JP7042684B2 - Ink set and inkjet recording method - Google Patents

Description

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

Among the color printing methods, the printing method using an inkjet printer (inkjet printing method) is one of the typical methods. This method is a method of generating small droplets of ink and adhering them to a base material such as paper for printing. In recent years, the inkjet printing method has been increasingly applied for industrial purposes. The colorants contained in the inkjet ink are roughly classified into water-soluble colorants and water-insoluble colorants. Of these, water-insoluble colorants typified by pigments are generally superior in various fastnesses as compared with water-soluble colorants. For this reason, industrial inkjet inks often contain water-insoluble colorants.

The base materials used for industrial applications are diversified, such as various types of paper, fibers, and films. Among such base materials, there are many non-ink-absorbent base materials and poorly-absorbent ink base materials (hereinafter referred to as "non-non-absorbent base materials"). As inks used for recording non-non-absorbent base materials, non-aqueous solvent inks, curable inks and the like are known. However, for example, from the viewpoint of safety against the natural environment and living organisms, there is a strong demand for water-based inks that can be printed on non-absorbent base materials. Such water-based inks contain a water-insoluble colorant and a dispersant, and generally also contain a polymer, a wax, or the like for the purpose of improving scratch resistance, solvent resistance, and the like. Therefore, such a water-based ink has a high solid content and is extremely easy to dry, and a large amount of solid matter is likely to be generated by drying. Ink drying tends to occur in long-term storage, storage in a high temperature / low humidity environment, and the like. Drying of the ink produces solid matter in the nozzles of the inkjet head and the ink flow path, which causes clogging. When clogging occurs in the inkjet head in this way, the ink cannot be ejected stably, which causes a problem that the image density is lowered. Further, the inkjet head itself may not be usable, which is a big problem. Generally, an industrial inkjet head is equipped with a cap member in the nozzle portion to prevent the ink from drying. However, it is still difficult to completely prevent the ink from drying out.

From the above situation, it is possible to record on a non-absorbent base material, and in order to improve scratch resistance, even when the ink with a high solid content dries to form solid matter, it 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 device. Patent Document 7 discloses an ink composition containing a wax. Patent Document 8 discloses an ink composition containing a polymer.
Patent No. 50274444 Patent No. 4649823 Patent No. 4397220 Patent No. 5618250 Patent No. 5819206 Patent No. 5819205 International release 2015/147192 Gazette International release 2015/152291 Gazette

The present invention comprises a water-based ink that can be recorded on a non-absorbent substrate and has good scratch resistance, and a cleaning liquid that can clean the solid even when the ink dries to form a solid. It is an object to provide a set of ink and a cleaning liquid having the above.

As a result of intensive research to solve the above-mentioned problems, the present inventors have at least,
The present invention has been found that the above-mentioned problems can be solved by an ink set containing an ink containing a colorant, 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)
Inks containing colorants, binders, and water,
A set of an ink and a cleaning liquid containing a compound represented by the following formula (1) and a cleaning liquid containing water.

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

According to the present invention, a water-based ink that can be recorded on a non-absorbent base material and has good scratch resistance, and a cleaning liquid that can clean the solid matter even when the ink dries to form a solid matter. And could provide a set of ink and cleaning solution with.

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. Further, these can be used in combination 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, and 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 include C.I. I. Pigment, C.I. I. Disperse and C.I. I. Colorants selected from Solvent may be mentioned.

Examples of the water-soluble colorant include direct dyes, acidic dyes, edible dyes, basic dyes, reactive dyes, vat dyes, soluble vat dyes and the like. Typical dyes include 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. Examples include dyes selected from Solubilated Vat.

As a colorant other than the above, a resin containing a colorant in which the colorant is contained in a transparent and water-insoluble resin can also be mentioned 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 oxides, hydroxides, sulfides; ferrocyanides; and metal chlorides.

Examples of carbon black include thermal black, acetylene black, oil furnace black, gas furnace black, lamp black, gas black, and channel black. Among 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, Columbia Carbon, Cabot, Degussa, Mitsubishi Chemical Corporation 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, anthracinone pigments and quinophthalones. Pigments can be mentioned.

Specific examples of the organic pigment include, for example, 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; C.I. 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; C.I. 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 the extender pigment 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.

Further, it is also possible to use a self-dispersing pigment obtained by chemically treating the surface of the pigment particles to impart self-dispersion.

Examples of the disperse dye 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; C.I. 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; C.I. 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; C.I. 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; and the like.

The content of the colorant in the total mass of the ink is usually 1 to 30%, preferably 1 to 15%, and 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 its derivatives; vinylnaphthalene and its derivatives; α, β-ethylenic unsaturated carboxylic acid aliphatic alcohol esters; acrylic acid and its derivatives; mylenic acid and its derivatives; itaconic acid and its derivatives. At least two monomers (preferably at least one of them) selected from the group of monomers consisting of; carboxylic acid and derivatives thereof; vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and derivatives thereof; One is a copolymer composed of a hydrophilic monomer).
Examples of the type of copolymer include block copolymers, random copolymers and graft copolymers, and / or salts thereof.
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 John Krill 62, 67, 68, 678, and 687 manufactured by Johnson Polymer Co., Ltd .; Movinyl S-100A (modified vinyl acetate manufactured by Hext Synthetic Co., Ltd.). Resin); Julimer AT-210 (polyacrylic acid ester copolymer manufactured by Nippon Junyaku Co., Ltd.); and the like.
When synthesizing the dispersant, the dispersant disclosed in International Publication No. 2013/115071 Gazette is preferably mentioned.
One type of dispersant may be used, or two or more types may be used in combination.

The weight average molecular weight (MW) of the dispersant is not particularly limited, but is usually 3000 to 50,000, preferably 7000 to 25000. The acid value is usually about 50 to 300 KOH mg / g, preferably 80 to 275 KOH mg / g, and more preferably about 80 to 250 KOH mg / g.

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

When the ink contains a water-insoluble colorant, it is preferable to prepare a dispersion liquid containing the colorant and the dispersant, and then mix the ink with other components to prepare the ink. As a method for preparing the dispersion liquid, a known method can be used.
As an example, if the dispersant is insoluble in water, a phase inversion emulsification method can be used. 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. By distilling off the organic solvent and a part of water under reduced pressure from the liquid thus obtained, a dispersion liquid of the target colorant 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, or 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 the filling rate of the beads can be appropriately set to perform the dispersion treatment.
The dispersion obtained as described above can be subjected to operations such as filtration and / or centrifugation. By this operation, the size of the particle size of the particles contained in the dispersion liquid can be made uniform.
If foaming occurs during the preparation of the dispersion, a very small amount of a known silicone-based or acetylene glycol-based defoaming agent can be added.
Other methods include acid analysis method, phase inversion emulsification method, interfacial polymerization method, in-situ polymerization method, in-liquid curing coating method, core selvation (phase separation) method, in-liquid drying method, melting dispersion cooling method, and the like. Examples include an air suspension coating method and a spray drying method. Among these, the phase inversion emulsification method, the acid analysis method, and the interfacial polymerization method are preferable.

The average particle size (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, still more preferably 50 to 250 nm.
Similarly, D90 is usually 300 nm or less, preferably 280 nm or less, and 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 kinds 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, acrylic-based, vinyl acetate-based, vinyl chloride-based, styrene-acrylic, acrylic-silicone-based, and styrene-butadiene-based polymers, or emulsions containing the same. Among these, polymers selected from urethane-based, acrylic-based, and styrene-butadiene-based polymers are preferable.
The polymer can be synthesized or purchased as a commercial product. When synthesizing the polymer, for example, the polymer disclosed in International Publication No. 2015/147192 Gazette or the like is preferable.
Examples of commercially available products include Superflex 126, 130, 150, 170, 210, 420, 470, 820, 830, 890 (urethane-based 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 manufactured by DIC Corporation); 0569, 0850Z, 2108 (styrene resin manufactured by JSR Corporation). Butadiene-based resin emulsion); AE980, AE981A, AE982, AE986B, AE104 (acrylic resin emulsion manufactured by E-Tech Co., Ltd.) and the like can be mentioned.
The polymer content 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%, still more preferably 0.2% to 1. %. With such a content, scratchability, redispersibility, and ejection property become good.

As the wax, a wax emulsion is preferable, and an aqueous wax emulsion is more preferable. As the wax, natural wax and synthetic wax can be used.
Examples of natural waxes include petroleum-based waxes such as paraffin wax and microcrystallin wax; brown charcoal-based waxes such as Montan wax; plant-based waxes such as carnauba wax and canderia wax; animal and plant-based waxes such as beeswax and lanolin. Examples thereof include an emulsion in which wax is dispersed in an aqueous medium.

Examples of the synthetic wax include polyalkylene wax (preferably poly C2-C4 alkylene wax), oxidized polyalkylene wax (preferably poly oxide C2-C4 alkylene wax), and paraffin wax. Among the above, one or more kinds of wax selected from polyethylene wax, polypropylene wax, polyethylene oxide wax, polypropylene oxide wax and paraffin wax are preferable.
The average particle size 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 CERAFLOUR 925, 929, 950, 991; AQUACER498, 515, 526, 513, 537, 359, 552, 1547; AQUAMAT 208, 263, 272; MINERPOL 221 and the like; Mitsui High Wax NL100, NL200, NL500, 4202E, 1105A, 2203A, NP550, NP055, NP505, etc. manufactured by Mitsui Chemicals Co., Ltd .; KUE-100, 11 etc. manufactured by Sanyo Chemicals Co., Ltd. can be mentioned.
Of these, AQUACER 515, 513, 537, 339, 1547 are preferred; AQUACER 515, 513, 537, 1547 are more preferred.
The wax content with respect to the total mass of the ink is usually 0% to 10%, preferably 0% to 8%, more preferably 0% to 5%, still more preferably 0% to 1%. With such a content, scratchability, redispersibility, and ejection property become good.

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, and more preferably 80/20 to 20/. It is 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 in R include linear alkylene groups such as methylene, ethylene, propylene, butylene and pentylene; 1-methyl-1,4-butanjiyl and 2-methyl-1,4-. Butanjiyl, 3-methyl-1,4-butanjiyl, 4-methyl-1,4-butanjiyl, 1-methyl-1,3-propanediyl, 2-methyl-1,3-propanediyl, 3-methyl-1, Examples thereof include 3-propanediyl, 1-methyl-1,2-ethandyl, 2-methyl-1,2-ethandyl 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. Further, in terms of high cleaning performance, R is preferably a branched chain.
In terms of high cleaning performance, (L + m) / n is usually 1.5 / 1 to 1 / 1.5, preferably 1.4 / 1 to 1 / 1.5, and more. It is preferably 1.4 / 1 to 1 / 1.4, and more preferably 1.3 / 1 to 1 / 1.3.
The number average molecular weight of the compound represented by the formula (1) is usually 100 to 5000, preferably 200 to 4000, and more preferably 250 to 3500.
The compound represented by the formula (1) can be synthesized by a known method. It can also be obtained as a commercial product. Specific examples of commercially available products include TEGO Wet 500, 505, 510 and the like manufactured by EVONIC.

[Glycol ether]
The cleaning liquid can contain glycol ether. As the glycol ether, a monoalkyl ether of di or tri-C2-C4 alkylene glycol is preferable.
Examples of the C2-C4 alkylene glycol moiety include ethylene glycol, propylene glycol, and butylene glycol. Among these, ethylene glycol and propylene glycol are preferable, and ethylene glycol is more preferable.
The range of the number of carbon atoms 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 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, and 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 solution is usually 0 to 15%, preferably 0.1 to 15%, more preferably 0.2 to 13%, still more preferably 0.5 to 10%. ..

The cleaning solution contains substantially no colorant. As used herein, "substantially" means that no colorant is intentionally added to the cleaning solution.

The ink and the cleaning liquid may further contain an ink preparation agent in addition to the above-mentioned components. Examples of the ink preparation include an organic solvent, a water-soluble polymer compound, a surfactant, a preservative, a fungicide, a pH adjuster, a chelating reagent, a rust preventive, a water-soluble ultraviolet absorber, an antioxidant, and an extinguishing agent. Examples include foaming agents.
The total content of the ink preparation 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 and the cleaning liquid.

[Organic solvent]
Organic solvents include C1-C6 alkanols having one hydroxy group, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, and third butanol; N, N-dimethylformamide, and N. , N-dimethylacetamide and other amides; 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-methylpyrrolidin-2-one and other lactams; 1,3-dimethylimidazolidine-2-one, and 1, Cyclic ureas such as 3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, 2-methyl-2-hydroxypentane-4-one, and ethylene carbonate; cyclics such as tetrahydrofuran and dioxane. Ether; ethylene glycol, diethylene glycol, 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- Hexadiol, 4,4-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, etc. , Mono, oligo or polyalkylene glycol or thioglycol having C2-C8 alkylene units; polyols (triols) such as glycerin, diglycerin, hexane-1,2,6-triol, trimethylolpropane; γ-butyrolactone, and dimethyl Examples thereof include organic solvents selected from 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 the nonionic polymer compound include polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, gelatin and the like.

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

Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether sulfates, N-acylamino acids or salts thereof, N-acylmethyl taurine salts, and the like. Alkyl Sulfonate Polyoxyalkyl Ether Sulfate, Alkyl Sulfate Polyoxyethylene Alkyl Ether Phosphate, Loginate Soap, Himasi Oil Sulfate Estel, Lauryl Alcohol Sulfate, Alkylphenol Phosphate, Alkyl Phosphate, Alkylaryl Sulfonic Examples thereof include acid salt, diethyl sulfo sulphate, diethyl hexyl sulfo sulphate, dioctyl sulfo sulphate and the like.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly4-vinylpyridine derivatives.

Nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyethylene di. Ether systems such as styrene phenyl ether (for example, Emargen A-60, A-90, A-500 manufactured by Kao Co., Ltd.); polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan mono. Esters such as stearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decine-4,7-diol , 3,6-Dimethyl-4-octin-3,6-diol, 3,5-dimethyl-1-hexin-3-ol and the like acetylene glycol (alcohol) type; polyglycol ether type and the like. Examples of these commercially available products include Surfinol 104, 104PG50, 82, 420, 440, 465, 485 of Nisshin Kagaku Co., Ltd .; Emargen A-60, A-90, A- of Kao Corporation. 500 and the like can be mentioned.

Examples of the amphoteric tenside include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, betaine coconut oil fatty acid amide propyldimethylaminoacetic acid, polyoctylpolyaminoethylglycine, and imidazoline derivatives. Can be mentioned.

Examples of the silicone-based surfactant include polyether-modified siloxane and polyether-modified polydimethylsiloxane. As an example, Dynol 960 and 980 manufactured by Air Products and Chemicals Co., Ltd .; Silface SAG001, SAG002, SAG003, SAG005, SAG503A, SAG008, SAG090, SAG010; and BYK-345 manufactured by Big Chemie Co., Ltd. 347, 348, 349, 3455, LP-X23288, LP-X23289, LP-X23347; TEGO Twin 4000, TEGO Wet KL 245, 250, 260, 265, 270, 280 manufactured by Evonik Tego Chemie.

Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group. Examples thereof include a polyoxyalkylene ether polymer compound contained in.

[Preservative]
Examples of preservatives include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloarylsulfone-based, iodopropagil-based, haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinolin-based, and benzothiazole-based. , Isothiazolin-based, dithiol-based, pyridine oxide-based, nitropropane-based, organic tin-based, phenol-based, tetraammonium salt-based, triazine-based, thiazine-based, anilide-based, adamantan-based, dithiocarbamate-based, brominated indanone-based, benzyl Examples thereof include bromacetate-based or inorganic salt-based compounds.
Specific examples of commercially available preservatives include Proxel GXL (S) and XL-2 (S) manufactured by Arch Chemical.

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

[PH regulator]
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 alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water). Alternatively, alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate and the like can be mentioned.

[Chelating reagent]
Specific examples of the chelating reagent include disodium ethylenediamine tetraacetate, sodium nitrilo triacetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like.

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

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

[Antioxidant]
As an example of the antioxidant, for example, various organic and metal complex-based anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilines, heterocycles and the like. Will be.

[Defoamer]
Examples of the defoaming agent include silicone-based, silica mineral oil-based, olefin-based, and acetylene-based. Examples of commercially available defoaming agents include Surfinol DF37, DF58, DF110D, DF220, MD-20, and Orfin SK-14 manufactured by Shin-Etsu Chemical Co., Ltd.
When a defoaming agent is used, the amount added thereof is usually 0.01 to 5%, preferably 0.03 to 3%, and more preferably 0.05 to 1%. At 0.01% or more, the effect as an antifoaming agent is obtained, and at 5% or less, the dispersion stability is good.

The ink and the cleaning liquid can be contained by selecting one of them for all the components described above. Further, two or more kinds may be selected and contained. For example, the cleaning liquid can be contained by selecting one kind of compound from the compounds represented by the formula (1). Moreover, it is also possible to select and contain two or more kinds of compounds. The same applies to other components.

[Ink application process]
When the ink is used as an ink for inkjet recording, it is recommended to use an ink having a low content of inorganic impurities such as chloride (for example, sodium chloride) and sulfate (for example, sodium sulfate) of metal cations in the ink. preferable. The guideline for 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 or less, that is, 0%.
Inorganic impurities are often mixed in colorants. Therefore, inorganic impurities can be removed as needed. As a purification method thereof, 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, after preparing an ink, exchange and adsorb inorganic impurities with an ion exchange resin. How to do it, etc.

The pH of the ink is usually preferably 7 to 11 and 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 tools, various types of printing, information recording, printing, etc., and is particularly preferably used for inkjet recording.

When the ink is used for inkjet recording, recording can be performed by ejecting droplets of the ink in response to a recording signal and adhering them to a recording medium. The ink nozzle of the inkjet printer, the inkjet method, and the like are not particularly limited and can be appropriately selected according to the purpose.
When performing inkjet recording, the recording can be performed as described above by loading the container containing the ink in a predetermined position of the inkjet printer.

As the inkjet method, a known method can be used. Specific examples of the inkjet method include a charge control method, a drop-on-demand (pressure pulse) method, an acoustic inkjet method, a thermal inkjet method, and the like.
In addition, a method of injecting a large number of inks with a low content of colorant in the ink in a small volume to improve the image quality; image quality using multiple inks having substantially the same hue but different concentrations of the colorant in the ink. A method for improving the fixability of the colorant by using a colorless and transparent ink; and the like are also included.

The recording medium means a substance to which the ink can adhere. Examples of recording media include, for example, paper, film and the like, fibers and cloth (cellulose, nylon, wool, etc.), leather, a base material for a color filter and the like.
The recording medium can be roughly classified into those having an ink receiving layer and those having no ink receiving layer.
The recording medium having an ink receiving layer is usually called an inkjet paper, an inkjet film, glossy paper, or the like. Typical examples of commercial products are professional photo paper, super photo paper, gloss gold and matte photo paper manufactured by Canon Corporation; photo paper Crispia (high gloss) and photo paper (gloss) manufactured by Seiko Epson Corporation. , Photomat paper; Advanced photo paper (glossy) manufactured by Nippon Hulett Packard Co., Ltd .; Colored photo finishing Pro manufactured by Fuji Film Co., Ltd. and the like.

Examples of the recording medium having no ink receiving layer include various types of paper such as coated paper and art paper used for gravure printing and offset printing; cast coated paper used for label printing and the like.
When a recording medium having no ink receiving layer is used, it is also preferable to perform a surface modification treatment on the recording medium for the purpose of improving the fixability of the colorant and the like.

As the surface modification treatment, it is preferable to perform at least one treatment selected from corona discharge treatment, plasma treatment and frame treatment. Known methods can be used for these treatments. It is also generally known that the effects of these treatments diminish over time. Therefore, when the information transmission sheet is subjected to the surface modification treatment, it is preferable to continuously perform inkjet recording without a delay.
The surface modification treatment can be performed by appropriately adjusting the number of treatments, the time, the voltage to be applied, and the like so that a desired effect can be obtained.

The cleaning method is a method of cleaning a recording device to which the ink is attached with the cleaning liquid. As an example of the cleaning method, for example, a method of absorbing the cleaning liquid with a sponge or the like and wiping off the ink adhering to the recording device can be mentioned. The recording device is not particularly limited, but an inkjet printer is preferable.
Further, when the inkjet head is heavily soiled, for example, when the ink adheres to the inkjet head and solidifies due to drying, the inkjet head can be filled with a cleaning liquid for cleaning.
When the inkjet head is filled with the cleaning liquid for cleaning, it is preferable to perform microfiltration of the cleaning liquid for the purpose of removing impurities from the cleaning liquid.
For microfiltration, a membrane filter and / or glass filter paper or the like can be used. The pore size of the filter or the like when performing microfiltration is usually 0.5 μm to 20 μm, preferably 0.5 μm to 10 μm.

The pH of the cleaning liquid is usually pH 5 to 11, preferably pH 7 to 10.5 for the purpose of not corroding the members of the inkjet 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.

For all the above-mentioned matters, the combination of preferable ones is more preferable, and the combination of more preferable ones is further preferable. The same applies to the combination of a preferable one and a more preferable one, a combination of a more preferable one and a more preferable one, and the like.
Further, as for all the above-mentioned components and the like, one of them can be used alone, or two or more of them can be used in combination.

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

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. Further, the cleaning liquid and the colored ink were all prepared under stirring unless otherwise specified.
The "water" used in the examples is ion-exchanged water.

[Preparation Example 1]: Preparation of cleaning solutions 1 to 8 for evaluation test.
Each component shown in Table 1 below is mixed to obtain a total amount of 100 parts of each, and then the obtained liquid is filtered through a 3 μm membrane filter to obtain cleaning liquids 1 to 8 for evaluation test, respectively. rice field.

The abbreviations and the like in Table 1 below have the following meanings. The numerical values in Table 1 are "parts".
Gly: Glycerin 2Py: 2-Pyrrolidone.
BDG: Butyl diglycol.
SN465: Nonion surfactant, Surfinol 465 manufactured by Nisshin Kagaku Co., Ltd.
EP-7025: Nonion surfactant, Softanol EP-7025 manufactured by Nippon Shokubai Co., Ltd.
LS-106: Nonion surfactant manufactured by Kao Corporation, Emargen LS-106.
D-1502: Pionin D-1502, a nonionic surfactant manufactured by Takemoto Oil & Fats Co., Ltd.
D-1305P: Pionin D-1305P, a nonionic surfactant manufactured by Takemoto Oil & Fats Co., Ltd.
TW500: EVONIC nonionic surfactant, TEGO Wet 500.
TW510: EVONIC nonionic surfactant, TEGO Wet 510.
TEA: Triethanolamine.
GXL (S): Proxel GXL (S).

[Preparation Example 2]: Preparation of polymer A to be used as a binder.
25 parts of John Krill 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. The obtained solution is referred to as a polymer A solution.

[Preparation Example 3]: Preparation of dispersion liquid.
The 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 prepare a uniform solution. A solution prepared by dissolving sodium hydroxide (0.4 parts) in water (50.6 parts) was added to this solution, a polymer A solution (4 parts) was added, and 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 a dispersion treatment was carried out in a sand grinder for 15 hours under the condition of 1500 rpm to obtain a liquid. Water (100 parts) was added dropwise to the obtained liquid, and then this 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 from the total solid content in the liquid by a dry weight method using MS-70 manufactured by A & D Co., Ltd. as a conversion value of the pigment content.

[Preparation Example 4] Preparation of polymer B to be used as a binder.
By further testing Preparation Example 4 of the International Publication No. 2015/147192 Gazette, a resin emulsion having an acid value of 6 KOHmg / g, a Tg of 0 ° C., and a solid content of 25% was prepared. This is referred to as "polymer B".

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

The abbreviations and the like 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: Nonion surfactant, Surfinol 465 manufactured by Nisshin Kagaku Co., Ltd.
AQ515: Polyethylene wax manufactured by Big Chemie, AQUACER 515 (solid content 35%).

[Inkjet recording]
The inks obtained in each Example and Comparative Example were filled in a cartridge of PX-205, an inkjet printer manufactured by Seiko Epson Corporation, and inkjet recording was performed on Finesse Matt 115 (coated paper) manufactured by UPM.
Inkjet recording was performed so as to be a solid image of 100% Duty, and a recorded image recorded with the ink of each Example or Comparative Example was obtained. This was used as a test piece and a scratch resistance test was performed.

[Ink scratch resistance test]
The scratchability of each test piece was determined by Yasuda Seiki Seisakusho Co., Ltd., No. 428 Evaluation was performed using a Gakushin type wear tester (friction tester type II). That is, with a load of 500 g applied to the test piece, the inkjet-recorded portion was rubbed 20 times, and the degree of deterioration of the image was evaluated according to the following three evaluation criteria. The results are shown in Table 3 below.
Dry scratchability evaluation criteria:
A: No scratches on the recorded image could be confirmed.
B: A few scratches could be confirmed on the recorded image.
C: The scratches on the recorded image are very large.

[Washing solution stability test]
Each cleaning solution obtained in Adjustment Example 1 was allowed to stand at room temperature for 12 hours, and then the state of the cleaning solution was visually observed to evaluate its stability. The evaluation criteria were the following three stages. 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 components separated from the washing liquid could not be confirmed, but non-uniform parts such as turbidity were observed.
C: It was observed that the liquid component separated from the cleaning liquid floated on the surface of the cleaning liquid.

[Washing property test of cleaning liquid]
20 microliters of the colored ink obtained in Preparation Example 5 was dropped onto a glass petri dish, and the ink was allowed to stand in a constant temperature bath at 60 ° C. for 1 hour to be dried to obtain a solidified ink.
10 ml of each cleaning solution obtained in Preparation Example 1 was added dropwise to the obtained solid material, and whether or not the solid material could be washed was visually evaluated. The evaluation criteria were the following four stages. The 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 matter remained, and the liquid became uniform.
B: Although a slight amount of solid matter remained, the liquid became almost uniform.
C: Clearly, solid matter remained, and it was not recognized as a uniform liquid.
D: The shape of the solid matter 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 "part".

As is clear from the results in Table 3, the cleaning solution of each example has excellent stability of the cleaning solution. In addition, it was confirmed that when the ink that can be recorded on a recording medium with poor ink absorption dries to form solid matter, regardless of whether the ink has good scratch resistance or not, the solid matter can be sufficiently washed. Was done. On the other hand, the cleaning liquids of the comparative examples could not sufficiently clean the solids even when the inks having good scratchability and the poor inks dried to produce solids.

The ink set of the present invention can record on a non-absorbent substrate and has good scratch resistance, and even when the ink dries to form a solid substance, the solid substance is washed. Since it has a cleaning solution that can be used, it is extremely useful as a set of ink and cleaning solution for various recordings, especially for use in inkjet printers.

Claims (7)

Inks containing colorants, binders, and water,
A set of an ink and a cleaning liquid containing a compound represented by the following formula (1) and a cleaning liquid containing water.

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