increase the detergency.
However, only the configuration described in Patent Document 4 may cause minute corrosion to the metal member, and the deterioration of the durability of the head or the like is a problem due to the corrosion.
Therefore, Patent Document 5 discloses a filling liquid to which a corrosion inhibitor that prevents such elution of the metal member and can be washed and stored is added. However, the compatibility with cleanability was not sufficient.
In recent years, microemulsion type pigments in which a pigment surface is coated with a poorly water-soluble resin have been developed as pigment dispersions with improved color development and fixing properties, which are excellent in color development and fixing properties. However, the dispersion stability is inferior to that of a self-dispersing pigment having a dispersion functional group covalently bonded to the pigment surface, and the redispersibility after drying is deteriorated. In addition, since the functional group is not bonded by a covalent bond, it is greatly influenced by the environment around the pigment, and is likely to cause aggregation due to temperature, pH, solvent composition, vehicle organicity, and the like.
These tend to be the same even after the inkjet head is washed with a washing liquid. Compared with a self-dispersing pigment, a pigment whose surface is coated with a poorly water-soluble resin is more stable in the liquid after washing. Tend to be bad.

  It is an object of the present invention to provide a cleaning / filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge, and a cartridge containing the cleaning / filling liquid.

（式中、ＲｆはＣＦ_３又はＣＦ_２ＣＦ_３を表し、ｑは１〜６の整数を表す。）
一般式（II）

（式中、Ｒは無置換の炭素数１〜４のアルキル基又はアリール基を表し、ｍ、ｎ及びａは５〜１５の整数、ｂは５〜１０の整数を表す。）
２） 前記水溶性有機溶剤がグリセリンであることを特徴とする１）記載のインクジェット記録装置及びインクカートリッジ用洗浄液兼充填液。
３） １）又は２）に記載の洗浄液兼充填液が容器中に収容されていることを特徴とするカートリッジ。 The above problems are solved by the following inventions 1) to 3).
1) A cleaning and filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge, at least a water-soluble organic solvent, a compound represented by general formula (I), a compound represented by general formula (II), and water An ink jet recording apparatus and an ink cartridge cleaning and filling liquid, characterized by comprising:
Formula (I)

(In the formula, Rf represents CF ₃ or CF ₂ CF ₃ , and q represents an integer of 1 to 6)
Formula (II)

(In the formula, R represents an unsubstituted alkyl group or aryl group having 1 to 4 carbon atoms, m, n and a represent an integer of 5 to 15 and b represents an integer of 5 to 10).
2) The ink-jet recording apparatus and ink cartridge cleaning and filling liquid according to 1), wherein the water-soluble organic solvent is glycerin.
3) A cartridge in which the cleaning / filling solution according to 1) or 2) is contained in a container.

  According to the present invention, it is possible to provide a cleaning / filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge, and a cartridge containing the cleaning / filling liquid.

It is the schematic which shows an example of the washing | cleaning liquid and filling liquid bag of the cartridge of this invention. It is the schematic which shows the cartridge which accommodated the washing | cleaning liquid and filling liquid bag of FIG. 1 in the cartridge case.

Hereinafter, the present invention will be described in detail.
The cleaning and filling liquid of the present invention contains the compound represented by the general formula (I) and the compound represented by the general formula (II).
These compounds are surfactants, and due to their structure, the compounds of the general formula (I) have a high cleaning function, and the compounds of the general formula (II) are excellent in leveling properties at the gas-liquid interface, and are cleaning and filling liquids. Since these compounds are used in combination, they have excellent cleaning properties, excellent ink filling properties when replacing with ink after head cleaning, and high-speed printing. A cleaning / filling solution having a high effect on ejection stability can be obtained.
In recent years, safety and environmental impact of fluorosurfactants (accumulation of PFOS and PFOA on the human body) are particularly concerned as an environmental problem, but the general formula (I) used in the present invention The fluorinated surfactant represented by the formula has received environmental safety approval from the US Environmental Protection Agency (EPA) and can be used without any problem from the viewpoint of safety.
Also particularly preferred as the silicone-based surfactant represented by the general formula (II) is a linear block copolymer in which dimethylpolysiloxane and polyalkylene oxide are alternately and repeatedly bonded. Products such as Toray Dow Corning Silicone are easily available.
The content of the compounds of the general formula (I) and the general formula (II) is preferably in the range of about 0.01 to 5% by mass. If it is 0.01% by mass or more, the cleaning property is not deteriorated, and the residual amount of the colorant is not excessive. Moreover, if it is 5 mass% or less, initial filling property will not worsen.

When the ink in the ink jet recording apparatus, which is one of the ink jet recording apparatuses, uses colored resin fine particles containing a water-insoluble or hardly soluble color material in the resin fine particles as the color material, the state after the ink jet head cleaning is Since the ink is extremely diluted with the cleaning liquid, the environment around the pigment is greatly changed, and it is difficult to maintain dispersion stability.
The cleaning and filling liquid of the present invention uses the compounds of the above general formula (I) and general formula (II), so that the penetrating power mixed with the ink in the liquid flow path in the ink jet head and the ink after mixing with the ink It is possible to have a dispersion force capable of maintaining the dispersion state of the pigment in the interior. Further, with respect to the foaming property and defoaming property, since the foam suppressing effect is high, it is possible to show the cleaning property and the storage property without affecting the foam in the ink jet recording apparatus.

A low-viscosity cleaning liquid has a high flow rate in the head and a high miscibility with ink. However, when there are a large number of nozzles as in an inkjet head, cleaning unevenness is likely to occur unless ink is uniformly removed from each nozzle. When a cleaning liquid having a viscosity lower than that of ink is replaced with ink and flows through the individual liquid chambers in the head, the fluid resistance is lower than that of the other liquid chambers, so that more cleaning liquid flows more easily than the other liquid chambers. Therefore, the nozzle completely replaced with the cleaning liquid is easy to flow, but the other nozzles remain difficult to flow, and the nozzle cannot be sufficiently cleaned.
Therefore, it is preferable to make the physical properties of the cleaning liquid close to the physical properties of the ink for cleaning the inside of the head. Actually, if the viscosity of the cleaning liquid at 25 ° C. is 2.5 mPa · s or more, the difference in viscosity from the ink in the head can be reduced, and the head can be cleaned uniformly.
Moreover, the higher the viscosity of the cleaning liquid can suppress the sedimentation of the pigment dispersion when mixed with the pigment ink, and the mixing stability can be improved. However, if the viscosity is too high, it is not preferable because it is separated from the physical properties of the ink. For this reason, it is preferable that the viscosity in 25 degreeC is 15 mPa * s or less.

  Examples of the water-soluble organic solvent used in the present invention include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, Examples include propylene carbonate and ethylene carbonate. These water-soluble organic solvents provide fluidity to the cleaning liquid and filling liquid by retaining a large amount of water even when the water in the cleaning and filling liquid evaporates and reaches an equilibrium state. To do. Of these, water-soluble organic solvents with a high equilibrium water content are preferred, and even when the water in the cleaning and filling liquid evaporates and reaches an equilibrium state, the water-soluble organic solvent retains a large amount of water and causes an extreme increase in viscosity. Can be suppressed. Here, the water-soluble organic solvent having a high equilibrium water content means a water-soluble organic solvent having an equilibrium water content of 30% by mass or more, preferably 40% by mass or more in the environment of temperature 23 ° C. and humidity 80% (hereinafter referred to as water-soluble). It is called organic solvent A). The upper limit of the equilibrium moisture content is not particularly limited, but glycerin is the highest among the widely used solvents, and is about 46% by mass in actual measurement.

By using such a water-soluble organic solvent A, the water-soluble organic solvent A can retain a large amount of water and prevent an increase in viscosity even when the water content of the ink evaporates and reaches a water balance. Equilibrium moisture content means that a mixture of water-soluble organic solvent and water is released to air at a constant temperature and humidity, and the water in the solution is evaporated and absorbed in the cleaning and filling liquid. The amount of water when the equilibrium is reached. Specifically, the equilibrium water content is determined by using a saturated aqueous solution of potassium chloride and maintaining the temperature in the desiccator at a temperature of 23 ± 1 ° C. and a humidity of 80 ± 3%, and weighing 1 g of each water-soluble organic solvent in the desiccator. It is stored for a period until the change disappears, and can be obtained by the following formula.

  Examples of the water-soluble organic solvent A suitably used in the present invention include polyhydric alcohols having an equilibrium water content in an environment of a temperature of 23 ° C. and a humidity of 80% of 30% by mass or more. Specific examples thereof include glycerin (bp 290 ° C., 49% by mass), diglycerin (bp 270 ° C./20 hPa, 38% by mass), 1,2,3-butanetriol (bp 175 ° C./33 hPa, 38% by mass), 1, 2,4-butanetriol (bp190-191 ° C / 24 hPa, 41% by mass), diethylene glycol (bp245 ° C, 43% by mass), triethylene glycol (bp285 ° C, 39% by mass), tetraethylene glycol (bp324-330 ° C, 37 mass%), 1,3-butanediol (bp 203-204 ° C., 35 mass%) and the like. Among them, glycerin and 1,3-butanediol are particularly suitable for reasons such as lowering the viscosity when water is contained, and keeping the pigment stable in the ink when it is replaced with ink after washing. Used for. When the water-soluble organic solvent A is used in an amount of 50% by mass or more based on the total amount of the water-soluble organic solvent, it is preferable because the discharge stability is excellent.

The cleaning and filling liquid of the present invention is a water-soluble organic solvent having an equilibrium water content of less than 30% by mass at 23 ° C. and 80% in addition to or in place of the water-soluble organic solvent A. (Hereinafter referred to as water-soluble organic solvent B) can be used in combination. Examples of such water-soluble organic solvents B include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene. Examples include carbonate and ethylene carbonate.
Examples of the polyhydric alcohols include dipropylene glycol (bp 232 ° C), 1,5-pentanediol (bp 242 ° C), 3-methyl-1,3-butanediol (bp 203 ° C), and propylene glycol (bp 187 ° C). 2-methyl-2,4-pentanediol (bp 197 ° C.), ethylene glycol (bp 196 to 198 ° C.), tripropylene glycol (bp 267 ° C.), hexylene glycol (bp 197 ° C.), polyethylene glycol (viscous liquid to solid) , Polypropylene glycol (bp 187 ° C.), 1,6-hexanediol (bp 253 to 260 ° C.), 1,2,6-hexane triol (bp 178 ° C.), trimethylol ethane (solid, mp 199 to 201 ° C.), trimethylol propane ( Solid, mp61 ° C) And the like.

Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether (bp 135 ° C.), ethylene glycol monobutyl ether (bp 171 ° C.), diethylene glycol monomethyl ether (bp 194 ° C.), diethylene glycol monoethyl ether (bp 197 ° C.), and diethylene glycol monoethyl ether. Examples include butyl ether (bp 231 ° C.), ethylene glycol mono-2-ethylhexyl ether (bp 229 ° C.), propylene glycol monoethyl ether (bp 132 ° C.), and the like.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether (bp 237 ° C.) and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone (bp 250 ° C., mp 25.5 ° C.), N-methyl-2-pyrrolidone (bp 202 ° C.), 1,3-dimethyl-2-imidazolidinone (bp 226 ° C.). ), Ε-caprolactam (bp 270 ° C.), γ-butyrolactone (bp 204 to 205 ° C.), and the like.
Examples of the amides include formamide (bp 210 ° C.), N-methylformamide (bp 199 to 201 ° C.), N, N-dimethylformamide (bp 153 ° C.), N, N-diethylformamide (bp 176 to 177 ° C.) and the like. Can be mentioned.
Examples of the amines include monoethanolamine (bp 170 ° C), diethanolamine (bp268 ° C), triethanolamine (bp360 ° C), N, N-dimethylmonoethanolamine (bp139 ° C), N-methyldiethanolamine (bp243 ° C). ), N-methylethanolamine (bp159 ° C.), N-phenylethanolamine (bp282-287 ° C), 3-aminopropyldiethylamine (bp169 ° C), and the like.
Examples of the sulfur-containing compounds include dimethyl sulfoxide (bp 139 ° C.), sulfolane (bp 285 ° C.), thiodiglycol (bp 282 ° C.), and the like.

The cleaning liquid is required to have a function of cleaning the ink flow path of the ink jet recording apparatus and flushing out the ink. In order to clean the ink flow path, it is required to separate the ink component from the ink flow path while mixing and replacing the ink. At this time, it is required that the ink flow path member is not deteriorated by the cleaning liquid.
Moreover, since a large amount of liquid and time are required to completely replace the state after cleaning with the cleaning liquid, the efficiency is poor. Therefore, it is necessary to maintain the recording quality of the ink jet recording apparatus even when the ink is mixed to a certain density. If the cleaning liquid does not match the ink, the ink remaining in the cleaning liquid aggregates and is attracted to the nozzles and filters of the inkjet head, causing ejection failure and increased resistance. Therefore, it is required that the liquid physical properties be stable even when the ink and the cleaning liquid are mixed.
Further, by satisfying the cleaning property and the mixing property with the ink, the refillability can be ensured when the ink is newly filled.

  The content of each of the fluorosurfactants (I) and (II) in the cleaning and filling liquid is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass in terms of solid content. If the amount is less than 0.01% by mass, the effect of suppressing bubbles may not be obtained. If the amount exceeds 5% by mass, the viscosity increases, and the ejection property due to bubbles in the head due to a decrease in foaming suppression effect is adversely affected. There is.

In general, the proportion of the water-soluble organic solvent in the entire cleaning / filling solution is preferably 20 to 60% by mass, more preferably 30 to 50% by mass. If the amount of the water-soluble organic solvent is small, the water retention capacity of the cleaning liquid is reduced, and drying during storage tends to proceed. On the other hand, when the amount of the water-soluble organic solvent is too large, the viscosity of the ink is increased, and the filling property to the head is reduced and the combustibility of the ink is improved.
However, depending on the characteristics of the water-soluble organic solvent, the moisturizing power and the organicity vary greatly. In particular, glycerin is known as a solvent having high moisture retention and high hydrophilicity. Therefore, there is an effect in suppressing the dispersion breakage of the pigment dispersion due to drying. However, when colored resin fine particles containing a water-insoluble or hardly soluble color material in the resin fine particles are used, the dispersion stability is deteriorated if the ratio of glycerin is too high.
Although there is no clear reason for the deterioration of the dispersion stability state, it is assumed that the resin is swollen by the organic property of the dispersion solvent. The resin fine particles have an affinity for both the coloring material and the dispersion solvent, but are designed to increase the resistance to the organic solvent used in the ink. Since the water-soluble organic solvent used in the ink is a slightly lipophilic solvent from the viewpoint of imparting a penetrating function, the resin is designed to withstand these solvents. When the ratio of glycerin is increased, the hydrophilicity is improved and the hydrophilicity of the dispersion solvent is increased. Therefore, it is considered that the dispersion solvent is different from the resistance of the resin, the affinity to the resin is improved, the resin is easily swollen with respect to the dispersion medium, and the dispersion stability is lowered.
In the case where the ink and the glycerin containing the coloring resin fine particles containing the water-insoluble or hardly soluble coloring material in the resin fine particles are used in combination, it is desirable that the addition amount is less than 20% by mass. If it is 20% by mass or more, the organicity of the cleaning and filling liquid is too low, which is not preferable.

Other additives that can be added to the cleaning and filling liquid include, but are not limited to, antiseptic / antifungal agents, chelating agents, rust inhibitors, pH adjusters, penetrants, and the like.
Examples of antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol and the like.
Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like.
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole.

Any pH adjuster can be used as long as it does not adversely affect the cleaning and filling liquid to be prepared, does not damage the ink flow path of the ink jet recording apparatus, and can adjust the pH to a desired value. Can be used.
For example, amines, alkali metal hydroxides, quaternary compound hydroxides, and alkali metal carbonates can be used when adjusting to basic, and inorganic acids and organic acids can be used when adjusting to acidic.
Specifically, amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary Examples thereof include alkali metal carbonates such as phosphonium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate.
Also, salts formed with inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and monovalent weak cations such as ammonium sulfate and ammonium phosphate, acetic acid, succinic acid, lactic acid, salicylic acid, benzoic acid, glucuronic acid, ascorbine Acid, arginic acid, cysteine, oxalic acid, fumaric acid, maleic acid, malonic acid, lysine, malic acid, citric acid, glycine, glutamic acid, succinic acid, tartaric acid, phthalic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid Organic acids such as furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, carborane acid, or derivatives of these compounds.
These pH adjusters are not limited to the above compounds. In addition, an optimal pKa having a characteristic corresponding to the pH variation of the ink may be used as appropriate, and one kind may be used alone, or two or more kinds may be used in combination, or a buffer agent may be used in combination. May be.

The penetrant is added as necessary to supplement the penetrability by the surfactant or the organic solvent.
As the penetrant, it is desirable to contain at least one polyol having a solubility in water of 20 ° C. of 0.2 to 5.0 mass%.
Among such polyols, aliphatic diols include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 2,2-diethyl-1,3. -Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1 , 2-diol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like.
Among these, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol are preferable.

Other penetrants that can be used in combination include polyethylene alcohols such as diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and tetraethylene glycol chlorophenyl ether. Examples include alkyl and aryl ethers, lower alcohols such as ethanol, and the like, as long as they can be dissolved in a cleaning solution and adjusted to desired physical properties.
The amount of penetrant added is preferably 4.0% by mass or less. When the amount added is more than 4.0% by mass, the dispersion stability of the pigment dispersion of the ink to be cleaned is impaired, the dispersion is aggregated, and the permeability to the ink flow path member is more than necessary. This causes liquid contact problems such as erosion of the member and swelling and elution of the adhesive.

  The combination of the cleaning / filling solution and the ink for inkjet recording is important. As will be described later, a water-dispersible colorant, a water-soluble organic solvent, a surfactant, a penetrating agent, a water-dispersible resin, and the like are blended in the ink for inkjet recording, but at least the water-soluble organic solvent and the surfactant are mixed. As for the penetrant, the same substances as the cleaning liquid and filling liquid can be used. What is necessary is just to optimize a compounding quantity in order to express the function aiming at printing.

Hereinafter, the ink for inkjet recording combined with the cleaning and filling liquid of the present invention will be described, but the present invention is not limited to this.
The ink for inkjet recording contains a water-dispersible colorant, a water-soluble organic solvent, a surfactant, a penetrating agent, and water. Further, it contains other additives as required.
As the water dispersible colorant, a pigment is mainly used from the viewpoint of weather resistance, but a dye may be contained within a range in which the weather resistance does not deteriorate for the purpose of adjusting the color tone. There is no restriction | limiting in particular as a pigment, According to the objective, it can select suitably, For example, the inorganic pigment, organic pigment, etc. for black or color are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Inorganic pigments include titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, as well as carbon produced by known methods such as the contact method, furnace method, and thermal method. Black can be used.
Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye type chelates, acidic dye type chelates), nitro pigments, nitroso pigments, aniline black, and the like can be used. Of these pigments, those having good affinity with water are particularly preferably used.

Among the above pigments, specific examples of pigments that are preferably used include black, carbon blacks such as furnace black, lamp black, acetylene black, and channel black (CI pigment black 7), copper, iron ( Examples thereof include metals such as CI Pigment Black 11), and organic pigments such as titanium oxide and aniline black (CI Pigment Black 1).
For color use, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183, 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: 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, 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.

When the colorant is a pigment, particularly preferable forms of the pigment used in the ink combined with the cleaning / filling liquid of the present invention include the following first to second forms. The first form is particularly preferable.
(1) First embodiment: A polymer emulsion (a dispersion of polymer fine particles containing a pigment in water) containing a fine polymer fine particle containing a water-insoluble or hardly water-soluble pigment.
(2) Second form: containing a pigment having at least one hydrophilic group on the surface and exhibiting water dispersibility in the absence of a dispersant (hereinafter also referred to as “self-dispersing pigment”). .
As the water-dispersible colorant of the first form, it is preferable to use a polymer emulsion in which a pigment is contained in polymer fine particles in addition to the pigment. The polymer emulsion in which the pigment is contained in the polymer fine particles is one in which the pigment is encapsulated in the polymer fine particles, or the pigment is adsorbed on the surface of the polymer fine particles. In this case, it is not necessary for all the pigments to be encapsulated or adsorbed, and the pigments may be dispersed in the emulsion as long as the effects of the present invention are not impaired. Examples of the polymer that forms the polymer emulsion (polymer in the polymer fine particles) include vinyl polymers, polyester polymers, polyurethane polymers, and the like. Particularly preferred are vinyl polymers and polyester polymers, and JP-A 2000-53897. And the polymers disclosed in JP 2001-139849 A can be used.

The self-dispersing pigment of the second form is a surface modified so that at least one hydrophilic group is bonded to the surface of the pigment directly or through another atomic group. The surface modification is a method in which a specific functional group (sulfone group, carboxyl group, etc.) is chemically bonded to the surface of the pigment, or wet oxidation is performed using hypohalous acid and / or a salt thereof. Is used. Among these, a form in which a carboxyl group is bonded to the surface of the pigment and dispersed in water is particularly preferable. Thus, when the pigment is surface-modified and the carboxyl group is bonded, not only the dispersion stability is improved, but also high-quality printing quality is obtained and the water resistance of the recording medium after printing is further improved. improves.
Ink containing a self-dispersing pigment is excellent in redispersibility after drying, so printing is suspended for a long period of time, and clogging does not occur even when ink moisture near the inkjet head nozzle evaporates. Makes it easy to print well.
The volume average particle diameter (D50) of the self-dispersing pigment is preferably 0.01 to 0.16 μm in the ink.

As the self-dispersing pigment, those having ionicity are preferable, and those having an anionic charge by an anionic hydrophilic group are preferable.
As the anionic hydrophilic group, for _{example, -COOM, -SO 3 M, -PO} 3 HM, -PO 3 M 2, -SO 2 NH 2, -SO 2 NHCOR ( although, M is an alkali metal, ammonium or And R represents an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Among these, those in which —COOM and —SO ₃ M are bonded to the surface of the color pigment are preferable.
The alkali metal “M” includes lithium, sodium, and potassium. Examples of the organic ammonium include mono to trimethyl ammonium, mono to triethyl ammonium, and mono to trimethanol ammonium.
As a method of obtaining the anionically charged color pigment, as a method of introducing —COONa to the color pigment surface, for example, a method of oxidizing the color pigment with sodium hypochlorite, a method of sulfonation, a diazonium salt The method of making it react is mentioned.

The hydrophilic group may be bonded to the surface of carbon black via another atomic group. Examples of other atomic groups include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Specific examples of the case where these hydrophilic groups are bonded to the surface of carbon black through other atomic groups include, for example, —C ₂ H ₄ COOM (where M represents an alkali metal or quaternary ammonium). , -PhSO ₃ M (wherein Ph represents a phenyl group, M represents an alkali metal or quaternary ammonium).
The content of the colorant in the ink for inkjet recording is preferably 2 to 15% by mass, more preferably 3 to 12% by mass in terms of solid content. If the content is less than 2% by mass, the color developability and the image density of the ink may be lowered, and if it exceeds 15% by mass, the ink may be thickened and the dischargeability may be deteriorated. It is not preferable.

As the water-soluble organic solvent used in the ink jet recording ink, the water-soluble organic solvent used in the cleaning and filling liquid is preferably used. The mass ratio of the water-dispersible colorant and the water-soluble organic solvent in the ink for ink jet recording affects the ink ejection stability from the head. For example, if the water-dispersible colorant has a large solid content but the blending amount of the water-soluble organic solvent is small, water evaporation near the ink meniscus of the nozzle may progress and cause ejection failure.
20-50 mass% is preferable and, as for content in the ink for inkjet recording of a water-soluble organic solvent, 20-45 mass% is more preferable. If the content is less than 20% by mass, there is a possibility that the ejection stability is lowered or the waste ink is fixed by the maintenance device of the ink jet recording apparatus. On the other hand, if it exceeds 50% by mass, the drying property on paper is inferior and the character quality on plain paper may be lowered.
Specific examples of the water-soluble organic solvent include glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6- Hexanediol, 2-methyl-2,4-hexanediol, 1,2-octanediol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, urea, tetramethylurea, etc. It is done.

The surfactant used in the ink for inkjet recording is preferably an anionic surfactant that does not impair dispersion stability by the combination of the type of the colorant or the water-soluble organic solvent, has low surface tension, and has high permeability and leveling properties. At least one selected from surfactants, nonionic surfactants, silicone surfactants and fluorosurfactants is preferred. Among these, silicone surfactants and fluorine surfactants are particularly preferable. These surfactants can be used individually by 1 type or in mixture of 2 or more types.
As the surfactant, a surfactant used in the cleaning / filling solution is preferably used.
The content of the surfactant in the inkjet recording ink is preferably 0.01 to 3.0% by mass, and more preferably 0.5 to 2.0% by mass. When the content is less than 0.01% by mass, the effect of adding a surfactant may not be obtained. When the content exceeds 3.0% by mass, the permeability to a recording medium becomes higher than necessary, and the image density is reduced. Decrease or strikethrough may occur.

  As the penetrant used in the ink for inkjet recording, the penetrant used in the cleaning liquid and filling liquid is preferably used. The content of the penetrant in the inkjet recording ink is preferably 0.1 to 4.0% by mass. If the content is less than 0.1% by mass, quick-drying may not be obtained and a blurred image may be obtained. If the content exceeds 4.0% by mass, the dispersion stability of the colorant is impaired, and the nozzle is easily clogged. The image density may be lowered or the image may be broken through, for example, the permeability to the recording medium may be higher than necessary.

In the case of the second form, it is preferable to include a water-dispersible resin.
The water-dispersible resin has excellent film-forming properties (image formability) and has high water repellency, high water resistance, and high weather resistance, and is used for image recording with high water resistance and high image density (high color development). Useful. Examples of water-dispersible resins include condensation-type synthetic resins, addition-type synthetic resins, natural polymer compounds, and the like.
Examples of the condensed synthetic resin include polyester resin, polyurethane resin, polyepoxy resin, polyamide resin, polyether resin, poly (meth) acrylic resin, acrylic-silicone resin, and fluorine-based resin.
Examples of the addition type synthetic resin include polyolefin resins, polystyrene resins, polyvinyl alcohol resins, polyvinyl ester resins, polyacrylic acid resins, unsaturated carboxylic acid resins, and the like.
Examples of the natural polymer compound include celluloses, rosins, and natural rubber.
Among these, polyurethane resin fine particles, acrylic-silicone resin fine particles, and fluorine-based resin fine particles are particularly preferable. Moreover, there is no problem in using two or more kinds of water-dispersible resins in combination.

As the fluorine resin fine particles, those having a fluoroolefin unit are preferable, and among these, fluorine-containing vinyl ether resin fine particles composed of a fluoroolefin unit and a vinyl ether unit are particularly preferable.
Wherein particularly limited fluoroolefin unit is not, can be appropriately selected depending on the intended purpose, for example, _{-CF 2 CF 2 -, - CF} 2 CF (CF 3) -, - CF 2 CFCl- and the like .
There is no restriction | limiting in particular as said vinyl ether unit, Although it can select suitably according to the objective, For example, group represented by the following structural formula is mentioned.

As the fluorine-containing vinyl ether resin fine particles composed of the fluoroolefin unit and the vinyl ether unit, an alternating copolymer obtained by alternately copolymerizing the fluoroolefin unit and the vinyl ether unit is preferable.
As such fluorine-based resin fine particles, those appropriately synthesized may be used, or commercially available products may be used. Examples of the commercially available products include Fluorate FEM-500, FEM-600, Dickguard F-52S, F-90, F-90M, F-90N, Aquafuran TE-5A manufactured by Dainippon Ink and Chemicals, Inc .; Asahi Glass Examples include Lumiflon FE4300, FE4500, FE4400, Asahi Guard AG-7105, AG-950, AG-7600, AG-7000, AG-1100, and the like manufactured by the company.
The water dispersible resin may be used as a homopolymer or a copolymer, and any of a single phase structure type, a core shell type, and a power feed type emulsion can be used.

As the water-dispersible resin, either a resin itself having a hydrophilic group and self-dispersibility, or a resin itself having no dispersibility and imparted with a surfactant or a resin having a hydrophilic group can be used. Among these, an emulsion of resin particles obtained by emulsion and suspension polymerization of an ionomer of a polyester resin or a polyurethane resin or an unsaturated monomer is optimal. In the case of emulsion polymerization of unsaturated monomers, the reaction can be facilitated by reacting in a system to which an unsaturated monomer, a polymerization initiator, a surfactant, a chain transfer agent, a chelating agent, and a pH adjusting agent are added. In addition, a water-dispersible resin emulsion can be obtained, and the resin structure can be easily changed, so that desired properties can be easily produced.
Examples of the unsaturated monomer include unsaturated carboxylic acids, monofunctional or polyfunctional (meth) acrylic acid ester monomers, (meth) acrylic acid amide monomers, and aromatic vinyl monomers. , Vinyl cyano compound monomers, vinyl monomers, allyl compound monomers, olefin monomers, diene monomers, oligomers having unsaturated carbon, etc., alone or in combination be able to. By combining these monomers, the properties can be flexibly modified, and the properties of the resin can be modified by performing a polymerization reaction or a graft reaction using an oligomer type polymerization initiator.
Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.

  Examples of the monofunctional (meth) acrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2 -Ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, methacryloxyethyltrimethylammonium Salt, 3-me Acryloxypropyltrimethoxysilane, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate , Dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl acrylate, acryloxyethyl trimethyl ammonium salt, and the like.

  Examples of the polyfunctional (meth) acrylic acid ester monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1, 4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, 2,2'-bis (4-methacryloxy) Diethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, polyethylene Glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol di Acrylate, polypropylene glycol diacrylate, 2,2'-bis (4-acryloxypropyloxyphenyl) propane, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, trimethylolpropane triacrylate, trimethylolethane Triacrylate, tetramethylol methane triacrylate, ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate Dipentaerythritol hexaacrylate, and the like.

Examples of the (meth) acrylic acid amide monomers include acrylamide, methacrylamide, N, N-dimethylacrylamide, methylenebisacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, 4-t-butylstyrene, chlorostyrene, vinyltoluene, vinylanisole, vinylnaphthalene, divinylbenzene, and the like.
Examples of the vinyl cyano compound monomers include acrylonitrile and methacrylonitrile.
Examples of the vinyl monomers include vinyl acetate, vinyl chloride, vinylidene chloride, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid or salts thereof, vinyl trimethoxysilane, vinyl triethoxysilane, and the like.
Examples of the allyl compound monomers include allyl sulfonic acid and its salt, allylamine, allyl chloride, diallylamine, diallyldimethylammonium salt and the like.
Examples of the olefin monomers include ethylene and propylene.
Examples of the diene monomers include butadiene and chloroprene.
Examples of the oligomers having unsaturated carbon include styrene oligomers having methacryloyl groups, styrene-acrylonitrile oligomers having methacryloyl groups, methyl methacrylate oligomers having methacryloyl groups, dimethylsiloxane oligomers having methacryloyl groups, and polyesters having acryloyl groups. An oligomer etc. are mentioned.

The water-dispersible resin has a strong alkalinity and strong acidity, which causes molecular breakage such as dispersion breakage and hydrolysis. Therefore, the pH is preferably 4 to 12, particularly from the viewpoint of miscibility with the water-dispersible colorant. As for pH, 6-11 are more preferable, and pH7-9 are still more preferable.
The average particle size (D50) of the water-dispersible resin is related to the viscosity of the dispersion. For the same composition, the viscosity at the same solid content increases as the particle size decreases. The average particle diameter (D50) of the water-dispersible resin is preferably 50 nm or more so that the viscosity does not become excessively high when used in ink. Further, when the particle size is several tens of μm, it becomes larger than the nozzle opening of the ink jet head and cannot be used. If particles having a large particle diameter are present in the ink even if they are smaller than the nozzle opening, the discharge property is deteriorated. Therefore, the average particle diameter (D50) is preferably 200 nm or less, and more preferably 150 nm or less, in order not to inhibit the ink discharge properties.

The water-dispersible resin has a function of fixing the water-dispersible colorant on the paper surface, and is preferably formed into a film at room temperature to improve the fixability of the color material. Therefore, the minimum film-forming temperature (MFT) of the water-dispersible resin is preferably 30 ° C. or lower. In addition, when the glass transition temperature of the water dispersible resin is less than −40 ° C., the viscosity of the resin film becomes strong and the printed matter is tacked. Is preferred.
The content of the water dispersible resin in the ink for inkjet recording is preferably 1 to 15% by mass, more preferably 2 to 7% by mass in terms of solid content.
Here, the solid content of the inkjet recording ink can be measured, for example, by a method of separating only the water-dispersible colorant and the water-dispersible resin component from the inkjet recording ink. Further, when a pigment is used as the water-dispersible colorant, the ratio of the pigment to the water-dispersible resin can be measured by evaluating the mass reduction rate by thermal mass spectrometry. In addition, when the molecular structure of the water-dispersible colorant is clear, the solid content of the colorant can be quantified using NMR for pigments and dyes, and the inorganic pigment contained in the heavy metal atom, molecular skeleton, For the metal-containing organic pigment and the metal-containing dye, the solid content of the colorant can be quantified by using fluorescent X-ray analysis.

The other additive is not particularly limited and may be appropriately selected as necessary.For example, a pH adjuster, an antiseptic / antifungal agent, a chelating reagent, an antirust agent, an antioxidant, an ultraviolet absorber, Examples include oxygen absorbers and light stabilizers.
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 to 11 without adversely affecting the ink jet recording ink to be prepared, and can be appropriately selected according to the purpose. , Alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like. When the pH is less than 7 or more than 11, the amount of the ink jet head or the ink supply unit that melts is large, and problems such as ink deterioration, leakage, and ejection failure may occur.
Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.

The ink for ink jet recording can be produced by dispersing or dissolving each of the above materials in an aqueous medium and appropriately stirring and mixing them. The stirring and mixing can be performed, for example, with a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using a normal stirrer blade, a magnetic stirrer, a high-speed disperser, or the like.
The physical properties of the ink for ink jet recording are not particularly limited and can be appropriately selected according to the purpose. For example, the ink viscosity at 25 ° C. is preferably 5 to 20 mPa · s. By setting the ink viscosity to 5 mPa · s or more, the effect of improving the printing density and the character quality can be obtained. Further, by suppressing the ink viscosity to 20 mPa · s or less, it is possible to ensure the discharge property. The viscosity can be measured at 25 ° C. using, for example, a viscometer (RE-550L, manufactured by Toki Sangyo Co., Ltd.).
Further, the static surface tension of the ink for inkjet recording is preferably 20 to 35 mN / m at 25 ° C., more preferably 20 to 30 mN / m. When the static surface tension is in the range of 20 to 35 mN / m, the effect of reducing bleeding by increasing the permeability is high, the drying property on plain paper printing is good, and the pretreatment layer is easily wetted. This improves color development and improves white spots. However, if the static surface tension exceeds 35 mN / m, leveling of the ink on the recording material is difficult to occur and the drying time may be prolonged.

The color of the ink for inkjet recording is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include yellow, magenta, cyan, and black. When recording is performed using an ink set in which two or more of these colors are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all the colors are combined, a full color image is formed. be able to.
The ink jet recording ink is a piezo type (see Japanese Patent Laid-Open No. 2-51734), a thermal type (see Japanese Patent Laid-Open No. 61-59911), or an electrostatic type (Japanese Patent Laid-open No. And the like can be satisfactorily used for an ink jet recording apparatus equipped with any one of them.
The ink for ink jet recording can be used, for example, in a printer having a function of accelerating print fixing by heating a recording medium and the ink for ink jet recording at 50 to 200 ° C. before or after printing.

  A method for cleaning the ink jet recording apparatus and the ink cartridge used in the apparatus using the cleaning / filling liquid of the present invention is not particularly limited, and the process of supplying and discharging the cleaning / filling liquid into the liquid flow path may be repeated. good. For example, a method of supplying and discharging cleaning liquid / filling liquid from a cartridge containing cleaning liquid / filling liquid into the ink flow path by using a supply / suction mechanism of the ink jet recording apparatus main body, a method of repeatedly supplying cleaning liquid / filling liquid from the outside. Examples thereof include a method in which a container is pressurized to supply a cleaning / filling solution, and a method in which suction is performed using an external pump from the head side. Further, after washing, it can be left as a filling liquid in the liquid flow path as necessary.

The cleaning and filling liquid of the present invention can be stored in a container and used as a cartridge. The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, a container having a bag formed of an aluminum laminate film, a resin film, or the like. Preferably mentioned. Since such a container is already known as an ink cartridge, a cleaning and filling liquid may be accommodated and used instead of ink.
The cartridge will be described with reference to FIGS. Here, FIG. 1 is a schematic view showing an example of the cleaning / filling liquid bag 241 of the cartridge, and FIG. 2 is a schematic view showing a cartridge 200 in which the cleaning / filling liquid bag 241 of FIG. It is.
As shown in FIG. 1, after the cleaning liquid / filling liquid bag 241 is filled with the cleaning liquid / filling liquid from the cleaning liquid / filling liquid inlet 242 and the air remaining in the cleaning liquid / filling liquid bag is exhausted, The filling liquid inlet 242 is closed by fusion. In use, the needle of the apparatus main body is pierced into the cleaning liquid filling liquid outlet 243 made of a rubber member and supplied to the apparatus. The cleaning / filling liquid bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, it is usually housed in a plastic cartridge case 244 and used as a cartridge 200 detachably attached to various ink jet recording apparatuses.
The cartridge of the present invention can be used by being detachably attached to an ink jet recording apparatus.

  Examples and Comparative Examples are shown below, but the present invention is not limited to these Examples.

Examples 1-14, Comparative Examples 1-13
<Preparation of cleaning solution>
Using the materials shown in each column of Examples 1-1 and Comparative Examples 1-2 in Table 1-1 and Table 1-2 and Comparative Examples 3-13 in Table 2-1, first, a pH adjuster and a surfactant And water were mixed and dissolved uniformly, and then the water-soluble organic solvent was mixed and stirred for one hour to mix uniformly. This mixed solution was subjected to pressure filtration with a 0.8 μm cellulose acetate membrane filter to remove coarse particles and dust to obtain each cleaning solution and filling solution. In addition, the numerical value which shows the component ratio in a table | surface is the mass%. Moreover, the kind of surfactant used is shown in Table 1-3 and Table 2-2.

<Preparation of pigment ink>
-Preparation of polymer solution-
After sufficiently replacing nitrogen gas in the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, Polyethylene glycol methacrylate 4.0 g, styrene macromer 4.0 g, mercaptoethanol 0.4 g and methyl ethyl ketone 40 g were mixed and heated to 65 ° C.
Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxylethyl methacrylate, 36.0 g of styrene macromer, 3.6 g of mercaptoethanol, azobismethylvaleronitrile A mixed solution of 2.4 g and methyl ethyl ketone 342 g was dropped into the flask over 2.5 hours.
Further, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours.
After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added and further aging was performed for 1 hour.
After completion of the reaction, 800 g of a polymer solution having a concentration of 50% by mass was obtained.

-Preparation of aqueous dispersion of yellow pigment-containing polymer fine particles-
28 g of the polymer solution, C.I. I. 26 g of Pigment Yellow 74, 13.6 g of a 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone and 13.6 g of ion-exchanged water were sufficiently stirred, and then kneaded using a roll mill.
The obtained paste was put into 200 g of pure water and stirred sufficiently, and then methyl ethyl ketone and water were distilled off using an evaporator, and water of yellow pigment-containing polymer fine particles having a solid content of 20% by mass and containing 15% by mass of pigment. A dispersion was obtained.

-Preparation of yellow pigment ink-
First, 15% by mass of 1,3-butanediol, 15% by mass of glycerin, Polyfox PF-151N manufactured by OMNOVA, 1% by mass, and 2% by mass of octanediol were mixed and stirred uniformly for 1 hour.
Next, 40% by mass of the yellow pigment-containing polymer fine particle aqueous dispersion was added to the mixed solution, and water was added so that the total amount was 100% by mass, followed by stirring for 1 hour.
Thereafter, the mixture was filtered under pressure through a 0.8 μm cellulose acetate membrane filter to remove coarse particles to obtain a yellow pigment ink.

-Preparation of aqueous dispersion of magenta pigment-containing polymer fine particles-
17.5 g of the polymer solution, C.I. I. 32.5 g of Pigment Red 122, 8.5 g of 1 mol / L potassium hydroxide aqueous solution, 13 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water were sufficiently stirred, and then kneaded using a roll mill.
The obtained paste was put into 200 g of pure water and sufficiently stirred, and then the methyl ethyl ketone and water were distilled off using an evaporator, and 15% by mass of pigment and magenta pigment-containing polymer fine particles having a solid content of 20% by mass. An aqueous dispersion was obtained.

-Preparation of magenta pigment ink-
First, 15% by mass of 3-methyl-1,3-butanediol, 15% by mass of glycerin, Zonyl FSO-100 manufactured by Dupont, 0.5% by mass, and 1% by mass of 1,2-hexanediol were mixed for one hour. Stirred to mix uniformly.
Next, 40% by mass of the magenta pigment-containing polymer fine particle aqueous dispersion was added to the mixed solution, and water was added so that the total amount was 100% by mass, followed by stirring for 1 hour.
Thereafter, the mixture was filtered under pressure through a 0.8 μm cellulose acetate membrane filter to remove coarse particles to obtain a magenta pigment ink.

<Uniformity of cleaning and filling liquid>
The cleaning and filling liquids of Examples and Comparative Examples prepared as described above were allowed to stand for 1 hour, and the state of the liquid after standing was visually observed and evaluated according to the following criteria. The results are shown in Tables 3-1 and 3-2.
○: There is no separation or insoluble matter, and it is in a uniform state.
X: A part of component isolate | separates or there exists an insoluble matter and it is a nonuniform state.

<Viscosity of cleaning and filling liquid>
Using a viscometer RE80L manufactured by Toki Sangyo Co., Ltd., the viscosity of the cleaning / filling solution was measured at 100 ° C. and 25 ° C. The results are shown in Tables 3-1 to 3-3.

<Mixability of cleaning and filling liquid and ink>
A mixed liquid of 97% by mass of the cleaning / filling liquid and 3% by mass of the ink was prepared, allowed to stand at 65 ° C. for 50 hours, visually observed for changes in appearance, and evaluated according to the following criteria. The results are shown in Tables 3-1 to 3-3.
○: It is not known whether or not the cleaning / filling solution and the ink are separated.
Δ: Concentration is observed in the mixed solution.
X: Separation of the cleaning liquid / filling liquid and the ink occurs.
Moreover, since the thing which cannot ensure the uniformity as a washing | cleaning liquid is uneven at the stage mixed with ink, it was excluded from evaluation.

<Detergency of cleaning liquid and filling liquid>
-Initial state setting A cartridge filled with magenta ink of an adjustment example instead of black ink and cyan ink after replacing the ink in the ink supply path of the ink jet printer (Ricoh IPSIO GX3000) and the ink in the head with pure water, In addition, a cartridge filled with the yellow ink of the preparation example was attached instead of the magenta ink and the yellow ink, and the head refreshing operation was repeated 10 times after the filling operation, and the ink in the ink supply path and the head was replaced with the ink of the preparation example. Thereafter, a nozzle check pattern was printed, and a head refreshing operation was performed until there was no missing nozzle.

-Cleaning treatment After confirming that the nozzles of the inkjet printer were not missing, a cartridge filled with the cleaning and filling liquid was attached instead of all the cartridges, and the head refreshing operation was performed 6 times. Thereafter, the operation of the maintenance unit of the printer was performed, and the operation of suctioning 4.5 cc from each head and refilling was repeated three times. After refilling the cleaning / filling solution again, 2 cc was sucked from each head and the nozzle surface was wiped to clean the path in the ink jet printer.

・ Evaluation of cleaning performance The cleaning and filling liquid sucked last is collected, the absorbance is measured at 421 nm for yellow ink and 563 nm for magenta ink, and compared with the absorbance at the same wavelength of the ink, thereby collecting the collected cleaning liquid. The concentration (mass%) of the ink coloring fine particles in the cum filling liquid was calculated, and the cleaning property was evaluated according to the following criteria. The results are shown in Tables 3-1 to 3-3.
○: Less than 3% ×: 3% or more <Mixability of cleaning / filling solution and ink> Comparative Examples 3, 8, 9, 11, and 13 where separation occurred in the evaluation (in Table 3-3, x The cleaning / filling liquid in Example) was excluded from the evaluation because when it was mixed with ink in the evaluation apparatus (inkjet printer), a precipitate having a large particle size was generated, resulting in nozzle clogging and filter clogging in the evaluation apparatus.

<Evaluation of initial fillability>
Using an inkjet printer (IPSIO GX3000 manufactured by Ricoh Co., Ltd.), the printer was washed by the washing process described in <Washing liquid and filling liquid>, and with the moisturizing cap on the nozzle surface while leaving the washing liquid and filling liquid. After being left for 1 month in an environment of 50 ° C. and 60% RH, an ink cartridge filled with the yellow ink and magenta ink shown in the preparation example was attached, and an initial filling operation was performed.
After that, a nozzle check pattern is printed, and the head refreshing operation is repeated after the filling operation. The number of head refreshing operations until there is no ejection failure (no-jet ejection or bending of the nozzle = white or black streaks are conspicuous in the image) in the nozzle check. (Up to 8 times) was measured and evaluated according to the following criteria. The results are shown in Tables 3-1 to 3-3.
○: Head refreshing 2 times or less △: Head refreshing 3 times or more and 4 times or less ×: Head refreshing 5 times or more required or unrecoverable In addition, Comparative Examples 3, 8 and 9 are the same as in the cleaning performance evaluation of the cleaning liquid and filling liquid. , 11 and 13 were excluded from the evaluation.

  From the above results, it was found that the cleaning and filling liquids of the examples had high mixing stability with ink, good cleaning properties, and excellent initial filling properties.

200 Cleaning liquid / filling liquid cartridge 241 Cleaning liquid / filling liquid bag 242 Cleaning liquid / filling liquid inlet 243 Cleaning liquid / filling liquid outlet 244 Cartridge case

JP 2007-119658 A JP 2007-169314 A JP 2007-091846 A JP 2005-146224 A JP 2009-012361 A

Claims (3)

A cleaning / filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge, comprising at least a water-soluble organic solvent, a compound represented by general formula (I), a compound represented by general formula (II), and water An ink jet recording apparatus and a cleaning / filling solution for an ink cartridge.
Formula (I)

(In the formula, Rf represents CF ₃ or CF ₂ CF ₃ , and q represents an integer of 1 to 6)
Formula (II)

(In the formula, R represents an unsubstituted alkyl group or aryl group having 1 to 4 carbon atoms, m, n and a represent an integer of 5 to 15 and b represents an integer of 5 to 10).   2. The cleaning / filling liquid for an ink jet recording apparatus and an ink cartridge according to claim 1, wherein the water-soluble organic solvent is glycerin.   A cartridge, wherein the cleaning and filling liquid according to claim 1 or 2 is contained in a container.

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