JP5957889B2 - Cleaning liquid / filling liquid, cartridge containing the cleaning liquid / filling liquid, and method for cleaning, filling, and storing an inkjet recording apparatus using the cleaning liquid / filling liquid - Google Patents

Description

The present invention relates to an inkjet recording apparatus, a cleaning / filling liquid for cleaning a liquid flow path of an ink cartridge used in the apparatus, a cartridge filled with the cleaning / packing liquid, and an inkjet recording apparatus using the cleaning / packing liquid. The present invention relates to a filling and storage method and an ink jet recording apparatus cleaned, filled and stored by this method.
About.
The ink cartridge also has a liquid flow path such as an ink passage part from the ink storage part to the ink supply port. When the ink cartridge is reused, it is necessary to clean these liquid flow paths.

The ink discharge head of the ink jet recording apparatus is composed of a nozzle portion having a fine orifice having a diameter of 50 μm or less, a pressure generating portion connected thereto, a liquid chamber portion, a filter portion, etc., and is processed with very high accuracy. The number of nozzles per head is large, and before shipping as a product, the entire system operates normally, and in order to confirm that there are no ejection defects, it is filled with test ink containing color materials and detected. doing. The ink used for these inspections will not cause problems during transportation, and the color material in the inspection ink may clog and clog until it is filled with ink by the user. In order not to cause a problem, it is necessary to wash away the ink in the ink jet recording apparatus after the inspection.
As a cleaning liquid for washing out ink, conventionally, a solution containing a main solvent (for example, water), a surfactant, a moisturizing agent, and the like and containing no solid content has been used (see Patent Document 1).
When these cleaning liquids are used, solids in the discharge liquid remain and do not clog the nozzle and clogging is unlikely to occur.However, a small amount of residue remains attached to the nozzle inner wall, discharge port, etc. Discharge defects such as bending cannot be solved sufficiently.
In addition, although maintenance liquids and cleaning liquids for removing the residue adhered in the nozzle have been proposed (see Patent Document 2), it is actually difficult to completely remove the residue in the nozzle. .

In particular, recently, high-resolution images and patterning accuracy have been demanded, and the tolerance to the bending of the ejected liquid has been reduced as compared with the prior art, and more precise ejection properties have been demanded. In addition, the ink contains various solids, and it is increasingly necessary to clean the liquid flow path, especially the nozzles, or at least to the extent that it does not affect ink ejection in subsequent use. The current situation is difficult.
Under such circumstances, the conventional cleaning liquid and filling liquid have insufficient cleaning properties, and even if the cleaning performance can be ensured, the ink filling performance is poor, causing ejection failure, or being used in the head. There is a problem that the adhesive is swollen and the strength of the head is reduced to prevent ejection stability, or the metal portion of the ink flow path is corroded during the storage period until the ink is filled.
On the other hand, Patent Document 3 discloses a detergent composition containing N, N-dimethyl-β-methoxypropionamide and water, and further containing a surfactant. However, the cleaning liquid was developed as a cleaning agent for precision mechanical parts or electrical / electronic parts, and when used for cleaning an inkjet recording apparatus, the ink components remaining in the apparatus are aggregated or the type of surfactant is used. Depending on the type of cleaning, the cleaning performance may be inferior or the cleaning solution itself may cause problems such as foaming.

  The present invention relates to a cleaning liquid and filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge used in the apparatus, the function of the cleaning liquid capable of sufficiently cleaning the ink flow path, and the ink used for the print inspection Cleaning liquid / filling liquid that has a function as a filling liquid that prevents aggregation of cleaning residues, does not erode into the ink flow path member, and does not cause problems when filling ink, a cartridge filled with the cleaning liquid / filling liquid, and the cleaning liquid It is an object of the present invention to provide a method for cleaning, filling and storing an ink jet recording apparatus using a cum filling liquid, and an ink jet recording apparatus which has been cleaned, filled and stored by this method.

（式中、Ｒは炭素数１〜４のアルキル基を表す。）

＜構造式（２）−１＞

（式中、Ｒ１、Ｒ３は水素、炭素数１〜６のアルキル基又は炭素数１〜６のパーフルオロアルキル基を表し、Ｒ２、Ｒ４は炭素数１〜６のパーフルオロアルキル基を表す。ｍ、ｎは０又は正の整数、ｐ、ｑ及びｒは正の整数を表す。）

＜構造式（２）−２＞

（式中、Ｍはアルカリ金属、アンモニウム、ホスホニウム、又はアルカノールアミンを表し、Ｒｆは−ＣＦ _３ 、又は−ＣＦ _２ ＣＦ _３ を表し、ｑは４〜１０の整数を表す。）

＜構造式（２）−３＞

（式中、Ｒ _１ は水素、炭素数１〜６のアルコキシ基、又は炭素数１〜６のパーフルオロアルキル基を表し、Ｒ _ｆ は炭素数１〜６のパーフルオロアルキル基を表す。ｘ、ｙ、ｚは正の整数を表す。）

＜構造式（２）−４＞
Ｃ _ｎ Ｆ _２ｎ＋１ −ＣＨ _２ ＣＨ（ＯＨ）ＣＨ _２ Ｏ（ＣＨ _２ ＣＨ _２ Ｏ）ａ−Ｙ

〔式中、Ｙは−Ｃ _ｂ Ｈ _２ｂ＋１ （ｂは１１〜１９の整数）、又は−ＣＨ _２ ＣＨ（ＯＨ）ＣＨ _２ −Ｃ _ｄ Ｆ _２ｄ＋１ （ｄは２〜６の整数）を表し、ｎは２〜６の整数、ａは１５〜５０の整数を表す。〕

＜構造式（２）−５＞

（式中、Ｍ ^＋ はＬｉ ^＋ 、Ｎａ ^＋ 、Ｋ ^＋ 、ＮＨ _４ ^＋ のいずれかを表す。）

＜構造式（２）−６＞
〔（ＲｆＳＯ _２ ） _２ 〕Ｎ ⁻ Ｍ ^＋
（式中、Ｒｆは炭素数１〜４のパーフルオロアルキル基を表し、Ｍ ^＋ はＬｉ ^＋ 、Ｎａ ^＋ 、Ｋ ^＋ 、ＮＨ _４ ^＋ のいずれかを表す。）

＜構造式（２）−７＞
〔（ＲｆＳＯ _２ ）（ＲＳＯ _２ ）〕Ｎ ⁻ Ｍ ^＋
（式中、Ｒｆは炭素数１〜４のパーフルオロアルキル基を表し、Ｒは炭素数１〜１０のアルキル基を表し、Ｍ ^＋ はＬｉ ^＋ 、Ｎａ ^＋ 、Ｋ ^＋ 、ＮＨ _４ ^＋ のいずれかを表す。）

＜構造式（２）−８＞
〔（ＦＳＯ _２ ） _２ 〕Ｎ ⁻ Ｍ ^＋
（式中、Ｍ ^＋ はＬｉ ^＋ 、Ｎａ ^＋ 、Ｋ ^＋ 、ＮＨ _４ ^＋ のいずれかを表す。）

２） 前記構造式（２）−４で示される化合物が、次の（ａ）〜（ｅ）のいずれかであることを特徴とする１）に記載のインクジェット記録装置用洗浄液兼充填液。
（ａ）Ｃ_４Ｆ_９−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_２１−Ｃ_１８Ｈ_３７
（ｂ）Ｃ_２Ｆ_５−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_２５−Ｃ_１２Ｈ_２５
（ｃ）Ｃ_４Ｆ_９−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_２３−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_４Ｆ_９
（ｄ）Ｃ_４Ｆ_９−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_３５−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_４Ｆ_９
（ｅ）Ｃ_２Ｆ_５−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_４５−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｃ_２Ｆ_５
３） 更にグリセリン及び／又は１，３−ブタンジオールを含有することを特徴とする１）又は２）に記載の洗浄液兼充填液。
４） １）〜３）の何れかに記載の洗浄液兼充填液を容器中に収容したことを特徴とするカートリッジ。
５） １）〜３）の何れかに記載の洗浄液兼充填液を通液してインク流路を洗浄した後、該洗浄液兼充填液を充填して保管することを特徴とするインクジェット記録装置の洗浄、充填、保管方法。 The above problems are solved by the following inventions 1) to 5 ).
1) A cleaning and filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge used in the apparatus, and a total amount of at least one amide compound represented by the following structural formula (1) is 10.0 to 45. The total amount of at least one fluorosurfactant selected from those represented by the following structural formulas (2) -1 to (2) -8 is 0 to 5.0% by mass. % cleaning filling liquid, characterized in that it contains.
<Structural formula (1)>

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)

<Structural Formula (2) -1>

(In the formula, R 1 and R 3 represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms, and R 2 and R 4 represent a perfluoroalkyl group having 1 to 6 carbon atoms. , N represents 0 or a positive integer, and p, q, and r represent a positive integer.)

<Structural Formula (2) -2>

(In the formula, M represents an alkali metal, ammonium, phosphonium, or alkanolamine, Rf represents —CF ₃ or —CF ₂ CF ₃ , and q represents an integer of 4 to 10).

<Structural Formula (2) -3>

(In the formula, R ₁ represents hydrogen, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms , and R _f represents a perfluoroalkyl group having 1 to 6 carbon atoms. _X , y and z represent a positive integer.)

<Structural Formula (2) -4>
_{C n F 2n + 1 -CH 2} CH (OH) CH 2 O (CH 2 CH 2 O) a-Y

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

<Structural Formula (2) -5>

(In the formula, M ⁺ represents any of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ .)

<Structural Formula (2) -6>
[(RfSO ₂ ) ₂ ] N ⁻ M ⁺
(In the formula, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and M ⁺ represents any one of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ .)

<Structural Formula (2) -7>
[(RfSO ₂ ) (RSO ₂ )] N ⁻ M ⁺
(In the formula, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, R represents an alkyl group having 1 to 10 carbon atoms, and M ⁺ is any one of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ . Represents.)

<Structural Formula (2) -8>
[(FSO ₂ ) ₂ ] N ⁻ M ⁺
(In the formula, M ⁺ represents any of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ .)

2 ) The cleaning / filling solution for an inkjet recording apparatus according to 1) , wherein the compound represented by the structural formula (2) -4 is any one of the following (a) to (e):
_{(A) C 4 F 9 -CH} 2 CH (OH) CH 2 O- (CH 2 CH 2 O) 21 -C 18 H 37
_{(B) C 2 F 5 -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) 23 -CH 2 CH (OH) CH 2 -C 4 F 9
_{(D) 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
_{(E) C 2 F 5 -CH} 2 CH (OH) CH 2 O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 2 F 5
3 ) The cleaning and filling liquid according to 1) or 2) , further comprising glycerin and / or 1,3-butanediol.
4 ) A cartridge in which the cleaning / filling solution according to any one of 1) to 3) is contained in a container.
5 ) An ink jet recording apparatus, wherein the cleaning liquid / filling liquid according to any one of 1) to 3) is passed through to wash the ink flow path, and then the cleaning liquid / filling liquid is filled and stored. Cleaning, filling and storage methods.

  According to the present invention, it is a cleaning liquid and filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge used in the apparatus, and the function of the cleaning liquid that can sufficiently clean the liquid flow path is used for printing inspection. A cleaning liquid / filling liquid that has a function as a filling liquid that prevents agglomeration of the ink cleaning residue, does not erode into the liquid flow path member, and does not cause a problem during ink filling, a cartridge filled with the cleaning liquid / filling liquid, It is possible to provide a method for cleaning, filling, and storing an ink jet recording apparatus using the cleaning / filling liquid, and an ink jet recording apparatus that has been cleaned, filled, and stored by this method.

FIG. 4 is a perspective explanatory view showing a state where an ink cartridge loading unit cover of the ink jet recording apparatus is opened. It is a schematic block diagram explaining the whole structure of an inkjet recording device. It is a schematic enlarged view of an example of an inkjet head. It is a principal part enlarged view of an example of an inkjet head. It is a principal part expanded sectional view of an example of an inkjet head.

Hereinafter, the present invention will be described in detail.
The cleaning and filling liquid of the present invention is characterized by containing at least one amide compound represented by the structural formula (1) and a fluorosurfactant.
The amide compound has a function of uniformly mixing a water-soluble solvent having a high equilibrium water content and a relatively hydrophobic organic solvent, and the ink used for the print inspection and the cleaning liquid / filling liquid are easily mixed, so that the cleaning performance is high. improves. Further, aggregation of the cleaning residue is prevented, and when filling the ink, the cleaning / filling liquid and the ink are quickly mixed so that the ink can be filled without aggregation. In addition, since it has a high boiling point and a high equilibrium moisture content, it has high moisturizing power and can improve drying resistance, so it can be used not only as a cleaning liquid but also as a filling liquid. Among them, the lower the number of carbons, the higher the equilibrium moisture content and the higher the moisturizing power, and the higher the number of carbons, the better the solubility and the higher the detergency. Therefore, it is preferable to use those having a small number of carbon atoms and those having a large number of carbon atoms.
The amount of the amide compound added is 10.0 to 45.0% by mass. If the amount is less than 10.0% by mass, the effect of uniform mixing cannot be sufficiently ensured, and if the amount exceeds 45.0% by mass, the liquid flow path member and the like are eroded, which adversely affects discharge and the like.

The fluorosurfactant is added to increase the cleaning property by lowering the surface tension of the liquid, to increase the mixing stability of the cleaning / filling liquid, and to increase the ink filling property after cleaning. Among these, the fluorine-based surfactants represented by the structural formulas (2) -1 to (2) -8 are preferable. Particularly, the fluorine-based surfactants represented by the structural formula (2) -4 are the above-described (a) to (e). Either of these is preferable.
In addition, these surfactants have a high ability to reduce the surface tension of the liquid and are excellent in cleaning performance, and are low in foaming properties, and bubbles do not remain in the tube or the head and cause no nozzle omission. . Furthermore, these surfactants are hardly soluble in water, but mixing with the amide compound improves the compatibility and improves the storage stability of the liquid. If the compatibility of the surfactant is poor, the surfactant may remain in the tube or the head and the mixing stability with the ink may be deteriorated. However, such a problem can be solved.
The addition amount of the fluorosurfactant is 1.0 to 5.0% by mass. It effect of lowering the surface tension as long as this range can be sufficiently obtained, or cause the aggregation dry燥時, does not or swell the liquid flow passage member.
Surfactants other than fluorosurfactants can be used in combination, and examples include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

  As an anionic surfactant, alkyl allyl or alkyl naphthalene sulfonate, alkyl phosphate, alkyl sulfate, alkyl sulfonate, alkyl ether sulfate, alkyl sulfosuccinate, alkyl ester sulfate, alkyl benzene sulfonate, Alkyl diphenyl ether disulfonate, alkyl aryl ether phosphate, alkyl aryl ether sulfate, alkyl aryl ether ester sulfate, olefin sulfonate, alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl Ether sulfate, ether carboxylate, sulfosuccinate, α-sulfo fatty acid ester, fatty acid salt, higher fatty acid and amino acid condensate, naphthenate, etc.

Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts, phosphonium salts, and the like.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol ester, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid ester, polyoxyethylene polyoxy Propylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, fatty acid alkanolamide, amine oxide, polyoxyethylene alkylamine, Glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fat Esters, polyoxyethylene sorbitol fatty acid esters, alkyl (poly) Gurikokishido like.
Examples of amphoteric surfactants include imidazoline derivatives such as imidazolinium betaine, dimethylalkyllauryl betaine, alkylglycine, and alkyldi (aminoethyl) glycine.

  The cleaning and filling liquid of the present invention contains a solvent, a humectant, other additives and the like in addition to the amide compound and the surfactant. In many cases, components that are common to the ink and do not contain a solid content are used, but there is no particular limitation. However, it is preferable to contain a moisturizing agent for preventing drying and foaming of the cleaning and filling liquid in the flow path.

The solvent is mainly water, but a water-soluble organic solvent or the like can be mixed and used. It is preferable to add a water-soluble organic solvent having a high equilibrium water content, since water evaporation is suppressed, the drying becomes stronger, and the storage property as a filling liquid is improved.
Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 1 Polyhydric alcohols such as 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Polyhydric alcohol alkyl ethers such as tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; Polyhydric alcohol aryl ethers such as phenyl ether and ethylene glycol monobenzyl ether, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam Nitrogen-containing heterocyclic compounds such as: formamide, N-methylformamide, amides such as N, N-dimethylformamide; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine; dimethyl sulfoxide, Sulfur-containing compounds such as sulfolane and thiodiethanol; propylene carbonate, ethylene carbonate, γ-butyrolactone and the like.

The moisturizing agent is contained mainly for the purpose of preventing the washing and filling liquid from drying in the flow path and preventing foaming. Such a humectant is preferably a water-soluble polyhydric alcohol, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl- 1,3-hexanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2, Examples include 3-butanetriol and petriol. Among them, those having an equilibrium water content of 30% by mass or more at 23 ° C. and 80% humidity are preferable, and glycerin and 1,3-butanediol correspond to this.
Nitrogen-containing hydrocarbon solvents, sulfur-containing hydrocarbon solvents and the like may be used in combination as humectants other than water-soluble polyhydric alcohols.

Examples of other additives include pH adjusters and antiseptic / antifungal agents.
Examples of pH adjusters include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; quaternary ammonium hydroxides. And amines such as diethanolamine and triethanolamine; ammonium hydroxide and quaternary phosphonium hydroxide.
Examples of antiseptic / antifungal agents include 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and the like.

Next, an example of an ink jet recording apparatus to which the cleaning / filling liquid of the present invention can be applied will be described.
The ink jet recording apparatus shown in FIG. 1 has an apparatus main body (101), a paper feed tray (102) for loading paper mounted on the apparatus main body (101), and an image mounted on the apparatus main body (101). A paper discharge tray (103) for stocking the formed paper and an ink cartridge loading section (104) are provided. On the upper surface of the ink cartridge loading unit (104), an operation unit (105) such as operation keys and a display is arranged. The ink cartridge loading unit (104) has an openable / closable front cover (115) for attaching and detaching the ink cartridge (201). (111) is the upper cover, and (112) is the front of the apparatus.
In the apparatus main body (101), as shown in FIGS. 2 and 3, a carriage (133) is composed of a guide rod (131), which is a guide member horizontally mounted on left and right side plates (not shown), and a stay (132). Is slidably held in the main scanning direction, and is moved and scanned in the direction of the arrow shown in FIG. 3 by a main scanning motor (not shown).
The carriage (133) includes a plurality of recording heads (134) including four inkjet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

As an inkjet recording head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator that utilizes a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a temperature change A shape memory alloy actuator using a metal phase change, an electrostatic actuator using an electrostatic force, or the like provided as an energy generating means for discharging ink can be used.
The carriage (133) is equipped with a sub tank (135) for each color for supplying ink of each color to the recording head (134). Ink is supplied to the sub tank (135) from the ink cartridge (201) of the present invention loaded in the ink cartridge loading section (104) via an ink supply tube (not shown).

On the other hand, as a paper feed unit for feeding the paper (142) stacked on the paper placement unit (pressure plate) (141) of the paper feed tray (103), the paper placement unit (141) to the paper (142). A sheet feeding roller (half-moon roller) (143) that separates and feeds the sheets one by one, and a sheet separation roller (144) made of a material having a large coefficient of friction, facing the sheet feeding roller (143). ) Is biased toward the paper feed roller (143).
A conveying belt (151) for electrostatically adsorbing and conveying the paper (142) as a conveying unit for conveying the paper (142) fed from the paper feeding unit below the recording head (134). A counter roller (152) for conveying the paper (142) sent from the paper supply unit via the guide (145) between the conveying belt (151) and a paper (substantially vertically upward) ( 142) and a leading guide roller 153 urged toward the conveying belt (151) by the holding member (154). (155) and a charging roller (156) which is a charging means for charging the surface of the conveyor belt (151).

The conveyance belt (151) is an endless belt, is stretched between the conveyance roller (157) and the tension roller (158), and can circulate in the belt conveyance direction. The transport belt (151) includes, for example, a surface layer serving as a sheet adsorbing surface formed of a resin material having a thickness of about 40 μm without resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), It has the same material as the surface layer and a back layer (medium resistance layer, earth layer) that has been subjected to resistance control by carbon. On the back side of the conveyance belt (151), a guide member (161) is arranged corresponding to the printing area by the recording head (134). As a paper discharge unit for discharging the paper (142) recorded by the recording head (134), a separation claw (171) for separating the paper (142) from the transport belt (151), and paper discharge A roller (172) and a paper discharge roller (173) are provided, and a paper discharge tray (103) is arranged below the paper discharge roller (172).
A double-sided paper feeding unit (181) is detachably attached to the back surface of the apparatus main body (101). The double-sided paper feeding unit (181) takes in and reverses the paper (142) returned by the reverse rotation of the transport belt (151) and feeds it again between the counter roller (152) and the transport belt (151). Make paper. A manual paper feed unit (182) is provided on the upper surface of the double-sided paper feed unit (181).

In this ink jet recording apparatus, the sheet (142) is separated and fed one by one from the sheet feeding unit, and the sheet (142) fed substantially vertically upward is guided by the guide (145) and the transport belt (151). ) And the counter roller (152). Further, the leading end is guided by the conveying guide (153) and pressed against the conveying belt (151) by the leading end pressure roller (155), and the conveying direction is changed by about 90 °.
At this time, the conveyance belt (157) is charged by the charging roller (156), and the paper (142) is electrostatically adsorbed to the conveyance belt (151) and conveyed. Therefore, by driving the recording head (134) according to the image signal while moving the carriage (133), ink droplets are ejected onto the stopped sheet (142) to record one line, and the sheet ( 142), the next line is recorded after a predetermined amount is conveyed. Upon receiving a recording end signal or a signal that the rear end of the paper (142) has reached the recording area, the recording operation is finished and the paper (142) is discharged to the paper discharge tray (103).
When the ink remaining amount near end in the sub tank (135) is detected, a required amount of ink is supplied from the ink cartridge (201) to the sub tank (135).

In this ink jet recording apparatus, when the ink in the ink cartridge (not shown) is used up, the casing of the ink cartridge can be disassembled and only the ink bag inside can be replaced. In addition, the ink cartridge can be stably supplied even when it is placed vertically and has a front loading configuration. Therefore, even when the upper part of the apparatus main body (101) is closed and installed, for example, even when it is stored in a rack or an object is placed on the upper surface of the apparatus main body (101), the ink The cartridge can be easily replaced.
Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.
The ink jet recording apparatus and the ink jet recording method can be applied to various types of recording by the ink jet recording method, and are particularly suitable for, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, and a printer / fax / copier multifunction machine. Can be applied to.

Next, the ink jet head will be described.
FIG. 4 is an enlarged view of a main part of an example of an ink jet head, and FIG.
This inkjet head includes a frame (10) formed with an engraving that becomes an ink supply port (not shown) and a common liquid chamber (1b), an engraving that becomes a fluid resistance portion (2a) and a pressurized liquid chamber (2b), A flow path plate (20) having a communication port (2c) communicating with the nozzle (3a), a nozzle plate (30) forming the nozzle (3a), a convex portion (6a), a diaphragm portion (6b), and ink A diaphragm (60) having an inlet (6c), a laminated piezoelectric element (50) joined to the diaphragm (60) via an adhesive layer (70), and the laminated piezoelectric element (50) are fixed. A base (40).
The base (40) is made of a barium titanate ceramic, and the laminated piezoelectric elements (50) are arranged in two rows and joined.
The laminated piezoelectric element (50) is composed of a lead zirconate titanate (PZT) piezoelectric layer having a thickness of 10 to 50 μm / layer, and an internal electrode layer made of silver / palladium (AgPd) having a thickness of several μm / layer. Are stacked alternately. The internal electrode layer is connected to the external electrode at both ends.

The laminated piezoelectric element (50) is divided onto comb teeth by half-cut dicing, and each one is used as a drive part (5f) and a support part (5g) (non-drive part). The length of the outside of the external electrode is limited by cutting or the like so as to be divided by half-cut dicing, and these become a plurality of individual electrodes. The other is not divided by dicing but is conductive and becomes a common electrode.
The FPC 8 is soldered to the individual electrodes of the drive unit. Further, the common electrode is provided with an electrode layer at the end of (50) of the laminated piezoelectric element, and is wound around to be joined to the Gnd electrode of the FPC 8. A driver IC (not shown) is mounted on the FPC 8 to control application of drive voltage to the drive unit (5f).
The diaphragm (60) is an island-shaped convex portion (island) that joins the thin film diaphragm portion (6b) and the laminated piezoelectric element (50) serving as the drive portion (5f) formed at the center portion of the diaphragm portion (6b). Part) (6a), a thick film part including a beam to be joined to the support part, and an opening serving as an ink inflow port (6c) are formed by stacking two Ni plating films by electroforming. The diaphragm portion has a thickness of 3 μm and a width of 35 μm (one side).
The island-shaped convex part (6a) of the diaphragm (60) and the movable part (5f) of the laminated piezoelectric element (50), and the connection between the diaphragm (50) and the frame (10) are bonded layers including a gap material ( 70) is bonded by patterning.
The flow path plate (20) is made of a silicon single crystal substrate, and has a fluid resistance portion (2a), an engraving that serves as a pressurized liquid chamber (2b), and a through-hole that serves as a communication port (2c) at a position relative to the nozzle (3a). Turned by etching method.
The portion left by etching becomes the partition wall (2d) of the pressurized liquid chamber (2b). Further, this head is provided with a portion for narrowing the etching width, and this is used as the fluid resistance portion (2a).

The nozzle plate (30) is formed of a metal material, for example, an Ni plating film by an electroforming method, and has a large number of nozzles (3a) which are fine discharge ports for causing ink droplets to fly. The inner shape (inner shape) of the nozzle (3a) is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle (3a) is approximately 20 to 35 μm on the ink droplet outlet side. The nozzle pitch of each row is 150 dpi. An ink repellent layer (not shown) subjected to an ink repellent surface treatment is provided on the ink ejection surface (nozzle surface side) or nozzle inner wall of the nozzle plate (30).
As the ink repellent layer, a resin layer such as a fluororesin silicone resin, a metal / resin composite film such as a fluorine-based silane coupling agent, a Ni / PTFE eutectoid film, etc. are used. In the case of an agent, the effect of the present invention becomes very remarkable.
The frame (10) that forms the engraving that becomes the ink supply port and the common liquid chamber (1b) is made by resin molding.

In the ink jet head configured as described above, a drive waveform (pulse voltage of 10 to 50 V) is applied to the drive unit (5f) according to the recording signal, thereby causing displacement in the stacking direction in the drive unit (5f). The pressurized liquid chamber (2b) is pressurized through the diaphragm (60) to increase the pressure, and ink droplets are ejected from the nozzle (3a).
Thereafter, the ink pressure in the pressurized liquid chamber (2b) decreases with the end of ink droplet ejection, and negative pressure is generated in the pressurized liquid chamber (2b) due to the inertia of the ink flow and the discharge process of the drive pulse. Then, the process proceeds to the ink filling process. At this time, the ink supplied from the ink tank flows into the common liquid chamber (1b), passes from the common liquid chamber (1b) through the ink inlet (6c), the fluid resistance portion (2a), and the pressurized liquid chamber ( 2b) is filled.
The fluid resistance portion (2a) has an effect on the attenuation of the residual pressure vibration after the discharge, but becomes resistant to the refilling due to the surface tension. By appropriately selecting the fluid resistance portion, it is possible to balance the attenuation of the residual pressure and the refill time, and to shorten the time (drive cycle) until the transition to the next ink droplet ejection operation.
When cleaning with the cleaning / filling liquid of the present invention, it is possible to further enhance the cleaning effect by using vibration by fine driving that does not cause ejection by a piezoelectric actuator like the piezoelectric element. This is an effective means that greatly improves the cleaning efficiency.
The ink jet nozzle plate and ink jet head are effective for application to these ink jet recording apparatuses (image forming apparatuses), but are not limited to this, and are also applicable to manufacturing apparatuses such as color filters and organic EL, and other various patterning apparatuses. Is possible.

  The cleaning / filling solution of the present invention is contained in a container to form a cartridge, which can be used for maintenance of the ink jet recording apparatus. The configuration may be the same as that of the ink cartridge, and it is sufficient to fill the cleaning and filling liquid instead of the ink. In the case of the ink jet recording apparatus shown in FIG. 1, the cartridge of the present invention may be used in place of the ink cartridge (201).

Next, the inkjet ink will be described.
Constituents of ink include coloring materials, wetting agents, water-soluble organic solvents, surfactants, and other additives (pH adjusters, antiseptic / antifungal agents, rust preventives, water-soluble UV absorbers, water-soluble infrared absorbers) Agent), resin and the like. When the ink dries, solid matters such as coloring materials and resins remain as sticking residues in the nozzles, which cause discharge defects such as bending. When a pigment is used as the coloring material or a resin emulsion is used as the resin, these are not dissolved in the solvent but are dispersed, so that they are likely to become sticky residues, and the present invention is effective. Some pigments have re-dispersibility, but once the resin emulsion is fixed, it may not be re-dispersed even when it comes into contact with the newly ejected liquid. Since it has many adhesive functions, it is very difficult to completely remove it when it adheres to the inner wall of the nozzle or the like, but this is possible with the present invention.

As the color material, known pigments and dyes can be appropriately used.
Examples of inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black produced by known methods such as the contact method, furnace method, and thermal method. Can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acid dye chelates), nitro pigments, nitroso pigments, aniline black, etc. . Among these, those having good affinity with the solvent are preferable.
In addition to the above, a self-dispersing pigment that can be dispersed in water by adding a functional group such as a sulfone group or a carboxyl group to the surface of the pigment (for example, carbon) can also be used. Further, a pigment may be included in a microcapsule so that the pigment can be dispersed in water.

The amount of pigment added as a coloring material in the ink is preferably about 0.5 to 25% by mass, more preferably about 2 to 15% by mass. In general, when the pigment concentration is increased, the image density is increased and the image quality is improved. However, the reliability such as fixing property, ejection stability, and clogging tends to be adversely affected.
The particle diameter of the pigment is not particularly limited, but a pigment ink having a particle diameter of 20 to 150 nm in terms of the maximum frequency in terms of the maximum number is preferable. When the particle diameter exceeds 150 nm, not only the pigment dispersion stability as an ink is deteriorated, but also ejection stability is deteriorated, and image quality such as image density is lowered, which is not preferable. If the particle size is less than 20 nm, the storage stability of the ink and the jetting characteristics in the printer are stable, but in order to disperse to such a fine particle size, the dispersion operation and classification operation become complicated and economical. It becomes difficult to produce a recording liquid.
When the pigment is dispersed using a dispersant, a known dispersant can be appropriately used. Examples thereof include a polymer dispersant and a water-soluble surfactant.

The resin is added as necessary for the purpose of improving the image fixing property, improving the image quality, and improving the pigment dispersibility.
Examples thereof include hydrophilic polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, etc. in natural systems; alginic acid, carrageenan, agar, etc. Seaweed polymers; animal polymers such as gelatin, casein, albumin, collagen; microbial polymers such as xanthene gum and dextran; and fibers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose in semisynthetic systems Organic polymers; starch polymers such as sodium starch glycolate and sodium starch phosphate; seaweed polymers such as sodium alginate and propylene glycol alginate, pure synthetic In the system, polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid Acid copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene -Acrylic acid copolymer, acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, Vinyl acetate-maleic acid ester copolymer, acetic acid Cycloalkenyl - crotonic acid copolymer, vinyl acetate - acrylic acid copolymers, and salts thereof.
The addition amount of these resins is appropriately selected in consideration of reliability.

Recently, in place of a resin that is soluble in a solvent, a so-called resin emulsion dispersed as fine particles in a solvent is often used. The resin emulsion is obtained by dispersing resin fine particles in a solvent as a continuous phase, and may contain a dispersing agent such as a surfactant as necessary. The content of the resin fine particles as the dispersed phase component (content of the resin fine particles in the resin emulsion) is generally about 10 to 70% by mass, and the particle size of the resin fine particles is particularly used for an ink jet recording apparatus. In consideration, the average particle size is preferably 10 to 1000 nm, more preferably 20 to 300 nm, but there is no particular limitation.
Examples of the resin fine particle component of the dispersed phase include acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, acrylic silicon resins, and the like. An acrylic silicon resin is particularly effective, but is not particularly limited, and is for ensuring reliability when a known resin is used, and a commercially available resin emulsion can also be used. .
Specific examples thereof include Microgel E-100, E-2002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint), Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals), Jonkrill 775. (Styrene-acrylic resin emulsion made by Johnson polymer), SAE1014 (styrene-acrylic resin emulsion made by Nippon Zeon), Cybinol SK-200 (acrylic resin emulsion made by Seiden Chemical), Primal AC-22, AC-61 (acrylic type) Resin Emulsion (Rohm and Haas), Nanocryl SBCX-2821, 3689 (Acrylic-silicone resin emulsion, manufactured by Toyo Ink), # 3070 (Methyl methacrylate polymer resin emulsion, Gokoku Motosei), and the like.

The content of the resin fine particles in the ink is generally 0.1 to 50% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, but is particularly limited. It is not a thing.
Other constituent components, such as a water-soluble organic solvent, a surfactant, a pH adjuster, and an antiseptic / antifungal agent, are the same as those of the cleaning / filling solution, and are not particularly limited.
The ink is prepared by dispersing or dissolving the above-described constituents in a medium and further stirring and mixing as necessary. Dispersion can be performed by a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser or the like, and stirring and mixing can be performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser or the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples , reference examples, and comparative examples applied to an inkjet recording apparatus, but the present invention is not limited to these examples.

Examples 5 to 10, Reference Examples 1 to 4, Comparative Examples 1 to 10
As shown in the columns of Examples , Reference Examples and Comparative Examples in Tables 1 and 2, the materials were mixed to prepare each cleaning and filling liquid. In addition, the numerical value in a table | surface is the mass%, and it added so that a pure water might be 100 mass% as a whole.

The details of the materials indicated by the product names and symbols in Tables 1 and 2 are as follows.
・ Zonyl FS-300 (fluorine-based surfactant): polyoxyethylene perfluoroalkyl ether (manufactured by DuPont, active ingredient 40 mass%)
ECTD-6NEX (surfactant): polyoxyethylene (6) sodium alkyl ether acetate (manufactured by Nikko Chemicals)

<Preparation of pigment ink>
-Preparation of polymer solution-
After sufficiently replacing nitrogen gas in the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, Polyethylene glycol methacrylate (4.0 g), styrene macromer (4.0 g), mercaptoethanol (0.4 g), and methyl ethyl ketone (40.0 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 hydroxyethyl methacrylate, 36.0 g of styrene macromer, 3.6 g of mercaptoethanol, azobismethylvaleronitrile A mixed solution of 2.4 g and 342.0 g of methyl ethyl ketone was dropped into the flask over 2.5 hours.
After dropping, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18.0 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, 20.0 g of methyl ethyl ketone and 13.6 g of ion-exchanged water were sufficiently stirred, and then kneaded using a roll mill.
The obtained paste was put into 200 g of pure water and sufficiently stirred, and then the methyl ethyl ketone and water were distilled off using an evaporator, and the yellow pigment-containing polymer fine particles containing 15% by mass of the pigment and containing 20% by mass of the solid pigment. An aqueous dispersion was obtained.

-Preparation of yellow pigment ink-
A yellow pigment ink was prepared by 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 were 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. Then, pressure filtration was performed using a 0.8 μm cellulose acetate membrane filter to remove coarse particles, and a yellow ink for evaluation 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, 13.0 g of methyl ethyl ketone and 13.6 g of ion-exchanged water were sufficiently stirred, and then kneaded using a roll mill.
The obtained paste was put into 200 g of pure water and sufficiently stirred, and then the methyl ethyl ketone and water were distilled off using an evaporator, and 15% by mass of pigment and magenta pigment-containing polymer fine particles having a solid content of 20% by mass. An aqueous dispersion was obtained.

-Preparation of magenta pigment ink-
A magenta pigment ink was prepared by the following procedure.
First, 15% by mass of 3-methyl-1,3-butanediol, 15% by mass of glycerol, 0.5% by mass of Zonyl FSO-100 manufactured by DuPont, and 1% by mass of 1,2-hexanediol were mixed and stirred for 1 hour. And mixed uniformly. 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. Then, pressure filtration was performed using a 0.8 μm cellulose acetate membrane filter to remove coarse particles to obtain a magenta ink for evaluation.

  Various characteristics were evaluated as described below using each of the cleaning / filling liquid and the evaluation ink. The results are summarized in Tables 4 and 5.

<Uniformity as a liquid>
Each washing and filling solution was allowed to stand for 1 hour, and the state of the solution after standing was visually observed and evaluated according to the following criteria.
○: Uniform state with no separation or insoluble matter ×: Part of the component is separated or there is insoluble matter and is in a non-uniform state

<Evaluation of mixing properties of cleaning liquid / filling liquid and ink>
A mixed liquid of 97% by mass of the cleaning / filling liquid and 3% by mass of ink was prepared and allowed to stand at 65 ° C. for 50 hours, and then the appearance change was evaluated according to the following criteria.
○: The presence or absence of separation is unknown △: Light and shade are seen ×: Separation is occurring

<Evaluation of cleaning properties of cleaning liquid and filling liquid>
-Initial state setting The ink supply path of the ink jet printer (IPSIO GX3000, manufactured by Ricoh) or the ink in the head is replaced with pure water, and then the cartridge filled with the magenta ink for evaluation instead of the black and cyan inks. A cartridge filled with the evaluation yellow ink instead of magenta and yellow ink was attached, and after the filling operation, the head refreshing operation was repeated 10 times, and the ink in the ink supply path and the head was replaced with the evaluation ink. Thereafter, a nozzle check pattern was printed, and a head refreshing operation was performed until there was no missing nozzle.
-Cleaning treatment After confirming that the nozzles of the inkjet printer were not missing, a cartridge filled with the cleaning and filling liquid was attached instead of all the cartridges, and the head refreshing operation was performed 6 times. Thereafter, the operation of the maintenance unit of the printer was performed, and the operation of suctioning 4.5 cc from each head and refilling was repeated three times. After filling again, 2 cc was sucked from each head, and the nozzle surface was wiped to clean the path in the ink jet recording apparatus.
・ Evaluation of cleaning performance Collect the last suction cleaning solution / filling solution, measure the absorbance at 563 nm with magenta ink and 421 nm with yellow ink, and compare the absorbance with the same wavelength of the ink. The concentration (mass%) of the ink coloring fine particles was calculated.

<Evaluation of ink filling properties>
After using an inkjet printer (IPSIO GX3000, manufactured by Ricoh Co., Ltd.) to wash the ink flow path of the inkjet printer with the cleaning and filling liquid, the same cleaning and filling liquid is filled, and the nozzle surface is covered with a moisture retention cap at 50 ° C., 60 It was left for 1 month in a% RH environment. Thereafter, an ink cartridge filled with the above-described evaluation yellow ink and magenta ink was attached, and an ink filling operation was performed. Next, print the nozzle check pattern, repeat the head refreshing operation after the ink filling operation, perform the nozzle check, until there is no ejection failure (nozzle ejection or ejection bending = white or black streaks are conspicuous in the image) The ink filling property was evaluated according to the following criteria by the number of head refreshing (up to 8 times).
◎: No head refreshing ○: Head refreshing 1 to 2 times △: Head refreshing 3 to 4 times ×: Head refreshing required 5 times or more, or unrecoverable

As can be seen from the results of Tables 4 and 5, Examples 5 to 10 contain an appropriate amount of the amide compound of the structural formula (1) and the fluorine-based surfactant of the structural formula (2) -1, so any of the mixed-washability Inc. filling property was good, detergency as compared with reference examples 1-4, especially is excellent.
On the other hand, when at least one of the amide compound and the fluorosurfactant is lacking, and when the content of the amide compound is not an appropriate amount, at least one of the miscibility with the ink, the cleaning property, and the ink filling property is poor or not. It is enough.

Examples 11-17, Comparative Examples 11-13
As shown in the columns of Examples and Comparative Examples in Tables 6 and 7, materials were mixed to prepare each cleaning / filling solution. In addition, the numerical value in a table | surface is the mass%, and it added so that a pure water might be 100 mass% as a whole.

The details of the materials indicated by the symbols in Tables 6 and 7 are as shown in Table 8 below.

Using the ink for evaluation prepared in the cleaning filling liquid and Example 5 -10 described above, in the same manner as in Example 5 -10 were evaluated various properties. The results are summarized in Tables 9 and 10.

As can be seen from the results of Tables 9 and 10, Examples 11 to 17 contain an appropriate amount of the amide compound represented by the structural formula (1), and therefore, the mixing with the ink, the cleaning property, and the ink filling property are all good. In addition, since it contains an appropriate amount of the fluorine-based surfactant represented by the structural formula (2) -2, the detergency is superior to those of Reference Examples 1 to 4.
On the other hand, since Comparative Example 11 does not contain an amide compound, the mixing with the ink is insufficient and the ink filling property is poor. In Comparative Examples 12 and 13, the content of the amide compound is not an appropriate amount, so that the detergency and ink filling are low. Or the miscibility with ink is insufficient.

Examples 18 to 25, Reference Example 26, Comparative Examples 14 to 16
As shown in the columns of Examples , Reference Examples and Comparative Examples in Tables 11 and 12, the materials were mixed to prepare each cleaning and filling liquid. In addition, the numerical value in a table | surface is the mass%, and it added so that a pure water might be 100 mass% as a whole.

Details of the materials indicated by reference numerals in Tables 11 and 12 are as shown in Table 13 below.

Using the ink for evaluation prepared in the cleaning filling liquid and Example 5 -10 described above and evaluated various properties in the same manner as in Example 5 -10. The results are summarized in Tables 14 and 15.

As can be seen from the results of Tables 14 and 15, Examples 18 to 25 contain an appropriate amount of the amide compound represented by the structural formula (1), and therefore, the mixing with the ink, the cleaning property, and the ink filling property are all good. In addition, since it contains an appropriate amount of the fluorine-based surfactant represented by the structural formula (2) -3, the cleaning properties are superior to those of Reference Examples 1 to 4.
On the other hand, Comparative Example 14 does not contain an amide compound, so the mixing property with ink and the ink filling property are poor, and Comparative Examples 15 and 16 have a mixing amount with ink and / or because the content of the amide compound is not appropriate. Insufficient cleanability.

Examples 27-31, Comparative Examples 17-20
As shown in the columns of Examples and Comparative Examples in Tables 16 and 17, the materials were mixed to prepare each cleaning / filling solution. In addition, the numerical value in a table | surface is the mass%, and it added so that a pure water might be 100 mass% as a whole.

The details of the materials indicated by the symbols in Table 16 and Table 17 are as follows.
_{(A) C 4 F 9 -CH} 2 CH (OH) CH 2 O- (CH 2 CH 2 O) 21 -C 18 H 37
_{(B) C 2 F 5 -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) 23 -CH 2 CH (OH) CH 2 -C 4 F 9
_{(D) 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
_{(E) C 2 F 5 -CH} 2 CH (OH) CH 2 O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 2 F 5

Using the ink for evaluation prepared in the cleaning filling liquid and Example 5 -10 described above and evaluated various properties in the same manner as in Example 5 -10. The results are summarized in Table 18 and Table 19.

As can be seen from the results of Tables 18 and 19, Examples 27 to 31 contain an appropriate amount of the amide compound of the structural formula (1), so that all of the mixing property with the ink, the cleaning property and the ink filling property are good. In addition, since it contains an appropriate amount of the fluorine-based surfactant represented by the structural formula (2) -4, the cleaning properties are superior to those of Reference Examples 1 to 4.
On the other hand, Comparative Examples 17 to 18 containing no amide compound have poor ink filling properties, and Comparative Examples 19 to 20 have an amide compound content that is not appropriate. One or more is insufficient.

Example 32-51, Comparative Examples 21 to 23
As shown in the columns of Examples and Comparative Examples in Table 20-1, Table 20-2, and Table 21, the materials were mixed to prepare each cleaning / filling solution. In addition, the numerical value in a table | surface is the mass%, and it added so that a pure water might be 100 mass% as a whole.

The details of the materials indicated by the symbols in Table 20-1, Table 20-2, and Table 21 are as follows.
A1: Fluorosurfactant (K salt) of structural formula (2) -5
A2: Fluorosurfactant (Na salt) of structural formula (2) -5
A3: Fluorosurfactant (Li salt) of structural formula (2) -5
A4: Fluorosurfactant (NH ₄ salt) of structural formula (2) -5
A5: fluorinated surfactant of structural formula (2) -6 (Rf = CF ₃ , K salt)
A6: fluorinated surfactant of structural formula (2) -6 (Rf = C ₄ F ₉ , Li salt)
A7: fluorinated surfactant of structural formula (2) -6 (Rf = C ₄ F ₉ , Na salt)
A8: fluorinated surfactant of structural formula (2) -6 (Rf = C ₄ F ₉ , NH ₄ salt)
A9: Fluorosurfactant (Rf = C ₄ F ₉ , R = CH ₃ , structural formula (2) -7
K salt)
A10: Fluorosurfactant of the structural formula (2) -7 (Rf = CF ₃ , R = C ₂ H ₅ ,
Li salt)
A11: Fluorosurfactant of the structural formula (2) -7 (Rf = C ₄ F ₉ , R = C ₄ H ₉ ,
Na salt)
A12: Fluorine-based surfactant of structural formula (2) -7 (Rf = C ₄ F ₉ , R = C ₈ H ₁₇ ,
NH ₄ salt)
A13: fluorinated surfactant of structural formula (2) -8 (Rf = C ₄ F ₉ , Na salt)
A14: Fluorine-based surfactant of structural formula (2) -8 (Rf = C ₄ F ₉ , K salt)

Using the ink for evaluation prepared in the cleaning filling liquid and Example 5 -10 described above and evaluated various properties in the same manner as in Example 5 -10. The results are summarized in Table 22-1, Table 22-2, and Table 23.

Table 22-1, Table 22-2, as can be seen from the results in Table 23, since the examples 32 to 51 containing a suitable amount of the amide compound of structure (1), mixed-washability Inc. with ink All of the filling properties are good, and since it contains an appropriate amount of the fluorine-based surfactants of the structural formulas (2) -5 to (2) -8, the detergency is superior to those of Reference Examples 1 to 4.
On the other hand, Comparative Example 21 containing no amide compound has poor ink mixing properties and ink filling properties, and Comparative Examples 22 to 23 have an amide compound content that is not appropriate. Ink filling property is insufficient.

1b Common liquid chamber 2a Fluid resistance part 2b Pressurized liquid chamber 2c Communication port 2d Partition 3a Nozzle 5f Drive part 5g Support part (non-drive part)
6a Convex part 6b Diaphragm part 6c Ink inlet 10 Frame 20 Channel plate 30 Nozzle plate 40 Base 50 Multilayer piezoelectric element 60 Vibration plate 70 Adhesive layer 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 105 Operation part 111 Upper cover 112 Front surface 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper placement section 142 Paper 143 Paper feed roller 144 Separation pad 145 Guide 151 Conveying belt 152 Counter roller 153 Conveying guide 154 Holding member 155 Addition Pressure roller 156 Charging roller 157 Conveying roller 158 Densation roller 161 Guide member 171 Separation claw 172 Paper discharge roller 173 Paper discharge roller 181 Double-sided paper feed unit Doo 182 hand paper feed unit 201 ink cartridge

JP 2000-127419 A JP 2001-49292 A Japanese Patent No. 4290486

Claims (5)

A cleaning and filling liquid for a liquid flow path of an ink jet recording apparatus and an ink cartridge used in the apparatus, and a total amount of at least one amide compound represented by the following structural formula (1) is 10.0 to 45.0 mass And at least one fluorosurfactant selected from those represented by the following structural formulas (2) -1 to (2) -8 in a total amount of 1.0 to 5.0% by mass A cleaning / filling solution characterized by:
<Structural formula (1)>

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)

<Structural Formula (2) -1>

(In the formula, R 1 and R 3 represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms, and R 2 and R 4 represent a perfluoroalkyl group having 1 to 6 carbon atoms. , N represents 0 or a positive integer, and p, q, and r represent a positive integer.)

<Structural Formula (2) -2>

(In the formula, M represents an alkali metal, ammonium, phosphonium, or alkanolamine, Rf represents —CF ₃ or —CF ₂ CF ₃ , and q represents an integer of 4 to 10).

<Structural Formula (2) -3>

(In the formula, R ₁ represents hydrogen, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms , and R _f represents a perfluoroalkyl group having 1 to 6 carbon atoms. _X , y and z represent a positive integer.)

<Structural Formula (2) -4>
_{C n F 2n + 1 -CH 2} CH (OH) CH 2 O (CH 2 CH 2 O) a-Y

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

<Structural Formula (2) -5>

(In the formula, M ⁺ represents any of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ .)

<Structural Formula (2) -6>
[(RfSO ₂ ) ₂ ] N ⁻ M ⁺
(In the formula, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and M ⁺ represents any one of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ .)

<Structural Formula (2) -7>
[(RfSO ₂ ) (RSO ₂ )] N ⁻ M ⁺
(In the formula, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, R represents an alkyl group having 1 to 10 carbon atoms, and M ⁺ is any one of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ . Represents.)

<Structural Formula (2) -8>
[(FSO ₂ ) ₂ ] N ⁻ M ⁺
(In the formula, M ⁺ represents any of Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ .) 2. The cleaning and filling liquid for an ink jet recording apparatus according to claim 1 , wherein the compound represented by the structural formula (2) -4 is any one of the following (a) to (e):
_{(A) C 4 F 9 -CH} 2 CH (OH) CH 2 O- (CH 2 CH 2 O) 21 -C 18 H 37
_{(B) C 2 F 5 -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) 23 -CH 2 CH (OH) CH 2 -C 4 F 9
_{(D) 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
_{(E) C 2 F 5 -CH} 2 CH (OH) CH 2 O- (CH 2 CH 2 O) 45 -CH 2 CH (OH) CH 2 -C 2 F 5 Furthermore, glycerin and / or 1,3-butanediol are contained, The washing | cleaning liquid and filling liquid of Claim 1 or 2 characterized by the above-mentioned. A cartridge characterized in that the cleaning and filling liquid according to any one of claims 1 to 3 is contained in a container. Washing an ink jet recording apparatus, wherein the cleaning liquid and filling liquid according to any one of claims 1 to 3 is passed through to wash an ink flow path, and then the cleaning liquid and filling liquid is filled and stored. Filling and storage method.

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