JP2019196424A - Ink set and inkjet recording method - Google Patents

Abstract

To provide an ink set that has an aqueous ink capable of printing even on non- or poorly absorbent base materials and a cleaning liquid capable of cleaning a solid matter even when the ink dries to produce a solid matter.SOLUTION: The ink set has an ink containing a coloring agent, a binder and water and a cleaning liquid containing a compound represented by formula (1) as given below and water. [In formula (1), R represents a straight-chain or branched-chain 1-5C hydrocarbon group and L, m and n satisfies (L+m)/n=1.5/1 to 1/1.5.]SELECTED DRAWING: None

Description

  The present invention relates to an ink set, an ink jet recording method using the ink set, and a recording material to which the ink is attached.

  Among color printing methods, a printing method using an inkjet printer (inkjet printing method) is one of representative methods. This method is a method in which ink droplets are generated and attached to a substrate such as paper for printing. In recent years, inkjet printing methods have been increasingly applied as industrial applications. Colorants contained in the inkjet ink are roughly classified into water-soluble colorants and water-insoluble colorants. Among these, water-insoluble colorants represented by pigments are generally excellent in various fastness properties compared to water-soluble colorants. For this reason, industrial inkjet inks often contain a water-insoluble colorant.

  Substrates used for industrial applications are diversified, such as various papers, fibers, and films. Among such substrates, there are many non-ink-absorbing substrates and non-ink-absorbing substrates (hereinafter referred to as “non-difficult-absorbing substrates”). As inks used for recording on non-hardly absorbable substrates, non-aqueous solvent inks and curable inks are known. However, for example, from the viewpoint of safety against the natural environment and a living body, there is a strong demand for a water-based ink that can be printed on a non-hardly absorbable substrate. Such a water-based ink contains a water-insoluble colorant and a dispersant, and further generally contains a polymer, a wax and the like for the purpose of improving scratch resistance and solvent resistance. For this reason, such a water-based ink has a high solid content, and is very easy to dry, and a large amount of solid matter is easily generated by drying. Ink drying tends to occur during long-term storage, storage in a high temperature / low humidity environment, and the like. Ink drying produces solid matter in the nozzles of the inkjet head and the ink flow path, which causes clogging. When clogging occurs in the ink jet head in this way, ink ejection cannot be performed stably, causing a problem that the image density decreases. Furthermore, the inkjet head itself may become unusable, which is a big problem. In general, industrial ink jet heads are devised such that a nozzle member is provided with a cap member to prevent ink drying. However, it is still difficult to completely avoid ink drying.

From the above situation, it is possible to record even non-absorptive absorbent substrates, and even when ink having a high solid content is dried to produce solid matter in order to improve scratch resistance, this is washed. There is a strong demand for a cleaning solution that can be used.
Patent Documents 1 to 6 disclose cleaning liquids used for cleaning an inkjet recording apparatus. Patent Document 7 discloses an ink composition containing a wax. Patent Document 8 discloses an ink composition containing a polymer.
Patent No. 5027444 Japanese Patent No. 4649823 Japanese Patent No. 4397220 Patent No. 5618250 Patent No. 5819206 Patent No. 5819205 International Publication No. 2015/147192 No. Gazette International Publication No. 2015/152291 Gazette

  The present invention is a water-based ink that can be recorded on a non-hardly absorbable substrate and has good scratch resistance, and a cleaning liquid that can wash the solid even when the ink is dried to form a solid. It is an object of the present invention to provide a set of ink and cleaning liquid.

As a result of intensive studies to solve the problems as described above, the present inventors have at least
The present invention has found that the above problems can be solved by an ink set comprising a colorant, an ink containing a binder and water, a compound represented by the following formula (1), and a cleaning liquid containing water. Was completed.
That is, the present invention relates to the following 1) to 7).

1)
An ink containing a colorant, a binder, and water;
A set of an ink and a cleaning liquid having a compound represented by the following formula (1) and a cleaning liquid containing water.

[In Formula (1), R represents a linear or branched C1-C5 hydrocarbon group, and L, m, and n are (L + m) /n=1.5/1-1 / 1.5. ]
2)
The set of the ink and the cleaning liquid according to 1), wherein the cleaning liquid further contains one or more kinds of glycol ethers.
3)
The set of the ink and the cleaning liquid according to 1) or 2), wherein the binder is one or more selected from a polymer and a wax.
4)
The set of ink and cleaning liquid according to 3), wherein the wax is one or more selected from polyalkylene wax, polyalkylene wax, and paraffin wax.
5)
The ink and cleaning liquid set according to 3) or 4), wherein the wax is at least one selected from polyethylene wax, polypropylene wax, oxidized polyethylene wax, oxidized polypropylene wax, and paraffin wax.
6)
A recording apparatus cleaning method, wherein the recording apparatus to which the ink according to any one of 1) to 5) is attached is cleaned with the cleaning liquid according to any one of 1) to 5).
7)
The cleaning method according to 6), wherein the recording apparatus is an inkjet printer.

  INDUSTRIAL APPLICABILITY According to the present invention, a water-based ink that can be recorded on a non-hardly absorbable substrate and has good scratch resistance, and a cleaning liquid that can wash a solid even when the ink is dried to form a solid And a set of ink and cleaning liquid.

  In the present specification, unless otherwise specified, “%” and “part” are both described on a mass basis.

[Colorant]
The colorant contained in the ink is not particularly limited, and a colorant selected from a water-soluble colorant and a water-insoluble colorant can be used. Moreover, these can also be used together as needed.
In the present specification, “water-insoluble” means that the solubility of the colorant in water at 25 ° C. is usually 3 g / liter or less, preferably 2 g / liter or less, more preferably 1 g / liter or less.
Examples of the water-insoluble colorant include pigments, disperse dyes, and solvent dyes. Typical examples of these colorants are C.I. I. Pigment, C.I. I. Disperse and C.I. I. Colorants selected from Solvent are mentioned.

  Examples of the water-soluble colorant include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, vat dyes, and soluble vat dyes. Representative examples of these dyes are C.I. I. Direct, C.I. I. Acid, C.I. I. Food, C.I. I. Basic, C.I. I. Reactive, C.I. I. Vat, C.I. I. Mention may be made of dyes selected from Solubilized Vat.

  As a colorant other than those described above, a resin containing a colorant in which the above colorant is contained in a transparent and water-insoluble resin can also be cited as a water-insoluble colorant.

Examples of the pigment include inorganic pigments, organic pigments and extender pigments.
Examples of the inorganic pigment include carbon black; metal oxide, hydroxide, sulfide; ferrocyanide; and metal chloride.

  Examples of carbon black include thermal black, acetylene black, oil furnace black, gas furnace black, lamp black, gas black, and channel black. Of these, furnace black, lamp black, acetylene black, channel black and the like are preferable. Various types of carbon black can be easily obtained from, for example, Columbian Carbon, Cabot, Degussa, Mitsubishi Chemical, and the like.

  Examples of organic pigments include soluble azo pigments, insoluble azo pigments, insoluble diazo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments and quinophthalones. Pigments.

  Specific examples of the organic pigment include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 55, 73, 74, 75, 83, 93, 94, 95, 97, 98, 108, 114, 128, 129, 138, 139, 150, 151, 154, 180, 185, 193, 199, 202; I. Pigment Red 5, 7, 12, 48, 48: 1, 57, 88, 112, 122, 123, 146, 149, 166, 168, 177, 178, 179, 184, 185, 202, 206, 207, 254, 255, 257, 260, 264, 272; I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 25, 60, 66, 80; C.I. I. Pigment Violet 19, 23, 29, 37, 38, 50; C.I. I. Pigment Orange 13, 16, 68, 69, 71, 73; C.I. I. Pigment Green 7, 36, 54; C.I. I. Pigment Black 1; and the like.

  Examples of extender pigments include silica, calcium carbonate, talc, clay, barium sulfate, and white carbon. These extender pigments are not used alone. Usually, it is used in combination with an inorganic pigment or an organic pigment for the purpose of improving the fluidity of the powder.

  In addition, a self-dispersing pigment imparted with a self-dispersibility by chemical treatment on the surface of the pigment particles can also be used.

  Examples of disperse dyes include C.I. I. Dispers Yellow 9, 23, 33, 42, 49, 54, 58, 60, 64, 66, 71, 76, 79, 83, 86, 90, 93, 99, 114, 116, 119, 122, 126, 149, 160, 163, 165, 180, 183, 186, 198, 200, 211, 224, 226, 227, 231, 237; I. Dispers Red 60, 73, 88, 91, 92, 111, 127, 131, 143, 145, 146, 152, 153, 154, 167, 179, 191, 192, 206, 221, 258, 283; I. Dispers Orange 9, 25, 29, 30, 31, 32, 37, 38, 42, 44, 45, 53, 54, 55, 56, 61, 71, 73, 76, 80, 96, 97; C.I. I. Dispers Violet 25, 27, 28, 54, 57, 60, 73, 77, 79, 79: 1; I. Dispers Blue 27, 56, 60, 79: 1, 87, 143, 165, 165: 1, 165: 2, 181, 185, 197, 202, 225, 257, 266, 267, 281, 341, 353, 354, 358, 364, 365, 368;

  The content of the colorant in the total mass of the ink is usually 1 to 30%, preferably 1 to 15%, more preferably 2 to 10%.

When the ink contains a water-insoluble colorant, it is preferable to further contain a dispersant. Dispersants include styrene and derivatives thereof; vinyl naphthalene and derivatives thereof; aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids; acrylic acid and derivatives thereof; maleic acid and derivatives thereof; itaconic acid and derivatives thereof At least two monomers selected from the group consisting of: vinyl acetate, vinyl alcohol, vinyl pyrrolidone, acrylamide, and derivatives thereof; and the like (preferably at least one of these); A copolymer composed of one hydrophilic monomer).
As a kind of copolymer, a block copolymer, a random copolymer, a graft copolymer, and / or their salts etc. are mentioned, for example.
The dispersant can be synthesized or obtained as a commercial product. Specific examples of commercially available products include, for example, styrene-acrylic resins such as Jonkrill 62, 67, 68, 678, and 687 manufactured by Johnson Polymer Co., Ltd .; Vinyl S-100A (modified vinyl acetate manufactured by Hoechst Chemical Co., Ltd.) Resin); Jurimer AT-210 (polyacrylic acid ester copolymer manufactured by Nippon Pure Chemicals Co., Ltd.);
When the dispersant is synthesized, a dispersant disclosed in International Publication No. 2013/115071 gazette is preferably exemplified.
One type of dispersant can be used, or two or more types can be used in combination.

  The weight average molecular weight (MW) of the dispersant is not particularly limited, but is usually 3000 to 50000, preferably 7000 to 25000. Moreover, as an acid value, it is 50-300 KOHmg / g normally, Preferably it is 80-275 KOHmg / g, More preferably, it is about 80-250 KOHmg / g.

  The dispersant can be used in a state mixed with a colorant. Further, the surface of the colorant can be coated with a dispersant and used as a so-called microencapsulated pigment. Moreover, both of these can also be used together.

When the ink contains a water-insoluble colorant, it is preferable to prepare a dispersion containing a colorant and a dispersant and then mix with other components to prepare the ink. A known method can be used as a method for preparing the dispersion.
As an example, a phase inversion emulsification method can be used when the dispersant does not dissolve in water. That is, the first polymer is dissolved in an organic solvent such as 2-butanone, and an aqueous solution of a neutralizing agent is added to prepare an emulsion. A colorant is added to the obtained emulsion to perform a dispersion treatment. An organic solvent and a part of water are distilled off under reduced pressure from the liquid thus obtained, whereby a target colorant dispersion can be obtained.
Examples of the dispersion treatment include a method in which a colorant and a polymer are placed in a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like to perform dispersion. As an example, when a sand mill is used, beads having a particle diameter of about 0.01 mm to 1 mm can be used, and a dispersion treatment can be performed by appropriately setting the filling rate of the beads.
Operations such as filtration and / or centrifugation can be performed on the dispersion obtained as described above. By this operation, the particle diameters of the particles contained in the dispersion can be made uniform.
When foaming occurs during the preparation of the dispersion, a very small amount of a known antifoaming agent such as silicone or acetylene glycol can be added.
Other methods include acid precipitation method, phase inversion emulsification method, interfacial polymerization method, in-situ polymerization method, submerged cured coating method, coacervation (phase separation) method, submerged drying method, melt dispersion cooling method, Examples thereof include an air suspension coating method and a spray drying method. Among these, a phase inversion emulsification method, an acid precipitation method, and an interfacial polymerization method are preferable.

The average particle diameter (D50) of the water-insoluble colorant in the dispersion is usually 300 nm or less, preferably 30 to 280 nm, more preferably 40 to 270 nm, and still more preferably 50 to 250 nm.
Similarly, D90 is usually 300 nm or less, preferably 280 nm or less, more preferably 270 nm or less. The lower limit is preferably 100 nm or more.
Similarly, D10 is usually 10 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and the upper limit is 100 nm or less.
The particle size can be measured using laser light scattering.

[binder]
As the binder in the ink, one or more selected from polymers and waxes are used. However, the pigment dispersant is not included in the binder.
Examples of the polymer include urethane-based, polyester-based, acrylic-based, vinyl acetate-based, vinyl chloride-based, styrene-acrylic-based, acrylic-silicone-based, styrene-butadiene-based polymers, and emulsions containing the same. Of these, polymers selected from urethane, acrylic, and styrene-butadiene are preferred.
The polymer can be synthesized or purchased as a commercial product. When a polymer is synthesized, for example, a polymer disclosed in International Publication No. 2015/147192 Gazette is preferable.
Examples of commercially available products include Superflex 126, 130, 150, 170, 210, 420, 470, 820, 830, 890 (urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); Hydran HW-350, HW- 178, HW-163, HW-171, AP-20, AP-30, WLS-201, WLS-210 (urethane resin emulsion made by DIC Corporation); 0569, 0850Z, 2108 (styrene made by JSR Corporation) Butadiene-based resin emulsion); AE980, AE981A, AE982, AE986B, AE104 (acrylic resin emulsion manufactured by Etec Co., Ltd.) and the like.
The content of the polymer with respect to the total mass of the ink is usually 0.1% to 10%, preferably 0.2% to 8%, more preferably 0.2% to 5%, and further preferably 0.2% to 1%. %. When the content is such, the scuffing property, the redispersibility, and the discharge property are improved.

As the wax, a wax emulsion is preferable, and an aqueous wax emulsion is more preferable. Natural wax and synthetic wax can be used as the wax.
Natural waxes include petroleum waxes such as paraffin wax and microcrystalline wax; lignite waxes such as montan wax; plant waxes such as carnauba wax and canderia wax; animal and plant waxes such as beeswax and lanolin An emulsion in which a wax is dispersed in an aqueous medium can be used.

Synthetic waxes include polyalkylene wax (preferably poly C2-C4 alkylene wax), oxidized polyalkylene wax (preferably oxidized poly C2-C4 alkylene wax), and paraffin wax. Among these, one or more waxes selected from polyethylene wax, polypropylene wax, oxidized polyethylene wax, oxidized polypropylene wax, and paraffin wax are preferable.
Further, the average particle diameter of the wax is preferably 50 nm to 5 μm, more preferably 100 nm to 1 μm in order to prevent clogging of the inkjet head.

Examples of commercially available wax emulsions include, for example, CERAFLOUR 925, 929, 950, 991 manufactured by Big Chemie; AQUACER 498, 515, 526, 531, 537, 539, 552, 1547; AQUAMAT 208, 263, 272; MINEPOL 221; Mitsui Chemicals, Inc. Mitsui High Wax NL100, NL200, NL500, 4202E, 1105A, 2203A, NP550, NP055, NP505, etc .; Sanyo Chemical KUE-100, 11 etc. are mentioned.
Of these, AQUACER 515, 531, 537, 539, 1547 is preferred; AQUACER 515, 531, 537, 1547 is more preferred.
The wax content relative to the total mass of the ink is usually 0% to 10%, preferably 0% to 8%, more preferably 0% to 5%, and even more preferably 0% to 1%. When the content is such, the scuffing property, the redispersibility, and the discharge property are improved.

  The content ratio of the polymer and the wax in the total mass of the polymer and the wax contained in the ink is usually 95/5 to 5/95, preferably 90/10 to 10/90, more preferably 80/20 to 20 /. 80. By setting such a ratio, a recorded image having a good balance between redispersibility and fixability can be obtained.

[Compound represented by Formula (1)]
In the formula (1), examples of the hydrocarbon group for R include linear alkylene such as methylene, ethylene, propylene, butylene, and pentylene; 1-methyl-1,4-butanediyl, 2-methyl-1,4- Butanediyl, 3-methyl-1,4-butanediyl, 4-methyl-1,4-butanediyl, 1-methyl-1,3-propanediyl, 2-methyl-1,3-propanediyl, 3-methyl-1, Examples include 3-propanediyl, 1-methyl-1,2-ethanediyl, 2-methyl-1,2-ethanediyl and the like. In terms of high cleaning performance, the carbon number of R is usually C1-C5, preferably C2-C5, more preferably C3-C5, and particularly preferably C5. In view of high cleaning performance, R is preferably a branched chain.
The above L, m and n are (L + m) / n is usually 1.5 / 1 to 1 / 1.5, preferably 1.4 / 1 to 1 / 1.5, in terms of high cleaning performance. Preferably it is 1.4 / 1-1 / 1.4, More preferably, it is 1.3 / 1-1 / 1.3.
Moreover, the number average molecular weight of the compound represented by Formula (1) is 100-5000 normally, Preferably it is 200-4000, More preferably, it is 250-3500.
The compound represented by the formula (1) can be synthesized by a known method. Moreover, it can also obtain as a commercial item. Specific examples of commercially available products include TEGO Wet 500, 505, and 510 manufactured by EVONIC.

[Glycol ether]
The cleaning liquid may contain glycol ether. The glycol ether is preferably a monoalkyl ether of di- or tri-C2-C4 alkylene glycol.
C2-C4 alkylene glycol moieties include ethylene glycol, propylene glycol, and butylene glycol. Among these, ethylene glycol and propylene glycol are preferable, and ethylene glycol is more preferable.
The carbon number range of the alkyl of the monoalkyl ether moiety is usually C1-C6, preferably C1-C5, more preferably C2-C4, still more preferably C3-C4, and particularly preferably C4.
Specific examples thereof include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether (butyl diglycol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether. , Ethylene glycol monoallyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, propylene glycol monopropyl ether, triethylene glycol monobutyl ether, and the like. Of these, butyl diglycol is preferred.
The total content of glycol ether in the total mass of the cleaning liquid is usually 0 to 15%, preferably 0.1 to 15%, more preferably 0.2 to 13%, and further preferably 0.5 to 10%. .

  The cleaning liquid contains substantially no colorant. In the present specification, “substantially” means that a coloring agent is not intentionally added to the cleaning liquid.

The ink and the cleaning liquid may further contain an ink preparation agent in addition to the components described above. Examples of the ink preparation agent include organic solvents, water-soluble polymer compounds, surfactants, preservatives, antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble UV absorbers, antioxidants, A foaming agent etc. are mentioned.
The total content of the ink preparation agent other than the organic solvent is usually 0% to 30%, preferably 0% to 20%, and more preferably about 0% to 10% with respect to the total mass of the ink or cleaning liquid.

[Organic solvent]
Examples of the organic solvent include C1-C6 alkanol having one hydroxy group such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol; N, N-dimethylformamide, and N Amides such as N-dimethylacetamide; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidin-2-one, and 1, Cyclic ureas such as 3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, 2-methyl-2-hydroxypentan-4-one and ethylene carbonate; cyclics such as tetrahydrofuran and dioxane Ether; ethylene glycol, diethylene glycol Coal, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1 , 2-pentanediol, 3,3-dimethyl-1,2-butanediol, 1,2-octanediol, 5-methyl-1,2-hexanediol, 4-methyl-1,2-hexanediol, 4, C2-C8 alkylene such as 4-dimethyl-1,2-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol or polypropylene glycol having a molecular weight of 400 or more, thiodiglycol or dithiodiglycol Mono, oligo or with unit Real sharp glycol or thio glycol; glycerin, diglycerin, hexane-1,2,6-triol, polyol (triol) such as trimethylolpropane; .gamma.-butyrolactone, and an organic solvent selected from dimethyl sulfoxide and the like.

[Water-soluble polymer compound]
Examples of the water-soluble polymer compound include anionic and nonionic polymer compounds. Examples of the anionic polymer compound include cellulose derivatives such as carboxymethyl cellulose, acrylic acid derivatives such as polyacrylic acid, and polystyrene derivatives such as polystyrene sulfonate. Examples of nonionic polymer compounds include polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, and gelatin.

[Surfactant]
Examples of the surfactant include anionic, cationic, nonionic, amphoteric, silicon-based, and fluorine-based surfactants. Among these, anionic and nonionic surfactants are preferable, and anionic surfactants are more preferable.

  Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids or salts thereof, N-acyl methyl taurate, Alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfone Acid salts, diethylsulfosuccinate, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like.

  Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene diether. Ether type such as styrenated phenyl ether (for example, Emulgen A-60, A-90, A-500 manufactured by Kao Corporation); polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan mono Esters such as stearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2, , 7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, etc. Examples include glycol (alcohol) type; polyglycol ether type. As these commercial products, for example, Surfinol 104, 104PG50, 82, 420, 440, 465, 485, Olphine STG manufactured by Nissin Chemical Co., Ltd., Emulgen A-60, A-90, A- manufactured by Kao Corporation 500 etc. are mentioned.

  Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and imidazoline derivatives. Can be mentioned.

  Examples of silicone surfactants include polyether-modified siloxane and polyether-modified polydimethylsiloxane. As an example, DYNOL 960, 980 manufactured by Air Products, Inc., Silface SAG001, SAG002, SAG003, SAG005, SAG503A, SAG008, SAG009, SAG010 manufactured by Nissin Chemical Co., Ltd., and BYK-345 manufactured by BYK Chemie, 347, 348, 349, 3455, LP-X23288, LP-X23289, LP-X23347; TEGO Twin 4000, TEGO Wet KL 245, 250, 260, 265, 270, and 280 manufactured by Evonic Tego Chemie.

  Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group as a side chain. And polyoxyalkylene ether polymer compounds.

[Preservative]
Examples of preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole , Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl Examples thereof include bromoacetate-based or inorganic salt-based compounds.
Specific examples of commercially available antiseptics include Proxel GXL (S) and XL-2 (S) manufactured by Arch Chemical Co., Ltd.

[Antidepressant]
Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. .

[PH adjuster]
As the pH adjuster, any substance can be used as long as the pH can be adjusted to 5 to 11 without adversely affecting the prepared ink composition.
Specific examples thereof include, for example, alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water) Or alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; and inorganic bases such as disodium phosphate.

[Chelating reagent]
Specific examples of the chelating reagent include, for example, disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.

[anti-rust]
Specific examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

[Water-soluble UV absorber]
Examples of water-soluble ultraviolet absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

[Antioxidant]
As examples of the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings. It is done.

[Defoaming agent]
Examples of the antifoaming agent include silicone-based, silica mineral oil-based, olefin-based, and acetylene-based. Examples of commercially available antifoaming agents include Surfinol DF37, DF58, DF110D, DF220, MD-20, and Olfin SK-14, all manufactured by Shin-Etsu Chemical Co., Ltd.
When using an antifoamer, the addition amount is 0.01 to 5% normally, Preferably it is 0.03 to 3%, More preferably, it is 0.05 to 1%. When it is 0.01% or more, an effect as an antifoaming agent is obtained, and when it is 5% or less, the dispersion stability is good.

  The ink and the cleaning liquid can be selected and contained as one of all the components described above. Two or more types can be selected and contained. For example, the cleaning liquid can contain one compound selected from the compounds represented by formula (1). Two or more kinds of compounds can be selected and contained. The same applies to the other components.

[Ink application process]
When the ink is used as an ink for ink jet recording, it is preferable to use an ink containing a small amount of inorganic impurities such as metal cation chloride (for example, sodium chloride) and sulfate (for example, sodium sulfate). preferable. The standard of the content of the inorganic impurities is about 1% or less with respect to the total mass of the colorant, and the lower limit includes the detection limit of the analytical instrument, that is, 0%.
Inorganic impurities are often mixed in the colorant. For this reason, an inorganic impurity can be removed as needed. As a purification method, for example, a method of suspending and purifying a solid colorant with a mixed solvent of C1-C4 alcohol such as methanol and water, or the like; And the like.

The pH of the ink is usually preferably 7 to 11 or 8 to 10.
The surface tension of the ink is usually preferably 10 to 50 mN / m and 20 to 40 mN / m.
The viscosity of the ink is usually preferably 2 mPa · s to 30 mPa · s, 3 mPa · s to 20 mPa · s.
The pH and surface tension of the ink can be appropriately adjusted with a pH adjuster, a surfactant, a water-soluble organic solvent, or the like.

  The ink can be used in various recordings. For example, it is suitable for writing instruments, various types of printing, information recording, textile printing, etc., and particularly preferably used for ink jet recording.

When the ink is used for ink jet recording, recording can be performed by ejecting ink droplets according to a recording signal and attaching them to a recording medium. There is no restriction | limiting in particular about the ink nozzle of an inkjet printer, an inkjet system, etc., It can select suitably according to the objective.
When ink jet recording is performed, recording can be performed as described above by loading a container containing the ink into a predetermined position of the ink jet printer.

As the ink jet method, a known method can be used. Specific examples of the ink jet method include a charge control method, a drop-on-demand (pressure pulse) method, an acoustic ink jet method, a thermal ink jet method, and the like.
In addition, a method of improving the image quality by ejecting a large amount of ink with a small colorant content in the ink in a small volume; using a plurality of inks having substantially the same hue and different concentrations of the colorant in the ink And a method for improving the fixing property of the colorant by using a colorless and transparent ink.

The recording medium means a substance to which the ink can adhere. Examples of the recording medium include, for example, paper, film and the like, fiber and cloth (cellulose, nylon, wool, etc.), leather, and a base material for a color filter.
Recording media can be broadly classified into those having an ink receiving layer and those having no ink receiving layer.
A recording medium having an ink receiving layer is usually called inkjet paper, inkjet film, glossy paper, or the like. Typical examples of commercially available products include Canon Photographic Professional Photo Paper, Super Photo Paper, Glossy Gold and Matte Photo Paper; Seiko Epson Photographic Paper Crispier (high gloss), and Photographic Paper (Glossy). , Photo matte paper; advanced photo paper (glossy) manufactured by Hewlett-Packard Japan; painting photo finishing Pro manufactured by Fuji Film Co., Ltd., and the like.

Examples of the recording medium having no ink receiving layer include various papers such as coated paper and art paper used for gravure printing, offset printing, and cast coated paper used for label printing.
When using a recording medium that does not have an ink receiving layer, it is also preferable to subject the recording medium to a surface modification treatment for the purpose of improving the fixability of the colorant.

As the surface modification treatment, it is preferable to perform at least one treatment selected from corona discharge treatment, plasma treatment and flame treatment. As these treatments, known methods can be used. In addition, it is generally known that the effects of these treatments decrease with time. For this reason, when surface modification processing is performed on the information transmission sheet, it is preferable to continuously perform ink jet recording without taking time.
The surface modification treatment can be performed by appropriately adjusting the number of treatments, time, applied voltage, and the like so as to obtain a desired effect.

The cleaning method is a method of cleaning the recording apparatus to which the ink is attached with the cleaning liquid. As an example of the cleaning method, for example, there is a method in which the cleaning liquid is absorbed by a sponge or the like and the ink attached to the recording apparatus is wiped off. The recording apparatus is not particularly limited, but an ink jet printer is preferable.
In addition, when the ink jet head is heavily soiled, for example, when the ink adheres to the ink jet head and is solidified by drying, the ink jet head can be filled with a cleaning liquid for cleaning.
When cleaning is performed by filling the inkjet head with the cleaning liquid, it is preferable to finely filter the cleaning liquid for the purpose of removing impurities from the cleaning liquid.
When performing microfiltration, a membrane filter and / or glass filter paper or the like can be used. The pore diameter of a filter or the like when performing microfiltration is usually 0.5 to 20 μm, preferably 0.5 to 10 μm.

The pH of the cleaning liquid is usually 5 to 11, preferably 7 to 10.5 for the purpose of not corroding the members of the ink jet printer.
The surface tension of the cleaning liquid is usually 10 mN / m to 50 mN / m, preferably 20 mN / m to 40 mN / m.
The viscosity of the cleaning liquid is usually 30 mPa · s or less, preferably 20 mPa · s or less, and the lower limit is about 0.1 mPa · s.

About all the above-mentioned matters, a combination of preferable ones is more preferable, and a combination of more preferable ones is further preferable. The same applies to combinations of preferable and more preferable, combinations of more preferable and more preferable.
Moreover, all the above-mentioned components etc. can be used individually by 1 type, and can also use 2 or more types together.

The cleaning liquid can be used for cleaning water-based inks containing various colorants. Examples of colorants include, for example, water-based dye inks containing water-soluble dyes such as acid dyes, direct dyes, and reactive dyes; water-based inks containing water-insoluble colorants containing disperse dyes and pigments, and the like. It is done.
Since the cleaning liquid has a high detergency, it can also be used for cleaning water-insoluble colorants, particularly water-based inks containing pigments.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example. Moreover, the preparation of the cleaning liquid and the colored ink was carried out under stirring unless otherwise specified.
In addition, “water” used in the examples is ion-exchanged water.

[Adjustment Example 1]: Preparation of cleaning liquids 1 to 8 for evaluation test.
After mixing each component described in Table 1 below to obtain a total amount of 100 parts of liquid, the obtained liquid was filtered through a 3 μm membrane filter to obtain cleaning liquids 1 to 8 for evaluation tests, respectively. It was.

Abbreviations and the like in the following Table 1 have the following meanings. The numerical values in Table 1 are “parts”.
Gly: glycerin 2Py: 2-pyrrolidone.
BDG: butyl diglycol.
SN465: Nissin Chemical Co., Ltd. nonionic surfactant, Surfynol 465.
EP-7025: Nippon Shokubai Co., Ltd. nonionic surfactant, Softanol EP-7025.
LS-106: Kao Corporation nonionic surfactant, Emulgen LS-106.
D-1502: Nonionic surfactant made by Takemoto Yushi Co., Ltd., Pionein D-1502.
D-1305P: Nonionic surfactant manufactured by Takemoto Yushi Co., Ltd., Pionine D-1305P.
TW500: Nonionic surfactant manufactured by EVONIC, TEGO Wet 500.
TW510: Nonionic surfactant manufactured by EVONIC, TEGO Wet 510.
TEA: triethanolamine.
GXL (S): Proxel GXL (S).

[Preparation Example 2]: Preparation of polymer A used as a binder.
25 parts of Joncryl 678 (MW: 8500) and 14.3 parts of triethanolamine were dissolved in 60.7 parts of ion-exchanged water and stirred for 1 hour to obtain a solution. Let the obtained solution be a polymer A solution.

[Preparation Example 3]: Preparation of dispersion.
A block copolymer described in Synthesis Example 3 of International Publication No. 2013/115071 was prepared, and the obtained block copolymer (5 parts) was dissolved in 20 parts of 2-butanone to obtain a uniform solution. A solution prepared by dissolving sodium hydroxide (0.4 parts) in water (50.6 parts) was added to this liquid, and after adding Polymer A solution (4 parts), the mixture was stirred for 1 hour to obtain an emulsion. . In this emulsion, C.I. I. Pigment Yellow 74 (20 parts, HANSA YELLOW 5GX01-JP manufactured by Clariant) was added, and dispersion treatment was performed in a sand grinder at 1500 rpm for 15 hours to obtain a liquid. Water (100 parts) was added dropwise to the obtained liquid, and then the liquid was filtered to obtain a filtrate. From the obtained filtrate, 2-butanone and a part of water were distilled off under reduced pressure with an evaporator to obtain a colored dispersion having a pigment content of 12.4%.
The pigment content in the colored dispersion was determined as a converted value of the pigment content from the total solid content in the liquid by dry weight method using MS-70 manufactured by A & D Corporation.

[Preparation Example 4] Preparation of polymer B used as binder.
By following Preparation Example 4 of International Publication No. 2015/147192 Gazette, a resin emulsion having an acid value of 6 KOH mg / g, Tg of 0 ° C., and a solid content of 25% was prepared. This is designated as “Polymer B”.

[Preparation Example 5]: Preparation of inks 1 and 2 for evaluation test.
Ingredients shown in Table 2 below were mixed to obtain a total amount of 100 parts of liquid, and then the obtained liquid was filtered through a 3 μm membrane filter to obtain inks 1 and 2 used in the evaluation test.

Abbreviations in Table 2 below have the following meanings. The numerical values in Table 2 below are “parts”.
Dispersion: Dispersion of Preparation Example 3.
TEG: Triethylene glycol.
1,2HD: 1,2-hexanediol.
SN465: Nissin Chemical Co., Ltd. nonionic surfactant, Surfynol 465.
AQ515: Polyethylene wax manufactured by Big Chemie, AQUACER 515 (solid content 35%).

[Inkjet recording]
The ink obtained in each Example and Comparative Example was filled in an ink jet printer manufactured by Seiko Epson Corporation, PX-205 cartridge, and ink jet recording was performed on Fine Matt 115 (coated paper) manufactured by UPM.
Inkjet recording was performed so as to obtain a 100% duty solid image, and a recorded image recorded with the ink of each example or comparative example was obtained. Using this as a test piece, a scratch test was conducted.

[Ink scuff test]
The fretting property of each test piece was measured by Yasuda Seiki Seisakusho, No. Evaluation was made using a 428 Gakushoku-type wear tester (friction tester type II). That is, with a 500 g load applied to the test piece, the ink jet recorded portions were rubbed 20 times, and the degree of image degradation was evaluated according to the following three evaluation criteria. The results are shown in Table 3 below.
Evaluation criteria for dry abrasion:
A: Scratches on the recorded image were hardly confirmed.
B: Some scratches were confirmed on the recorded image.
C: The scratch on the recorded image is very large.

[Cleaning liquid stability test]
Each of the cleaning liquids obtained in Preparation Example 1 was allowed to stand at room temperature for 12 hours, and then the state of the cleaning liquid was visually observed to evaluate its stability. The evaluation criteria were as follows. The evaluation results are shown in Table 3 below.
[Evaluation criteria]
A: There was no change in the state of the cleaning solution.
B: The component separated from the cleaning liquid cannot be confirmed, but a non-uniform portion such as turbidity was observed.
C: It was observed that the liquid component separated from the cleaning liquid floated on the surface of the cleaning liquid.

[Cleaning test of cleaning liquid]
20 microliters of the colored ink obtained in Preparation Example 5 was dropped on a glass petri dish, and left in a constant temperature bath at 60 ° C. for 1 hour to dry, thereby obtaining a solid material in which the ink was solidified.
Ten milliliters of each cleaning liquid obtained in Preparation Example 1 was dropped on the obtained solid, and it was visually evaluated whether the solid could be washed. The evaluation criteria were as follows. Ink sets and evaluation results of Examples 1 to 3 and Comparative Examples 1 to 8 are shown in Table 3 below.
[Evaluation criteria]
A: No solid residue was observed and a uniform liquid was obtained.
B: A slight solid residue was observed, but the liquid became almost uniform.
C: The solid substance remained clearly and was not recognized as a uniform liquid.
D: The shape of the solid did not change at all or hardly changed.

  In Table 3 below, “binder” means the total amount of binder contained in each ink, and the unit is “parts”.

  As is clear from the results in Table 3, the cleaning liquid of each example is excellent in the stability of the cleaning liquid. Also, it is confirmed that the solid matter can be sufficiently washed when the ink that can be recorded on the recording medium with poor ink absorption is dried to produce a solid matter regardless of whether the ink is rubbed or not. It was done. On the other hand, the cleaning liquid of each comparative example was not able to sufficiently wash the solid matter even when the ink was good and the poor ink dried to form a solid matter.

  The ink set of the present invention can be recorded on a non-hardly absorbable substrate and has good scratch resistance, and even when the ink dries to produce a solid, the solid is washed. Since it has a cleaning liquid that can be used, it is extremely useful as a set of ink and cleaning liquid for various recordings, particularly for an ink jet printer.

Claims (7)

An ink containing a colorant, a binder, and water;
A set of an ink and a cleaning liquid having a compound represented by the following formula (1) and a cleaning liquid containing water.

[In Formula (1), R represents a linear or branched C1-C5 hydrocarbon group, and L, m, and n are (L + m) /n=1.5/1 to 1 / 1.5. ]   The ink and cleaning liquid set according to claim 1, wherein the cleaning liquid further contains at least one glycol ether.   The ink and cleaning liquid set according to claim 1, wherein the binder is one or more selected from a polymer and a wax.   The ink and cleaning liquid set according to claim 3, wherein the wax is at least one selected from polyalkylene wax, oxidized polyalkylene wax, and paraffin wax.   The ink and cleaning liquid set according to claim 3 or 4, wherein the wax is at least one selected from polyethylene wax, polypropylene wax, oxidized polyethylene wax, oxidized polypropylene wax, and paraffin wax.   A cleaning method for a recording apparatus, wherein the recording apparatus to which the ink according to any one of claims 1 to 5 is attached is cleaned with the cleaning liquid according to any one of claims 1 to 5.   The cleaning method according to claim 6, wherein the recording apparatus is an ink jet printer.