JP2015229696A - Ink set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set excellent in cleaning property in an ink flow passage and charging property to a recording device.SOLUTION: The ink set includes a cleaning liquid containing a permeation solvent and a surfactant having an HLB value of 10 or less, and an ink composition containing a permeation solvent; and the ink set has such a property that when the cleaning liquid and the ink composition are mixed in equal amounts on a volume basis to obtain a mixture liquid, a separation parameter of the mixture liquid calculated by the formula below is 0.50 or more. In the formula, substances 1, 2, 3, ... represent surfactants having an HLB value of over 10 included in the mixture liquid; and substances a, b, c, ... represent surfactants having an HLB value of 10 or less included in the mixture liquid.

Description

  The present invention relates to an ink set.

  The ink jet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields. Among them, various studies have been made on the maintenance aspect of the recording apparatus. For example, Patent Document 1 discloses an existing inkjet printer that exhibits excellent cleaning properties even when applied to an inkjet printer that has a high colorant concentration and that uses ink containing a pigment, and that does not violate members. At least water and an alkylene glycol monoalkyl ether in the range of 0.3 to 15% by weight are used for the purpose of providing a novel maintenance liquid for ink jet recording that can be used and has excellent antifoaming properties and antiseptic and antifungal effects. A maintenance liquid for ink-jet recording characterized by containing is disclosed.

JP 2009-269407 A

  In order to further enhance the cleaning power or cleaning performance (hereinafter collectively referred to as “cleaning performance”) of the cleaning liquid (maintenance liquid), it is preferable to use a relatively hydrophobic surfactant. However, the higher the hydrophobicity of the surfactant, the lower the compatibility between the ink composition and the cleaning liquid. Therefore, when the ink composition and the cleaning liquid are replaced, both are easily separated in the ink flow path, and the property (fillability) of being quickly filled into the ink flow path of the ink composition or the cleaning liquid into the recording apparatus is reduced. There is a problem of doing. The decrease in filling property appears as a phenomenon such as nozzle missing.

  The present invention has been made to solve at least a part of the above-described problems, and an object of the present invention is to provide an ink set that is excellent in the cleaning properties of the ink flow path and the filling properties of the recording apparatus.

  The present inventors diligently studied to solve the above problems. As a result, the inventors have found that the above-described problems can be solved by using a cleaning liquid and an ink composition having a predetermined relationship, thereby completing the present invention.

（式中、物質１，２，３，…は、前記混合液に含まれ得るＨＬＢ値１０超過の界面活性剤を示し、物質ａ，ｂ，ｃ，…は、前記混合液に含まれる前記ＨＬＢ値１０以下の界面活性剤を示す。）
〔２〕
前記洗浄液に含まれるＨＬＢ値１０以下の前記界面活性剤は、下記式（１）で表されるアセチレングリコール系界面活性剤を含む、請求項１に記載のインクセット。

（式（１）中、Ｒ¹、Ｒ²、及びＲ³は、各々独立して、炭素数１〜６のアルキル基を表し、ｍ、ｎ、ｐ、及びｑは、１〜５０の整数である。）
〔３〕
前記洗浄液に含まれる前記浸透溶剤は、グリコールエーテル系化合物を含む、請求項１又は２に記載のインクセット。
〔４〕
前記インク組成物に含まれる前記浸透溶剤は、グリコールエーテル系化合物を含む、請求項１〜３のいずれか１項に記載のインクセット。
〔５〕
前記インク組成物が、染料を含む、請求項１〜４のいずれか１項に記載のインクセット。 That is, the present invention is as follows.
[1]
A cleaning liquid containing a surfactant having a HLB value of 10 or less and a penetrating solvent;
An ink composition containing a penetrating solvent,
An ink set in which, when equal amounts of the cleaning liquid and the ink composition are mixed to obtain a mixed liquid, a separation parameter calculated by the following formula of the mixed liquid is 0.50 or more.

(In the formula, substances 1, 2, 3,... Represent surfactants having an HLB value exceeding 10 which can be contained in the mixed solution, and substances a, b, c,... Are contained in the HLB contained in the mixed solution. Indicates a surfactant with a value of 10 or less.)
[2]
The ink set according to claim 1, wherein the surfactant having an HLB value of 10 or less contained in the cleaning liquid contains an acetylene glycol surfactant represented by the following formula (1).

(In the formula ^{(1), R 1, R} 2, and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms, m, n, p, and q is 1 to 50 integer is there.)
[3]
The ink set according to claim 1 or 2, wherein the penetrating solvent contained in the cleaning liquid contains a glycol ether compound.
[4]
The ink set according to any one of claims 1 to 3, wherein the penetrating solvent contained in the ink composition contains a glycol ether compound.
[5]
The ink set according to claim 1, wherein the ink composition contains a dye.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

（式中、物質１，２，３，…は、前記混合液に含まれ得るＨＬＢ値１０超過の界面活性剤を示し、物質ａ，ｂ，ｃ，…は、前記混合液に含まれる前記ＨＬＢ値１０以下の界面活性剤を示す。） [Ink set]
The ink set of this embodiment includes a cleaning liquid containing a penetrating solvent and a surfactant having an HLB value of 10 or less, and an ink composition containing a penetrating solvent that is the same as or different from the penetrating solvent, and the cleaning liquid and the ink composition When the same amount is mixed on a volume basis to obtain a mixed solution, the separation parameter calculated by the following formula of the mixed solution is 0.50 or more.

(In the formula, substances 1, 2, 3,... Represent surfactants having an HLB value exceeding 10 which can be contained in the mixed solution, and substances a, b, c,... Are contained in the HLB contained in the mixed solution. Indicates a surfactant with a value of 10 or less.)

  Usually, it is effective to use a relatively hydrophobic surfactant in order to further improve the cleaning performance of the cleaning liquid. In particular, since a recording apparatus having a continuous ink supply system often uses an ink flow path or an ink tank made of a hydrophobic material, the cleaning liquid used in the continuous ink supply system has a relatively hydrophobic surface activity. It is effective to use an agent. However, since the hydrophobic surfactant has low solubility in water, when the cleaning liquid containing the hydrophobic surfactant and the ink composition are replaced, they are easily separated in the ink flow path. When the separation occurs, the hydrophobic surfactant tends to increase in viscosity, and the filling property of the ink composition or the cleaning liquid into the recording apparatus decreases.

  In contrast, the ink set of the present embodiment improves the cleaning performance of the cleaning liquid by making the cleaning liquid and the ink composition having a predetermined composition have a relationship such that the separation parameter is 0.50 or more. In addition, the filling property can be improved.

  Here, the “cleaning liquid” is a liquid pre-filled in at least one of the ink container and the ink flow path before ink filling or when the recording apparatus is not used for a long period of time for the purpose of defoaming effect at the time of ink filling. . The location and amount of the cleaning liquid to be filled are not particularly limited, and the cleaning liquid may be filled into at least a part of the ink container or the ink flow path.

  Further, when the image recording using the ink jet recording apparatus is not performed for a long time or when ejection failure occurs, at least one of the ink container and the ink flow path can be replaced with the cleaning liquid. The replacement with the cleaning liquid is performed by causing the cleaning liquid to flow into at least one of the ink storage container or the ink flow path filled with ink and replacing at least one of the ink in the ink storage container or the ink flow path with the cleaning liquid. It can be carried out. At this time, prior to the inflow of the cleaning liquid, at least one of the ink in the ink container or the ink flow path may be discharged out of the system.

  On the other hand, when resuming image recording using the ink jet recording apparatus, ink is allowed to flow into at least one of the ink container filled with the cleaning liquid or the ink flow path, and the cleaning liquid is discharged from the nozzle opening. Thus, the cleaning liquid may be replaced with ink. At this time, prior to the inflow of ink, at least one of the cleaning liquid in the ink container or the ink flow path may be discharged from the nozzle opening.

  In addition, in order to fill at least one of the ink container and the ink flow path with the ink or the cleaning liquid, the ink and the cleaning liquid may be filled so as to be replaced by a normal cleaning operation. Also, the nozzle opening surface of the recording head is sealed with a cap, connected to the cap with a suction pump, negative pressure is generated in the cap by the suction pump, and ink or cleaning liquid is circulated in the ink flow path. It may be filled.

  Here, the “ink channel” means a channel for distributing ink in the ink jet recording apparatus. As the ink flow path, for example, an ink supply path for supplying ink from an ink container that stores ink to the ink jet recording head, or a flow path for distributing ink to the nozzle opening in the ink jet recording head Is mentioned.

  The “ink supply system” refers to an ink container (ink tank) having an air inlet, a print head having a nozzle for discharging ink in the ink container, and the ink container and the print head. And an ink supply path for supplying ink from the ink container to the print head.

[Cleaning liquid]
The cleaning liquid contains a surfactant having an HLB value of 10 or less and a penetrating solvent. In the present specification, the “HLB value” is a value defined by the Griffin method.

(Penetration solvent)
The penetrating solvent that can be contained in the cleaning liquid is not particularly limited. For example, ethylene glycol mono (di) methyl ether, ethylene glycol mono (di) ethyl ether, ethylene glycol mono (di) propyl ether, ethylene glycol mono (di) Butyl ether, diethylene glycol mono (di) methyl ether, diethylene glycol mono (di) ethyl ether, diethylene glycol mono (di) propyl ether, diethylene glycol mono (di) butyl ether, triethylene glycol mono (di) methyl ether, triethylene glycol mono (di) Ethyl ether, triethylene glycol mono (di) propyl ether, triethylene glycol mono (di) butyl ether, propylene glycol mono (di) methyl ether Propylene glycol mono (di) ethyl ether, propylene glycol mono (di) propyl ether, propylene glycol mono (di) butyl ether, dipropylene glycol mono (di) methyl ether, dipropylene glycol mono (di) ethyl ether, dipropylene glycol mono (Di) propyl ether, dipropylene glycol mono (di) butyl ether, tripropylene glycol mono (di) methyl ether, tripropylene glycol mono (di) ethyl ether, tripropylene glycol mono (di) propyl ether, tripropylene glycol mono ( Di) glycol ether compounds such as butyl ether; 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, alkyldiol compounds such as 2-ethyl-1,3-hexane diol. The penetrating solvent may be used alone or in combination of two or more.

  In particular, the penetrating solvent contained in the cleaning liquid preferably contains a glycol ether compound or an alkyl diol compound, and more preferably contains a glycol ether compound. Among the glycol ether compounds, preferably ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol Examples include propylene glycol monomethyl ether and tripropylene glycol monomethyl ether. By including such a cleaning liquid, the filling property tends to be further improved.

  The total content of the osmotic solvent in the cleaning liquid is preferably 3.0 to 15 parts by mass, more preferably 4.0 to 12 parts by mass with respect to the total amount (100 parts by mass) of the cleaning liquid. Preferably it is 5.0-10 mass parts. When the content of the penetrating solvent is 4.0 parts by mass or more, the filling property tends to be further improved. Moreover, it exists in the tendency for a washability to improve more because content of a osmosis | permeation solvent is 12 mass parts or less.

(Surfactant)
The surfactant that can be contained in the cleaning liquid is not particularly limited, and examples thereof include nonionic surfactants. The nonionic surfactant is not particularly limited, but examples thereof include acetylene dialcohol, polyoxyethylene acetylenic glycol ether, polyoxyethylene alkyl and alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene Ethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, ester type, polyethylene glycol fatty acid ester, glycerin Ester, polyglycerol ester, sorbitan ester, propylene glycol ester, Esters, fatty acid alkanol amides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amide, fluorine-based surfactants, and the like. Surfactant may be used individually by 1 type, or may use 2 or more types together.

  The cleaning liquid contains a surfactant having an HLB value of 10 or less among the above-mentioned surfactants, and may contain a surfactant having an HLB value exceeding 10 as necessary. The cleaning liquid preferably contains a surfactant having an HLB value of 10 or less, and more preferably contains a surfactant having an HLB value of 7 or less. When the cleaning liquid contains a surfactant having an HLB value of 10 or less, the cleaning property tends to be further improved.

（式（１）中、Ｒ¹、Ｒ²、及びＲ³は、各々独立して、炭素数１〜６のアルキル基を表し、ｍ、ｎ、ｐ、及びｑは、１〜５０の整数である。） The surfactant having an HLB value of 10 or less contained in the cleaning liquid preferably contains an acetylene glycol surfactant represented by the following formula (1). Of these, polyoxyethylene (4) acetylenic glycol ether, 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, 2,4,7,9-tetramethyl- Examples include 5-decine-4,7-diol and 2,4,7,9-tetramethyldec-5-in-4,7-diol. By including such a surfactant, the detergency tends to be further improved.

(In the formula ^{(1), R 1, R} 2, and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms, m, n, p, and q is 1 to 50 integer is there.)

  The content of the surfactant having an HLB value of 10 or less in the cleaning liquid is preferably 0.10 to 1.0 part by mass, and more preferably 0.3 to 0. 0 part by mass with respect to the total amount (100 parts by mass) of the cleaning liquid. 5 parts by mass. When the content of the surfactant having an HLB value of 10 or less is 0.10 parts by mass or more, the detergency tends to be further improved. Moreover, it exists in the tendency for a filling property to improve more because content of surfactant with HLB value 10 or less is 1.0 mass part or less.

  The total content of the surfactant in the cleaning liquid is preferably 0.3 to 4.0 parts by mass, more preferably 1.0 to 2.0 parts by mass with respect to the total amount (100 parts by mass) of the cleaning liquid. is there. When the surfactant content is 0.3 parts by mass or more, the detergency tends to be further improved. Moreover, it exists in the tendency for a filling property to improve more because content of surfactant is 4.0 mass parts or less.

  The penetrating solvent contained in the cleaning liquid may be referred to as a first penetrating solvent, and the surfactant may be referred to as a first surfactant.

(Humectant)
The cleaning liquid may contain a humectant. Although it does not specifically limit as a moisturizer, For example, lower alcohols, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; dimethylformamide, dimethylacetamide Amides such as acetone, ketones such as acetone and diacetone alcohol, or keto alcohols; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, di Alkyles such as propylene glycol, tripropylene glycol, thiodiglycol and hexylene glycol Glycol; glycerin; 2-pyrrolidone; N- methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone. The cleaning liquid may be used alone or in combination of two or more.

(water)
The cleaning liquid may contain water. Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the cleaning liquid is stored for a long period of time, and the storage stability tends to be further improved. The water content is not particularly limited and can be appropriately determined as necessary.

(Other ingredients)
The cleaning liquids are various, such as dissolution aids, viscosity modifiers, pH adjusters, antioxidants, antiseptics, antifungal agents, corrosion inhibitors, and chelating agents for capturing metal ions that affect dispersion. These additives may be included as appropriate.

[Ink composition]
The ink composition includes a penetrating solvent.

(Penetration solvent)
The penetrating solvent that can be contained in the ink composition is not particularly limited, and examples thereof include those exemplified as the penetrating solvent in the cleaning liquid. The penetrating solvent may be used alone or in combination of two or more.

  The penetrating solvent contained in the ink composition preferably contains a glycol ether compound or an alkyl diol compound, and more preferably contains a glycol ether compound. Among the glycol ether compounds, preferably ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol Examples include propylene glycol monomethyl ether and tripropylene glycol monomethyl ether. By including such a penetrating solvent, the filling property tends to be further improved. The penetrating solvent that can be contained in the ink composition and the penetrating solvent that can be contained in the cleaning liquid may be the same or different, but are preferably the same solvent from the viewpoint of compatibility.

  The total content of the penetrating solvent in the ink composition is preferably 3.0 to 15 parts by mass, more preferably 4.0 to 12 parts by mass with respect to the total amount (100 parts by mass) of the ink composition. More preferably, it is 5.0 to 10 parts by mass. When the content of the osmotic solvent is 3.0 parts by mass or more, the filling property tends to be further improved. Moreover, it exists in the tendency for a discharge characteristic to improve more because content of a osmosis | permeation solvent is 16 mass parts or less.

(Surfactant)
The ink composition may contain a surfactant. The surfactant that can be contained in the ink composition is not particularly limited, and examples thereof include those exemplified as the surfactant in the cleaning liquid. Surfactant may be used individually by 1 type, or may use 2 or more types together. The ink composition may include at least one of the surfactants having an HLB value of 10 or less and those having an HLB value exceeding 10. The surfactant that can be included in the ink composition and the surfactant that can be included in the cleaning liquid may be the same or different.

  The content (100 parts by mass) of the surfactant having an HLB value of 10 or less in the ink composition is preferably from 0.1 to 1.0 part by mass, more preferably from 0.1 to 1.0 part by mass relative to the total amount of the ink composition. 3 to 0.5 parts by mass. When the content of the surfactant having an HLB value of 10 or less is 0.1 part by mass or more, the detergency tends to be further improved. Moreover, it exists in the tendency for a filling property to improve more because content of surfactant with HLB value 10 or less is 1.0 mass part or less.

  The content (100 parts by mass) of the surfactant having an HLB value exceeding 10 in the ink composition is preferably 0.3 to 4.0 parts by mass with respect to the total amount of the ink composition, more preferably 1. 0 to 2.0 parts by mass. When the content of the surfactant having an HLB value exceeding 10 is 0.3 parts by mass or more, the filling property tends to be further improved. Moreover, when the content of the surfactant having an HLB value exceeding 10 is 4.0 parts by mass or less, the discharge characteristics tend to be further improved.

  The total content of the surfactant in the ink composition is preferably 0.3 to 4.0 parts by mass, and more preferably 1.0 to 2.0, with respect to the total amount (100 parts by mass) of the ink composition. Part by mass. When the content of the surfactant is 0.3 parts by mass or more, the filling property tends to be further improved. Moreover, it exists in the tendency for a filling property to improve more because content of surfactant is 4.0 mass parts or less.

  The penetrating solvent contained in the ink composition may be referred to as a second penetrating solvent, and the surfactant may be referred to as a second surfactant.

(Color material)
The ink composition may include a color material. Examples of the color material include pigments and dyes, and among these, it is preferable to include a dye. By including the dye, there is a problem that the wettability of the ink composition is changed due to the interaction between the dye and the surfactant, and the filling property is lowered. Since the sex can be controlled, the present invention is particularly useful. Although it does not specifically limit as dye, For example, the following are mentioned.

  The dye for the yellow ink composition is not particularly limited. I. Reactive Yellow 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95, 102 Reactive dyes such as C., 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176; I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 67, 72, 73, 79 99, 104, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246, etc .; I. Disperse Yellow 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135, 140 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, 227 , 231, 232 and the like.

  The dye for the magenta ink composition is not particularly limited. I. Reactive Red2, 3, 3: 1, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66, 78 83, 84, 106, 111, 112, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180, 183, 184, 187, 190 Reactive dyes such as C., 193, 194, 195, 198, 218, 220, 222, 223, 226, 228, 235; I. Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127, 131 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289 Acidic dyes such as 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415; I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 22 Include disperse dyes such as 227,229,239,240,257,258,277,278,279,281,288,298,302,303,310,311,312,320,324,328.

  The dye for the cyan ink composition is not particularly limited. I. Direct Blue 87 is exemplified.

  The dye for the orange ink composition is C.I. I. Acid Orange 33 and C.I. I. It will not be specifically limited if it contains at least 1 sort of Acid Orange94. The fourth dye may contain other dyes, and examples of such dyes include C.I. I. Reactive Orange 1, 4, 5, 7, 11, 12, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91, 92 , 93, 95, 107, etc .; I. Acid Orange 3, 7, 8, 10, 19, 22, 24, 51, 51S, 56, 67, 74, 80, 86, 87, 88, 89, 95, 107, 108, 116, 122, 127, 140, 142 Acidic dyes such as 144, 149, 152, 156, 162, 166, 168; I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49 , 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139 , 142 and the like.

  The dye for the blue ink composition is not particularly limited. I. Reactive Blue 2, 3, 4, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77, 79 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191, 194 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236, C.I. I. Reactive dyes such as Reactive Violet 1, 2, 4, 5, 6, 22, 23, 33, 36, 38; I. Acid Blue 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127: 1, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239, 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350, C.I. I. Acid dyes 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126; I. Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81 , 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 97,301,315,330,333, C. I. Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, Disperse dyes such as 69 and 77 are listed.

(Humectant)
The ink composition may contain a humectant, and examples of the humectant include those exemplified as the humectant in the cleaning liquid. A moisturizer may be used individually by 1 type, or may use 2 or more types together.

(Other ingredients)
Ink compositions include dissolution aids, viscosity modifiers, pH adjusters, antioxidants, antiseptics, antifungal agents, corrosion inhibitors, and chelating agents for capturing metal ions that affect dispersion. Various additives may be included as appropriate.

（式中、物質１，２，３，…は、前記混合液に含まれ得るＨＬＢ値１０超過の界面活性剤を示し、物質ａ，ｂ，ｃ，…は、前記混合液に含まれる前記ＨＬＢ値１０以下の界面活性剤を示す。） [Separation parameters]
When the cleaning liquid and the ink composition are mixed in equal amounts on a volume basis to obtain a mixed liquid, the separation parameter calculated by the following equation of the mixed liquid is 0.50 or more, preferably 0.60 or more. Yes, more preferably 0.70 or more. The separation parameter is a value obtained by the following equation obtained through experiments, and indicates the difficulty of separating the cleaning liquid and the ink composition. When the separation parameter is 0.50 or more, the cleaning property and the filling property tend to be further improved.

(In the formula, substances 1, 2, 3,... Represent surfactants having an HLB value exceeding 10 which can be contained in the mixed solution, and substances a, b, c,... Are contained in the HLB contained in the mixed solution. Indicates a surfactant with a value of 10 or less.)

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

オルフィンＰＤ００２Ｗ（アセチレン系界面活性剤、日信化学工業社製）
サーフィノール１０４ＰＧ５０（アセチレン系界面活性剤、日信化学工業社製）
サーフィノールＭＤ２０（アセチレン系界面活性剤、日信化学工業社製） [Material for ink composition]
The main materials for the ink compositions used in the following examples and comparative examples are as follows.
[Coloring material (dye)]
Direct Blue 119
Reactive Red 141
Direct Yellow 86
Direct Yellow 132
[Humectant]
Glycerin (penetrating solvent)
Triethylene glycol monobutyl ether 1,2-hexanediol [surfactant]
New Coal 1006 (nonionic surfactant, manufactured by Nippon Emulsifier Co., Ltd.)
Olfine E1010 (acetylene surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)
Betaine surfactant (represented by a compound of the following general formula (9))

Orphin PD002W (acetylene surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)
Surfynol 104PG50 (acetylene surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)
Surfynol MD20 (acetylene surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)

[Preparation of cleaning liquid and ink composition]
Each material was mixed with the composition shown in Table 1 below and stirred sufficiently to obtain a cleaning liquid and an ink composition. In Table 1 below, the numerical unit is mass%, and the total is 100.0 mass%.

[Examples 1-7, Comparative Examples 1-6]
[Cleanability]
A silicon substrate was prepared assuming an ink flow path in the recording apparatus. 0.5 μL of the cleaning liquid was dropped on the silicon substrate, and the contact angle 20 seconds after the dropping was measured. The detergency was evaluated according to the following evaluation criteria based on the obtained contact angle.
(Evaluation criteria)
○: The contact angle was 5 ° or less.
(Triangle | delta): The contact angle was 5 degrees or more and less than 10 degrees.
X: The contact angle was 10 ° or more.

[Separation risk]
In the mixed liquid in which the cleaning liquid and the ink composition were mixed at a ratio of 1: 1 on a volume basis, the state near the liquid surface was visually observed. Based on the observation results, the separation risk was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: No separation was observed near the liquid surface of the mixed solution.
X: Separation was observed near the liquid surface of the mixed solution.

[Fillability]
20 g of the cleaning liquid was filled in an ink tank of an ink jet printer (L100 [product name], manufactured by Seiko Epson Corporation). Thereafter, according to the initial filling sequence defined by L100, the cleaning liquid was discharged out of the head via the ink supply path and the ink storage chamber. Next, after the ink composition is filled in the ink tank, the power ink flushing determined by L100 is operated twice to perform the filling operation to the ink head, and the ink composition is removed from the ink container of the ink tank. The head was filled up through the supply path and the ink storage chamber. Thereafter, a nozzle check was performed to confirm whether ink could be ejected from all nozzles of the head. The number of missing nozzles was confirmed, and the filling property was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: Nozzle missing was 0-2.
X: Nozzle missing was 3 or more.

  The ink jet printer (L100 [product name], manufactured by Seiko Epson Corporation) is an ink container having an air inlet, a print head having a nozzle for ejecting ink, an ink container, and the print head connected to each other. And an ink supply path for supplying ink from the ink container to the print head, and a filter provided in the ink supply path.

Here, the separation parameters of the third embodiment will be described. Example 3 is a combination of ink (M-1) and cleaning liquid (W-1). As the separation parameter, since a solution in which the cleaning liquid and the ink are mixed at a ratio of 1: 1 is considered, the composition of 100 g of the solution in which M-1 and W-1 are mixed at 1: 1 is calculated. In the separation parameter equation, substance 1 represents Neucor 1006, substance 2 represents orphine E1010, substance 3 represents a betaine surfactant, substance a represents Surfinol 104PG50, and substance b represents Surfinol MD20.
Calculation formula of molecule (I) = {1.5 / (13.4-10)} + {0.15 / (13-10)} + {0.5 / (10.4-10)} + (10 / 10).
The denominator formula (II) = (0.15 / 4) + (0.15 / 4).
Therefore, the separation parameter = (I) / (II) × (1/70) = 0.52.

Claims (5)

A cleaning liquid containing a surfactant having a HLB value of 10 or less and a penetrating solvent;
An ink composition containing a penetrating solvent,
An ink set in which, when equal amounts of the cleaning liquid and the ink composition are mixed to obtain a mixed liquid, a separation parameter calculated by the following formula of the mixed liquid is 0.50 or more.

(In the formula, substances 1, 2, 3,... Represent surfactants having an HLB value exceeding 10 which can be contained in the mixed solution, and substances a, b, c,... Are contained in the HLB contained in the mixed solution. Indicates a surfactant with a value of 10 or less.) The ink set according to claim 1, wherein the surfactant having an HLB value of 10 or less contained in the cleaning liquid contains an acetylene glycol surfactant represented by the following formula (1).

(In the formula ^{(1), R 1, R} 2, and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms, m, n, p, and q is 1 to 50 integer is there.)   The ink set according to claim 1 or 2, wherein the penetrating solvent contained in the cleaning liquid contains a glycol ether compound.   The ink set according to any one of claims 1 to 3, wherein the penetrating solvent contained in the ink composition contains a glycol ether compound.   The ink set according to claim 1, wherein the ink composition contains a dye.