WO2022118519A1 - Encre noire pour jet d'encre et ensemble d'encres - Google Patents

Encre noire pour jet d'encre et ensemble d'encres Download PDF

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Publication number
WO2022118519A1
WO2022118519A1 PCT/JP2021/033567 JP2021033567W WO2022118519A1 WO 2022118519 A1 WO2022118519 A1 WO 2022118519A1 JP 2021033567 W JP2021033567 W JP 2021033567W WO 2022118519 A1 WO2022118519 A1 WO 2022118519A1
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Prior art keywords
pigment
ink
inkjet ink
resin
organic solvent
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PCT/JP2021/033567
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English (en)
Japanese (ja)
Inventor
真由子 速水
雄司 亀山
真広 杉原
良介 矢吹
睦子 正時
Original Assignee
東洋インキＳｃホールディングス株式会社
トーヨーカラー株式会社
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Publication of WO2022118519A1 publication Critical patent/WO2022118519A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to a black inkjet ink and an ink set containing the black inkjet ink.
  • the inkjet printing method is a method in which minute droplets of ink are ejected onto a recording medium from a very fine nozzle in an inkjet head and landed to form an image or a character (hereinafter, an image and / or). Recording media on which characters are recorded are collectively referred to as "printed matter").
  • the inkjet printing method is superior to other printing methods in terms of the size and cost of the printing device, the running cost at the time of printing, the ease of full-color printing, and the like, and is widely used. Further, with the remarkable improvement in the performance of the inkjet head in recent years, it is expected that the inkjet printing method will be developed in the industrial printing market where the offset printing method has been conventionally used.
  • the inkjet ink permeates inside the high-absorbency recording medium and the print density decreases, or the inkjet ink droplets on the low-absorbency recording medium are combined with each other.
  • problems such as deterioration of image quality occur. Therefore, in general, after printing the inkjet ink, the action of drying the inkjet ink on the recording medium is taken. At that time, from the viewpoint of downsizing of the printing apparatus and speeding up of printing, an infrared drying method and a hot air drying method are often used as the drying method. Therefore, in order to promote the spread and development of the inkjet printing method, it is required to provide an inkjet ink suitable for any of these drying methods.
  • Patent Document 1 proposes an inkjet ink using a self-dispersing pigment.
  • Patent Documents 2 to 3 disclose an inkjet ink in which a self-dispersed pigment and a pigment dispersed using a pigment-dispersed resin (resin-dispersed pigment) are used in combination.
  • the density of the obtained printed matter can be lowered depending on the recording medium used and the drying method after printing.
  • the inkjet ink described in Patent Document 1 is inferior in print density when printed on a low absorption recording medium
  • the inkjet ink described in Patent Documents 2 to 3 is printed on a low absorption recording medium and dried by infrared rays.
  • the method was used, there was a problem that sufficient print density was not obtained.
  • the inkjet ink described in Patent Document 2 has a problem that the printed matter printed on a low-absorption recording medium is inferior in scratchability, and the inkjet ink described in Patent Document 3 has poor ejection stability from an inkjet head. , There is a further problem.
  • the present invention has been made to solve the above-mentioned problems, and an object thereof is to have high print density regardless of the type of recording medium and the drying method, scratchability of printed matter, and ink jet ejection stability. Is also to provide excellent black inkjet inks. Another object of the present invention is to provide an ink set containing the black inkjet ink, which is excellent in image quality of printed matter in addition to the above.
  • the present invention is a black inkjet ink containing water, a pigment, an organic solvent, and a wax.
  • the pigment contains a self-dispersed pigment and a resin-dispersed pigment.
  • the present invention relates to a black inkjet ink in which the content of the organic solvent is 29% by mass or less in the total amount of the black inkjet ink.
  • the present invention also relates to the above black inkjet ink in which the P value defined by the following general formula (1) is 1.6 or less.
  • i represents the type of the organic solvent contained in the black inkjet ink
  • b i represents the boiling point (° C.) of the organic solvent i under 1 atm
  • c i Represents the content (% by mass) of the organic solvent i with respect to the total amount of the black inkjet ink
  • s i represents the static surface tension (mN / m) of the organic solvent i at 25 ° C.
  • n represents the content. Represents the number of types of organic solvents to be used.
  • the present invention also relates to the black inkjet ink in which the wax contains a polyolefin wax.
  • the present invention further contains resin particles as a binder resin, and the present invention further comprises resin particles.
  • the black inkjet contains one or more resin particles selected from the group consisting of acrylic resin particles, styrene acrylic resin particles, urethane resin particles, styrene butadiene resin particles, and vinyl chloride resin particles. Regarding ink.
  • the present invention further relates to the above-mentioned black inkjet ink, which further contains a water-soluble resin as a binder resin.
  • the present invention also comprises a surfactant, which further comprises.
  • the present invention relates to the above-mentioned black inkjet ink, wherein the surfactant contains a surfactant having an HLB value of 10 or less.
  • the present invention also relates to the black inkjet ink in which the content of the organic solvent having a boiling point of 250 to 300 ° C. under 1 atm is 9% by mass or less in the total amount of the black inkjet ink.
  • the present invention is an ink set including black inkjet ink, cyan inkjet ink, magenta inkjet ink, and yellow inkjet ink.
  • the black inkjet ink is the black inkjet ink.
  • the cyan inkjet ink, the magenta inkjet ink, and the yellow inkjet ink each contain water, a pigment, and an organic solvent, and the amount of the organic solvent having a boiling point of 250 to 300 ° C. at 1 atm is 5 mass. % Or less, related to ink sets.
  • the black inkjet ink of the present invention (hereinafter, also simply referred to as “ink”) will be described with reference to preferred embodiments.
  • the "aqueous medium” means a medium composed of at least a liquid containing water.
  • the black inkjet ink of the present invention contains water, a self-dispersing pigment, a resin-dispersed pigment, an organic solvent, and a wax.
  • a method such as increasing the pigment concentration in the ink or using a self-dispersing pigment is adopted.
  • the pigment concentration is increased, there may be a problem that the ejection stability from the inkjet head is deteriorated.
  • the self-dispersing pigment is used, it is not possible to obtain a desired print density because the wet spread on a low-absorbing recording medium such as coated paper is poor.
  • the dispersion of the self-dispersing pigment may be broken and the ejection stability may be deteriorated. There is sex.
  • the pigment (resin-dispersed pigment) dispersed in the ink using the pigment-dispersed resin has excellent stability against the above-mentioned organic solvent and surfactant, and is suitable for improving the print density for a low-absorption recording medium. It can be said that it is a material.
  • the pigment dispersion resin by using the pigment dispersion resin, the viscosity of the microscopic ink becomes large, which may adversely affect the ejection stability. Further, although the detailed reason is unknown, the ink containing only the resin dispersion pigment has a problem that the print density is inferior to that of the high-absorbency recording medium.
  • the drying method of the inkjet printing method a method of directly or indirectly contacting the ink with a heat source (heat drying method, hot air drying method, drum drying method, etc.) and a method of irradiating electromagnetic waves (infrared rays). Drying method, microwave drying method, ultraviolet drying method, etc.) are known.
  • the printing density tends to increase in proportion to the pigment density blended in the ink.
  • components such as pigments contained in the ink absorb electromagnetic waves and generate heat, so that the aqueous medium (water and organic solvent) volatilizes from the inside of the ink.
  • the combined use of the self-dispersion pigment and the resin dispersion pigment is indispensable.
  • the ink needs to contain an organic solvent.
  • the dispersion of the self-dispersing pigment may be broken.
  • the specific heat of the organic solvent used in the ink is smaller than the specific heat of water. Therefore, if the amount of the organic solvent in the ink is too large, the heat source is directly or indirectly brought into contact with the ink.
  • the present invention by setting the amount of the organic solvent to 29% by mass or less in the total amount of the ink, a high printing density is maintained regardless of the drying method, the dispersion stability of the self-dispersed pigment is enhanced, and the inkjet ejection stability is improved. Furthermore, the scratch resistance of the printed matter is improved.
  • the ink of the present invention also contains wax. It is generally known that adding wax to an inkjet ink improves the scratch resistance of printed matter. However, the present inventors have found that not only the scratch resistance of the printed matter but also the print density and the inkjet ejection stability are improved.
  • the printing density may decrease depending on the drying method selected.
  • the wax melts without being decomposed or volatilized during drying and remains so as to cover the surface of the print layer, so that a printed matter having a high print density can be obtained. Be done.
  • the presence of wax around the self-dispersing pigment prevents the organic solvent from interfering with the self-dispersing pigment, and the wax existing around the resin-dispersed pigment prevents the pigment from interfering with the self-dispersing pigment.
  • the ink ejection stability is improved by inhibiting the network that can be formed between the dispersed resin molecules and suppressing the slight increase in the viscosity of the ink.
  • the composition of the ink of the present application is indispensable.
  • the self-dispersing pigment is a pigment that can be dispersed in an aqueous medium without using a dispersant such as a pigment-dispersing resin or a surfactant for pigment dispersion, and is self-dispersing. It is the pigment that has been surface-treated to impart properties.
  • a single type or a plurality of types may be used in combination.
  • achromatic color refers to a color having no hue and saturation and is represented only by lightness
  • chromatic color refers to a color other than achromatic color.
  • black pigment for example, black organic pigments such as aniline black, perylene black and azo black, and black inorganic pigments such as carbon black, triiron tetroxide and copper chrome black can be used. .. In the present invention, it is preferable to use carbon black from the viewpoints of high blackness and colorability, the fact that a printed matter having a high print density can be obtained even with a small amount of addition, and easy availability.
  • the carbon black used in the self-dispersing pigment is not particularly limited, and an example is described below, but the carbon black is not limited thereto.
  • the carbon black is not limited thereto.
  • the classification according to the molecular structure there are amorphous carbon, graphite, carbon nanotubes and the like, and any of them can be used.
  • self-dispersed carbon black on the surface of carbon black, at least one functional group selected from a carboxyl group, a carbonyl group, a hydroxyl group, a sulfone group, a phosphoric acid group, a phenyl group, a quaternary ammonium and salts thereof.
  • a functional group selected from a carboxyl group, a carbonyl group, a hydroxyl group, a sulfone group, a phosphoric acid group, a phenyl group, a quaternary ammonium and salts thereof.
  • those introduced by chemical bonding directly or via other functional groups can be mentioned.
  • the type and amount of the functional group are appropriately determined in consideration of the dispersion stability, print density, ejection stability, drying property, etc. of the self-dispersed carbon black in the ink.
  • an anionic functional group as the functional group in that a printed matter having a particularly high print density can be obtained.
  • the anionic functional group include a carboxyl group, a carbonyl group, a hydroxyl group, a sulfone group, a phosphoric acid group, and a functional group selected from salts thereof.
  • the functional group contains a group selected from a carboxyl group, a carbonyl group, and a hydroxyl group.
  • Examples thereof include a chemical treatment method according to the above method, a functional group or a chemical treatment method by a graft reaction using a molecule containing a functional group, and the like.
  • Japanese Patent Application Laid-Open No. 8-3498 Japanese Patent Application Laid-Open No. 2003-96372, Japanese Patent Application Laid-Open No. 2000-513396, Japanese Patent Application Laid-Open No. 2008-524400, Japanese Patent Application Laid-Open No. 2009-515007, Japanese Patent Application Laid-Open No. 2011-515535 It can be obtained by the method described in Japanese Patent Application Laid-Open No. 2018-70815 and the like.
  • a commercially available product may be used as the self-dispersing pigment.
  • Examples of the commercially available products include CAB-O-JET series manufactured by Cabot Corporation, BONJET series manufactured by Orient Chemical Industry Co., Ltd., Aqua-Black series manufactured by Tokai Carbon Co., Ltd., and Fuji-JET Black series manufactured by Fuji Dye Co., Ltd. Be done.
  • the average secondary particle size of the self-dispersing pigment is, for example, preferably 30 nm to 200 nm, more preferably 50 nm to 170 nm, and particularly preferably 80 nm to 150 nm.
  • the average secondary particle diameter (D50) is measured by a dynamic light scattering method using a particle size distribution measuring machine (in the present specification, Nanotrack UPAEX-150 manufactured by Microtrac Bell). Represents a volume-based median diameter.
  • the self-dispersing pigment is preferably contained in an amount of 0.5 to 10% by mass, more preferably 1 to 8% by mass, and particularly preferably 2 to 7% by mass in the total amount of the ink.
  • the resin-dispersed pigment is a pigment in which at least a part of the surface is covered with a pigment-dispersed resin and can be dispersed in an aqueous medium.
  • the pigment contained in the resin-dispersed pigment is different from the self-dispersed pigment described above, and a pigment-dispersed resin is required as a dispersant for dispersing the pigment.
  • the example of the pigment contained in the resin dispersion pigment is the same as the case of the self-dispersion pigment.
  • carbon black is used because it has high blackness and colorability, and a printed matter having a high print density can be obtained on both a high-absorbency recording medium and a low-absorbency recording medium, and it is easy to obtain.
  • the primary particle size of carbon black is preferably 11 to 40 nm, more preferably 11 to 30 nm.
  • the specific surface area by the BET method is preferably 50 to 400 m 2 / g, more preferably 90 to 360 m 2 / g.
  • the volatile content is preferably 0.5 to 10% by weight.
  • carbon black When carbon black is used as the pigment, it is preferable to use a slurry having a pH value of 2 to 10, and it is particularly preferable to use acidic carbon or neutral carbon.
  • the acidic carbon is carbon black showing an acidic pH value (for example, a pH value of 2 or more and less than 6), and an acidic group such as a carboxyl group is present on the surface thereof. It is similar to the self-dispersed carbon black described above in that it has a functional group on the surface, but the acidic carbon on the market generally shows some hydrophilicity, but the amount of acidic groups is smaller than that of the self-dispersed carbon black. .. Therefore, it cannot be dispersed alone in an aqueous medium without using a dispersant.
  • an acidic pH value for example, a pH value of 2 or more and less than 6
  • an acidic group such as a carboxyl group
  • the neutral carbon is carbon black showing a neutral pH value (for example, a pH value of 6 or more and 8 or less), and is generally not subjected to an oxidation treatment like acidic carbon.
  • the pigment contained in the resin dispersion pigment may be the same as or different from the pigment used as the self-dispersion pigment. Further, as in the case of the self-dispersion pigment, the pigment contained in the resin dispersion pigment may be a single substance or a mixture.
  • the type of the pigment-dispersed resin used for the resin-dispersed pigment is not particularly limited, and for example, (meth) acrylic resin, styrene (meth) acrylic resin, (anhydrous) maleic acid-based resin, and styrene (anhydrous) maleic acid-based resin.
  • Olefin (anhydrous) maleic acid-based resin, urethane-based resin, polyester-based resin (for example, a polycondensate of polyvalent carboxylic acid and polyhydric alcohol) and the like can be used, but the present invention is not limited thereto.
  • (meth) acrylic resin from the group consisting of (meth) acrylic resin, styrene (meth) acrylic resin, urethane resin, and polyester resin in terms of discharge stability, size of material selectivity, ease of synthesis, etc. It is preferable to use one or more selected. Further, from the viewpoint of improving the dispersion stability and ejection stability of the ink, when a binder resin described later is used, it is preferable to use a resin of the same type as the binder resin as the pigment dispersion resin.
  • (meth) acrylic resin means an acrylic resin, a methacrylic resin, or an acrylic-methacrylic resin.
  • the "acrylic-methacrylic resin” means a resin using acrylic acid and / or acrylic acid ester and methacrylic acid and / or methacrylic acid ester as a polymerizable monomer.
  • (anhydrous) maleic acid means maleic anhydride or maleic acid.
  • the above pigment dispersion resin can be synthesized by a known method or a commercially available product can be used. Further, the structure is not particularly limited, and for example, a resin having a random structure, a block structure, a comb-shaped structure, a star-shaped structure, or the like can be used. Further, as the pigment dispersion resin, a water-soluble resin may be selected or a water-insoluble resin may be selected. In the present specification, the "water-soluble resin” refers to a resin in which a 1% by mass water mixture having a temperature of 25 ° C. of the target resin is transparent to the naked eye, and the "water-insoluble resin" is used. Others, that is, those in which the 1% by mass water mixture of the target pigment dispersion resin at a temperature of 25 ° C. is not transparent to the naked eye.
  • a water-soluble resin when used as the pigment dispersion resin, its acid value is preferably more than 100 mgKOH / g and 450 mgKOH / g or less, and more preferably 120 to 400 mgKOH / g. Particularly preferably, it is 150 to 350 mgKOH / g.
  • the acid value is preferably more than 100 mgKOH / g and 450 mgKOH / g or less, and more preferably 120 to 400 mgKOH / g. Particularly preferably, it is 150 to 350 mgKOH / g.
  • a water-insoluble resin when used as the pigment dispersion resin, its acid value is preferably 0 to 100 mgKOH / g, more preferably 5 to 90 mgKOH / g, and 10 to 80 mgKOH / g. More preferred. When the acid value is within the above range, a printed matter having excellent drying property and scratch resistance can be obtained.
  • the acid value of the resin can be measured by a known device.
  • the acid value of the resin in the present specification is a value measured by a potentiometric titration method according to JIS K2501.
  • a specific measurement method AT-610 manufactured by Kyoto Denshi Kogyo Co., Ltd. is used, the resin is dissolved in a toluene-ethanol mixed solvent, titrated with a potassium hydroxide solution, and the acid value is determined from the titration to the end point. There is a method of calculating.
  • the pigment-dispersed resin used for the resin-dispersed pigment of the present invention it is preferable to introduce an aromatic group into the pigment-dispersed resin from the viewpoint of improving the adsorption ability to the pigment and ensuring the dispersion stability.
  • the surface of the carbon black interacts with the aromatic ring structure contained in the pigment-dispersed resin, so that the ability of the pigment-dispersed resin to be adsorbed on the carbon black is increased. Significantly improved. As a result, it is possible to secure the dispersion stability and the ejection stability of the ink for a long period of time.
  • aromatic group examples include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, a tolyl group, a xylyl group, a mesitylene group, an anisyl group and the like.
  • a phenyl group, a naphthyl group and a tolyl group are preferable from the viewpoint of sufficiently ensuring dispersion stability.
  • the amount of the aromatic ring-containing monomer introduced into the resin is 5 to 75 with respect to the total amount of the pigment-dispersed resin. It is preferably by mass, more preferably 5 to 65% by mass, and even more preferably 10 to 50% by mass.
  • an alkyl group having 8 to 36 carbon atoms into the pigment dispersion resin.
  • the number of carbon atoms of the alkyl group is more preferably 10 to 30, and even more preferably 12 to 24 carbon atoms.
  • the alkyl group can be either linear or branched as long as it has 8 to 36 carbon atoms, but a linear group is preferable.
  • linear alkyl group examples include an octyl group (C8), a lauryl group (C12), a myristyl group (C14), a cetyl group (C16), a stearyl group (C18), an araquil group (C20), and a behenyl group (C22).
  • the amount of the monomer containing an alkyl chain having 8 to 36 carbon atoms introduced into the resin is 5 with respect to the total amount of the pigment dispersion resin from the viewpoint of achieving both low viscosity of the pigment dispersion and scratch resistance of the printed matter. It is preferably to 60% by mass, more preferably 10 to 55% by mass, and particularly preferably 15 to 50% by mass.
  • the acid group in the resin is neutralized with a base in order to increase the solubility in ink. Whether or not the amount of the base added is excessive can be confirmed, for example, by preparing a 10% by mass aqueous solution of the pigment-dispersed resin and measuring the pH of the aqueous solution. From the viewpoint of improving the dispersion stability and ejection stability of the ink containing the resin dispersion pigment, the pH of the aqueous solution is preferably 7 to 11, and more preferably 7.5 to 10.5.
  • Examples of the base for neutralizing the pigment dispersion resin include organic amine-based solvents such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, and aminomethylpropanol, and aqueous ammonia.
  • organic amine-based solvents such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, and aminomethylpropanol
  • Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate can be mentioned, but are limited to these. Not done.
  • a water-soluble resin When a water-soluble resin is used as the pigment dispersion resin, its weight average molecular weight is preferably in the range of 1,000 to 50,000, more preferably in the range of 5,000 to 40,000, 10. It is more preferably in the range of 000 to 35,000, and particularly preferably in the range of 15,000 to 30,000.
  • the weight average molecular weight is in the above range, the pigment is stably dispersed in water, and it is easy to adjust the viscosity when used in ink.
  • the weight average molecular weight is 1,000 or more, the pigment-dispersed resin is difficult to dissolve in the organic solvent added to the ink, so that the adsorption of the pigment-dispersed resin to the pigment is strengthened, and the dispersion stability and dispersion stability are enhanced.
  • Discharge stability is improved.
  • the weight average molecular weight is 50,000 or less, the viscosity at the time of dispersion is suppressed to a low level, the dispersion stability of the ink and the ejection stability from the inkjet head are improved, and stable printing over a long period of time becomes possible.
  • the weight average molecular weight of the resin in the present invention is a polystyrene-equivalent value that can be measured by, for example, a method according to JIS K7252.
  • a specific measurement method there is a method of measuring using a Tosoh TSKgel column equipped with a Tosoh HLC-8120GPC equipped with an RI detector and using THF as a developing solvent.
  • the blending amount of the pigment-dispersed resin is preferably 1 to 100% by mass with respect to the blending amount of the pigment contained in the resin-dispersed pigment (also referred to as "pigment for resin dispersion" in the present specification).
  • pigment for resin dispersion also referred to as "pigment for resin dispersion” in the present specification.
  • the blending amount of the pigment dispersion resin with respect to the resin dispersion pigment is more preferably 2 to 50% by mass, and particularly preferably 4 to 45% by mass.
  • a part of the pigment-dispersed resin is released in the ink, so that a part of the pigment-dispersed resin may be adsorbed on the surface of the self-dispersed pigment.
  • a small amount of the liberated pigment-dispersed resin may be adsorbed on a part of the surface of the self-dispersed pigment.
  • a large amount of the pigment-dispersed resin is adsorbed, its characteristics are the same as those of the resin-dispersed pigment.
  • the adsorption rate of the pigment-dispersed resin with respect to the self-dispersed pigment is 50% by mass or less (however, it may be 0% by mass) with respect to the amount of the self-dispersed pigment.
  • the ink is produced by a method of mixing the dispersion liquid of the resin dispersion pigment and the dispersion liquid of the self-dispersion pigment, the amount of the free pigment dispersion resin contained in the dispersion liquid of the resin dispersion pigment is the self-dispersion pigment. It is preferable that the amount is 50% by mass or less (however, it may be 0% by mass) with respect to the amount of the self-dispersion pigment contained in the dispersion liquid of.
  • pigment dispersion resin a single type or a plurality of types may be used in combination.
  • a dispersion aid may be used in combination.
  • the dispersion aid is a material that contributes to improving the adsorption rate of the pigment dispersion resin with respect to the pigment.
  • conventionally known materials can be arbitrarily used as the dispersion aid, and in particular, a compound called a dye derivative can be preferably used.
  • the dye derivative is a compound in which a substituent is introduced into the organic dye molecule, and the organic dye includes a monoazo dye, a disazo dye, a polyazo dye, an anthraquinone dye, an isoindolinone dye, and an isoindoline dye.
  • the organic dye includes a monoazo dye, a disazo dye, a polyazo dye, an anthraquinone dye, an isoindolinone dye, and an isoindoline dye.
  • the above-mentioned "d "dye” is a general term for pigments and dyes.
  • the blending amount thereof is preferably 0.1 to 10% by mass, particularly preferably 0.5 to 5% by mass with respect to the blending amount of the pigment. In the above range, the addition ratio of the dispersion aid to the pigment becomes sufficient, and the dispersion stability and the ejection stability are improved.
  • the dispersion liquid of the resin dispersion pigment that can be used for the ink of the present invention can be produced, for example, by the following method.
  • a pigment-dispersed resin, water, and an organic solvent are mixed and stirred to form a pigment.
  • a pigment for resin dispersion, a dispersion aid, additional water, and an additional organic solvent are added to the pigment-dispersed resin aqueous solution, mixed and stirred (premixed), and then dispersed using a disperser. Perform processing. Then, if necessary, centrifugation, filtration, and adjustment of the solid content are performed to obtain a dispersion liquid of the resin dispersion pigment.
  • Pigment Dispersed Resin which is a Water-Insoluble Resin
  • a pigment-dispersed resin solution is prepared by dissolving a pigment-dispersed resin in an organic solvent for dissolving the resin and neutralizing the pigment-dispersed resin, if necessary.
  • a pigment for resin dispersion, water, a dispersion aid, an organic solvent, and an additional organic solvent are added to the pigment dispersion resin solution, and the mixture and stirring (premixing) are performed using a disperser. Perform distributed processing. Then, the organic solvent for dissolving the resin is distilled off by distillation under reduced pressure, and if necessary, centrifugation, filtration, and adjustment of the solid content are performed to obtain a dispersion liquid of the resin dispersion pigment.
  • the disperser used for the dispersion treatment of the resin dispersion pigment may be any generally used disperser, and for example, a ball mill, a roll mill, a sand mill, or a bead mill. And nanomizers and the like.
  • bead mills are preferably used, and specifically, they are commercially available under trade names such as super mills, sand grinders, agitator mills, grain mills, dyno mills, pearl mills and cobol mills.
  • the size of the pulverized media used in the above-mentioned disperser is adjusted, the material of the pulverized media is changed, and the above.
  • Increasing the filling rate of the pulverized media, changing the shape of the stirring member (agitator), lengthening the dispersion treatment time, classifying by filtration or centrifugation after the dispersion treatment, and the combination of these methods Can be mentioned.
  • the diameter of the pulverized media of the disperser is preferably 0.1 to 3 mm.
  • the material of the crushing media glass, zircon, zirconia and titania are preferably used.
  • the following method of grinding and kneading can also be preferably used. After kneading the pigment for resin dispersion, the pigment dispersion resin, the organic solvent, the inorganic salt, and if necessary, the dispersion aid with a kneader, water is added to the obtained mixture, and the mixture and stirring are performed. Then, the inorganic salt and, if necessary, the organic solvent are removed by centrifugation, filtration, and washing, and the solid content is further adjusted to obtain a dispersion liquid of the resin dispersion pigment.
  • the kneader used in the above method (3) may be any disperser that is generally used, but a high-viscosity mixture can be kneaded and a pigment dispersion liquid containing fine pigments can be used to obtain image quality.
  • a kneader or a remix is preferably used because a printed matter having excellent color development and color reproducibility can be obtained.
  • sodium chloride, barium chloride, potassium chloride, sodium sulfate, potassium sulfate and the like can be preferably used.
  • the average secondary particle size (D50) of the resin dispersion pigment is preferably 40 to 500 nm, more preferably 50 to 400 nm, and particularly preferably 60 to 300 nm.
  • the pigment dispersion treatment step may be controlled as described above.
  • the average secondary particle size (D50) of the resin-dispersed pigment can be measured by the same method as in the case of the self-dispersed pigment.
  • the resin-dispersed pigment of the present invention is preferably contained in an amount of 0.5 to 10% by mass, more preferably 1 to 8% by mass, and particularly preferably 2 to 7% by mass, based on the total amount of the ink.
  • the total amount of the self-dispersed pigment and the resin-dispersed pigment is preferably 5 to 15% by mass, more preferably 6 to 10% by mass, based on the total amount of the ink, in order to improve the printing density on various recording media. It is particularly preferably 7 to 9% by mass. Within the above range, in addition to the print density, the ink storage stability and ejection stability are also excellent.
  • the black inkjet ink of the present invention contains an organic solvent in an amount of 29% by mass or less in the total amount of the ink.
  • organic solvent refers to an organic compound used to dissolve and / or disperse a substance, which is a liquid under the conditions of 25 ° C. and 1 atm.
  • water-soluble organic solvent refers to an organic solvent having a solubility in water of 5 g / 100 gH 2 O or more under the conditions of 25 ° C. and 1 atm.
  • the organic solvent is selected from the viewpoints of permeability to the recording medium, drying property and wettability of the ink, and ensuring moisturizing property.
  • the amount of the organic solvent in the ink is large in consideration of the permeability to the recording medium and the drying property and the wettability of the ink.
  • the dispersion of the self-dispersing pigment may be destroyed.
  • the self-dispersed pigment and the resin-dispersed pigment coexist in the ink as in the present invention
  • the amount of the organic solvent exceeds 29% by mass in the total amount of the ink
  • the resin-dispersed pigment interacts with the self-dispersed pigment.
  • the effect of the present invention may be weakened. As a result, the inkjet ejection stability deteriorates due to the above phenomenon.
  • the amount of the organic solvent contained in the ink of the present invention is preferably 1 to 29% by mass, and 5 to 27% by mass in the total amount of the ink. Is more preferable, and 10 to 25% by mass is particularly preferable.
  • the ink permeates into the inside of the highly absorbent recording medium, especially in a highly absorbent recording medium. Is gone. As a result, the amount of pigment remaining on the surface increases, and the print density increases. Further, by selecting an organic solvent having suitable drying properties, it is possible to prevent the organic solvent from rapidly volatilizing in the ink, especially in a low absorption recording medium. As a result, unevenness does not occur on the surface of the ink layer after drying, and it is possible to prevent a decrease in print density.
  • the organic solvent to be used is appropriately selected and permeated into the recording medium. It is preferable to adjust the property, the drying property and the wet spreading property of the ink, and the moisturizing property.
  • the P value defined by the following general formula (1) is preferably 1.6 or less. Above all, the P value is more preferably 0.2 to 1.6, and particularly preferably 0.5 to 1.5.
  • i represents the type of organic solvent contained in the ink.
  • bi represents the boiling point (° C.) of the organic solvent i under 1 atm
  • c i represents the content (% by mass) of the organic solvent i with respect to the total amount of ink
  • s i represents the organic solvent i.
  • n represents the number of types of organic solvents contained.
  • the boiling point under 1 atm can be measured by using a thermal analyzer such as DSC (Differential Scanning Calorimetry).
  • the static surface tension under the condition of 25 ° C. is a value measured by the Wilhelmy method, specifically, a value that can be measured using a platinum plate using CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. ..
  • the organic solvent having bi ⁇ s i of 7 or more in the above general formula (1 ) is less than 75% by mass in the total amount of the organic solvent contained in the ink. It is preferably (may be 0% by mass), more preferably less than 50% by mass (may be 0% by mass), and particularly preferably less than 40% by mass (0% by mass). May be%).
  • Dipropylene glyco Ludimethyl ether (boiling point 171 ° C., surface tension 21.1 mN / m), diethylene glycol methyl butyl ether (boiling point 212 ° C., surface tension 26.7 mN / m), triethylene glycol methyl butyl ether (boiling point 261 ° C., surface tension 28.7 mN / m). m), tetraethylene glycol dimethyl ether (boiling point 275 ° C., surface tension 33 mN / m) and the like.
  • the content of the organic solvent having a boiling point under 1 atm (bi in the general formula (1)) of 250 to 300 ° C. is 9% by mass or less (may be 0 % by mass) with respect to the total amount of ink. Is preferable.
  • the boiling point at 1 atm is 250 to 300 ° C. from the viewpoint of obtaining a printed matter having excellent print density and scratch resistance with respect to a low-absorbency recording medium such as coated paper regardless of the drying method.
  • the content of the water-soluble organic solvent is more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass, based on the total amount of the ink.
  • organic solvents having a boiling point of 250 to 300 ° C. under 1 atm examples include glycerin (boiling point 290 ° C.), 1,6-hexanediol (boiling point 250 ° C.), triethylene glycol monobutyl ether (boiling point 271 ° C.), and the like.
  • Triethylene glycol methylbutyl ether (boiling point 261 ° C), tetraethylene glycol dimethyl ether (boiling point 275 ° C), triethylene glycol (boiling point 287 ° C), tripropylene glycol (boiling point 271 ° C), tetrapropylene glycol (boiling point 250 ° C or higher), polyethylene Examples thereof include glycol 200 (boiling point 250 ° C. or higher), polyethylene glycol 400 (boiling point 250 ° C. or higher), polyethylene glycol 600 (boiling point 250 ° C. or higher), N-methyloxazolidinone (boiling point 257 ° C.), and the like.
  • organic solvent preferably used in the present invention
  • a monohydric alcohol solvent ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-butanol, isobutanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, etc.
  • dihydric alcohol-based solvents dihydric alcohol-based solvents
  • 1,2-propanediol propylene glycol, boiling point 188 ° C.
  • 1,2-butanediol bisiling point 194 ° C.
  • 1,2-ethanediol ethylene glycol, boiling point.
  • glycol solvent As a trivalent or higher alcohol solvent (polyol solvent), glycerin, 1,2,4-butanetriol, diglycerin and the like can be used.
  • Glycol monoalkyl ether-based solvents include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, and triethylene glycol.
  • Monomethyl ether triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether (boiling point 271 ° C), tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether , Dipropylene glycol monomethyl ether, Tripropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, Dipropylene glycol monopropyl ether, Dipropylene glycol mono n-butyl ether, etc.
  • glycol dialkyl ether-based solvents diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (boiling point 275 ° C.), diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol methyl Ethyl ether, tetraethylene glycol methyl ethyl ether, diethylene glycol butyl methyl ether, triethylene glycol methyl butyl ether (boiling point 261 ° C.), tetraethylene glycol butyl methyl ether, etc.
  • N N-dimethylformamide, N, N-dimethyl- ⁇ -methoxypropionamide, N, N-dimethyl- ⁇ -ethoxypropionamide, N, N-dimethyl- ⁇ -butoxypropionamide, N, N-dimethyl- ⁇ -pentoxypropionamide, N, N-dimethyl- ⁇ -hexoxypropionamide, N, N-dimethyl- ⁇ -heptoxypropionamide, N, N-dimethyl- ⁇ -2-ethyl Hexoxypropionamide, N, N-dimethyl- ⁇ -octoxypropionamide, N, N-diethyl- ⁇ -butoxypropionamide, N, N-diethyl- ⁇ -pentoxypropionamide, N, N-diethyl- ⁇ -Hexoxypropionamide, N, N-diethyl- ⁇ -heptoxypropionamide, N, N-diethyl- ⁇ -octoxypropionamide, etc.
  • heterocyclic compound examples include 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-methyloxazoledinone, N-ethyloxazolidinone, piperazine, morpholine, N-methylmorpholine, N-ethylmorpholine, ⁇ -butyrolactone and ⁇ -caprolactone.
  • N, N-dimethylaminoethanol (boiling point 134 ° C.), N, N-diethylaminoethanol (boiling point 162 ° C.), N, N-dibutylaminoethanol (boiling point 226 ° C.), N- ( ⁇ -amino) Ethyl) Ethanolamine (boiling point 244 ° C), N-methylethanolamine (boiling point 156 ° C), N-methyldiethanolamine (boiling point 245 ° C), 2-ethylaminoethanol (boiling point 169 ° C), N-ethyldiethanolamine (boiling point 251 ° C) ), Mono-n-butylethanolamine (boiling point 199 ° C.), Mono-n-butyldiethanolamine (boiling point 270 ° C.), N-tert-butylethanolamine
  • the organic solvent used in the present invention preferably contains a water-soluble organic solvent, and in particular, among those listed above, a monohydric alcohol solvent, a dihydric alcohol solvent (diol solvent), and a trihydric or higher alcohol. It is preferable to use a solvent (polyol solvent), glycol monoalkyl ether solvent, or the like. Further, from the viewpoint of permeability to a recording medium, print density, and inkjet ejection stability, a compound having one or two hydroxyl groups is particularly preferably selected as the water-soluble organic solvent. As the organic solvent having one or two hydroxyl groups, it is preferable to include the above-mentioned glycol monoalkyl ether solvent or dihydric alcohol solvent (diol solvent).
  • diol solvent dihydric alcohol solvent
  • the compound having one or two hydroxyl groups is preferably contained in an amount of 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% or more in the total amount of the ink.
  • the diol-based solvent is preferably contained in an amount of 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more in the total amount of the ink.
  • the organic solvent has a specific heat of 0.40 to 0.70 cal / at 20 ° C. It is preferably g ⁇ ° C., more preferably 0.45 to 0.65 cal / g ⁇ ° C., and particularly preferably 0.50 to 0.60 cal / g ⁇ ° C.
  • the specific heat is 0.70 cal / g ⁇ ° C.
  • the ink contains two or more kinds of organic solvents, it is preferable that the specific gravity of all of the two or more kinds of organic solvents satisfies the above conditions.
  • the weighted average value of the specific heat is preferably 0.40 to 0.70 cal / g ⁇ ° C., preferably 0.45 to 0.65 cal. It is more preferably / g ⁇ ° C., and particularly preferably 0.52 to 0.60 cal / g ⁇ ° C.
  • the specific heat of the organic solvent can be measured by, for example, DSC (Differential Scanning Calorimetry). Specifically, a high-sensitivity differential scanning calorimeter Thermo plus EV02 DSC8231 (manufactured by Rigaku) was used, about 10 g of an organic solvent to be measured was added to an aluminum sample pan, and then the sample was sealed using a sample sealer. The specific heat of the organic solvent can be calculated from the obtained DSC chart by measuring the bread (empty container) and the three substances whose specific heat is known under the same conditions.
  • DSC Different Scanning Calorimetry
  • the organic solvent used in the ink of the present invention preferably has a weighted average boiling point of 100 to 235 ° C., more preferably 120 to 220 ° C., and more preferably 150 to 215 ° C. under 1 atm. Especially preferable.
  • the weighted average value of the boiling point is 100 ° C. or higher, the ejection stability from the inkjet head is improved, and the density of the printed matter when printed on a high-absorbency recording medium is improved.
  • the weighted average value of the boiling point is 235 ° C. or less, drying failure does not occur on the recording medium, and the remaining organic solvent does not cause a sudden temperature change of the ink coating film, so that the drying method can be used.
  • the density of the printed matter is improved. Further, when the weighted average value of the boiling point is 235 ° C. or lower, the scratch resistance of the printed matter to a low-absorbency recording medium such as coated paper is also improved. In addition, in the calculation of the weighted average value of the boiling point, the organic solvent having a boiling point of 250 ° C. or higher at 1 atm described above is also included.
  • the weighted average value of the specific heat or the weighted average value of the boiling point at 1 atm is the specific heat or the boiling point at 1 atm calculated for each organic solvent when the ink contains a plurality of kinds of organic solvents. , It is a value obtained by adding the multiplication value with the mass ratio to the total amount of the organic solvent.
  • ion-exchanged water deionized water
  • the content thereof is preferably in the range of 30 to 90% by mass, more preferably 40 to 80% by mass, based on the total mass of the ink.
  • the black inkjet ink of the present invention contains wax.
  • the term "wax” is an organic compound that is solid at room temperature (25 ° C.) and becomes liquid when heated. For example, it has a melting point of 40 to 200 ° C. and melts in a temperature environment higher than the melting point without decomposition.
  • the melting point of the wax is preferably 60 to 200 ° C, more preferably 100 to 180 ° C, and particularly preferably 120 to 160 ° C. Although the reason is not clear, it is possible to obtain a printed matter having a high print density within the above range, especially when it is dried by a method of irradiating electromagnetic waves such as an infrared drying method.
  • the wax may be a water-soluble material or a water-insoluble material, but is preferably a water-insoluble material, particularly resin particles (emulsion).
  • examples of the chemical structure include hydrocarbon wax, ester wax (for example, fatty acid ester wax), silicone wax, and polyalkylene glycol wax.
  • ester wax for example, fatty acid ester wax
  • silicone wax for example, silicone wax
  • polyalkylene glycol wax for example, an acrylic-silicone copolymer emulsion having a glass transition temperature of 50 ° C. or higher is generally unlikely to satisfy the above melting point conditions, and therefore does not fall under the wax in the present invention.
  • the wax that can be used in the present invention can be mentioned, for example, natural wax and synthetic wax.
  • Natural waxes include petroleum-based waxes such as paraffin wax, microcrystallin wax, petrolatum, etc .; plant-based waxes such as carnauba wax, candelilla wax, and rice wax; animal-based waxes such as lanolin and beeswax; mineral waxes. Some Montan wax, Celesin, etc .; can be mentioned.
  • Synthetic waxes include polyolefin waxes, Fisher Trobsch waxes, acrylic silicone copolymers, urethane silicone copolymers, polyethylene glycols (those with an average molecular weight of 1,000 or more), paraffin wax derivatives, Montan wax derivatives, and micros. Examples thereof include crystallin wax derivatives. These waxes can be used alone or in combination of two or more in black inkjet ink.
  • a hydrocarbon wax or a silicone wax is preferable in that high scratch resistance and a high printing density can be obtained, and a polyolefin wax which is a hydrocarbon wax is more preferably used in that it is also excellent in ejection stability. Be done.
  • polyolefin wax examples include polyethylene wax and polypropylene wax.
  • polypropylene-based wax is preferable in terms of obtaining a high printing density
  • polyethylene-based wax is preferable in terms of ejection stability and scratch resistance. In each case, one type or two or more types can be used in combination.
  • polyolefin wax is preferably a soft polyolefin having a molecular weight of less than 10,000.
  • the wax is a resin particle
  • its average particle size is preferably 5 to 300 nm, more preferably 30 to 250 nm, and particularly preferably 40 to 200 nm. If the average particle size of the wax is 5 nm or more, the scratch resistance of the printed matter is improved, and if it is 300 nm or less, not only the inkjet ejection stability is improved, but also high printing is performed regardless of the drying method and the type of recording medium. A printed matter of density can be obtained.
  • the wax having the form of resin particles can be produced, for example, by mixing a room temperature solid wax melted by heating, hot water, and an emulsifier.
  • Commercially available waxes can also be used, for example, AQUACER-507, AQUACER-513, AQUACER-515, AQUACER-526, AQUACER-531, AQUACER-533, AQUACER-535, AQUACER-535 manufactured by Big Chemie.
  • the blending amount of the wax is preferably 0.2 to 8% by mass, preferably 0.3 to 8% by mass, based on the total amount of the ink, in that it has excellent ejection stability, excellent scratch resistance of the printed matter, and a high-concentration printed matter can be obtained. It is more preferably to 5% by mass, and particularly preferably 0.5 to 4% by mass.
  • Binder resin In the black inkjet ink of the present invention, it is preferable to use a binder resin because of high print density, scratch resistance of printed matter, and ejection stability.
  • the "binder resin” in the present specification is a resin used for binding a layer of printed matter (printing layer, ink layer) to a recording medium.
  • the ink of the present invention contains a pigment-dispersed resin, but when the resin contained in the ink is a water-soluble resin, whether or not the resin corresponds to a binder resin is adsorbed on the resin-dispersed pigment. Distinguished by rate. For example, when an attempt is made to produce a resin-dispersed pigment dispersion 1 using the materials and methods described in Examples, except that the same amount of the target resin is used instead of the aqueous solution of the pigment-dispersed resin 1.
  • the adsorption rate of the target resin to the resin dispersion pigment is 50 mass by mass. If it is less than%, it is determined that the target resin is a binder resin.
  • the ink diluted with water is subjected to a centrifugation treatment (for example, at 30,000 rpm for 4 hours) to separate the pigment and the supernatant liquid. Then, when the solid content contained in the supernatant liquid is measured, if the solid content is 50% by mass or more with respect to the total amount of the resin having the same composition contained in the ink, the resin is a binder resin. Judge.
  • a water-soluble resin and (water-dispersible) resin particles are generally known, and in the present invention, either one is selected and used. Alternatively, both may be used in combination.
  • the resin particles have a higher molecular weight than the water-soluble resin, can enhance the scratch resistance of the printed matter, and are also excellent in the image quality of the printed matter.
  • the voids of the high-absorbency recording medium can be effectively filled, so that a printed matter having a high print density can be obtained.
  • the black inkjet ink using a water-soluble resin as the binder resin is excellent in ejection stability.
  • the black inkjet ink of the present invention preferably contains resin particles as a binder resin.
  • the inclusion of the resin particles not only enhances the scratch resistance of the printed matter, but also makes it possible to obtain a printed matter having a high print density for various recording media.
  • the black inkjet ink of the present invention preferably contains resin particles and a water-soluble resin as the binder resin.
  • resin particles and the water-soluble resin By containing the resin particles and the water-soluble resin, not only a printed matter having a higher print density can be obtained, but also the ejection stability is excellent.
  • resin particles resin particles of acrylic type, styrene acrylic type, epoxy type, urethane type, styrene butadiene type, polyether type, polyamide type, polyester type, vinyl chloride type and the like, or copolymers thereof can be used. (However, those containing silicone chains are excluded). From the viewpoint of scratch resistance and ejection stability of the printed matter, acrylic, styrene acrylic, urethane, styrene butadiene, and vinyl chloride resin particles are preferable, and acrylic, styrene acrylic, and urethane resin particles are further preferable.
  • Acrylic-based and styrene-acrylic-based resin particles are particularly preferable from the viewpoint of the density and ejection stability of the printed matter.
  • the above resin particles can be synthesized by a known method or a commercially available product can be used.
  • the structure is not particularly limited, and for example, a resin having a random structure, a block structure, a comb-shaped structure, a star-shaped structure, or the like can be used.
  • the content of the resin particles with respect to the total amount of the ink is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and further preferably 3 to 7% by mass in terms of solid content.
  • the binder resin contains resin particles and a water-soluble resin
  • the content of the resin particles is 20 with respect to the total amount of the binder resin (total amount of the content of the resin particles and the content of the water-soluble resin). It is preferably ⁇ 95% by mass, more preferably 35 to 90% by mass, and particularly preferably 50 to 80% by mass.
  • water-soluble resin examples include acrylic type, styrene acrylic type, urethane type, urethane / acrylic type, styrene butadiene type, vinyl chloride type, styrene maleic acid type, polyester type and the like (however, the silicone chain is used. Except for those included).
  • acrylic type styrene acrylic type, urethane type, urethane / acrylic type, styrene butadiene type, vinyl chloride type, styrene maleic acid type, polyester type and the like (however, the silicone chain is used. Except for those included).
  • the silicone chain is used. Except for those included.
  • the silicone chain is used.
  • the above water-soluble resin can be synthesized by a known method or a commercially available product can be used.
  • the structure is not particularly limited, and for example, a resin having a random structure, a block structure, a comb-shaped structure, a star-shaped structure, or the like can be
  • the content of the water-soluble resin with respect to the total amount of the ink is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and 1 to 5% by mass in terms of solid content. Is more preferable.
  • the acid value of the resin particles or the water-soluble resin used as the binder resin is preferably 1 to 80 mgKOH / g, preferably 3 to 60 mgKOH / g, and particularly preferably 5 to 40 mgKOH / g. .. Within the above range, the dispersion stability of both the self-dispersed pigment and the resin-dispersed pigment can be ensured, and the binder resin quickly moves to the gas-liquid interface to obtain a printed matter having excellent image quality. When a high-absorbency recording medium is used, a printed matter having a high print density can be obtained by rapidly moving so as to fill the voids on the surface of the recording medium.
  • the acid value of the resin particles or the water-soluble resin can be measured in the same manner as the acid value of the pigment-dispersed resin described above.
  • the glass transition temperature of the resin particles or the water-soluble resin used as the binder resin is preferably 60 to 140 ° C., more preferably 70 to 135 ° C. from the viewpoint of scratch resistance and ejection stability of the printed matter. It is preferably 80 to 130 ° C., and particularly preferably 80 to 130 ° C. In particular, when a method of irradiating electromagnetic waves such as an infrared drying method is adopted, the glass transition temperature is preferably 80 ° C. or higher.
  • the resin particles form a film in the vicinity of the self-dispersing pigment, so that the surface of the self-dispersing pigment is uniformly covered and the surface of the recording medium is smooth. Therefore, a printed matter having a high print density can be obtained.
  • the glass transition temperature is a value measured using a DSC (Differential Scanning Calorimetry), and can be measured as follows, for example, according to JIS K7121. Approximately 2 mg of a sample obtained by drying the resin is weighed on an aluminum pan, and the aluminum pan is set in a holder in a DSC measuring device (for example, DSC-60Plus manufactured by Shimadzu Corporation) as a test container. Then, the temperature at the intersection of the baseline on the low temperature side and the tangent at the inflection point read from the obtained DSC chart obtained by measuring under the heating condition of 5 ° C./min is referred to as the glass transition temperature in the present specification. do.
  • DSC Different Scanning Calorimetry
  • the weight average molecular weight of the water-soluble resin used as the binder resin ensures stability of ejection from the inkjet nozzle, and a printed matter having excellent scratch resistance to various recording media can be obtained. It is preferably 5,000 to 50,000, and more preferably 8,000 to 45,000 from the viewpoint of excellent color development and color reproducibility when printed on a high absorption recording medium. It is more preferably 10,000 to 40,000.
  • the weight average molecular weight of the water-soluble resin can be measured in the same manner as the acid value of the pigment-dispersed resin described above.
  • the ink contains one or more surfactants from the viewpoints of ejection stability, scratch resistance of the printed matter, and obtaining a printed matter having a high print density.
  • the surfactant include acetylene diol-based, acetylene alcohol-based, siloxane-based, acrylic-based, fluorine-based, polyoxyalkylene ether-based, and various other surfactants depending on the intended use.
  • nonionic surfactants selected from the group consisting of acetylene diol-based surfactants, siloxane-based surfactants, and polyoxyalkylene ether-based surfactants, and acetylene diol-based surfactants. It is more preferable to contain one or more selected from the group consisting of a surfactant and a siloxane-based surfactant, and it is particularly preferable to contain a siloxane-based surfactant.
  • the surfactant that can be used in the present invention may be water-soluble or water-insoluble.
  • the siloxane-based surfactant that is solid at room temperature and melts at, for example, 40 to 200 ° C. when heated may be a material that also serves as the above-mentioned silicone wax.
  • the acetylene diol-based surfactant and the siloxane-based surfactant are rapidly contained in the ink droplets after landing on the recording medium without being affected by the self-dispersing pigment and the resin-dispersed pigment existing in the droplets. , It is considered to be oriented toward the gas-liquid interface and the recording medium-droplet interface. As a result, the wettability of the ink can be improved even on a low-absorption recording medium, and the ink droplets can be quickly smoothed. It is possible to obtain a printed matter having excellent image quality with a small amount of ink.
  • the scratch resistance of the printed matter is also improved, and although the details are unknown, when printing on a highly absorbent recording medium such as uncoated paper, the printing is performed. Excessive penetration and diffusion of ink are suppressed, and a printed matter having a high print density can be obtained.
  • an acetylene diol-based surfactant and a siloxane-based surfactant are used in combination because an ink having excellent ejection stability can be obtained in addition to the above-mentioned improvement in characteristics. Is preferable.
  • Examples of the acetylene diol-based surfactant used in the present invention include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,5,8,11-tetramethyl-6-dodecyne. -5,8-diol, hexadeca-8-in-7,10-diol, 6,9-dimethyl-tetradeca-7-in-6,9-diol, 7,10-dimethylhexadeca-8-in-7 , 10-Glycol, and ethylene oxide and / or propylene oxide adducts thereof, but are not limited thereto.
  • siloxane-based surfactant for example, 8032ADDITIVE, FZ-2104, FZ-2120, FZ-2122, FZ-2162, FZ-2164, FZ-2166 manufactured by Toray Dow Corning Co., Ltd. FZ-2404, FZ-7001, FZ-7002, FZ-7006, L-7001, L-7002, SF8427, SF8428, SH3748, SH3749, SH3771M, SH3772M, SH3773M, SH3775M, SH8400, BYK-331 manufactured by BYK Chemie.
  • TEGO Glide 450 TEG -351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-640, KF-642, KF-643, KF-644, KF-945, KF-6011, KF-6012 , KF-6015, KF-6017, KF-6020, KF-6204, X-22-4515, Silface SAG series of Nissin Chemical Industry Co., Ltd.
  • siloxane-based surfactant in which one or more ethylene oxide groups and / or one or more propylene oxide groups are introduced into the side chains and / or both ends of the polydimethylsiloxane chain can be preferably used.
  • polyoxyalkylene ether-based surfactant examples include compounds represented by the following general formula (2).
  • R has an alkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, an alkylcarbonyl group having 8 to 22 carbon atoms, or an alkyl carbonyl group having 8 to 22 carbon atoms.
  • the R may have a branched structure.
  • EO represents an ethylene oxide group
  • PO represents a propylene oxide group.
  • m indicates the average number of added moles of EO and is a number of 2 to 50
  • n indicates the average number of added moles of PO and is a number of 0 to 50. When n is not 0, the addition order of (EO) m and (PO) n does not matter, and the addition may be block or random.
  • the surfactant used in the present invention exists separately in a hydrophobic group and a hydrophilic group in the molecule. Therefore, among the surfactants exemplified above, those having a hydrophilic ethylene oxide group are particularly preferably selected.
  • the HLB value is 10 from the viewpoint of enhancing the affinity with the self-dispersion pigment, the resin dispersion pigment and the wax, obtaining an ink having excellent dispersion stability and ejection stability, and obtaining a printed matter having a high print density.
  • the following surfactant is preferably contained, more preferably 0 to 5, and particularly preferably 0 to 4.
  • a printed matter having a high print density can be obtained regardless of the recording medium and the drying method, and the HLB value is 0 to 12 (preferably 0 to 8, more. It is preferable to use the polyoxyalkylene ether-based surfactant and the siloxane-based surfactant which are 0 to 6) in combination.
  • the HLB (Hydrophile-Lipophile Balance) value is one of the parameters indicating the hydrophilicity or hydrophobicity of the material, and the smaller the value, the higher the hydrophobicity, and the larger the value, the higher the hydrophilicity.
  • Various methods for calculating the HLB value from the chemical structure are known, and various methods for actually measuring the HLB value are also known. However, in the present invention, as in the case of an acetylenediol-based surfactant or a polyoxyalkylene ether-based surfactant. If the structure of the compound is clearly known, the HLB value is calculated using the Griffin method.
  • the Griffin method is a method of calculating an HLB value using the following formula (3) using the molecular structure and molecular weight of the target material.
  • the HLB value of the surfactant can be determined experimentally by the following method described in 324. Specifically, 0.5 g of a surfactant is dissolved in 5 mL of ethanol, and then the solution is titrated with a 2% by mass phenol aqueous solution while stirring at 25 ° C., and the end point is where the solution becomes turbid. .. When the amount of the aqueous phenol solution required up to the end point is A (mL), the HLB value can be calculated by the following formula (4).
  • the content of the surfactant in the inkjet ink of the present invention is preferably 0.2 to 4% by mass with respect to the total amount of the ink. More preferably, it is 0.5 to 2% by mass.
  • a pH adjuster can be added, if necessary, in order to obtain an ink having a desired physical characteristic value.
  • the pH adjuster the above-mentioned alkanolamine-based solvent can be used, and in addition, Other nitrogen-containing compounds include aqueous ammonia, monoethylamine, diethylamine, triethylamine, cyclohexylamine, benzylamine, urea, piperidine, etc.
  • alkali metal hydroxides lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.
  • Acidic compounds include hydrochloric acid, sulfuric acid, acetic acid, citric acid, maleic acid, maleic anhydride, succinic acid, tartrate acid, malic acid, phosphoric acid, boric acid, fumaric acid, malonic acid, ascorbic acid, glutamate, etc. Can also be used. Further, the above pH adjuster may be used alone or in combination of two or more.
  • the blending amount of the pH adjuster is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.2 to 1.5% by mass with respect to the total amount of the ink. Is most preferable.
  • additives such as an antifoaming agent, a preservative, an infrared absorber, and an ultraviolet absorber are appropriately added as necessary in order to obtain an ink having a desired physical property value. Can be added to.
  • the amount of these additives added is preferably 0.01 to 10% by mass with respect to the total mass of the ink.
  • the ink of the present invention does not substantially contain the polymerizable monomer.
  • the ink of the present invention may contain a nitrogen-containing compound as an organic solvent and / or a pH adjuster.
  • a nitrogen-containing compound as an organic solvent and / or a pH adjuster.
  • the dispersion stability and ejection stability of the pigment may be adversely affected. Therefore, in the present invention, it is preferable to limit the amount of the nitrogen-containing compound, particularly the amount of the nitrogen-containing compound having a molecular weight of 500 or less, which easily affects the above-mentioned characteristics.
  • the dispersed state of the pigment is maintained by the charge repulsion generated between the pigment particles, and the dispersion stability is ensured.
  • a method of maintaining dispersion stability for a long period of time there is a method of adjusting the pH of the ink to neutral to weakly basic. By maintaining the pH at neutral to weakly basic, the ion concentration in the electric double layer covering the pigment surface can be increased, the repulsive force of the electric double layer can be increased, and a large repulsive force can be generated between the pigment particles.
  • some nitrogen-containing compounds are acidic or strongly basic, and by using these compounds in combination with a self-dispersing pigment and a resin-dispersed pigment, the self-dispersing pigment and the self-dispersing pigment can be used.
  • the dispersion stability of the resin dispersion may be deteriorated, and the print density and ejection stability of the printed matter may be deteriorated accordingly.
  • wax when wax is used in combination, the compatibility of the wax with ink may deteriorate, and the image quality and print density of the printed matter may deteriorate.
  • the pKa value at 25 ° C. is 2 or less (preferably, the pKa value is less than 4), or 10 or more (preferably, the pKa value is 10 or more).
  • the total amount of the nitrogen-containing compound having a molecular weight of 500 or less, which is more than 9.5), is preferably 3% by mass or less, more preferably 1% by mass or less, based on the total amount of the black inkjet ink. .. This is because these compounds are acidic or strongly basic, and if they are blended in a large amount, they may adversely affect the dispersion stability, the ejection stability, and the print density and image quality of the printed matter as described above.
  • a nitrogen-containing compound when used, it is preferable to use a basic organic compound having a pKa value of 4 to 9.5 at 25 ° C. Although the detailed factors are unknown, it is considered that the acid dissociation constant (pKa value) is moderately small and the organic compound suppresses damage to the self-dispersed pigment, the resin-dispersed pigment and the wax. Be done.
  • alkanolamine from the viewpoint of high solubility in an aqueous medium and safety to the human body, and it is particularly preferable to contain triethanolamine having a small pKa value. It should be noted that only one kind of the above compound may be used, or two or more kinds thereof may be used in combination.
  • the content thereof is preferably 1.25% by mass or less with respect to the total amount of ink. Further, it is more preferably 0.1 to 1.0% by mass. Within the above range, deterioration of the print density and image quality of the printed matter can be prevented without deteriorating the dispersion stability and the ejection stability.
  • the total amount of the nitrogen-containing compound compounded is the total amount of the black inkjet ink regardless of the pKa value. It is preferably 3% by mass or less, and more preferably 1.25% by mass or less.
  • the pKa value of the present invention can be measured by a known method, for example, a potentiometric titration method.
  • urea 0.2
  • the black inkjet ink of the present invention containing the above-mentioned components can be produced by a known method.
  • the dispersion liquid of the self-dispersing pigment and a dispersion liquid of a resin dispersion pigment are used.
  • a production method of mixing a dispersion liquid, an organic solvent, a wax, and, if necessary, a binder resin, a surfactant, or the like is preferably selected.
  • An example of the method for producing the black inkjet ink of the present invention will be described below, but as described above, the production method is not limited to the following.
  • An example of a method for producing a dispersion liquid of a resin dispersion pigment is as described above.
  • the self-dispersing pigment the self-dispersing pigment is mixed well with water and, if necessary, an organic solvent or other additives, and then filtered or centrifuged as necessary to obtain coarse particles. By removing the above, a dispersion liquid of the self-dispersing pigment is produced.
  • the dispersion liquid of the self-dispersion pigment and the dispersion liquid of the resin dispersion pigment thus obtained are mixed, and further, an organic solvent, a wax, and, if necessary, a binder resin, a surfactant, water, and pH. Add modifiers and other additives, stir and mix. If necessary, the mixture may be stirred and mixed while heating in the range of 40 to 100 ° C.
  • the coarse particles contained in the above mixture are removed by a method such as filtration or centrifugation to obtain black inkjet ink.
  • a method for filtration separation a known method can be appropriately used, but when a filter is used, the opening diameter thereof is preferably 0.3 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
  • the filter when performing filtration, the filter may be a single type or a plurality of types may be used in combination.
  • the black inkjet ink of the present invention preferably has a viscosity at 25 ° C. of 3 to 20 mPa ⁇ s. Within this viscosity region, stable ejection characteristics are exhibited not only in a head having a frequency of 4 to 10 KHz but also in a head having a high frequency of 10 to 70 KHz. In particular, by setting the viscosity at 25 ° C. to 4 to 10 mPa ⁇ s, stable ejection can be achieved even when used for an inkjet head having a design resolution of 600 dpi or more.
  • the viscosity can be measured by a conventional method. Specifically, an E-type viscometer (TVE25L-type viscometer manufactured by Toki Sangyo Co., Ltd.) can be used for measurement using 1 mL of ink.
  • the black inkjet ink of the present invention has a static surface tension of 18 to 35 mN / m at 25 ° C. from the viewpoint that a water-based inkjet ink that can be ejected stably can be obtained and a printed matter having excellent print density and image quality can be obtained. It is preferably 20 to 32 mN / m, and particularly preferably 20 to 32 mN / m.
  • the static surface tension refers to the surface tension measured by the Wilhelmy method in an environment of 25 ° C. Specifically, CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. can be used, and measurement can be performed using a platinum plate.
  • the inkjet ink of the present invention preferably has a dynamic surface tension of 26 to 36 mN / m, more preferably 28 to 36 mN / m, and particularly preferably 30 to 30 mN / m in 10 milliseconds by the maximum foam pressure method. It is 36 mN / m.
  • the dynamic surface tension in the present specification is a value measured in an environment of 25 ° C. using a bubble pressure dynamic surface tension meter BP100 manufactured by Kruss.
  • the black inkjet ink of the present invention may be used as a single color, or may be used as a set of water-based inkjet inks by combining a plurality of colors according to the intended use. Above all, the black inkjet ink of the present invention is preferable because when used in combination with an ink exhibiting process colors such as cyan, magenta, and yellow, a color printed image having a jet-black feeling and excellent image quality can be obtained. Further, when printing on a recording medium other than white, a clear image can be obtained by using white ink together.
  • the color inkjet ink having a process color such as cyan ink, magenta ink, and yellow ink used in combination with the black inkjet ink of the present invention contains pigment and water.
  • these color inkjet inks may contain an organic solvent, a pigment dispersion resin, a dispersion aid, a binder resin, a surfactant, a pH adjuster, and other components. The details regarding these components are the same as in the case of the black inkjet ink described above.
  • an organic solvent contained in each of cyan inkjet ink, magenta inkjet ink, and yellow inkjet ink and having a boiling point of 250 to 300 ° C. under 1 atm is preferably 5% by mass or less (may be 0% by mass) with respect to the total amount of ink, and is 3% by mass or less (may be 0% by mass) with respect to the total amount of ink. Is more preferable, and it is particularly preferable that it is 2% by mass or less (may be 0% by mass).
  • the ink set comprises black inkjet ink, cyan inkjet ink, magenta inkjet ink, and yellow inkjet ink, wherein the cyan inkjet ink, magenta inkjet ink, and yellow inkjet ink are water, pigment, and yellow ink, respectively.
  • the amount of the organic solvent containing the organic solvent and having a boiling point of 250 to 300 ° C. under 1 atm is 5% by mass or less.
  • the boiling point of the organic solvent contained in the ink at 1 atm (two or more kinds of the organic solvent are used).
  • the weighted average value of the boiling point) is 1 ° C or more smaller than the boiling point of the organic solvent contained in the black inkjet ink under 1 atm (if two or more of the organic solvents are contained, the weighted average value of the boiling point). It is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and particularly preferably 10 ° C. or higher.
  • the black inkjet ink, the cyan inkjet ink, the magenta inkjet ink, and the yellow inkjet ink are dried at the same time by using a drying method that irradiates an electromagnetic wave such as an infrared drying method, the print density of all colors is increased. Can be enhanced.
  • the cyan inkjet ink, the magenta inkjet ink, and the yellow inkjet ink each contain wax.
  • the wax those exemplified above can be used as the wax that can be used for the black inkjet ink.
  • the blending amount of the wax is preferably 0.2 to 8% by mass, and 0.3 to 5% by mass, respectively, based on the total amount of the ink, from the viewpoint of obtaining an ink having excellent ejection stability and scratch resistance of the printed matter. Is more preferable, and 0.5 to 4% by mass is particularly preferable.
  • the blending amount thereof is preferably 0.5% by mass or more less than the blending amount of the wax in the black inkjet ink, preferably 1.0 mass. % Or more is preferable, and 1.5% by mass or more is particularly preferable.
  • the black inkjet ink, the cyan inkjet ink, the magenta inkjet ink, and the yellow inkjet ink are dried at the same time by using a drying method that irradiates an electromagnetic wave such as an infrared drying method, the print density of all colors is increased. Can be enhanced.
  • cyan inkjet ink examples include C.I. I. Pigment Blue 1, 2, 3, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66 and the like. Above all, from the viewpoint of excellent color development and light resistance, C.I. I. One or more selected from the group consisting of Pigment Blue 15: 3 and 15: 4 is preferable. In addition, for the purpose of improving color reproducibility, C.I. I. Pigment Green 7, 36, 43, 58 and other green pigments may be mixed.
  • magenta pigment used in the magenta inkjet ink examples include C.I. I. Pigment Red 5, 7, 12, 22, 23, 31, 48 (Ca), 48 (Mn), 49, 52, 53, 57 (Ca), 57: 1, 112, 122, 146, 147, 150, 185. , 238, 242, 254, 255, 266, 269, and 282, and C.I. I. Pigment Bio Red 19, 23, 29, 30, 37, 40, 43, 50 and the like. Above all, from the viewpoint of excellent color development and light resistance, C.I. I. Pigment Red 122, 146, 150, 185, 202, 209, 254, 266, 269, and 282, and C.I. I. One or more pigments selected from the group consisting of Pigment Violet 19 are preferred.
  • ⁇ Yellow inkjet ink> As the yellow organic pigment used in the yellow inkjet ink, for example, C.I. I. Pigment Yellow 10, 11, 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, Examples thereof include 148, 150, 151, 154, 155, 166, 168, 180, 185, and 213. Above all, from the viewpoint of excellent color development, C.I. I. One or more selected from the group consisting of Pigment Yellow 12, 13, 14, 74, 83, 120, 150, 151, 154, 155, 180 and 185 is preferable.
  • the above-mentioned water-based inkjet ink set includes black inkjet ink, and in addition to the above-mentioned cyan inkjet ink, magenta inkjet ink, and yellow inkjet ink, inkjet inks exhibiting spot colors such as violet, blue, red, orange, green, and brown. May include.
  • the black inkjet ink of the present invention or a set of water-based inkjet ink containing the black inkjet ink can also be used in the form of an ink (or ink set) -pretreatment liquid set in combination with a pretreatment liquid containing a flocculant.
  • a pretreatment liquid containing the flocculant onto the recording medium, it is possible to form a layer (ink agglomerate layer) that intentionally aggregates the solid components contained in the ink.
  • the scratch resistance and blocking resistance of the printed matter can also be improved. Further, when a highly absorbent recording medium is used as the recording medium, it is possible to obtain a printed matter having excellent color development and color reproducibility as well as image quality.
  • the term "aggregating agent" refers to a component contained in an ink that can destroy and aggregate the dispersed state of pigments and resin particles, and / or insolubilize a water-soluble resin and thicken the ink. means.
  • a flocculant it is preferable to contain at least one selected from a metal salt and a cationic polymer compound from the viewpoint of significantly improving image quality, color development and color reproducibility.
  • a metal salt as the flocculant, and it is a group consisting of Ca 2+ , Mg 2+ , Zn 2+ and Al 3+ .
  • salts of polyvalent metal ions selected from.
  • the content thereof is preferably 2 to 30% by mass, particularly preferably 3 to 25% by mass, based on the total amount of the pretreatment liquid.
  • an organic solvent e.g., a surfactant, a pH adjuster, an antifoaming agent, an antiseptic, etc.
  • a surfactant e.g., a surfactant, a pH adjuster, an antifoaming agent, an antiseptic, etc.
  • a pH adjuster e.g., a pH adjuster
  • an antifoaming agent e.g., an antiseptic, etc.
  • an antiseptic e.g., a surfactant, a pH adjuster, an antifoaming agent, an antiseptic, etc.
  • the materials that can be specifically used are the same as in the case of black inkjet ink.
  • the static surface tension of the pretreatment liquid is preferably 20 to 45 mN / m from the viewpoint of obtaining a printed matter having excellent image quality when used in combination with the black inkjet ink of the present invention. It is more preferably 23 to 40 mN / m. Particularly preferably, it is 25 to 37 mN / m.
  • the static surface tension of the pretreatment liquid can be measured by the same method as the static surface tension of the black inkjet ink.
  • the black inkjet ink of the present invention or a set of water-based inkjet ink containing the black inkjet ink is used for a recording method (inkjet recording method) of ejecting from an inkjet head and applying the ink onto a recording medium.
  • the black inkjet ink is preferably used in a printing apparatus having an ink circulation mechanism configured to communicate with the inkjet head.
  • the pass method in the inkjet recording method there are a single pass method in which inkjet ink is ejected to a recording medium only once for recording, and a short shuttle head is reciprocally scanned in a direction perpendicular to the transport direction of the recording medium.
  • Either the serial method of discharging and recording may be adopted.
  • the serial method it is necessary to adjust the ejection timing in consideration of the movement of the inkjet head, and the landing position is likely to shift. Therefore, when printing the black inkjet ink of the present invention, a single-pass method, particularly a method in which a recording medium is passed under a fixed inkjet head, is preferably used.
  • a method of ejecting black inkjet ink which is a known method, for example, a drop-on-demand method (pressure pulse method) that utilizes the vibration pressure of a piezo element, or a method that heats ink to form bubbles.
  • a thermal inkjet (bubble jet (registered trademark)) method that uses pressure can be used.
  • the amount of ink droplets ejected from the inkjet head is preferably 0.2 to 30 picolitres from the viewpoint of greatly reducing the drying load and improving color reproducibility and image quality. More preferably, it is 1 to 20 picolitres.
  • the printing apparatus equipped with the black inkjet ink of the present invention or a set of water-based inkjet ink containing the black inkjet ink is a recording medium for the set of the black inkjet ink or the water-based inkjet ink containing the black inkjet ink by an inkjet printing method. It is preferable to have a mechanism for drying the ink on the recording medium after applying the ink on the printing medium.
  • the drying method used in the drying mechanism one of a method of directly or indirectly contacting the ink and the heat source and a method of irradiating electromagnetic waves may be used, or a plurality of types may be used. May be used in combination. For example, by using the infrared drying method and the hot air drying method in combination, the ink can be dried more quickly than when each of them is used alone.
  • the drying temperature is set to 35 to 100 ° C.
  • the hot air temperature is 50 to 250 ° C.
  • an infrared drying method as a method for drying the black inkjet ink of the present invention.
  • 50% or more of the integrated value of the total output of infrared rays used for infrared irradiation is present in the wavelength region of 700 to 1500 nm. Is preferable.
  • Examples of light sources that irradiate infrared rays used in the infrared drying method include infrared lamps (halogen lamps, sheathed lamps, carbon lamps, etc.), infrared LEDs, infrared LDs, and the like.
  • halogen lamps and infrared LEDs are preferably selected from the viewpoint of easily achieving the above-mentioned infrared output conditions.
  • An optical filter and / or a reflection mirror may be used in combination with the light source that irradiates the infrared rays.
  • the recording medium for printing the black inkjet ink of the present invention or a set of water-based inkjet ink containing the black inkjet ink is not particularly limited, and is a high-absorbency recording medium, a low-absorbency recording medium, and a non-absorbent recording medium. Etc., all known ones can be used arbitrarily. As described above, the ink of the present invention can obtain a printed matter having excellent scratch resistance and print density regardless of the permeability of the recording medium.
  • the permeability of the recording medium shall be judged by the amount of water absorption measured by the dynamic scanning liquid absorption meter.
  • a recording medium having a water absorption amount of pure water of less than 1 g / m 2 at a contact time of 100 msec, which is measured by the following method is referred to as a “non-absorbable recording medium”, and is 1 g / m 2 or more and 10 g / m 2 .
  • a recording medium having a value of less than or less than 10 g / m 2 is referred to as a “low absorption recording medium”, and a recording medium having a value of 10 g / m 2 or more is referred to as a “high absorption recording medium”.
  • the amount of water absorbed by the recording medium can be measured under the following conditions.
  • a KM500win manufactured by Kumagai Riki Kogyo Co., Ltd. is used as a dynamic scanning liquid absorption meter, and a recording medium having a size of about 15 to 20 cm square is used under the conditions of 23 ° C. and 50% RH, and pure water is used under the conditions shown below.
  • the amount of metastasis is measured.
  • high-absorbency recording media examples include non-coated paper such as stencil paper, medium-quality paper, wood-free paper, and recycled paper, cotton, synthetic fiber woven fabric, silk, linen, non-woven fabric and leather.
  • uncoated paper such as stencil paper, medium-quality paper, wood-free paper, and recycled paper is preferable from the viewpoint of obtaining printed matter having excellent ink print density, color development, and image quality.
  • non-absorbent recording media or low-absorbent recording media include plastic substrates such as polyvinyl chloride, polyethylene terephthalate (PET), polypropylene, polyethylene, nylon, polystyrene, and polyvinyl alcohol, coated paper, and art paper.
  • plastic substrates such as polyvinyl chloride, polyethylene terephthalate (PET), polypropylene, polyethylene, nylon, polystyrene, and polyvinyl alcohol, coated paper, and art paper.
  • coated paper base materials such as cast paper, metal base materials such as aluminum, iron, stainless steel, and titanium, and glass base materials.
  • the recording media listed above may have a smooth surface, an uneven surface, or may be transparent, translucent, or opaque. Further, two or more of these recording media may be bonded to each other. Further, a peeling adhesive layer or the like may be provided on the opposite side of the printed surface, or an adhesive layer or the like may be provided on the printed surface after printing. Further, the shape of the recording medium used in the above-mentioned inkjet recording method may be a roll shape or a sheet-fed shape.
  • the scratch resistance can also be improved. It is also preferable to perform surface modification such as corona treatment and plasma treatment.
  • ⁇ Self-dispersed pigment dispersion 1> As a self-dispersing pigment, "BONJET BLACK CW-3" (manufactured by Orient Chemical Industry Co., Ltd., carbon black having a carboxyl group and a hydroxyl group introduced on the surface, an average particle size of 100 nm, a pigment concentration of 13%) is used, and the pigment concentration is used. Water was partially volatilized and removed so that the concentration was 15%, and the self-dispersed pigment dispersion liquid 1 was obtained.
  • ⁇ Self-dispersed pigment dispersion 2> As a self-dispersing pigment, "BONJET BLACK CW-1" (manufactured by Orient Chemical Industry Co., Ltd., carbon black having a carboxyl group and a hydroxyl group introduced on the surface, an average particle size of 65 nm, and a pigment concentration of 20%) is used, and the pigment concentration is used. Water was added so that the concentration was 15%, and the self-dispersed pigment dispersion liquid 2 was prepared.
  • the pigment dispersion resin 1 was water-soluble.
  • the weight average molecular weight of the pigment-dispersed resin 1 measured by the method described above was 16,000, and the acid value was 230.
  • ⁇ Production example of a methyl ethyl ketone solution of pigment dispersion resin 2 95 parts of methyl ethyl ketone was charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and as a polymerizable monomer, 70 parts of styrene, 5 parts of acrylic acid, 10 parts of methyl methacrylate, 15 parts of polypropylene glycol methacrylate (Blemmer PP-500 manufactured by Nichiyu Co., Ltd.), and a polymerization initiator.
  • the pigment-dispersed resin 2 was water-insoluble. The weight average molecular weight of the pigment-dispersed resin measured by the method described above was 25,500, and the acid value was 30.
  • ⁇ Production example of resin dispersion pigment dispersion liquid 1> In a mixing container equipped with a stirrer, 15 parts of carbon black (primary particle diameter 16 nm, BET specific surface area 200 nm), 15 parts of an aqueous solution of the pigment dispersion resin 1 (solid content 30%), and 70 parts of water are placed. After putting them in order, premixing was performed. Then, the main dispersion was carried out using a dynomill having a volume of 0.6 L filled with 1800 g of zirconia beads having a diameter of 0.5 mm to obtain a resin-dispersed pigment dispersion 1 (pigment concentration 15%, solid content 19.5%). Obtained.
  • the "aqueous solution” means a solution containing an aqueous medium and components dispersed and / or dissolved in the aqueous medium.
  • 1.5 parts of the prepared emulsion precursor was added to a reaction vessel containing an aqueous surfactant solution and mixed well.
  • the inside of the reaction vessel was heated to 60 ° C., replaced with nitrogen gas, and then 1 part of a 5% aqueous solution of potassium persulfate and 0.2 part of a 1% aqueous solution of anhydrous sodium bicarbonate were added to the inside of the reaction vessel.
  • the polymerization reaction was started while keeping the temperature at 60 ° C. After reacting at 60 ° C.
  • Table 1 also shows the acid value of the resin particles 1 to 3, the glass transition temperature, and the weight average molecular weight.
  • the abbreviations of the polymerizable monomers shown in Table 1 are as follows. -St: Styrene-MAA: Methacrylic acid-MMA: Methyl methacrylate-BA: Butyl acrylate-PME-400: Methoxypolyethylene glycol methacrylate (NOF Blemmer PME-400)
  • black inkjet inks 2 to 42 were obtained by the same method as that of black inkjet ink 1 except that the materials shown in Table 3 below were used.
  • (wax) -P5300 Hi-Tech P5300 (manufactured by Toho Chemical Industry Co., Ltd., polypropylene wax, water dispersion with a solid content of 30%, melting point 146 ° C., average particle diameter 78 nm)
  • AQ515 AQUACER 515 (polyethylene wax manufactured by BYK Chemie, aqueous dispersion with a solid content of 35%, melting point 135 ° C., average particle size 36 nm).
  • AQ541 AQUACER 541 (polyethylene wax manufactured by BYK Chemie, aqueous dispersion with a solid content of 30%, melting point 80 ° C., average particle size 180 nm)
  • FE230N Charine FE230N (manufactured by Nissin Chemical Industry Co., Ltd., silicone wax, aqueous dispersion with a solid content of 30%, average particle size of 270 nm) (Water-soluble organic solvent)
  • OD value optical density
  • a spectroscopic densitometer eXact manufactured by X-RITE
  • the light source was D50
  • the viewing angle was 2 °
  • the density status was ISO Status T
  • the density white standard was an absolute value.
  • the evaluation criteria are as follows, and the evaluation reference values 2 to 4 are set as the practical range. 4: OD value 1.30 or more 3: OD value 1.20 or more and less than 1.30 2: OD value 1.10 or more and less than 1.20 1: OD value less than 1.10
  • the light source, viewing angle, density status, and density white standard were the same as the conditions in Evaluation 1 above.
  • the evaluation criteria are as follows, and the evaluation reference values 2 to 4 are set as the practical range. 4: OD value 2.00 or more 3: OD value 1.90 or more and less than 2.00 2: OD value 1.80 or more and less than 1.90 1: OD value less than 1.80
  • ⁇ Evaluation 3 Evaluation of printed matter density (coated paper, infrared drying)> After filling the inkjet printing apparatus used in Evaluation 1 with the black inkjet inks 1 to 42 manufactured above, the drop volume is 12 pL, and Oji Paper Co., Ltd. OK top coat + (coated paper, basis weight 104.7 g / m). 2 ) A solid image (printing rate 100%, equivalent to ink film thickness 6 ⁇ m) was printed on the top. Next, the obtained solid image was passed through the infrared drying device at a speed of 50 m / min.
  • an infrared lamp having a peak wavelength of 1.5 ⁇ m was arranged so that infrared rays could be irradiated over 12 cm in a direction parallel to the transport direction of the recording medium. Further, the output power was adjusted in advance so that the surface temperature of the solid image portion immediately after the completion of infrared irradiation was 90 ° C. Then, the optical density (OD value) of the printed matter after passing through the infrared drying device was measured in the same manner as in Evaluation 2.
  • the evaluation criteria are as follows, and the evaluation reference values 2 to 4 are set as the practical range. 4: OD value 2.00 or more 3: OD value 1.90 or more and less than 2.00 2: OD value 1.80 or more and less than 1.90 1: OD value less than 1.80
  • ⁇ Evaluation 4 Evaluation of scratch resistance> After filling the inkjet printing apparatus used in Evaluation 1 with the black inkjet inks 1 to 42 manufactured above, the drop volume is 12 pL, and Oji Paper Co., Ltd. OK top coat + (coated paper, basis weight 104.7 g / m). 2 ) A solid image (printing rate 100%, equivalent to ink film thickness 6 ⁇ m) was printed on the print, and the printed matter was put into an air oven at 70 ° C. within 10 seconds. After drying for 1 minute, the printed matter is taken out of the oven, rubbed with a test white cotton cloth (Kanakin No.
  • the evaluation criteria are as follows, and the evaluation reference values 2 to 4 are set as the practical range. No scratches or ink peeling were observed on the printed surface even after rubbing 4:20 times. No scratches or ink peeling were observed on the printed surface even after rubbing 3: 10 times, but printing was performed after rubbing 20 times. Surface scratches and ink peeling were seen 2: 5 times rubbing did not show scratches on the printed surface or ink peeling, but 10 times rubbing showed scratches on the printed surface and ink peeling. After rubbing 1: 5 times, scratches on the printed surface and peeling of ink were observed.
  • ⁇ Evaluation 5 Evaluation of discharge stability>
  • the inkjet printing apparatus used in Evaluation 1 was filled with the black inkjet inks 1 to 42 produced above, respectively. After printing the nozzle check pattern and confirming that there was no nozzle omission, the product was allowed to stand by for a predetermined time in an environment of 25 ° C. After that, the nozzle check pattern was printed again and the number of missing nozzles was counted to evaluate the ejection stability.
  • the evaluation criteria are as follows, and the evaluation criteria values 2 to 4 are set as the practical range. There was no nozzle omission even after waiting for 4: 3 hours. Nozzle omission was not found even after waiting for 3: 2 hours, but nozzle omission was 1 after waiting for 3 hours. Nozzle omission occurred at all even after waiting for 2: 1 hour, but after waiting for 2 hours, one or more nozzles had occurred. Waiting for 1: 1 hour. Later, one or more nozzles were missing.
  • the black inkjet inks 1 to 38 containing the self-dispersed pigment, the resin-dispersed pigment, and the wax and having an organic solvent content of 29% by mass or less were printed when the recording medium and the drying method were changed. It was confirmed that the printed matter had practical quality in all of the density, the scratch resistance of the printed matter, and the ejection stability.
  • cyan pigment dispersion liquid 1 As a pigment, C.I. I. 20 parts of Pigment Blue 15: 3, 10 parts of an aqueous solution of pigment dispersion resin 1 and 70 parts of water were mixed, pre-dispersed with a disper, and then filled with 1,800 g of zirconia beads having a diameter of 0.5 mm. This dispersion was carried out using a 0.6 L dynomill to obtain a cyan pigment dispersion liquid 1.
  • cyan inkjet inks 1 to 5 The following materials were sequentially added to the mixing vessel while stirring with a disper, and stirred until sufficiently uniform. Then, filtration was performed with a membrane filter having a pore size of 1 ⁇ m to obtain cyan inkjet ink 1 (C1).
  • Cyan pigment dispersion 1 (pigment concentration 20%) 20 parts ⁇ AQUACER 515 (solid content 35%) 4 parts ⁇ Resin particles 1 (solid content 40%) 8 parts ⁇ Water-soluble resin 1 (solid content 40%) 4 parts ⁇ 15 parts of 1,2-propanediol ⁇ 6 parts of 1,2-hexanediol ⁇ Surfinol 104 1 part ⁇ TEGO Wet 280 1 part ⁇ Triethanolamine 0.5 part ⁇ Proxel GXL 0.05 part ⁇ Ion exchanged water 40 .45 copies
  • Cyan inkjet inks 2 to 5 (C2 to C5) were produced in the same manner as in the production example of cyan inkjet ink 1 except that the raw materials shown in Table 5 were used.
  • magenta pigment dispersion liquid 1 As a pigment, C.I. I. 20 parts of Pigment Red 150, 10 parts of an aqueous solution of pigment dispersion resin 1 and 70 parts of water were mixed, pre-dispersed with a disper, and then filled with 1,800 g of zirconia beads having a diameter of 0.5 mm. This dispersion was carried out using a 6 L dynomill to obtain a magenta pigment dispersion liquid 1.
  • Magenta pigment dispersion 1 (pigment concentration 20%) 20 parts ⁇ AQUACER 515 (solid content 35%) 4 parts ⁇ Resin particles 1 (solid content 40%) 8 parts ⁇ Water-soluble resin 1 (solid content 40%) 4 parts ⁇ 15 parts of 1,2-propanediol ⁇ 6 parts of 1,2-hexanediol ⁇ Surfinol 104 1 part ⁇ TEGO Wet 280 1 part ⁇ Triethanolamine 0.5 part ⁇ Proxel GXL 0.05 part ⁇ Ion exchanged water 40 .45 copies
  • magenta inkjet inks 2 to 5 were produced in the same manner as in the production example of magenta inkjet ink 1 except that the raw materials shown in Table 5 were used.
  • yellow pigment dispersion liquid 1 As a pigment, C.I. I. 20 parts of Pigment Yellow 14, 10 parts of an aqueous solution of pigment dispersion resin 1 and 70 parts of water were mixed, pre-dispersed with a disper, and then filled with 1,800 g of zirconia beads having a diameter of 0.5 mm. This dispersion was carried out using a 6 L dynomill to obtain a yellow pigment dispersion liquid 1.
  • Yellow pigment dispersion 1 (pigment concentration 20%) 20 parts ⁇ AQUACER 515 (solid content 35%) 4 parts ⁇ Resin particles 1 (solid content 40%) 8 parts ⁇ Water-soluble resin 1 (solid content 40%) 4 parts ⁇ 15 parts of 1,2-propanediol ⁇ 6 parts of 1,2-hexanediol ⁇ Surfinol 104 1 part ⁇ TEGO Wet 280 1 part ⁇ Triethanolamine 0.5 part ⁇ Proxel GXL 0.05 part ⁇ Ion exchanged water 40 .45 copies
  • yellow inkjet inks 2 to 5 (Y2 to Y5) were produced in the same manner as in the production example of yellow inkjet ink 1 except that the raw materials shown in Table 5 were used.
  • Examples 39 to 43> The black inkjet ink, cyan inkjet ink, magenta inkjet ink, and yellow inkjet ink produced above were used in the combinations (ink sets) shown in Table 6 and evaluated as follows. The evaluation results obtained were as shown in Table 6.
  • ⁇ Evaluation 7 Evaluation of print density (sharpness)> After filling each of the ink jet printing devices used in Evaluation 6 with the ink combinations shown in Table 6 as an ink set, the drop volume is 12 pL, and Oji Paper Co., Ltd. OK top coat + (coated paper, basis weight 104.7 g /). A natural image N1 (portrait) of JIS X 9201 high-definition color digital standard image data (CMYK / SCID) was printed on m 2 ). Then, the obtained image was passed through the infrared drying device at a speed of 50 m / min.
  • an infrared lamp having a peak wavelength of 1.5 ⁇ m was arranged so that infrared rays could be irradiated over 12 cm in a direction parallel to the transport direction of the recording medium. Further, the output power was adjusted in advance so that the surface temperature of the image portion immediately after the end of infrared irradiation was 90 ° C. Then, the printed matter after passing through the infrared drying device was visually observed, and the print density (sharpness) was evaluated.
  • the evaluation criteria are as follows, and the evaluations of 2 and 3 are set as practical areas. 3: It was sufficiently clear and the print density was sufficiently high. 2: The print density was sufficiently high although it was slightly unclear, or the image was sufficiently clear even though the print density was slightly low. 1 : The sharpness was clearly low, and the print density was also low.
  • ⁇ Evaluation 8 Evaluation of scratch resistance> Of the color chart image printed matter produced in evaluation 6, the same method and evaluation as in evaluation 4 described above are used except that the portion having a total print rate of 320% (that is, the print rate of each color is 80%) is used. The scratch resistance was evaluated according to the evaluation criteria.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention concerne : une encre noire pour jet d'encre contenant de l'eau, un pigment, un solvant organique et de la cire, le pigment comprenant un pigment auto-dispersible et un pigment dispersé dans une résine, et la teneur en solvant organique étant d'au plus 29 % en masse par rapport à la quantité totale de l'encre ; et un ensemble d'encres comprenant ladite encre noire pour jet d'encre, et une encre cyan pour jet d'encre, une encre magenta pour jet d'encre et une encre jaune pour jet d'encre dans lesquelles la quantité d'un solvant organique ayant un point d'ébullition de 250-300 °C sous 1 atm est d'au plus 5 % en masse.
PCT/JP2021/033567 2020-12-04 2021-09-13 Encre noire pour jet d'encre et ensemble d'encres WO2022118519A1 (fr)

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JP2002079740A (ja) * 2000-06-21 2002-03-19 Canon Inc インクジェットプリント方法
JP2012171987A (ja) * 2011-02-17 2012-09-10 Fujifilm Corp インク組成物、インクセット、及び画像形成方法
JP2014091772A (ja) * 2012-11-02 2014-05-19 Seiko Epson Corp インクジェット記録用のインク、インクジェット記録システム
JP2015183027A (ja) * 2014-03-20 2015-10-22 東洋インキＳｃホールディングス株式会社 インクジェットインキおよびそれを用いた印刷方法
WO2016080140A1 (fr) * 2014-11-17 2016-05-26 株式会社Ｓｃｒｅｅｎホールディングス Composition aqueuse d'encre pour jet d'encre
JP2017008294A (ja) * 2015-06-23 2017-01-12 株式会社リコー インク、インク収納容器、インクジェット記録装置、及び印刷物
JP2018127536A (ja) * 2017-02-08 2018-08-16 花王株式会社 水性インク
JP2018172502A (ja) * 2017-03-31 2018-11-08 ブラザー工業株式会社 インクジェット記録用水性インク
JP2019202419A (ja) * 2018-05-21 2019-11-28 キヤノン株式会社 インクジェット記録方法、及びインクジェット記録装置
JP2020070334A (ja) * 2018-10-30 2020-05-07 東洋インキＳｃホールディングス株式会社 インキセット、及び印刷物の記録方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000239589A (ja) * 1998-12-22 2000-09-05 Canon Inc インク、インク容器、インクセット、インクジェット記録装置及びインクジェットプリント方法
JP2002079740A (ja) * 2000-06-21 2002-03-19 Canon Inc インクジェットプリント方法
JP2012171987A (ja) * 2011-02-17 2012-09-10 Fujifilm Corp インク組成物、インクセット、及び画像形成方法
JP2014091772A (ja) * 2012-11-02 2014-05-19 Seiko Epson Corp インクジェット記録用のインク、インクジェット記録システム
JP2015183027A (ja) * 2014-03-20 2015-10-22 東洋インキＳｃホールディングス株式会社 インクジェットインキおよびそれを用いた印刷方法
WO2016080140A1 (fr) * 2014-11-17 2016-05-26 株式会社Ｓｃｒｅｅｎホールディングス Composition aqueuse d'encre pour jet d'encre
JP2017008294A (ja) * 2015-06-23 2017-01-12 株式会社リコー インク、インク収納容器、インクジェット記録装置、及び印刷物
JP2018127536A (ja) * 2017-02-08 2018-08-16 花王株式会社 水性インク
JP2018172502A (ja) * 2017-03-31 2018-11-08 ブラザー工業株式会社 インクジェット記録用水性インク
JP2019202419A (ja) * 2018-05-21 2019-11-28 キヤノン株式会社 インクジェット記録方法、及びインクジェット記録装置
JP2020070334A (ja) * 2018-10-30 2020-05-07 東洋インキＳｃホールディングス株式会社 インキセット、及び印刷物の記録方法

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