JP7059589B2 - Cleaning liquid, cleaning method, inkjet recording method, cleaning equipment, inkjet recording equipment, and ink and cleaning liquid set - Google Patents

Description

The present invention relates to a cleaning liquid, a cleaning method, an inkjet recording method, a cleaning device, an inkjet recording device, and a set of ink and a cleaning liquid.

Conventionally, dye inks have been the mainstream of inkjet inks because of their good color development and high reliability, but in recent years, they have excellent water resistance and light resistance, for example, in commercial printing applications using high-speed continuous business machines. Pigment inks are often used. In commercial printing applications, it is required to obtain image quality comparable to that of conventional offset printing even for printing coated paper having low ink absorption. Ink containing a resin having film-forming property is used in order to secure the high-speed drying property (high-speed fixing property) required for the high-speed continuous book machine and the fixing property to the base material having low ink absorption. However, since the resin having a film-forming property adheres firmly to the discharge head of the recording device, cleaning of the adhered resin may be insufficient even if a cleaning liquid is used. In such a case, it becomes difficult to secure the ink ejection reliability.

Therefore, a maintenance liquid for an inkjet printer containing at least one of glycol ethers and glycol esters in the maintenance liquid in an amount of 80% by mass or more has been proposed (see, for example, Patent Document 1).

The pigment ink containing a urethane resin having a low glass transition point has excellent adhesion to a base material and drying property, and has high film-forming property. However, the conventional cleaning liquid has a problem that the cleaning property for the pigment ink having a high film-forming property is not sufficient and the ejection reliability after cleaning cannot be ensured.

（ただし、前記一般式（１）中、Ｍｅはメチル基を表し、Ｒ^１は、炭素数１以上４以下のアルキル基を表す。） The inkjet recording apparatus of the present invention as a means for solving the above-mentioned problems is an inkjet recording apparatus having an ejection head for ejecting ink, ink, and a cleaning liquid.
The ink contains water, a urethane resin having a glass transition point of 0 ° C. or lower, a pigment, a compound represented by the following general formula (1), and a surfactant.
The cleaning liquid contains water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant.

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.)

According to the present invention, it is possible to provide an inkjet recording apparatus having a cleaning liquid having excellent detergency for pigment ink having high film-forming property and capable of improving ejection reliability after cleaning.

FIG. 1 is a perspective explanatory view showing an example of a serial type image forming apparatus. FIG. 2 is a perspective explanatory view showing an example of the main tank of the apparatus of FIG. FIG. 3 is a schematic view showing an example of the cleaning device of the present invention.

(Cleaning liquid)
The cleaning liquid of the present invention is used for cleaning water, a urethane resin having a glass transition point of 0 ° C. or less, a pigment, a compound represented by the following general formula (1), and an ink containing a surfactant. It contains a compound represented by the general formula (1), a glycol ether compound, and a surfactant, and further contains other components as necessary.

（ただし、前記一般式（１）中、Ｍｅはメチル基を表し、Ｒ^１は、炭素数１以上４以下のアルキル基を表す。）

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.)

<Compound represented by the general formula (1)>
Examples of the compound represented by the general formula (1) include those having a methyl, ethyl, propyl, and butyl group as ^R1 . By using both the above compound and the glycol ether compound, it is possible to obtain higher detergency than when used alone, and even when separation occurs with the glycol ether compound alone, sufficient storage stability is achieved. It is possible to obtain sex. The cleaning liquid contains a compound represented by the general formula (1), and in particular, softens the adhered material with respect to an ink-adhered material containing a urethane resin having a glass transition point (hereinafter referred to as Tg) of 0 ° C. or less. And high cleaning is obtained.

The addition rate of the compound represented by the general formula (1) contained in the cleaning liquid is preferably 1% by mass or more and 50% by mass or less, and 20% by mass or more and 30% by mass or less from the viewpoint of improving the cleaning property. Is even more preferable.

-Example of synthesis in the case of ^R1 : ethyl group in the general formula (1) N, N-dimethylacrylamide 19.828 g, ethanol 19 in a 300 mL separable flask equipped with a stirrer, a thermocouple, and a nitrogen gas introduction tube. Add 868 g and stir while introducing nitrogen gas. Next, 0.338 g of sodium-t-butoxide is added, and the reaction is carried out at 35 ° C. for 4 hours. After completion of the reaction, 150 mg of phosphoric acid is added to homogenize the solution, and then the solution is allowed to stand for 3 hours. The obtained solution is filtered to remove the precipitate, and the unreacted substance is removed by an evaporator. The compound represented by the general formula (1) (3-ethoxy-N, N-dimethylpropionamide, general formula (1). ) R ¹ : Ethyl group) is obtained.

（ただし、前記一般式（１）中、Ｒ^１は、エチル基を表す。）

(However, in the general formula (1), R ¹ represents an ethyl group.)

A commercially available product may be used as the compound represented by the general formula (1). Examples of such a commercially available product include Equamid M100 manufactured by Idemitsu Kosan Co., Ltd.

<Glycol ether compound>
The glycol ether compound is not particularly limited and may be appropriately selected depending on the intended purpose.
Examples of the glycol ether compound include ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol. Examples include glycol ethers such as monoethyl ether, dipropylene glycol monobutyl ether, propylene glycol-n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and tripropylene glycol monomethyl ether. Be done. These may be used alone or in combination of two or more.
Among these, it is preferable that the glycol ether compound contains a dialkyl glycol ether compound represented by the following general formula (2).

（ただし、前記一般式（２）中、Ｒ^２はＨ、又はＣＨ_３を表し、Ｒ^３はＣ_ｍＨ_２ｍ＋１を表し、ｎは１乃至３の数を表し、ｍは１乃至４の数を表す。）

(However, in the general formula (2), R ² represents H or CH ₃ , R ³ represents C _m H _{2m + 1} , n represents a number of 1 to 3, and m represents a number of 1 to 4. show.)

Examples of the compound represented by the general formula (2) include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether. The glycol ether compound has a strong action on the ink film, and the cleaning property is improved by including the glycol ether compound in the cleaning liquid, and the dialkyl glycol ether compound is more likely to soften the stain by the solvent. Cleanability is improved.

The addition rate of the glycol ether compound contained in the cleaning liquid is not particularly limited, but is preferably 1% by mass or more and 70% by mass or less from the viewpoint of improving the cleaning property. When the addition rate is 20% by mass or more and 30% by mass or less, the detergency, discharge stability, and storage stability are particularly excellent, which is preferable.

Further, it is desirable that the cleaning liquid contains, in addition to the above-mentioned glycol ether compound, a glycol ether compound having a solubility in water of 5 g / 100 g (water) or less. By containing a glycol ether compound having a solubility in water of 5 g / 100 g (water) or less, the cleaning liquid can also act on hydrophobic stains, and can be used for stains on ink films having a large amount of resin. It is possible to strengthen the force acting on it, and the detergency is improved. Further, especially when combined with a dialkyl glycol ether compound, it is possible to obtain more effects than those used alone in terms of detergency.

<< Other solvents >>
In the present invention, the cleaning liquid may contain other solvents as long as the effects of the present invention are not impaired.
The other solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include water-soluble organic solvents.
The water-soluble organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyhydric alcohols; ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, and the like. Examples thereof include nitrogen heterocyclic compounds; amides; amines; sulfur-containing compounds, propylene carbonate, ethylene carbonate, polyol compounds having 8 or more carbon atoms, and side chain glycol ether compounds. These may be used alone or in combination of two or more.

Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. 2,3-Butanediol, 3-Methyl 1,3-Butanediol, Triethylene Glycol, Polyethylene Glycol, Polypropylene Glycol, 1,2-Pentanediol, 1,3-Pentanediol, 1,4-Pentanediol, 2, 4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1 , 2,6-Hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanediol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3 -Pentanediol, petriol, etc. can be mentioned.

Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-. Butyrolactone and the like can be mentioned.

Examples of the amides include formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like.

Examples of the amines include monoethanolamine, diethanolamine, triethylamine and the like.

Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, and thiodiethanol.

Examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.

Examples of the glycol ether compound in the side chain include diethylene glycol isobutyl ether.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Among these, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, side chain double-ended modified polydimethylsiloxane, and the like. Those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counter ions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
These may be used alone or in combination of two or more.

Among the surfactants, polyoxyalkylene surfactants are preferable, and polyoxyethylene distyrene phenyl ethers and polyoxyethylene polyoxypropylene alkyl ethers are more preferable from the viewpoint of detergency and storage stability.

The polyoxyalkylene surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a commercially available product can be used. Examples of the commercially available product include Emulgen A-60 (polyoxyethylene distyrene phenyl ether), Emargen LS-106 (polyoxyethylene polyoxypropylene alkyl ether), and Emargen LS-110 (polyoxyethylene polyoxypropylene alkyl). Ether) (above, manufactured by Kao Co., Ltd., higher alcohol-based ether type nonionic surfactant) and the like. These may be used alone or in combination of two or more.

The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd. and the like.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) is dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

一般式（Ｓ－１）
（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。

General formula (S-1)
(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)
Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (Shinetsu Chemical Industry Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

Further, as the silicone-based surfactant, WET-240 (manufactured by Nissin Chemical Co., Ltd.), BYK-349 (manufactured by Big Chemie Co., Ltd.) and the like can also be suitably used. These may be used alone or in combination of two or more.

As the fluorine-based surfactant, a compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine is more preferable.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain.
Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has less foaming property, and is particularly a fluorine-based compound represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.

一般式（Ｆ－１）
上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。
一般式（Ｆ－２）
Ｃ_ｎＦ_{２ｎ＋１－}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－Ｏ－（ＣＨ_２ＣＨ_２Ｏ）_ａ－Ｙ
上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣｍＦ_２ｍ＋１でｍは１～６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－ＣｍＦ_２ｍ＋１でｍは４～６の整数、又はＣｐＨ_２ｐ＋１でｐは１～１９の整数である。ｎは１～６の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。
この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス製）、ポリフォックスＰＦ－１３６Ａ，ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ－３１００、ＦＳ－３４、ＦＳ－３００、株式会社ネオス製のＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ、オムノバ社製のポリフォックスＰＦ－１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ－４０３Ｎが特に好ましい。

General formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
C _n F _{2n + 1-} CH ₂ CH (OH) CH ₂ -O- (CH ₂ CH ₂ O) _a -Y
In the compound represented by the above general formula (F-2), Y is H or CmF _{2m + 1} and m is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ -CmF _{2m + 1} and m is 4 to 6. It is an integer, or CpH _{2p + 1} and p is an integer of 1 to 19. n is an integer of 1 to 6. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant.
Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by The Chemours Company); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omniova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.), etc. Among these, FS-3100, FS-34, and FS-300 manufactured by The Chemours Co., Ltd. are significantly improved in good print quality, particularly color development, permeability to paper, wettability, and leveling property. , FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omninova, and Unidyne DSN-403N manufactured by Daikin Industries Co., Ltd. Is particularly preferable.

The surfactant in the cleaning liquid has an action of infiltrating the cleaning liquid into the solid matter in which the ink is solidified. The content of the surfactant in the cleaning liquid is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is excellent in wettability and ejection stability, and 0.001 mass is improved in terms of image quality. % Or more and 5% by mass or less are preferable, and 0.05% by mass or more and 5% by mass or less are more preferable.

<Water>
The content of the water is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 80% by mass or less, preferably 10% by mass or more and 60% by mass or less, based on the total amount of the cleaning liquid. Is more preferable. When the content is 10% by mass or more, ink stains can be sufficiently wiped from the interface of the nozzle surface, and sufficient ejection reliability can be obtained. When the content is 80% by mass or less, the stains can be sufficiently removed. It is possible to swell. Further, it is possible to eliminate the flash point by adding water.

<Other ingredients>
The cleaning agent may contain other components. The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include penetrants, antifoaming agents, antiseptic and antifungal agents, rust preventives and pH adjusters.

<Defoamer>
The defoaming agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

<Preservatives and fungicides>
The antiseptic and antifungal agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,2-benzisothiazolin-3-one.

<Rust inhibitor>
The rust preventive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acidic sulfites and sodium thiosulfate.

<pH adjuster>
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or more, and can be appropriately selected depending on the intended purpose. Examples thereof include amines such as diethanolamine and triethanolamine. ..

The method of using the cleaning liquid of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an inkjet head having a nozzle surface having a nozzle opening of a nozzle for discharging the liquid is used. In an inkjet recording device that records an image on a recording medium using inkjet recording ink, the nozzle surface is sprayed with the cleaning liquid or wiped off with a cloth or the like impregnated with the cleaning liquid. It is preferable to clean the nozzle and the nozzle. Further, the cleaning liquid may be replaced with the ink of the inkjet recording device and discharged from the ejection portion to clean the inside of the flow path of the inkjet recording device, the inside of the head, and the periphery of the nozzle.

<Ink>
The ink used in the present invention contains at least water, a urethane resin having a glass transition point (Tg) of 0 ° C. or lower, a pigment as a coloring material, and a compound represented by the following general formula (1), and is further required. Contains other ingredients accordingly.

（ただし、前記一般式（１）中、Ｍｅはメチル基を表し、Ｒ^１は、炭素数１以上４以下のアルキル基を表す。）

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.)

By containing a urethane resin having a Tg of 0 ° C. or lower and a compound represented by the general formula (1), the film-forming property of the resin is improved. High drying properties can be obtained, a uniform coating film can be obtained, and high adhesion to a non-permeable substrate can be obtained. In particular, when the Tg of the polycarbonate urethane resin is −20 ° C. or lower, higher adhesion and drying property can be obtained.

The above-mentioned inks have high film-forming properties, so that high adhesion and high drying properties can be obtained, but on the other hand, the inks tend to adhere to the ink ejection head, and ejection defects are likely to occur. By using the above-mentioned cleaning liquid for this ink, it is possible to suppress sticking to the ink ejection head, and it is possible to achieve both high adhesion to the substrate, high drying property and ejection stability.

<< Urethane resin >>
The urethane resin is not particularly limited as long as the glass transition point (Tg) is 0 ° C. or lower, and can be appropriately selected depending on the intended purpose. For example, a polyurethane resin obtained by reacting a polyol with a polyisocyanate. Examples include particles. Preferably, a polycarbonate polyurethane resin having a Tg of −20 ° C. or lower is preferable from the viewpoint of adhesion to the substrate.

-Polyol-
Examples of the polyol include polyether polyols, polycarbonate polyols, polyester polyols and the like. These may be used alone or in combination of two or more.

－－Polyether polyol －－
Examples of the polyether polyol include those obtained by addition-polymerizing an alkylene oxide using at least one compound having two or more active hydrogen atoms as a starting material.

Examples of the compound having two or more active hydrogen atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylolglycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane. Examples thereof include diol, glycerin, trimethylolethane, and trimethylolpropane. These may be used alone or in combination of two or more.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These may be used alone or in combination of two or more.

The polyether polyol is not particularly limited and may be appropriately selected depending on the intended purpose. However, polyoxytetramethylene glycol and polyoxy can be obtained from the viewpoint of obtaining an ink binder capable of imparting extremely excellent scratch resistance. Propylene glycol is preferred. These may be used alone or in combination of two or more.

－－Polycarbonate polyol－－
Examples of the polycarbonate polyol that can be used for producing the polyurethane resin particles include those obtained by reacting a carbonic acid ester with a polyol, those obtained by reacting phosgene with bisphenol A, and the like. These may be used alone or in combination of two or more.

Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenylcarbonate and the like. These may be used alone or in combination of two or more.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1, 2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Octane diol, 1,9-nonane diol, 1,10-decane diol, 1,11-undecane diol, 1,12-dodecane diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcin , Bisphenol-A, Bisphenol-F, 4,4'-Biphenol and other relatively low molecular weight dihydroxy compounds; Polyether polyols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol; Polyhexamethylene adipate, polyhexamethylene Examples thereof include polyester polyols such as succinate and polycaprolactone. These may be used alone or in combination of two or more.

－－Polyester polyol－－
Examples of the polyester polyol include those obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, polyester obtained by ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymerization thereof. Examples include polyester. These may be used alone or in combination of two or more.

Examples of the low molecular weight polyol include ethylene glycol and propylene glycol. These may be used alone or in combination of two or more.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecandicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof. These may be used alone or in combination of two or more.

-Polyisocyanate-
Examples of the polyisocyanate include aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxyli. Examples thereof include aliphatic or alicyclic diisocyanates such as range isocyanate and 2,2,4-trimethylhexamethylene diisocyanate. These may be used alone or in combination of two or more. Among these, the ink of the present invention is also used for outdoor applications such as posters and signboards, and therefore requires a coating film having extremely high long-term weather resistance. From the viewpoint of the long-term weather resistance, the alicyclic is required. The formula diisocyanate is preferred.

Further, by using at least one kind of alicyclic diisocyanate, it becomes easy to obtain the desired coating film strength and scratch resistance.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate.
The content of the alicyclic diisocyanate is preferably 60% by mass or more with respect to the total amount of the isocyanate compound.

[Manufacturing method of polyurethane resin particles]
The polyurethane resin particles can be obtained by a conventionally commonly used production method, and examples thereof include the following methods.
First, the polyol and the polyisocyanate are reacted at an equivalent ratio in which the isocyanate group becomes excessive in the absence of a solvent or in the presence of an organic solvent to produce an isocyanate-terminated urethane prepolymer.
The anionic group in the isocyanate-terminated urethane prepolymer is then neutralized with a neutralizing agent, if necessary, and then reacted with a chain extender to finally remove the organic solvent in the system, if necessary. Can be obtained by

Examples of the organic solvent that can be used for producing the polyurethane resin particles include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethyl. Examples thereof include amides such as formamide, N-methylpyrrolidone and N-ethylpyrrolidone. These may be used alone or in combination of two or more.
Examples of the chain extender include polyamines and other active hydrogen group-containing compounds.

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazin, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamines; Polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine; Hydrazines such as hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; , Dihydrazides such as glutarate dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide and the like. These may be used alone or in combination of two or more.

Examples of the other active hydrogen group-containing compound include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol. Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc. Kind; water and the like. These may be used alone or in combination of two or more as long as the storage stability of the ink is not deteriorated.

As the polyurethane resin particles, polycarbonate-based polyurethane resin particles are preferable from the viewpoints of water resistance, heat resistance, abrasion resistance, weather resistance, and scratch resistance of the image due to the high cohesive force of the carbonate group. In the case of the polycarbonate-based polyurethane resin particles, an ink suitable for a recorded material used in a harsh environment such as outdoor use can be obtained.

Commercially available products may be used as the polyurethane resin particles, for example, U-coat UX-485 (polyester-based polyurethane resin particles), U-coat UWS-145 (polyester-based polyurethane resin particles), and permarin UA-368T (polyurethane-based polyurethane). Resin particles), Permarin UA-200 (polyester-based polyurethane resin particles) (all manufactured by Sanyo Kasei Kogyo Co., Ltd.) and the like. These may be used alone or in combination of two or more.

Commercially available products may be used as the polyurethane resin particles, for example, polyester-based polyurethane resin emulsion WBR-601U (Tg = -30 ° C.) manufactured by Taisei Fine Chemicals Co., Ltd. and polycarbonate-based polyurethane emulsion manufactured by Daiichi Pharmaceutical Co., Ltd. A certain Superflex 430 and the like can be mentioned.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Further, a mixed crystal may be used.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, carbon black produced by known methods such as contact method, furnace method, thermal method, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acid dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, etc., or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, 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, 138, 150, 153, 155, 180, 185, 213, 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, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Calcium 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, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As the dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52,80,82,249,254,289, C.I. I. Acid Blue 9,45,249, C.I. I. Acid Black 1,2,24,94, C.I. I. Hood Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1,2,15,71,86,87,98,165,199,202, C.I. I. Dilekdo Black 19,38,51,71,154,168,171,195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3, 4, 35 can be mentioned.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass, from the viewpoint of improving the image density, good fixing property and ejection stability. It is as follows.

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effect of the present invention is not impaired. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and Naphthalene sulfonic acid Na formalin condensate can also be suitably used as a dispersant.
The dispersant may be used alone or in combination of two or more.

The volume average particle size of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

The content of the resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of fixability and storage stability of the ink, 1% by mass or more and 30% by mass or less with respect to the total amount of the ink. Is preferable, and 5% by mass or more and 20% by mass or less is more preferable.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with a pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. A disperser may be used for dispersion.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, and more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, good ejection stability can be obtained and the image density is increased by 0.1 mass. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
It is preferable that the pigment dispersion is degassed by filtering coarse particles with a filter, a centrifuge, or the like, if necessary.

<Compound represented by the general formula (1)>
The compound represented by the general formula (1) described as a component of the cleaning liquid can be used for ink. Of the arbitrary compounds represented by the general formula (1), the compound represented by the general formula (1) used for ink and the compound represented by the general formula (1) used for the cleaning liquid are the same. It may or may not be different. By including the compound represented by the general formula (1) in the ink, the adhesion between the ink and the base material is improved.

The addition rate of the compound represented by the general formula (1) contained in the ink is preferably 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 30% by mass or less, from the viewpoint of improving the adhesion. It is more preferably mass% or more and 16% by mass or less.

<Surfactant>
The type and amount of the surfactant used in the ink are not particularly limited. The surfactant described as a component of the cleaning liquid can be used for ink. The surfactant used in the ink and the surfactant used in the cleaning liquid may be the same or different.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of excellent wettability and ejection stability and improvement in image quality, 0.001 mass is used. % Or more and 5% by mass or less are preferable, and 0.05% by mass or more and 5% by mass or less are more preferable.

<< Other solvents >>
In the present invention, the ink may contain other solvents as long as the effects of the present invention are not impaired. Other solvents described as components of the cleaning solution can be used in the ink. The other solvent used for the ink and the other solvent used for the cleaning liquid may be the same or different.

The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'× R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, and more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member that comes into contact with the liquid.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, or the like can be used, but good image formation is possible even if a non-permeable base material is used.
The non-permeable base material is a base material having a surface having a low water permeability and absorbability, and includes a material that does not open to the outside even if there are many cavities inside, and more quantitatively. , A substrate having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.
As the impermeable substrate, for example, a plastic film such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, polypropylene, polyethylene, or a polycarbonate film can be preferably used.

The recording medium is not limited to that used as a general recording medium, and wallpaper, flooring, building materials such as tiles, cloth for clothing such as T-shirts, textiles, leather and the like can be appropriately used. Further, ceramics, glass, metal, or the like can be used by adjusting the configuration of the path for transporting the recording medium.

<Inkjet recording ink set>
The ink jet recording ink set has the cleaning liquid described above and the ink described above as the inkjet recording ink. Since the ink contains a urethane resin having a Tg of 0 ° C. or lower, it has high adhesion to the substrate, but makes it difficult to maintain the ejection reliability of the recording device. By using the ink jet recording ink set described above, even if printing is performed using ink having high adhesion and drying property, ejection defects do not occur and ejection reliability can be maintained.

（ただし、前記一般式（１）中、Ｍｅはメチル基を表し、Ｒ^１は、炭素数１以上４以下のアルキル基を表す。）
本発明の洗浄方法は、払拭部材に洗浄液を付与する工程（以下、「洗浄液付与工程」と称することがある）と、
前記洗浄液を付与した前記払拭部材で前記ノズル面を払拭する工程（以下、「払拭工程」と称することがある）と、を含み、更に必要に応じてその他の工程を含むことが好ましい。 (Washing method and cleaning equipment)
The cleaning method of the present invention is a cleaning method for cleaning the nozzle surface of the ejection head for ejecting ink with a cleaning liquid, wherein the ink is water, a urethane resin having a glass transition point of 0 ° C. or less, a pigment, and the following. Using an ink containing a compound represented by the general formula (1) and a surfactant,
The cleaning liquid contains water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant.

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.)
The cleaning method of the present invention includes a step of applying a cleaning liquid to a wiping member (hereinafter, may be referred to as a "cleaning liquid applying step").
It is preferable to include a step of wiping the nozzle surface with the wiping member to which the cleaning liquid is applied (hereinafter, may be referred to as a “wiping step”), and further include other steps as necessary.

（ただし、前記一般式（１）中、Ｍｅはメチル基を表し、Ｒ^１は、炭素数１以上４以下のアルキル基を表す。）
本発明の洗浄装置は、払拭部材に洗浄液を付与する手段（以下、「洗浄液付与手段」と称することがある）と、
前記洗浄液を付与した前記払拭部材で前記ノズル面を払拭する手段（以下、「払拭手段」と称することがある）と、を有し、更に必要に応じてその他の手段を有する。 The cleaning device of the present invention is a cleaning device that cleans the nozzle surface of the ejection head that ejects ink.
The ink contains water, a urethane resin having a glass transition point of 0 ° C. or lower, a pigment, a compound represented by the following general formula (1), and a surfactant.
The cleaning liquid contains water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant.

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.)
The cleaning device of the present invention includes means for applying a cleaning liquid to a wiping member (hereinafter, may be referred to as "cleaning liquid applying means").
It has a means for wiping the nozzle surface with the wiping member to which the cleaning liquid is applied (hereinafter, may be referred to as “wiping means”), and further has other means as needed.

<Cleaning liquid application process and cleaning liquid application means>
The cleaning liquid applying step is a step of applying the cleaning liquid to the wiping member, and it is preferable to apply the cleaning liquid to the wiping member on the pressing member, which is carried out by the cleaning liquid applying means.
The pressing member is not particularly limited as long as it is a member capable of pressing the nozzle surface via the wiping member, and can be appropriately selected depending on the intended purpose. Combinations, wipers, blades, etc. can be mentioned. Among these, the pressing roller is preferable.
The cleaning liquid applying means is not particularly limited as long as a certain amount of cleaning liquid can be applied, and can be appropriately selected depending on the intended purpose. Examples thereof include application with a dropper, a nozzle, a spray, a dispenser, and a coating device. ..
The wiping member is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include non-woven fabric and cloth. These are preferably wound in a roll shape, and a roll-shaped non-woven fabric is preferable because it is difficult to generate dust and has high reliability.

The amount of the cleaning liquid applied is preferably controlled by the recording time. In this case, it is more preferable that the amount of the cleaning liquid applied is selected from a plurality of set values. Examples of the plurality of set values include a method of applying the cleaning liquid (for example, “pressure”, “number of application times”, “number of application nozzles”) and the like. Further, it is preferable that the amount of the cleaning liquid applied is controlled by the pressure applied to the cleaning liquid application nozzle as the cleaning liquid application means. Further, when the cleaning liquid is applied from a plurality of cleaning liquid application nozzles, it is preferable that the amount of the cleaning liquid applied to the wiping member is controlled by the number of the cleaning liquid application nozzles. Further, it is preferable that the amount of the cleaning liquid applied to the wiping member is controlled by the number of times the cleaning liquid is applied from the cleaning liquid application nozzle.

<Wipe process and wiping means>
The wiping step is a step of wiping the nozzle surface with the wiping member to which the cleaning liquid is applied, and is preferably carried out by the wiping means.
The method of wiping the nozzle surface with the wiping member to which the cleaning liquid is applied is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a non-woven fabric as the wiping member to which the cleaning liquid is applied can be used as the pressing member. A method of pressing the nozzle surface of the ink ejection head with the pressing roller of the ink ejection head may be mentioned.

<Other processes and other means>
Examples of the other steps and the other means include a control step and control means.
Examples of the control means include devices such as sequencers and computers.

Here, FIG. 3 is a schematic view showing an example of the cleaning device of the present invention. The cleaning device 300 shown in FIG. 3 is a device that cleans the nozzle surface 301a on the ink ejection side of the ink ejection head 301 of the ink ejection head.

The cleaning device 300 includes a non-woven fabric 303 as a wiping member, a cleaning liquid applying nozzle 302 as a cleaning liquid applying means, a pressing roller 305 as a pressing member, and a winding roller 304 for winding the non-woven fabric after the wiping process. There is.

The cleaning liquid is supplied from the cleaning liquid tank via the cleaning liquid supply tube. By driving a pump provided in the middle of the cleaning liquid supply tube, cleaning liquid is applied to the non-woven fabric 303 as a wiping member from the cleaning liquid application nozzle 302 in an amount of cleaning liquid applied according to the recording time. The nonwoven fabric 303 is wound in a roll shape.
Then, as shown in FIG. 3, the non-woven fabric 303 to which the cleaning liquid is applied is pressed against the nozzle surface 301a of the ink ejection head 301 by the pressing roller 305 as a pressing member, whereby the nozzle surface 301a is cleaned. .. After the wiping process is completed, the nonwoven fabric 303 is wound by the winding roller 304.

A plurality of cleaning liquid application nozzles 302 as cleaning liquid application means can be provided, and pressure can be applied based on the control of the control means, and the amount of cleaning liquid applied can be adjusted by appropriately changing the pressure. can. Further, based on the control of the control means, the amount of the cleaning liquid applied can be adjusted by changing the number of nozzles to which the cleaning liquid is applied. Further, based on the control of the control means, the amount of the cleaning liquid applied can be adjusted by changing the number of times the cleaning liquid is applied.

Examples of the method for cleaning the nozzle surface on the ink ejection side of the ink ejection head include the following embodiments.
When the cleaning liquid is applied, pressure is applied to the cleaning liquid application nozzle, and the amount of the cleaning liquid applied can be adjusted to a desired amount by changing the pressure. Further, the cleaning liquid application amount can be adjusted by changing the number of nozzles to which the cleaning liquid is applied among a plurality of cleaning liquid application nozzles, and further, the application amount is adjusted by changing the number of times the cleaning liquid is applied from the cleaning liquid application nozzle. be able to. In this way, the nozzle surface after the recording is completed may be wiped by using the wiping member to which the cleaning liquid is applied.

(Inkjet recording method and inkjet recording device)
The inkjet recording method of the present invention includes a ejection step of ejecting the ink from a nozzle of an ejection head for ejecting ink, and a ejection step of ejecting the ink.
It includes a cleaning step of cleaning the nozzle surface of the discharge head, and further includes other steps as necessary.
The cleaning step is performed by the cleaning method of the present invention.

（ただし、前記一般式（１）中、Ｍｅはメチル基を表し、Ｒ^１は、炭素数１以上４以下のアルキル基を表す。） The inkjet recording apparatus of the present invention preferably has a ejection head for ejecting ink, ink, and a cleaning liquid, and preferably has a wiping member for wiping the nozzle surface of the ejection head, and further has other means as necessary. ..
The ink contains water, a urethane resin having a glass transition point of 0 ° C. or lower, a pigment, a compound represented by the following general formula (1), and a surfactant.
The cleaning liquid contains water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant.

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.)

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method for recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, a pretreatment device, a device called a posttreatment device, and the like. ..
The recording device and the recording method may have a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printed surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form three-dimensional images are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous book printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism portion 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided behind the opening when the cover 401c of the main body of the apparatus is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

Further, in the terms of the present invention, image formation, recording, printing, printing, etc. are all synonymous.

As the recording device of the present invention, a device in which the cleaning device of FIG. 3 is mounted on the main body of the device of FIG. 1 is exemplified.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

<Preparation Example 1 of Black Pigment Dispersion>
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Symmal Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm) to disperse the black pigment dispersion (pigment solid). Mineral concentration: 15% by mass) was obtained.
・ Carbon black pigment (trade name: Monarch800, manufactured by Cabot Corporation) ・ ・ ・ 15 parts by mass ・ Anionic surfactant (trade name: Pionin A-51-B, manufactured by Takemoto Oil & Fat Co., Ltd.) ・ ・ ・ 2 parts by mass ・Ion-exchanged water: 83 parts by mass

<Preparation of polyurethane resin emulsion 1>
In a 2 L capacity reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler, 100 parts by mass of methyl ethyl ketone (MEK), polyester polyol (1) (iPA / AA = 6/4 (molar ratio) and EG / Polyester polyol obtained from NPG = 1/9 (molar ratio), number average molecular weight = 2,200, average number of functional groups = 2, iPA: isophthalic acid, AA: adipic acid, EG: ethylene glycol, NPG: neo 345 parts by mass of pentyl glycol) and 9.92 parts by mass of 2,2-dimethylolpropionic acid DMPA were charged and mixed uniformly at 60 ° C. Then, 45.1 parts by mass of triethylene glycol diisocyanate TEGDI and 0.08 part by mass of dioctyltin dilaurate DOTDL were further charged in the reactor and reacted at 72 ° C. for 3 hours to obtain a polyurethane solution.

80 parts by mass of iPA, 220 parts by mass of MEK, 3.74 parts by mass of triethylamine (TEA), and 596 parts by mass of water were added to this polyurethane solution for phase inversion, and then MEK and iPA were removed by a rotary evaporator. Then, the polyurethane resin emulsion 1 was obtained. After cooling the obtained polyurethane resin emulsion 1 to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 30% by mass and pH 8. Using this polyurethane resin emulsion 1, the glass transition point (= Tg) measured by "Thermo plus EVO2" (manufactured by Rigaku) was -3 ° C.

(Example 1)
<Preparation of ink and cleaning solution>
-Preparation of black ink-
20% by mass of black pigment dispersion produced by the method shown in the above (Preparation Example 1 of black pigment dispersion), 23.3% by mass of polyurethane resin emulsion 1 (solid content concentration: 30% by mass), 1,2-propane. 12% by mass of diol, 10% by mass of 1,3-propanediol, 3% by mass of 1,2-butanediol, 16% by mass of the compound of the general formula (1) (R ¹ is a methyl group) (trade name: Equamid M100, Idemitsu) Kosan Co., Ltd.), as a surfactant, trade name "FS-300" (Dupont, fluorosurfactant, solid content concentration 40%) is 2% by mass, and as a preservative, trade name: Proxel LV (Abyssia) (Manufactured by) 0.1% by mass and high pure water are added so as to be the remaining amount, mixed and stirred, and a polypropylene filter having an average pore diameter of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M). The black-colored ink used in Example 1 was produced by filtering with.

-Preparation of cleaning solution-
Tripropylene glycol monomethyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 20% by mass, compound of general formula (1) (R ¹ is a methyl group) (trade name: Equamid M100, manufactured by Idemitsu Kosan Co., Ltd.) 30% by mass, fluorine-based Add 2% by mass of a surfactant (trade name: FS-300, solid content concentration 40%) and the remaining amount of ion-exchanged water (the total amount of the materials added is 100% by mass, and the remaining amount). The mixture was stirred for 1 hour to obtain the cleaning solution used in Example 1.

(Example 2)
The polyurethane resin emulsion of the ink was changed to the polyester polyurethane emulsion "WBR-601U" manufactured by Taisei Fine Chemical Co., Ltd., and the glycol ether compound of the cleaning liquid was changed from tripropylene glycol monomethyl ether to dipropylene glycol methyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.). ), And an ink and a cleaning liquid were prepared in the same manner as in Example 1.
Polyester polyurethane emulsion WBR-601U (manufactured by Taisei Fine Chemical Co., Ltd., Tg: -30 ° C)

(Example 3)
The polyurethane resin emulsion of the ink was changed to the polycarbonate polyurethane emulsion "Superflex 430" manufactured by Daiichi Pharmaceutical Co., Ltd., and the glycol ether compound of the cleaning liquid was changed from tripropylene glycol monomethyl ether to triethylene glycol monomethyl ether (Tokyo Kasei Kogyo). Ink in the same manner as in Example 1 except that the addition amount was changed from 20% by mass to 30% by mass and the addition amount of Equamid M100 was changed from 30% by mass to 20% by mass. , And a cleaning solution was prepared.
Polycarbonate polyurethane emulsion: Superflex 430 (manufactured by Dai-ichi Pharmaceutical Co., Ltd., Tg: -24 ° C)

(Example 4)
An ink and a cleaning liquid were prepared in the same manner as in Example 1 except that the glycol ether compound of the cleaning liquid was changed from tripropylene glycol monomethyl ether to diethylene glycol diethyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

(Example 5)
The glycol ether compound of the cleaning liquid was changed from tripropylene glycol monomethyl ether to diethylene glycol diethyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the surfactant of the cleaning liquid was changed from the fluorosurfactant "FS-300" to polyoxyalkylene monoalkyl. An ink and a cleaning liquid were prepared in the same manner as in Example 1 except that the ether (manufactured by Kao Co., Ltd., trade name: Emargen A-60 (higher alcohol-based ether type nonionic surfactant)) was changed.

(Example 6)
The polyurethane resin emulsion of the ink was changed to the polycarbonate polyurethane emulsion "Superflex 430" manufactured by Daiichi Pharmaceutical Co., Ltd., and the glycol ether compound of the cleaning liquid was changed from tripropylene glycol monomethyl ether to diethylene glycol dibutyl ether, and the addition thereof was performed. The amount was changed from 20% by mass to 30% by mass, the amount of Equamid M100 added was changed from 30% by mass to 20% by mass, and the surfactant of the cleaning liquid was changed from the fluorosurfactant "FS-300" to the polyoxyalkylene mono. An ink and a cleaning liquid were prepared in the same manner as in Example 1 except that they were changed to alkyl ether (manufactured by Kao Co., Ltd., trade name: Emargen LS-106 (higher alcohol-based ether type nonionic surfactant)). ..

(Example 7)
In Example 1, the same as in Example 1 except that R1 of the compound of the general formula (1) constituting the cleaning liquid was changed to a compound having a butyl group (trade name: Equamid B100, manufactured by Idemitsu Kosan Co., Ltd.). , Ink, and cleaning solution were prepared and evaluated.

(Comparative Example 1)
Ink and cleaning liquid were prepared and evaluated in the same manner as in Example 1 except that tripropylene glycol monomethyl ether was not added to the cleaning liquid and the amount of Equamid M100 added was changed from 30% by mass to 50% by mass. rice field.

(Comparative Example 2)
An ink and a cleaning liquid were prepared in the same manner as in Example 1 except that the amount of tripropylene glycol monomethyl ether added to the cleaning liquid was changed from 20% by mass to 50% by mass and Equamid M100 was not added.

Table 1-1 and Table 1-2 show a list of the inks used in each Example and Comparative Example and the constituent materials of the cleaning liquid. In addition,% in Table 1-1 shows mass%.

・ Evaluation method <cleanability>
Using the printer shown in FIG. 1, the ink of Example 1 was continuously ejected for 45 minutes. The nozzle surface of the discharge head was dried for 12 hours after the discharge was stopped. Then, 3 mL of the cleaning liquid of Example 1 was applied to anticon (clean wiper anticon GOLD, polyester filament) using a dropper, and the nozzle surface was wiped back and forth by the apparatus of FIG. Then, "cleanability" was evaluated based on the following evaluation criteria. It is desirable in actual use that the evaluation is "Δ" or higher. The other examples and other comparative examples were also evaluated in the same manner as above except that the ink and the cleaning liquid were changed to the set shown in Table 1-1.

[Evaluation criteria]
◎: No ink stains left uncleaned ○: Ink stains left less than 10%, but not near the nozzle △: Ink stains left less than 10% ×: Ink stains wiped off There is more than 10% left

<Discharge reliability>
Using the printer shown in FIG. 1, the ink of Example 1 was continuously ejected for 45 minutes, and the nozzle surface of the ejection head was dried for 30 minutes after the ejection was stopped. Then, 3 mL of the cleaning liquid of Example 1 was applied to anticon (clean wiper anticon GOLD, polyester filament) using a dropper, and the nozzle surface was wiped using the apparatus of FIG. Then, the ink of Example 1 was used for ejection again, and the "ejection reliability" was evaluated based on the following evaluation criteria. It is desirable in actual use that the evaluation is "Δ" or higher. The other examples and other comparative examples were also evaluated in the same manner as above except that the ink and the cleaning liquid were changed to the set shown in Table 1-1.

[Evaluation criteria]
◯: No discharge turbulence or non-ejection

<Adhesion>
How to create an evaluation image The IPSiO GXe5500 modified machine (manufactured by Ricoh Co., Ltd.) can reproduce a record equivalent to a recording speed of 30 m ² / hr with a print width of 150 cm in A4 size, and for the image after printing. It was modified so that it could be heated with a pot plate by changing the heating conditions (heating temperature, heating time). The IPSiO GXe5500 modified machine was filled with the black ink of Example 1, and a solid image was recorded so that the amount of ink adhered to the recording medium was 0.6 g / cm ² . As a recording medium, a PP film recording medium (manufactured by Toyobo Co., Ltd., P2161) was used. After recording, heating was performed on a pot plate. The heating conditions were the following two conditions.
Condition 1: 60 ° C for 5 minutes Condition 2: 70 ° C for 5 minutes

-Adhesion evaluation method-
For the solid image after heating, the number of remaining squares of 100 test squares was counted by a grid peeling test using a cloth adhesive tape (Nichiban Co., Ltd., 123LW-50), and based on the following evaluation criteria, The "adhesion" to the recording medium was evaluated. It is desirable in actual use that the evaluation is B or higher. The other examples and other comparative examples were also evaluated in the same manner as above except that the ink was changed to that used in the example.
〔Evaluation criteria〕
AA: Number of remaining cells is 98 or more A: Number of remaining cells is 90 or more and less than 98 B: Number of remaining cells is 70 or more and less than 90 C: Number of remaining cells is less than 70

Table 1-2 shows a list of evaluation results of cleanability, discharge reliability, and adhesion of each example and comparative example.

(Comparison between Examples and Comparative Examples)
In Example 1, a cleaning solution containing both the compound of the general formula (1) and the glycol ether compound was used, whereas in Comparative Example 1, a cleaning solution containing no glycol ether compound was used, and in Comparative Example 2, the general formula ( A cleaning solution to which the compound of 1) was not added was used. In comparison with Example 1, Comparative Example 1, and Comparative Example 2, Comparative Example 1 and Comparative Example 2 are inferior in detergency and discharge stability as compared with Example 1.
In comparison with Example 1, Example 2, and Example 3, the resin in the ink in Example 3 is a polycarbonate-based polyurethane resin having a Tg-20 ° C. or lower, which is a base as compared with Example 1 and Example 2. Good adhesion of the material. In comparison with Examples 1 and 4, the glycol ether compound used the compound of the general formula (2) in Example 4, and the detergency is better than that of Example 1. In the comparison between Example 4 and Example 5, the surfactant of the cleaning liquid of Example 5 uses a polyoxyalkylene surfactant, and the cleaning property is further improved as compared with Example 4. Table 2 shows the components contained in the inks and cleaning liquids of each example and each comparative example. In Table 2, "○" indicates that it is included, and "×" indicates that it is not included.

400 Image forming device 401 Image forming device exterior 401c Device body cover 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 Ink storage unit 413 Ink discharge port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube

Japanese Patent No. 4872781

Claims (14)

An inkjet recording device having an ejection head for ejecting ink, ink, and a cleaning liquid.
The ink contains water, a urethane resin having a glass transition point of 0 ° C. or lower, a pigment, a compound represented by the following general formula (1), and a surfactant.
An inkjet recording apparatus, wherein the cleaning liquid contains water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant.

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.) The inkjet recording apparatus according to claim 1, further comprising a wiping member for wiping the nozzle surface of the discharge head. The urethane resin is a polycarbonate-based urethane resin.
The inkjet recording apparatus according to claim 1 or 2, wherein the glass transition point of the urethane resin is −20 ° C. or lower. The inkjet recording apparatus according to any one of claims 1 to 3, which contains the dialkyl glycol ether compound represented by the following general formula (2) as the glycol ether compound.

(However, in the general formula (2), R ² represents H or CH ₃ , R ³ represents C _m H _{2m + 1} , n represents a number of 1 to 3, and m represents a number of 1 to 4. show.) The inkjet recording apparatus according to any one of claims 1 to 4, wherein the surfactant contained in the cleaning liquid is a polyoxyalkylene surfactant. A cleaning device that cleans the nozzle surface of the ejection head that ejects ink with a cleaning liquid.
The ink contains water, a urethane resin having a glass transition point of 0 ° C. or lower, a pigment, a compound represented by the following general formula (1), and a surfactant.
A cleaning device comprising water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant.

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.) A cleaning device that cleans the nozzle surface of the ejection head that ejects ink.
A means to apply the cleaning liquid to the wiping member,
It has a means for wiping the nozzle surface with the wiping member to which the cleaning liquid is applied.
The ink contains water, a urethane resin having a glass transition point of 0 ° C. or lower, a pigment, a compound represented by the general formula (1), and a surfactant.
The cleaning apparatus according to claim 6, wherein the cleaning liquid contains water, a compound represented by the general formula (1), a glycol ether compound, and a surfactant. A cleaning method in which the nozzle surface of the ejection head for ejecting ink is cleaned with a cleaning liquid. The ink is water, a urethane resin having a glass transition point of 0 ° C. or less, a pigment, and is represented by the following general formula (1). Using an ink containing the compound and the surfactant
A cleaning method comprising water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant.

(However, in the general formula (1), Me represents a methyl group, and R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.) It is a cleaning method that cleans the nozzle surface of the ejection head that ejects ink with a cleaning liquid, and is a process of applying the cleaning liquid to the wiping member.
A step of wiping the nozzle surface with the wiping member to which the cleaning liquid is applied is included.
The ink used is an ink containing water, a urethane resin having a glass transition point of 0 ° C. or lower, a pigment, the compound represented by the general formula (1), and a surfactant.
The cleaning method according to claim 8, wherein the cleaning liquid contains water, a compound represented by the general formula (1), a glycol ether compound, and a surfactant. The ejection process of ejecting the ink from the nozzle of the ejection head,
Including a cleaning step of cleaning the nozzle surface of the discharge head.
An inkjet recording method in which the cleaning step is performed by the cleaning method according to claim 8 or 9. Ink containing water, a urethane resin having a glass transition point of 0 ° C. or less, a pigment, a compound represented by the following general formula (1), and a surfactant.
A cleaning solution containing water, a compound represented by the following general formula (1), a glycol ether compound, and a surfactant,
A set of ink and cleaning liquid characterized by having.

(However, in the general formula (1), Me represents a methyl group, and R ¹ Represents an alkyl group having 1 or more and 4 or less carbon atoms. ) The urethane resin is a polycarbonate-based urethane resin.
The set of ink and cleaning liquid according to claim 11, wherein the glass transition point of the urethane resin is −20 ° C. or lower. The set of ink and cleaning liquid according to claim 11 or 12, which contains the dialkyl glycol ether compound represented by the following general formula (2) as the glycol ether compound.

(However, in the general formula (2), R ² Is H or CH ₃ Represents R ³ Is C _m H _{2m + 1} , N represents a number of 1 to 3, and m represents a number of 1 to 4. ) The set of ink and cleaning liquid according to any one of claims 11 to 13, wherein the surfactant contained in the cleaning liquid is a polyoxyalkylene surfactant.

Images