JP2013241552A - Cleaning and filling liquid for inkjet recording apparatus, cartridge containing the liquid, and cleaning method of inkjet recording apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleaning and filling liquid for inkjet recording apparatus, which is excellent in wettability and cleaning properties with less bubbling, secures, even in use of a pigment ink for printing test, excellent compatibility with the ink, and never causes a discharge failure during refilling of the ink.SOLUTION: A cleaning and filling liquid for inkjet recording includes: at least a water-soluble organic solvent, a surfactant and water. The surfactant includes at least a fluorine-based surfactant and an acetylene glycol-based surfactant, and the fluorine-based surfactant is at least one compound represented by general formula (1). (In the formula, n represents an integer of 2-6, and a represents an integer of 15-50. Y represents -CHor -CHCH(OH)CH-CF, b represents an integer of 11-19, and d represents an integer of 2-6).

Description

The present invention relates to a cleaning and filling liquid for an ink jet recording apparatus, a cartridge containing the cleaning and filling liquid, and a method for cleaning an ink jet recording apparatus using the cleaning and filling liquid.

Inkjet recording devices are usually shipped after printing confirmation (discharge confirmation) with test ink, etc., so it is necessary to wash the remaining ink after washing the print test. As the cleaning liquid, wettability and detergency to the ink path are required, and for the purpose of ensuring wettability and detergency, a cleaning liquid to which a surfactant has been added has been used conventionally.

However, conventional surfactant-containing cleaning liquids tend to foam due to the inclusion of surfactants, causing problems due to bubbles during cleaning, and the initial filling of ink with cleaning liquid that remains in trace amounts in the device after shipment. There was a problem that defects occurred. Depending on the type of the surfactant, the member in the ink flow path may be deteriorated, the metal member may be corroded, and the compatibility with the print inspection ink remaining in a minute amount in the apparatus may be poor, resulting in ejection failure. There was also. Further, the ink ejecting head is usually subjected to an ink repellency treatment, but there is a problem that the ink repellency is lowered.

Regarding troubles caused by bubbles, a cleaning solution using a surfactant having low foaming property has also been proposed. In Patent Document 1, a cleaning solution containing a polyoxyalkylene monoalkyl ether having a specific structure is used. Although foamability can be suppressed and compatibility with the test ink or the like can be ensured, it is still insufficient in terms of cleaning efficiency. In addition, depending on the refilled ink, the foam suppression property is insufficient, and thus the problem cannot be solved from the viewpoint of refillability. In addition, in this cleaning liquid composition, minute corrosion may occur in the metal part, which may cause a problem that the durability of the head or the like is lowered.

  In addition, in Patent Document 2, the use of an ethynediol nonionic surfactant having a solubility in water at 25 ° C. of less than 1% prevents foaming and ensures freezing resistance. In addition, the compatibility with the pigment is still insufficient, and the surface tension of the cleaning liquid itself is 28 to 40 nN / m, so that it may not be possible to ensure sufficient cleaning performance for ink having a lower surface tension.

The present invention has been made in view of the above prior art, has less foaming, is excellent in wettability and cleanability, and has excellent compatibility with the ink even when a pigment ink is used for print inspection. An object of the present invention is to provide a cleaning and filling liquid for an ink jet recording apparatus that does not cause ejection failure when refilling. It is another object of the present invention to provide a cleaning method that can achieve both high cleaning efficiency and refillability using the cleaning / filling liquid and a cartridge that contains the cleaning / filling liquid used in the cleaning method.

The present invention uses a fluorine-based surfactant having a specific structure and an acetylene glycol-based surfactant having a specific structure to reduce the surface tension of the cleaning liquid and improve the wettability to the ink flow path member. In addition to improving the cleaning performance, the foaming efficiency is reduced and the foaming efficiency is improved, the cleaning efficiency is improved, the compatibility with the color material in the ink is improved, and the ejection stability after refilling the ink is improved. And the above-mentioned problems have been solved.

Therefore, the above-mentioned problem is (1) “a cleaning / filling liquid for inkjet recording comprising at least a water-soluble organic solvent, a surfactant and water, wherein the surfactant is at least a fluorine-based surfactant and an acetylene. A glycol surfactant, wherein the fluorine surfactant is at least one compound represented by the following general formula (1), and the acetylene glycol surfactant is a compound represented by the following general formula (2): A cleaning and filling liquid for an ink jet recording apparatus, wherein the cleaning liquid is at least one kind.

（式中、ｎは２〜６の整数を示し、ａは１５〜５０の整数を示す。Ｙは−Ｃ_ｂＨ_２ｂ＋１または−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_ｄＦ_２ｄ＋１を示し、ｂは１１〜１９の整数を示し、ｄは２〜６の整数を示す）

(In the formula, n represents an integer of 2 to 6, a represents an integer of 15 to 50, Y represents —C _b H _{2b + 1} or —CH ₂ CH (OH) CH ₂ —C _d F _{2d + 1} , b Represents an integer of 11 to 19, and d represents an integer of 2 to 6)

（式中、ｍ及びｎ互いに独立し、ｍ＋ｎは０〜３０の数を表す。）

(In formula, m and n are mutually independent, and m + n represents the number of 0-30.)

(2) “The cleaning and filling liquid for an ink jet recording apparatus according to the item (1), wherein m + n of the compound of the general formula (2) is 0 to 10,”
(3) “The surfactant represented by the general formula (1) is
The surfactant represented by the general formula (1) is
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 21 -C 12 H 25,
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 25 -C 12 H 25,
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9,
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 35 -CH 2 CH (OH) CH 2 -C 4 F 9
And _{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 4 F 9
The cleaning and filling liquid for an ink jet recording apparatus according to item (1) or (2), wherein the liquid is at least one of the following:
(4) The item (1) to (1), wherein the water-soluble organic solvent is at least one water-soluble organic solvent having an equilibrium water content of 30 wt% or more in an environment of a temperature of 23 ° C. and a humidity of 80%. The cleaning and filling liquid for an ink jet recording apparatus according to any one of items (3), "
(5) “Ink cartridge comprising the ink-jet recording cleaning liquid according to any one of (1) to (4)” in a container,
(6) “Inkjet recording apparatus in which an ink supply path is filled with ink and cleaning by passing the cleaning liquid for an inkjet recording apparatus according to any one of (1) to (4) above” Recording device cleaning method ",
Is achieved.

In the present invention, a specific fluorine-based surfactant and a specific acetylene glycol-based surfactant are used in combination as a surfactant in a cleaning / filling solution for inkjet recording containing at least a water-soluble organic solvent, a surfactant, and water. As a result, the wettability to the ink flow path member is improved, the low wrapping and containment properties are improved, the washing property and the washing efficiency are improved, and the compatibility with the color material component in the ink is further improved. Thus, the ejection stability after refilling with ink can be improved.

  The required characteristics of the inkjet recording device as cleaning liquid are high cleaning ability to remove and push away foreign matter in the ink flow path. For cleaning in the ink flow path, the ink components are separated from the ink flow path while being mixed and replaced with ink. At this time, it is required that the ink flow path member is not deteriorated by the cleaning liquid.

In the present invention, when the fluorinated surfactant is used alone in the cleaning liquid, there is a problem of bubbles and compatibility with the inspection ink or refilling ink, and the acetylene glycol interface in the cleaning liquid. When the activator is used alone, the cleaning performance may be insufficient and the metal member of the ink flow path may be corroded, but the specific fluorosurfactant and acetylene glycol surfactant Incorporation of the agent at the same time not only compensates for the shortcomings of both, but also compatibility with a small amount of colorant components in the ink remaining in the device, which was insufficient when each was used alone Has been ensured, and it has been found that the above-mentioned cleaning liquid can sufficiently satisfy its functions.

  In addition, the filling liquid that fills the ink flow path of the ink jet recording apparatus and stores the ink jet head and the ink flow path system also has the same function as the cleaning liquid, and therefore can be used as the filling liquid. It is.

Hereinafter, components constituting the cleaning liquid and filling liquid of the present invention (hereinafter also referred to as cleaning liquid) will be described.
<Fluorosurfactant>
The fluorosurfactant in the present invention is at least one selected from fluorosurfactants represented by the following general formula (1) having a perfluoroalkyl group.

（式中、ｎは２〜６の整数を示し、ａは１５〜５０の整数を示し、Ｙは−Ｃ_ｂＨ_２ｂ＋１又は−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_ｄＦ_２ｄ＋１を示し、ｂは１１〜１９の整数であり、ｄは２〜６の整数である。）

(Wherein, n represents an integer of 2 to 6, a is an integer of 15 to 50, Y is _-C b _{H 2b + 1} or _{-CH 2 CH (OH) CH 2} -C indicates _{d F 2d + 1,} b Is an integer from 11 to 19, and d is an integer from 2 to 6.)

Preferable specific examples of the compound of the general formula (1) include
_{a) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 21 -C 12 H 25,
_{b) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 25 -C 12 H 25,
_{c) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 30 -C 12 H 25,
_{d) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 20 -C 14 H 29,
_{e) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 30 -C 14 H 29,
_{f) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 23 -C 16 H 33,
_{g) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 20 -C 16 H 33,
_{h) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 25 -C 16 H 33,
_{i) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 30 -C 16 H 33,
_{j) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 40 -C 16 H 33,
_{k) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 20 -C 18 H 37,
_{l) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 30 -C 18 H 37,
_{m) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 40 -C 18 H 37,
_{n) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9,
_{o) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 35 -CH 2 CH (OH) CH 2 -C 4 F 9,
_{p) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 4 F 9
Is mentioned.

More preferably,
_{a) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 21 -C 12 H 25,
_{b) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 25 -C 12 H 25,
_{n) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9,
_{o) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 35 -CH 2 CH (OH) CH 2 -C 4 F 9,
_{p) C 4 F 9 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 4 F 9,
It is.

The content of the fluorosurfactant with respect to the cleaning liquid is preferably less than 0.01 to 10% by mass, and more preferably less than 0.03 to 5% by mass. If the content is less than 0.001% by mass, the wettability cannot be ensured and the compatibility with the colorant component is also poor. On the other hand, when the content is 10% by mass or more, the dissolution stability is deteriorated and a problem due to foaming or the like occurs.

<Acetylene glycol surfactant>
The acetylene glycol surfactant of the present invention is at least one selected from compounds represented by the following general formula (2).

（式中、ｍ及びｎ互いに独立し、ｍ＋ｎは０〜３０の数を示す）

(In the formula, m and n are independent of each other, and m + n represents a number of 0 to 30)

As a compound of the said General formula (2), m + n has preferable 0-30, More preferably, m + n is 0-10. If m + n is within this range, the effect of suppressing bubbles can be obtained. Examples of such compounds include Surfinol 104 (m + n = 0), Surfinol 420 (m + n = 1.3), Surfinol 440 (m + n = 3.5), Surfinol 465 (m + n) manufactured by Air Products Japan Co., Ltd. = 10.0), Surfynol 485 (m + n = 30.0).

The content of the acetylene glycol surfactant in the cleaning liquid is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass. When the content is less than 0.01% by mass, the effect of suppressing bubbles may not be obtained. When the content exceeds 10% by mass, the effect of suppressing foaming reaches its peak, and the viscosity, particle size, etc. Physical properties may be adversely affected.

  Furthermore, a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, etc. can also be added, if the effect by combined use with the said fluorine-type surfactant and an acetylene glycol type surfactant is not prevented.

<Water-soluble organic solvent>
The water-soluble organic solvent of the present invention is intended to prevent the cleaning liquid from drying in the flow path and to easily mix with the ink even if the cleaning liquid remains when refilling the ink. is there. Therefore, it is preferable that the ink is highly compatible with the inspection ink for confirming the ejection before shipment and the ink used for normal printing, and the same water-soluble organic solvent as that used for the ink-jet ink can be used. .

Examples of such water-soluble organic solvents include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, and propylene carbonate. Among them, ethylene carbonate is preferable, and among these, it is preferable to use a water-soluble organic solvent having a high equilibrium water content. Since such a water-soluble organic solvent having a high equilibrium water content can retain a large amount of water, Sex can be imparted.

Here, the water-soluble organic solvent having a high equilibrium water content (hereinafter referred to as water-soluble organic solvent A) has an equilibrium water content of 30 wt% or more, preferably 40 wt% or more in an environment of a temperature of 23 ° C. and a humidity of 80%. . By using such a water-soluble organic solvent A, even when the water in the cleaning liquid evaporates and reaches a water balance, the water-soluble organic solvent A retains a large amount of water to prevent an increase in viscosity and the flow of the cleaning liquid. Sex can be maintained.

Equilibrium water content means that a mixture of water-soluble organic solvent and water is opened to air at a constant temperature and humidity, and the evaporation of water in the solution and the absorption of water in the ink into the ink are in an equilibrium state. Says the amount of water when it becomes. Specifically, the equilibrium water content is determined by using a saturated aqueous solution of potassium chloride, keeping the temperature and humidity in the desiccator at 23 ± 1 ° C. and 80 ± 3%, and weighing 1 g of each water-soluble organic solvent in the desiccator. The petri dish can be stored for a period until the mass change disappears, and can be obtained by the following formula.

  The boiling point of the water-soluble organic solvent A is preferably 140 ° C. or higher, more preferably 250 ° C. or higher. If the boiling point of the water-soluble organic solvent A is 140 ° C. or higher, vaporization does not occur in the environment of use, so that it is possible to prevent a decrease in water that can be retained by vaporization of the water-soluble organic solvent.

  Specific examples of the water-soluble organic solvent A having a high equilibrium water content include 1,2,3-butanetriol (bp175 ° C./33 hPa, 38 wt%), 1,2,4-butanetriol (bp190-191 ° C.). / 24 hPa, 41 wt%), glycerin (bp 290 ° C., 49 wt%), diglycerin (bp 270 ° C./20 hPa, 38 wt%), triethylene glycol (bp 285 ° C., 39 wt%), tetraethylene glycol (bp 324-330 ° C., 37 wt%) ), Diethylene glycol (bp 245 ° C., 43 wt%), 1,3-butanediol (bp 203-204 ° C., 35 wt%), and the like.

Among these, glycerin and 1,3-butanediol are reduced in viscosity when containing water, so that the fluidity of the cleaning liquid can be improved.

When the water-soluble organic solvent A is used in an amount of 50 wt% or more of the total amount of the water-soluble organic solvent agent, it is preferable because it is excellent in ensuring ejection stability and preventing waste ink sticking in the ink flow path.

  In addition to the water-soluble organic solvent A, instead of a part of the water-soluble organic solvent A as necessary, or in addition to the water-soluble organic solvent A, the equilibrium water content at 23 ° C. and 80% is A water-soluble organic solvent (hereinafter referred to as water-soluble organic solvent B) of less than 30 wt% 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.

  Specific examples of the polyhydric alcohols of the water-soluble organic solvent B include, for example, dipropylene glycol (bp 232 ° C), 1,5-pentanediol (bp 242 ° C), 3-methyl-1,3-butanediol (bp 203 ° C). ), Propylene glycol (bp 187 ° C.), 2-methyl-2,4-pentanediol (bp 197 ° C.), ethylene glycol (bp 196-198 ° 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 (bp253-260 ° C), 1,2,6-hexanetriol (bp178 ° C), trimethylolethane (solid, mp199- 201 ° C), trimethylolpropane Solid, MP61 ° C.), and the like.

  Examples of 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 monobutyl 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 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., 47-48 wt%), N-methyl-2-pyrrolidone (bp 202 ° C.), 1,3-dimethyl-2-imidazolide. Non (bp 226 ° C.), ε-caprolactam (bp 270 ° C.), γ-butyrolactone (bp 204-205 ° C.) and the like.

Examples of amides include formamide (bp 210 ° C.), N-methylformamide (bp 199-201 ° C.), N, N-dimethylformamide (bp 153 ° C.), N, N-diethylformamide (bp 176-177 ° C.), and the like. It is done.

Examples of 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 and filling liquid of the present invention can be added with other additives such as antiseptic / antifungal agents, chelating agents, rust preventives, pH adjusters, penetrants, etc., as necessary. The same components as those described above are preferred.

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 antirust agent include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dichloroammonium nitrite, and benzotriazole.

As the pH adjuster, any substance can be used as long as it does not adversely affect the prepared cleaning and filling liquid and damages the ink flow path of the ink jet recording apparatus.
For example, when adjusting to basic, amines such as diethanolamine and triethanolamine, alkali metal hydroxides such as sodium hydroxide, quaternary compound hydroxides such as quaternary ammonium hydroxide, sodium carbonate When adjusting to acidity, hydrochloric acid, sulfuric acid, and the like include inorganic acids, and organic acids such as acetic acid and oxalic acid.

  The wetting agent supplements the permeability by a surfactant or a water-soluble organic solvent, and is preferably a polyol having a solubility in water at 20 ° C. of 0.2 to 5.0% by mass. Examples thereof include aliphatic diols such as ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.

  Furthermore, polyhydric alcohol alkyls and aryl ethers such as diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, and diethylene glycol monobutyl ether, and lower alcohols such as ethanol may be used in combination.

A saccharide sugar solid wetting agent may be added. Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Specific examples include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose. Derivatives of these saccharides include reducing sugars (for example, sugar alcohols (general _{formula: HOCH 2 (CHOH) nCH 2} OH ( where, n is represented by an integer of 2-5). ), Oxidized sugars (for example, aldonic acid, uronic acid, etc.), amino acids, thioic acids, etc. Among these, sugar alcohols are preferable, and specific examples include maltitol, sorbit, and the like.

The method for cleaning an ink jet recording apparatus of the present invention may simply repeat the steps of supplying and discharging the cleaning liquid and filling liquid into the ink flow path. For example, using the supply and suction mechanism of the ink jet recording apparatus main body, A method of repeatedly supplying and discharging the cleaning / filling liquid from the cartridge containing the filling liquid into the ink flow path, putting the cleaning / filling liquid into the ink container provided in the main body of the inkjet recording apparatus, and pressurizing the ink container from the outside. Examples include a method of supplying and discharging into the ink flow path, a method of supplying a cleaning / filling liquid into the ink flow path using an external pump from the head side, and discharging by suction, and the like. It is preferable to use a cartridge containing a filling liquid because cleaning can be performed easily.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Adjustment of cleaning and filling liquid>
Example 1
(Prescription)
0.1% by mass of compound of general formula (1) -a)
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 21 -C 12 H 25)
Surfynol 440 (m + n = 3.5) 0.4% by mass
Glycerin 15% by mass
1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain the cleaning / filling solution of Example 1.

Example 2
(Prescription)
0.1% by mass of compound of general formula (1) -b)
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 25 -C 12 H 25)
Surfynol 440 (m + n = 3.5) 0.4% by mass
Glycerin 15% by mass
Diethylene glycol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain the cleaning / filling solution of Example 2.

Example 3
(Prescription)
Compound of general formula (1) -n) 0.1% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 465 (m + n = 10.0) 5% by mass
Glycerin 15% by mass
3-methyl-1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain the cleaning / filling solution of Example 3.

Example 4
Compound of general formula (1) -b) 0.05% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 25 -C 12 H 25)
Compound of general formula (1) -n) 0.05% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 440 (m + n = 3.5) 0.1% by mass
Glycerin 15% by mass
1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain the cleaning / filling solution of Example 4.

Example 5
Compound of general formula (1) -o) 0.03% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 35 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 104 (m + n = 0) 0.2% by mass
Surfynol 485 (m + n = 30.0) 0.2% by mass
1,3-butanediol 30% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Example 5.

Example 6
(Prescription)
Compound of general formula (1) -p) 5% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 485 (m + n = 30.0) 0.4% by mass
Glycerin 30% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain the cleaning / filling solution of Example 6.

Example 7
(Prescription)
Compound of general formula (1) -o) 0.02% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 35 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 440 (m + n = 3.5) 0.4% by mass
Diethylene glycol 30% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain the cleaning / filling solution of Example 7.

Example 8
(Prescription)
Compound of general formula (1) -n) 6% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 465 (m + n = 10.0) 6% by mass
1,3-butanediol 15% by mass
3-methyl-1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Example 8.

Example 9
(Prescription)
Compound of general formula (1) -n) 0.1% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 440 (m + n = 3.5) 0.09 mass%
Glycerin 15% by mass
1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a washing / filling solution of Example 9.

Comparative Example 1
(Prescription)
0.1% by mass of compound of general formula (1) -a)
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 21 -C 12 H 25)
Glycerin 15% by mass
1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Comparative Example 1.

Comparative Example 2
(Prescription)
Surfynol 465 (m + n = 10.0) 0.4% by mass
Glycerin 15% by mass
Diethylene glycol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Comparative Example 2.

Comparative Example 3
(Prescription)
0.1% by mass of compound of general formula (1) -b)
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 25 -C 12 H 25)
Softanol EP-7025 0.4% by mass
(Polyoxyalkylene alkyl ether (Nippon Shokubai Co., Ltd., active ingredient 100% by mass))
Glycerin 15% by mass
3-methyl-1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Comparative Example 3.

Comparative Example 4
(Prescription)
Surfynol 485 (m + n = 30.0) 0.4% by mass
Softanol EP-7025 0.4% by mass
(Polyoxyalkylene alkyl ether (Nippon Shokubai Co., Ltd., active ingredient 100% by mass))
Glycerin 15% by mass
3-methyl-1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Comparative Example 4.

Comparative Example 5
(Prescription)
Compound of general formula (1) -o) 0.009 mass%
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 35 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 440 (m + n = 3.5) 0.008 mass%
Ethylene glycol 15% by mass
3-methyl-1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Comparative Example 5.

Comparative Example 6
(Prescription)
Compound of general formula (1) -p) 10% by mass
_{(C 4 F 9 -CH 2 CH} (OH) CH 2 O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 4 F 9)
Surfynol 465 (m + n = 10.0) 10% by mass
15% by weight of polyethylene glycol
3-methyl-1,3-butanediol 15% by mass
The remaining components of the ion-exchanged water were sufficiently stirred and mixed at room temperature, and then filtered through a membrane filter having an average pore size of 0.8 μm to obtain a cleaning / filling solution of Comparative Example 5.

Next, an evaluation ink for evaluating the cleaning / filling liquid of the present invention will be described.
<Evaluation ink adjustment>
The evaluation ink was prepared by the method shown below.

-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. After dropping, 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 and 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 an aqueous dispersion of yellow pigment-containing polymer fine particles having a pigment content of 15% by mass and a solid content of 20% by mass. Got.

-Preparation of yellow pigment ink-
The yellow pigment ink was prepared according to the following procedure. First, 15% by mass of 1,3-butanediol, 15% by mass of glycerin, 1% by mass of Polyfox PF-151N manufactured by OMNOVA, and 2% by mass of octanediol are mixed and stirred uniformly for 1 hour. 40% by mass of the yellow pigment-containing polymer fine particle aqueous dispersion was added to the mixed solution, and the remaining amount of 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 μ cellulose acetate membrane filter to remove coarse particles, and an evaluation ink was obtained.

-Preparation of aqueous dispersion of magenta pigment-containing polymer fine particles-
17.5 g of the polymer solution and 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 stirred sufficiently, and then methyl ethyl ketone and water were distilled off using an evaporator, and an aqueous dispersion of magenta pigment-containing polymer fine particles containing 15% by mass of pigment and 20% by mass of solids. Got.

-Preparation of magenta pigment ink-
The magenta pigment ink was prepared according to the following procedure. First, 15% by mass of 3-methyl-1,3-butanediol, 15% by mass of glycerin, 0.5% by mass of Zonyl FSO-100 manufactured by Dupont, and 1% by mass of 1,2-hexanediol were mixed and stirred uniformly for 1 hour. To mix. 40% by mass of the magenta pigment-containing polymer fine particle aqueous dispersion was added to the mixed solution, and the remaining amount of 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 μ cellulose acetate membrane filter to remove coarse particles, and an evaluation ink was obtained.

-Preparation of cyan pigment-containing polymer fine particle water dispersion-
The coloring material is C.I. I. An aqueous dispersion of cyan pigment-containing polymer fine particles was obtained in the same manner as the preparation of the yellow pigment-containing polymer fine particle aqueous dispersion except that the pigment blue was changed to 15: 3.

-Preparation of cyan pigment ink-
The cyan pigment ink was prepared according to the following procedure. First, 15% by mass of 1,3-butanediol, 15% by mass of glycerin, 1% by mass of Polyfox PF-151N manufactured by OMNOVA, and 2% by mass of octanediol are mixed and stirred uniformly for 1 hour. 40% by mass of the yellow pigment-containing polymer fine particle aqueous dispersion was added to the mixed solution, and the remaining amount of 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, and an evaluation ink was obtained.

-Adjustment of black pigment ink-
KM-9036 (Toyo Ink, self-dispersing pigment) 50% by mass
Glycerin 10% by mass
1,3-butanediol 15% by mass
2-ethyl-1,3-hexanediol 2% by mass
2-pyrrolidone 2% by mass
Nissin Chemical Industry Olfin 1010 1% by mass
Silicone defoamer KS508 (Shin-Etsu Chemical) 0.1% by mass
Residual amount of ion-exchanged water An ink composition having the above formulation was prepared and sufficiently stirred at room temperature, and then filtered through a membrane filter having an average pore size of 1.5 μm to obtain an evaluation ink.

The following evaluations 1 to 4 were performed using the cleaning and filling liquids of Examples and Comparative Examples.
In addition, evaluation 1 is evaluation about the cleaning liquid of an Example and a comparative example. Evaluations 2 to 4 were evaluated using the cleaning and filling liquids of Examples and Comparative Examples and the above evaluation inks, and all the above four inks were evaluated and the evaluation results were based on the worst color. It is.

Evaluation 1: Evaluation of foaming and defoaming properties of cleaning liquid / filling liquid 10 ml of the prepared cleaning liquid / filling liquid was placed in a 100 ml measuring cylinder, and air was injected into the cleaning liquid in an environment of 10 ° C. The injection of air was stopped when the total volume of the ink and foaming reached 100 ml, or when 60 seconds had elapsed.
The time from the injection of air to the stop of the injection of air was taken as the foaming time, and the time from when the injection of air was stopped until the total volume of the ink and bubbles reached 20 ml was measured. Evaluated by criteria.
The worse foaming / defoaming results were taken as foaming evaluation results.

(Foamability)
A: Foaming time is 60 seconds or more (including the case where bubbles do not hit)
○: Foaming time of 40 seconds or more and less than 60 seconds Δ: Foaming time of 20 seconds or more and less than 40 seconds ×: Foaming time of less than 20 seconds
(Defoaming property)
A: Defoaming time is less than 100 seconds O: Defoaming time is 100 seconds or more and less than 200 seconds Δ: Defoaming time is 200 seconds or more and less than 400 seconds X: Defoaming time is 400 seconds or more

Evaluation 2: Detergency evaluation of cleaning liquid and filling liquid An ink jet printer (IPSIO GX3000, manufactured by Ricoh Co., Ltd.) is attached with a cartridge filled with each color evaluation ink, filled as described above, printed with a nozzle check pattern, and no nozzle missing. It was confirmed.
Thereafter, a cartridge filled with the cleaning / filling solution was attached instead of all the cartridges, and the head refreshing operation was performed six times. Thereafter, the maintenance unit of the printer was operated, and the operation of sucking 4.5 cc from each head and refilling was repeated three times. Finally, the absorbance of each liquid sucked from each head was measured. The pigment concentration was calculated from the absorbance at the wavelength of λMax of each color, and it was judged according to the following criteria.
◎: Less than 0.5% of ink absorbance ○: 0.5% or more of ink absorbance, less than 1% Δ: 1% or more of ink absorbance, less than 2% ×: 2% or more of ink absorbance

Evaluation 3: Compatibility Evaluation 97 g of cleaning / filling solution and 3 g of ink were mixed and left in a thermostatic bath at 90 ° C. for 8 hours.
Then, it took out and left still for 2 hours and observed the state of the liquid visually. The judgment was made according to the following criteria.
◎: no separation is observed ○: slight shading is observed Δ: slight precipitation of color material is observed x: color material is precipitated

Evaluation 4: Refillability Evaluation The inkjet printer (IPSIO GX3000, manufactured by Ricoh Co., Ltd.) after washing in Evaluation Evaluation 2 is left in a constant temperature bath at 40 ° C. for 24 hours, and an ink cartridge filled with the evaluation ink is attached to the initial stage. A filling operation was performed. After that, the nozzle check pattern is printed, the head refreshing operation is repeated after the filling operation, and the number of head refreshing until the ejection failure (nozzle ejection or ejection bending = white or black streaks are conspicuous in the image) is eliminated. Was evaluated. (Up to 8 times)
◎: Head refreshing 1 time or less ○: Head refreshing 2 to 3 times △: Head refreshing 3 to 4 times ×: Head refreshing 5 times or more required or unrecoverable

Evaluations 1 to 4 are shown in the following table. (For evaluations 2 to 4, bad colors were used as evaluation results for each color)

  As shown in Table 1, in Examples 1 to 5, the addition amount of the surfactant represented by the general formulas (1) and (2) is within the optimum range, and excellent results in all of the evaluations 1 to 4 Was obtained. In Examples 6 to 9, since the addition amount of the surfactant represented by the general formulas (1) and (2) exceeds the optimum range, any one of foamability, detergency, compatibility, and refillability The result was slightly inferior.

On the other hand, as shown in Table 2, Comparative Examples 1 and 2 lacked either of the compounds represented by the general formulas (1) and (2), and thus each resulted in an unsatisfactory result. In Comparative Examples 3 to 4, when any of the compounds represented by the general formulas (1) and (2) was used with a surfactant different from the present invention, the results were not good. In Comparative Examples 5 to 6, the addition amount of the compounds represented by the general formulas (1) and (2) exceeded the preferable range, and the results were not good.

Japanese Patent No. 4397220 JP 2007-091846 A

Claims (6)

A cleaning and filling liquid for inkjet recording containing at least a water-soluble organic solvent, a surfactant and water, wherein the surfactant contains at least a fluorine-based surfactant and an acetylene glycol-based surfactant, and the fluorine-based interface The activator is at least one compound represented by the following general formula (1), and the acetylene glycol surfactant is at least one compound represented by the following general formula (2). Cleaning and filling liquid for inkjet recording devices.

(In the formula, n represents an integer of 2 to 6, a represents an integer of 15 to 50, Y represents —C _b H _{2b + 1} or —CH ₂ CH (OH) CH ₂ —C _d F _{2d + 1} , b Represents an integer of 11 to 19, and d represents an integer of 2 to 6)

(In formula, m and n are mutually independent, and m + n represents the number of 0-30.) 2. The cleaning and filling liquid for an ink jet recording apparatus according to claim 1, wherein m + n of the compound of the general formula (2) is 0 to 10. The surfactant represented by the general formula (1) is
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 21 -C 12 H 25,
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 25 -C 12 H 25,
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 23 -CH 2 CH (OH) CH 2 -C 4 F 9,
_{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 35 -CH 2 CH (OH) CH 2 -C 4 F 9
And _{C 4 F 9 -CH 2 CH (} OH) CH 2 -O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 4 F 9
The cleaning liquid / filling liquid / filling liquid for an ink jet recording apparatus according to claim 1, wherein the cleaning liquid / filling liquid is an ink jet recording apparatus. The water-soluble organic solvent is at least one of water-soluble organic solvents having an equilibrium water content of 30 wt% or more in an environment with a temperature of 23 ° C and a humidity of 80%. Cleaning and filling liquid for inkjet recording apparatus. 5. An ink cartridge comprising the ink-jet recording cleaning liquid and filling liquid according to claim 1 contained in a container. An inkjet recording apparatus having an ink supply path filled with ink, wherein the cleaning and filling liquid for an inkjet recording apparatus according to any one of claims 1 to 4 is passed through and washed. Cleaning method.