JP5872144B2 - Water-based inkjet ink - Google Patents

Description

  The present invention relates to an aqueous inkjet ink used for inkjet printing.

  Two major features of the ink jet method are that no plate is produced and that printing can be performed without contact. Examples of advantages of the former include a reduction in cost for plate production and the ability to print different data for each print. An advantage of the latter is that printing can be performed regardless of the surface state of the media and the material.

  Therefore, in recent years, a system that can perform full color and on-demand printing at high speed on various recording media (for example, plain paper, coated paper, art paper, film, plain paper double-sided printing, etc.) using an inkjet recording method. Needs are increasing.

  For example, as a means for executing such a method, a head array with nozzles arranged so as to cross the width of the paper is arranged instead of the shuttle-type printing method currently used in the mainstream, and the paper is below that. There is a line head (one pass) type printing method in which an image is formed only by passing once.

  In the case of this method, a large number of nozzles can be arranged, and the time lag generated by the acceleration / deceleration of folding can be eliminated by the shuttle method, so that printing can be performed at high speed.

  In the case of conventional shuttle printing, maintenance can be performed easily, and defects such as discharge failure and bending can be used in combination with each pass to make it inconspicuous (such as interleaving). It was an easy problem.

  On the other hand, in the case of the line head method, the number of nozzles is large, the number of nozzles to be guaranteed is increased, maintenance is difficult due to the configuration of the device, and technology that disperses discharge defects for each pass cannot be used. It is a problem.

  Aqueous inkjet inks are widely used as inks used in inkjet systems. Such a water-based inkjet ink is a preferable method because water, which is an ink solvent, can be safely evaporated and removed from a printed matter. On the other hand, if it is left at the tip of an inkjet nozzle, the water evaporates and discharge failure (non-discharge) ) And bending problems such as bending occur.

  For this reason, regular maintenance is essential for water-based ink-jet inks, and there is a tendency for the dischargeability guarantee to be low.

  As a method for solving these problems, for example, there is a method for reducing the amount of water in the ink (see, for example, Patent Documents 1 and 2). These solutions have good dischargeability because a solvent that does not damage the discharge remains even when water evaporates, and also solves the problem of plain paper curling, which is another major problem with aqueous inkjet inks.

  However, in these methods, since the solvent remains in the paper, if a large amount of printed material with a high printing rate is piled up immediately after printing, a phenomenon such as blocking is caused, or writing is performed when writing on the printed material with a marker or the like. Effects such as blurring of characters were also observed. In addition, the blocking mentioned here refers to a phenomenon in which the overlapped papers stick together when the papers are stacked and stored. In the case of inkjet printing, the solvent contained in the ink does not dry and remains in the paper in large quantities. It may occur when

  Accordingly, there has been a demand for a water-based inkjet ink that has no curling, has no marker bleeding or blocking, and has good ejection properties.

Japanese Patent Application Laid-Open No. 2001-353962 JP 2005-220296 A

  The problem to be solved by the present invention is to provide an aqueous ink-jet ink that is stable in ejection properties, has no curling, and does not cause a phenomenon such as marker bleeding or blocking of printed matter.

1. And coloring material water-dispersible, and 40 mass% or more water, of 8 wt% to 25 wt% or less, 1200 and smaller diol type polypropylene glycol greater than the average molecular weight of 300, and water wherein the diol type polypropylene glycol A water-based inkjet ink comprising 10% by mass or more of an organic solvent that is compatible and has a boiling point higher than that of water.

  2. 2. The organic solvent is alkylene glycol monoalkyl ether, 1,4-diol having 4 or more carbon atoms, 1,3-diol having 4 or more carbon atoms, or a water-soluble cyclic compound. Water-based inkjet ink.

  3. 2. Said alkylene glycol monoalkyl ether is dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, or triethylene glycol monoethyl ether Water-based inkjet ink.

  4). The 1,2-diol having 4 or more carbon atoms or the 1,3-diol having 4 or more carbon atoms is substituted with 1,2-butanediol, 1,2-pentanediol or 2-methyl-2,4-pentanediol (1, 3. The water-based inkjet ink as described in 3 above, which corresponds to 3-diol.

  5. 5. The aqueous inkjet ink according to any one of 1 to 4, wherein the diol-type polypropylene glycol has an average molecular weight of more than 300 and less than 750.

  According to the present invention, it is possible to provide a water-based inkjet ink with improved ejection reliability, no curling of printed matter after printing, and no problems such as marker bleeding and blocking.

  The present invention relates to an aqueous inkjet ink containing a large amount of water. By using a diol type polypropylene glycol insoluble in water (8% or more) in the ink and coexisting an organic solvent compatible with water. By containing it in a dissolved state with water, it was possible to prevent the dye from precipitating at the nozzle tip, and to prevent problems such as curling and marker bleeding and blocking of the printed matter after printing.

  The improvement in ejection reliability, which is the greatest effect of the present invention, is presumed to be due to the following characteristics of the diol type polypropylene glycol.

The characteristics of the diol type polypropylene glycol having an average molecular weight of more than 300 and less than 1200 are as follows:
1) Hydrophobic with water solubility of about 5% 2) Low viscosity compared to molecular weight, difficult to thicken even when mixed with water 3) High boiling point, high molecular weight and difficult to evaporate Therefore, even if water or other solvent evaporates, it remains in the vicinity of the nozzle, so it seems that the nozzle tip is covered with a polypropylene glycol (oil) layer to prevent evaporation of the ink solvent. .

  Since the diol type polypropylene glycol is dissolved in water in a small amount, it can be contained in the ink in a dissolved state by using it together with an organic solvent in order to suppress evaporation from the nozzle. In the vicinity of the nozzle interface, the (oil) layer of diol-type polypropylene glycol does not exist in a form separated from the ink, and a continuous concentration gradient through the solvent without forming an interface from the polypropylene glycol layer on the surface to the ink at the back of the nozzle It is considered to have. For this reason, the water-dispersible colorant in the ink (usually concentrated and present by evaporation of the ink solvent near the nozzle) easily moves from the oil layer near the nozzle to the ink side where it can exist stably. It is assumed that the nozzle can be prevented from being clogged with the concentrated color material.

  The diol type polypropylene glycol has a low viscosity relative to the molecular weight, does not increase in viscosity even when mixed with water, and serves as an advantageous point for ejection.

  Furthermore, the diol type polypropylene glycol can simultaneously achieve performance after printing (for example, curling and marker bleeding). This is because it has a large molecular weight and has hydroxyl groups at both ends, so it can exist stably in paper (cellulose), and even if it remains in paper, it does not adversely affect the printed matter (such as curling and blocking). I guess that.

  Hereinafter, the present invention will be described in more detail.

<Water content>
The ink-jet ink of the present invention contains 40% by mass or more of water. By setting the water content to 40% by mass or more and further setting the diol type polypropylene glycol to 8% by mass or more and 25% by mass or less, the amount of the organic solvent that adversely affects the printed matter can be suppressed to a low range. As a result, it is possible to greatly suppress the problems caused by the solvent remaining after printing. A more preferable water content is 50% by mass or more.

  When the water content is less than 40% by mass, problems such as a phenomenon that the marker bleeds and blocking occur. Therefore, the water content needs to be 40% by mass or more, and preferably 50% by mass or more. On the other hand, since it becomes more difficult to maintain ejection stability as the amount of water increases, it is preferably 75% by mass or less, although it depends on the amount of solids contained in the ink.

<Diol type polypropylene glycol>
The diol type polypropylene glycol of the present invention is obtained by anion ring-opening polymerization reaction of propylene oxide. The polymerization initiator is an alcohol and a catalytic amount of a base. Usually, potassium hydroxide is used as the base, and ethylene glycol or water is used as the alcohol. In addition to this, there is a polyprene glycol obtained by polymerizing propylene glycol with glycerin called triol type polypropylene glycol (PPG (T)), but these are compatible with water and have high viscosity. It was difficult to obtain and was found to be undesirable.

  The average molecular weight of the diol type polypropylene glycol of the present invention needs to be larger than 300. Polypropylene glycol with an average molecular weight smaller than this (for example, the molecular weight of single propylene glycol is 250 and the molecular weight of tripropylene glycol is 192) is too high in water solubility, which is the same as ordinary solvents. Only the effect of improving the discharge stability can be obtained. In particular, tripropylene glycol and the like are not preferable because a phenomenon called minus curl in which the printed matter curls with the printing surface convex after printing occurs.

  The average molecular weight of the diol type polypropylene glycol of the present invention is smaller than 1200. If the average molecular weight exceeds 1200, the solubility in water becomes small, making it difficult to produce ink. Particularly preferably, it is larger than 300 and smaller than 750. In this range, solubility in water is also preferable, and prescription design is easy to perform, so that the effects of the present invention are easily exhibited.

  The average molecular weight of the diol type polypropylene glycol used in the present invention is a weight average molecular weight obtained based on polystyrene by gel permeation chromatography (GPC).

<Amount of diol type polypropylene glycol>
In order to obtain the effects of the present invention, the diol type polypropylene glycol is contained in an amount of 8% by mass to 25%. By making it in the above-mentioned range, the effect of ejection stability can be sufficiently obtained. More preferably, it is more than 15% by mass and 25% by mass or less. In this range, the ink design is easy to perform, the ejection stability is improved, the marker bleeding is suppressed, and the curling of the printed matter is also suppressed. .

<Organic solvent>
The organic solvent used in the present invention is a solvent for compatibilizing water and diol type polypropylene glycol. From the nature, it is preferable that the solvent is compatible with water and has a certain degree of hydrophobicity.

  Moreover, it is necessary to have a boiling point higher than water. If a solvent having a boiling point lower than that of water is used, only the diol-type polypropylene glycol and water will be generated near the nozzle, which may cause liquid separation. Will be reduced. In order to form a diol type polypropylene glycol layer near the nozzle, it is preferable to use a solvent having a higher vapor pressure than the polypropylene glycol used.

  Examples of such organic solvents include alkylene glycols, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, alkylene glycol monoesters, 1,2- or 1,3-diols, cyclic ethers, cyclic Examples thereof include esters and cyclic nitrogen compounds.

  Preferred examples include alkylene glycol monoalkyl ethers, 1,4-diols having 4 or more carbon atoms, 1,3-diols having 4 or more carbon atoms, and water-soluble cyclic compounds. When these compounds are used, the ejection stability is high and the amount of the organic solvent in the ink is not increased, so that the quality of the printed material is easily maintained.

  Among these solvents, as alkylene glycol monoalkyl ethers, particularly preferred solvents include, for example, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol mono Examples of 1,2-diols or 1,3-diols having 4 or more carbon atoms, such as ethyl ether and 3-methyl-3-methoxybutanol, include 1,2-hexanediol, 1,2-butanediol, Examples of 1,3-diols having 4 or more carbon atoms such as 1,2-pentanediol include 2-methyl-2,4-pentanediol (corresponding to 1,3-diol) and the like. For example, N-methyl Pyrrolidone, dioxane, tetrahydrofuran, 2-pyrrolidinone, and the like.

  The amount of such a solvent is preferably more than 10% by mass, and preferably 35% by mass or less. When the content is more than 10% by mass, the diol type polypropylene glycol is easily dissolved in water, and a solvent design that does not adversely affect the printed matter can be easily performed. When the amount of the solvent is 35% by mass or less, bleeding of characters when writing with a marker on the printed matter is suppressed.

  Among the above solvents, (poly) ethylene glycol monoalkyl ethers and (poly) propylene glycol monoalkyl ethers are particularly good ejection stability and are less likely to cause curling of printed matter.

  On the other hand, 1,2-hexanediol is a solvent having a high effect of compatibilizing water and a diol type polypropylene glycol in a small amount, but is a solvent that easily causes minus curl when remaining in a large amount in paper. Therefore, an alkylene glycol monoether selected from dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, using a small amount of 1,2-hexanediol. In combination with the above, it is possible to formulate an ink formulation that does not have a problem with the quality of the printed matter.

  3-Methyl-3-methoxybutanol, 1,2-butanediol, 1,2-pentanediol, 2-methyl-2,4-pentanediol and the like have the performance as an organic solvent to be used alone and are used alone However, the amount of the solvent can be relatively suppressed, and the use of these solvents is also preferable. Of course, 1,2-hexanediol is added to 3-methyl-3-methoxybutanol, 1,2-butanediol, 1,2-pentanediol and 2-methyl-2,4-pentanediol as necessary. It doesn't matter.

<Water dispersible colorant>
The ink of the present invention contains a water-dispersible color material.

  A water-dispersible color material is a color material that is insoluble in the solvent constituting the ink-jet ink and forms a dispersion containing fine pigment particles, or a color composed of a dispersion of a polymer polymer colored with the colorant. Material.

  As the hue of the colorant used in the present invention, for example, yellow, magenta, cyan, black, blue, green, and red are preferably used, and yellow, magenta, cyan, and black are particularly preferable.

  In addition, for oil-soluble dyes that form colored fine particles together with polymers and become colorants, dyes that are soluble in organic solvents that do not have water-soluble groups such as carboxylic acids and sulfonic acids and are insoluble in water, such as disperse dyes Etc. are selected. Also included are dyes that exhibit oil solubility by salting water-soluble dyes with long-chain bases, such as acid dyes, direct dyes, salt-forming dyes of reactive dyes and long-chain amines, etc. it can.

<Pigment>
In the ink of the present invention, it is preferable to use a pigment as the colorant, and a pigment having no solubility in the solvent system is preferable from the viewpoint of exhibiting the object effect of the present invention.

  As the pigment that can be used in the present invention, conventionally known pigments can be used without particular limitation, and any of water-dispersible pigments, solvent-dispersible pigments, and the like can be used, for example, organic pigments such as insoluble pigments and lake pigments, An inorganic pigment such as carbon black can be preferably used.

  The insoluble pigment is not particularly limited, for example, azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, Dioxazine, thiazole, phthalocyanine, diketopyrrolopyrrole and the like are preferable.

  Specific pigments that can be preferably used include the following pigments.

  Examples of the magenta or red pigment include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the pigment for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 15: 3, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 94, C.I. I. And CI Pigment Yellow 138.

  Examples of the pigment for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

  In addition to the above, when red, green, blue and intermediate colors are required, the following pigments are preferably used alone or in combination. I. Pigment red 209, 224, 177, 194, C.I. I. Pigment orange 43, C.I. I. Bat Violet 3, C.I. I. Pigment violet 19, 23, 37, C.I. I. Pigment green 36, 7, C.I. I. Pigment Blue 15: 6, etc. are used.

  Examples of black pigments include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7 and the like.

  The pigment used in the present invention is preferably used after being dispersed by a disperser together with a dispersant and other necessary additives according to various desired purposes. As the disperser, a conventionally known ball mill, sand mill, line mill, high-pressure homogenizer, or the like can be used.

  The average particle size of the pigment dispersion used in the ink of the present invention is preferably 10 nm to 200 nm, more preferably 10 nm to 100 nm, and still more preferably 10 nm to 50 nm. When the average particle size of the pigment dispersion exceeds 100 nm, the dispersion becomes unstable, and even when the average particle size of the pigment dispersion is less than 10 nm, the stability of the pigment dispersion tends to deteriorate, and the storage stability of the ink Tend to deteriorate.

  The particle size of the pigment dispersion can be determined by a commercially available particle size measuring device using a light scattering method, an electrophoresis method, a laser Doppler method or the like. It is also possible to obtain a particle image with a transmission electron microscope on at least 100 particles and perform statistical processing on the image using image analysis software such as Image-Pro (manufactured by Media Cybernetics). Is possible.

  In the aqueous inkjet ink of the present invention, a surfactant can be used as an additive during dispersion. As the surfactant used in the present invention, any of cationic, anionic, amphoteric and nonionic can be used.

  Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

  Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, acylated peptide, alkyl sulfonate, Alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate, secondary higher alcohol Sulfate ester, alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene alkyl phenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether phosphate ester, alkyl phosphate ester Examples include tellurium salts.

  Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like.

  Nonionic activators include polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, Oxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene Fatty acid amide, polyoxyethylene alkylamine, alkylamine oxide, acetyl Glycol, acetylene alcohol, and the like.

<Fixing resin>
The aqueous inkjet ink of the present invention preferably contains a fixing resin in order to obtain rub resistance after printing. In particular, ink containing a resin tends to have poor ejection stability. However, the ejection stability can be improved by employing the configuration of the present invention.

  The fixing resin may be water-soluble or water-dispersible. Specific examples of the resin include polyurethane resin, polyethylene resin, polystyrene resin, polyacrylic acid resin, polymethacrylic acid resin, vinyl chloride resin, modified polyvinyl alcohol resin, polymaleic acid resin, polypyrrolidone resin, polyester resin, or these And modified copolymers thereof, and copolymers thereof.

  These resins are preferably neutralized with some base, and particularly preferably neutralized with an amine compound.

  Moreover, you may have a modification group, a crosslinking group, etc. as needed.

  The resin content is not particularly limited as long as the constitution of the present invention is not impaired, but is preferably 1% by mass or more and 10% by mass or less from the viewpoint of the viscosity that can be discharged and the fixing effect.

<Others>
In the aqueous inkjet ink of the present invention, the total content of calcium ions, magnesium ions and iron ions, which are polyvalent metal ions, is preferably 10 ppm or less, more preferably 0.1 to 5 ppm, particularly preferably. Is 0.1-1 ppm.

  By setting the content of the polyvalent metal ion in the aqueous inkjet ink to the amount specified above, an ink having high dispersion stability can be obtained.

  In the water-based inkjet ink of the present invention, in addition to the above description, if necessary, according to the purpose of improving the emission stability, print head and ink cartridge compatibility, storage stability, image storage stability, and other various performances, Various known additives such as polysaccharides, viscosity modifiers, specific resistance modifiers, film forming agents, ultraviolet absorbers, antioxidants, anti-fading agents, anti-fouling agents, rust preventives and the like are appropriately selected and used. For example, oil droplet fine particles such as liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, and ultraviolet absorbers described in JP-A Nos. 57-74193, 57-87988 and 62-261476 JP-A-57-74192, JP-A-57-87989, JP-A-60-72785, JP-A-61-146591, JP-A-195091 and JP-A-3-1. 376 and the like, described in JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-228771 and JP-A-4-219266. An optical brightener or the like can be used.

<Inkjet head>
In the image forming method using the water-based ink-jet ink of the present invention, for example, an ink-jet print is obtained by ejecting ink as droplets from an ink-jet head based on a digital signal and attaching the ink to a medium with a printer loaded with ink-jet ink. It is done.

  When forming an image by ejecting the ink-jet ink of the present invention, the ink-jet head used may be an on-demand system or a continuous system. In addition, as a discharge method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion method (for example, thermal ink jet) Any ejection method such as a mold, a bubble jet (registered trademark) mold, or the like may be used.

  In addition, the present invention is useful when printing is performed using a line head type recording head, but the same effect can be achieved in a shuttle type printing method.

  The line head type ink jet head refers to an ink jet head having a length equal to or greater than the width of the printing range. As a line head type inkjet head, one head may be larger than the width of the printing range, or a combination of a plurality of heads as disclosed in Japanese Patent Application Laid-Open No. 2007-320278 may exceed the width of the printing range. It may be configured.

<Ink physical properties for inkjet>
In the ink-jet ink of the present invention, the surface tension of the ink is preferably 20 to 40 mN / m at 25 ° C., more preferably 20 to 35 mN / m, and still more preferably 22 to 35 mN / m. The ink viscosity is preferably 1 to 40 mPa · s at 25 ° C., more preferably 5 to 40 mPa · s, and still more preferably 5 to 15 mPa · s. Further, the dissolved oxygen concentration in the ink-jet ink of the present invention is preferably 2 ppm or less at 25 ° C. By setting this dissolved oxygen concentration condition, the formation of bubbles can be suppressed, and emission is also possible in high-speed printing. An ink jet recording method having excellent stability can be realized. As a method for measuring the dissolved oxygen dissolved in the ink, for example, it can be measured using a dissolved oxygen measuring device DO-14P (manufactured by Toa Radio).

<Printed coated paper>
The recording medium used in the present invention is not particularly limited, but non-coated paper, special printing paper, and non-coated paper belonging to a part of information paper, and white pigment and starch or rubber latex on the paper surface. It is desirable to use a printing coated paper having a coating layer.

  The composition of the non-coated paper according to the present invention is mainly made by chemical pulp, sizing agent and filler represented by LBKP and NBKP, and other paper making aids are used as necessary, and paper is made by a conventional method. As the pulp material used for the plain paper according to the present invention, mechanical pulp and recycled paper recycled pulp may be used in combination, and there is no problem even if these are used as the main material.

  The configuration of the coated paper according to the present invention is such that a coating layer containing a white pigment made of kaolin, calcium carbonate, etc., and starch, SB latex, etc. as a binder is provided on the non-coated paper.

The paper thickness and wrinkle amount are preferably 50 g / m ² to 360 g / m ² .

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

Example 1
<Preparation of pigment dispersion>
15 parts by mass of MA100 (manufactured by Mitsubishi Chemical Corporation) as a pigment, 33 parts by mass of Jonkrill 501 (manufactured by BASF, 30% aqueous resin content) as a dispersion resin, and 5 parts by mass of triethylene glycol monobutyl ether (TEGMBE) And 47 parts by mass of water were mixed together, and placed in a polypropylene plastic bottle together with 200 g of zirconia beads having a diameter of 0.5 mm, and sealed with a paint shaker for 5 hours. A black pigment dispersion having a pigment concentration of 15% Got.

<Preparation of ink>
The diol type polypropylene glycol (PPG) of the present invention or a comparative compound and a solvent, and a fixing resin solution so as to have the composition shown in Table 1 with respect to 20 parts by mass of the pigment dispersion, Joncrill J70 (manufactured by BASF, 30% resin content aqueous solution) ) 8.3 parts by mass and, if necessary, 0.2 part by mass of Olfine E1010 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an activator are mixed and adjusted to 100 parts by mass with water. After filtration with a 3500 mesh metal filter, membrane deaeration treatment using a hollow fiber membrane was performed, and inks of Examples 1 to 13 and Comparative Examples 1 to 11 were produced.

  For each ink composition, the PPG amount, comparative compound amount, each solvent amount, solid content, and total water content (water content) are shown in Table 2. The amount added or the numerical value of each item represents mass%.

  The compounds used are shown below.

[Diol type polypropylene glycol]
PPG400: Diol type polypropylene glycol # 400
(Wako Pure Chemical Industries, Ltd. average molecular weight 400)
PPG700: Diol type polypropylene glycol # 400
(Wako Pure Chemical Industries, Ltd. average molecular weight 700)
PPG1000: Diol type polypropylene glycol # 1000
(Wako Pure Chemical Industries, Ltd. average molecular weight 1000)
PPG (T): Triol type polypropylene glycol: Sannix GP400
(Meano Chemical Industries, Ltd. average molecular weight 400)
PPG3000: Diol type polypropylene glycol # 3000
(Wako Pure Chemical Industries, Ltd. average molecular weight 3000)
[Other solvents and abbreviations]
PEG400: Polyethylene glycol # 400
DEGEE: Diethylene glycol diethyl ether (boiling point 189 ° C)
2HD: 1,2-hexanediol (boiling point 223 ° C.)
DPGME: Dipropylene glycol methyl ether (boiling point 190 ° C)
TPGME: Tripropylene glycol methyl ether (boiling point)
TEGME: Triethylene glycol methyl ether (boiling point 249 ° C)
TEGEE: Triethylene glycol ethyl ether (boiling point 256 ° C)
2PDN: 2-pyrrolidinone (boiling point 242 ° C.)
3Mt3MtOBuOH: 3-methyl-3-methoxybutanol (boiling point 173 ° C.)
TEGMBE: Triethylene glycol monobutyl ether (boiling point 278 ° C.)
2Mt2,4PeDO: 2-methyl-2,4-pentanediol (197.5 ° C.)
IPA: i-propyl alcohol (boiling point 82.4 ° C.)
[Evaluation]
Each ink was evaluated as follows.

<Discharge stability evaluation>
A piezo inkjet head having a nozzle diameter of 22 μm and a nozzle number of 512 was filled with the inks of Examples 1 to 13 and Comparative Examples 1 to 11. Although each ink has a different viscosity, the drive voltage at the time of ejection was adjusted so that each ink had a droplet amount of 7 pl. In this state, after discharging continuously from all nozzles for 1 minute, stop discharging all nozzles at the same time, and after 2 hours have passed, perform continuous emission from all nozzles again for 1 minute, then all nozzles all at once. The operation was carried out under the condition that the discharge was stopped, the mixture was left for 10 hours and then continuously emitted from all the nozzles for 1 minute again. The environment at this time was performed under a constant condition of 23 ° C. and 50% RH. The following ranking was performed from the time when one nozzle out of 512 nozzles caused ejection failure.

◎: More than 10 hours ○: More than 2 hours and less than 10 hours ×: Less than 2 hours <Curl evaluation>
A new NPI (made by Oji Paper Co., Ltd.) with a weight of 79.1 g / m ² cut into A5Y eyes is adsorbed to an adsorption plate, and each ink is applied to the entire surface of the paper with a # 3 wire bar, and 15 seconds with a dryer. Drying was performed. Then, it removed from the adsorption | suction board and measured the standup | rising of the edge part of the paper piece 1 week after that.

  The suction disk used at this time is a plate having a large number of air suction holes on one side, and the paper can be sucked by negative pressure by sucking air from the suction holes.

A: Rising edge of the paper is less than 3 mm on average ○: Rising edge of the paper is on average 3 mm or more and less than 7 mm ×: Rising edge of the paper is on average 7 mm or more, or the center of the paper surface It has an arch-shaped projection of 7 mm or more.

<Evaluation of blocking>
Prepare 100 sheets of new NPI (made by Oji Paper Co., Ltd.) with a weight of 79.1 g / m ² cut by A5Y and coated with ink with # 3 wire bar and dried for 10 seconds with a dryer. After stacking, they were stored in a plastic bag for a week. The case where blocking occurred after 1 week was indicated as x, and the case where no blocking was indicated as ◯.

<Evaluation of marker blur>
Marker bleeding was evaluated simultaneously with the evaluation of the blocking. In the blocking evaluation, a line was written with oily magic (Mackey (Zebra Co., Ltd.)) on the 30th sheet from the top, and the following evaluation was performed after storage for one week.

◎: No particular change ○: Some line thickening is observed ×: Set off to the back of the 29th sheet. Or it is blurred.

  It shows in Table 3 about each evaluation result.

  Based on the above results, according to the configuration of the present invention, it is possible to obtain an ink that has good ejection stability and can perform printing with no problem in the quality of the printed matter.

Claims (5)

And coloring material water-dispersible, and 40 mass% or more water, of 8 wt% to 25 wt% or less, 1200 and smaller diol type polypropylene glycol greater than the average molecular weight of 300, and water wherein the diol type polypropylene glycol A water-based inkjet ink comprising 10% by mass or more of an organic solvent that is compatible and has a boiling point higher than that of water.   The organic solvent is alkylene glycol monoalkyl ether, 1,2-diol having 4 or more carbon atoms, 1,3-diol having 4 or more carbon atoms, or a water-soluble cyclic compound. The water-based inkjet ink of description.   3. The alkylene glycol monoalkyl ether is dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, or triethylene glycol monoethyl ether. The water-based inkjet ink of description.   The 1,2-diol having 4 or more carbon atoms or the 1,3-diol having 4 or more carbon atoms is substituted with 1,2-butanediol, 1,2-pentanediol or 2-methyl-2,4-pentanediol (1, The water-based inkjet ink according to claim 3, which corresponds to 3-diol.   5. The water-based inkjet ink according to claim 1, wherein the diol-type polypropylene glycol has an average molecular weight of more than 300 and less than 750. 6.