WO2021240970A1 - Ensemble d'encres jet d'encre aqueuses et procédé de production d'un article imprimé - Google Patents

Ensemble d'encres jet d'encre aqueuses et procédé de production d'un article imprimé Download PDF

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Publication number
WO2021240970A1
WO2021240970A1 PCT/JP2021/011635 JP2021011635W WO2021240970A1 WO 2021240970 A1 WO2021240970 A1 WO 2021240970A1 JP 2021011635 W JP2021011635 W JP 2021011635W WO 2021240970 A1 WO2021240970 A1 WO 2021240970A1
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Prior art keywords
pigment
ink
group
water
yellow
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PCT/JP2021/011635
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English (en)
Japanese (ja)
Inventor
睦子 正時
純 依田
雄司 亀山
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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 WO2021240970A1 publication Critical patent/WO2021240970A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/18—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides
    • C09B29/20—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides of the naphthalene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • 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

Definitions

  • An embodiment of the present invention relates to an ink set containing a water-based inkjet magenta ink and a water-based inkjet yellow ink, and a method for manufacturing a printed matter.
  • the inkjet printing method is a method of forming an image and / or characters on the recording medium by flying and landing minute droplets of ink from the inkjet head on the recording medium, and does not require a plate. It is a feature. Compared to the electrophotographic method, which is another printing method that does not require a plate, the inkjet printing method is superior in terms of price and size of printing equipment, running cost at the time of printing, high-speed printing characteristics, etc., and future growth is expected. It is expected.
  • ink used in the inkjet printing method such as oil-based, solvent-based, active energy ray-curing, and water-based.
  • the active energy ray-curable inkjet printing method has been widely used because it can print on a non-permeable substrate such as plastic or glass, has excellent resistance to printed matter, and can realize high-speed printing. ..
  • regulations on polymerizable monomers have been promoted from the viewpoint of dealing with harmful effects on the environment and humans.
  • the inkjet printing method will be developed in the industrial printing market and the package printing market, where the plate printing method such as the offset printing method has been conventionally used.
  • the productivity and color reproducibility of printed matter are very important. For example, many spot color inks are used in the offset printing method, and printed matter having an excellent color reproduction area is produced. Therefore, in order to achieve the practical application of the inkjet printing method in the above printing market, excellent colors are used. Achieving reproducibility is important.
  • colorants are roughly classified into dyes and pigments.
  • dyes have the advantages of good color development and low cost, but have the disadvantages of being inferior in water resistance, light resistance, etc., and easily discolored.
  • these drawbacks can often be fatal, and the inks used in those markets use pigments as colorants.
  • pigments used in magenta ink include laked azo pigments, naphthol-based azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments and the like.
  • naphthol-based azo pigments are relatively inexpensive, have high coloring power, and often have superior properties to the other pigments listed above. It is widely used as a colorant for inkjet inks.
  • the naphthol pigment has a drawback that the dispersion stability is poor and the ejection stability from the inkjet head is poor.
  • Patent Document 2 C.I. I. Pigment Red 150 and the C.I. I. A pigment composition obtained by simultaneously synthesizing a compound different from Pigment Red 150 is disclosed. According to Patent Document 2, a pigment composition having good dispersion stability can be obtained, but there is a problem that the effect of improving the dispersion stability cannot be obtained depending on the material used in combination with the pigment composition. be.
  • Patent Document 3 discloses an aqueous inkjet magenta ink that does not form a solid solution (mixed crystal) with each other and contains two kinds of pigments having different hue angles, it is not always good from the viewpoint of versatility of the base material. I wouldn't say that. Specifically, the above-mentioned water-based inkjet magenta ink has a problem that the color development property is poor with respect to the high-quality paper often used in the industrial printing market.
  • color reproducibility is very important in the industrial printing market and the package printing market, but in particular, red with high light resistance as a design for sales promotion, corporate color of a company, national color of an emerging country, etc. Color is often required.
  • the red color is formed by superimposing the process colors yellow and magenta, but from the viewpoint of improving the color reproducibility of the red region, it is essential to improve the color reproducibility and color development of the base magenta ink. It is essential.
  • a processing liquid is applied to the recording medium, and the recording medium is dried every time one color is printed. Techniques such as doing have been taken. However, in either method, it was inevitable that the printing equipment would become larger and the price would increase.
  • Patent Document 4 a good image, particularly a good hue image, is realized in addition to light resistance and water resistance by forming an ink set in which a cyan, magenta, and yellow ink composition containing a specific colorant is combined. It is suggested that you can do it.
  • the quinacridone pigment used in the magenta ink composition is inferior in color development. Even if the quinacridone pigment is changed to a naphthol-based pigment, there is a problem that a sufficient hue cannot be obtained depending on the organic solvent or the like used in combination, and further, fading of the printed matter occurs.
  • Japanese Unexamined Patent Publication No. 2009-24702 Japanese Unexamined Patent Publication No. 2010-195907 Japanese Unexamined Patent Publication No. 2017-155092 Japanese Unexamined Patent Publication No. 2008-291103
  • An embodiment of the present invention has been made to solve the above problems, and an object thereof is to have a water-based inkjet magenta ink having excellent dispersion stability and ejection stability, and has image quality, color development and color reproduction. It is an object of the present invention to provide a water-based inkjet ink which has excellent properties and can obtain a printed matter which does not cause discoloration or fading over time.
  • magenta ink as a magenta ink in which a basic organic compound and a naphthol-based mixed crystal pigment are used in combination to limit the amount of an organic solvent having a high boiling point.
  • the present invention has been completed by finding that the above-mentioned problems can be solved by an inkjet ink set containing a yellow ink containing the yellow pigment of the above.
  • one embodiment of the present invention is an inkjet ink set including a water-based inkjet magenta ink and a water-based inkjet yellow ink.
  • the water-based inkjet magenta ink contains magenta pigment (A), a water-soluble organic solvent, a basic organic compound, and water.
  • the magenta pigment (A) contains a mixed crystal pigment (A-1) containing two or more kinds of pigments having a structure represented by the following general formula (1).
  • the content of the mixed crystal pigment (A-1) is 1 to 10% by mass in the total amount of the water-based inkjet magenta ink.
  • the basic organic compound contains 0.1 to 1.25% by mass of the basic organic compound (B) having a pKa value of 9.5 or less at 25 ° C. in the total amount of the aqueous inkjet magenta ink.
  • the content of the organic solvent having a boiling point of 240 ° C. or higher under 1 atm is 8% by mass or less in the total amount of the aqueous inkjet magenta ink.
  • the water-based inkjet yellow ink contains a yellow pigment having a structure represented by the following general formula (3) and water.
  • the present invention relates to an inkjet ink set in which the content of the yellow pigment is 1 to 10% by mass in the total amount of the water-based inkjet yellow ink.
  • R 1 , R 2 and R 3 are independently hydrogen atoms, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an anilide group and a carbamoyl group, respectively.
  • R 4 is a hydrogen atom having 1 to 2 carbon atoms.
  • R 5 is any one of a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an amino group, or a nitro group.
  • each of R 6 and R 7 is independently a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an amino group, or a nitro group.
  • R 6 and R 7 are bonded to each other to form an imidazolidinone ring.
  • the * part is a bond.
  • General formula (3) (In the general formula (3), R 8 , R 9 , R 10 and R 11 are independently hydrogen atom, chlorine atom, alkyl group having 1 to 2 carbon atoms and alkoxy having 1 to 2 carbon atoms, respectively. It is either a group or an amino group. Further, when x is 1 or 2, and x is 1, R 12 is either a hydrogen atom, a chlorine atom, or a nitro group, and the x is either a hydrogen atom, a chlorine atom, or a nitro group. In the case of 2, the R 12 is a direct bond.)
  • the yellow pigment having the structure represented by the general formula (3) is C.I. I. Pigment Yellow 12 and C.I. I.
  • the present invention relates to the above inkjet ink set, which comprises at least one selected from the group consisting of Pigment Yellow 74.
  • the pigment having the structure represented by the general formula (1) is C.I. I.
  • the inkjet ink set comprising at least one selected from the group consisting of Pigment Red 31, 32, 146, 147, 150, 176, 185, 266, and 269.
  • the pigment having the structure represented by the general formula (1) is C.I. I.
  • the present invention relates to the inkjet ink set including Pigment Red 150.
  • the water-based inkjet yellow ink contains a basic organic compound (B) having a pKa value of 9.5 or less at 25 ° C. in 0.1 to the total amount of the water-based inkjet yellow ink.
  • B basic organic compound having a pKa value of 9.5 or less at 25 ° C. in 0.1 to the total amount of the water-based inkjet yellow ink.
  • the present invention relates to the above-mentioned inkjet ink set containing 1.25% by mass.
  • one embodiment of the present invention relates to the above-mentioned inkjet ink set in which the water-based inkjet magenta ink and / or the water-based inkjet yellow ink contains amino alcohols as the basic organic compound (B).
  • one embodiment of the present invention relates to a method for manufacturing a printed matter, which comprises a step of printing the inkjet ink set on a recording medium by an inkjet printing method.
  • a printed matter having a water-based inkjet magenta ink having excellent dispersion stability and ejection stability, having excellent image quality, color development and color reproducibility, and not causing discoloration and fading over time can be obtained. It becomes possible to provide a water-based inkjet ink set that can be used.
  • a water-based inkjet ink set (hereinafter, also simply referred to as “ink set”) according to the embodiment of the present invention will be described with reference to preferred embodiments.
  • the "aqueous medium” means a medium composed of at least a liquid containing water.
  • chromatic color generally refers to all colors other than colors having no saturation (black, light black (gray), and white).
  • the ink set of the embodiment of the present invention includes a water-based inkjet magenta ink and a water-based inkjet yellow ink.
  • the water-based inkjet magenta ink (hereinafter, also simply referred to as “magenta ink”) contains a magenta pigment (A), a water-soluble organic solvent, a basic organic compound, and water, and the magenta pigment (A) contains.
  • magenta pigment contains 1 to 10% by mass of a mixed crystal pigment (A-1) composed of two or more kinds of pigments having a structure represented by the following general formula (1) in the total amount of the aqueous inkjet magenta ink.
  • the compound contains 0.1 to 1.5% by mass of the basic organic compound (B) having a pKa value of 9.5 or less at 25 ° C. in the total amount of the aqueous inkjet magenta ink, and has a boiling point of 240 at 1 atm.
  • the content of the organic solvent having a temperature of ° C. or higher is 8% by mass or less based on the total amount of the aqueous inkjet magenta ink.
  • the water-based inkjet yellow ink (hereinafter, also simply referred to as “yellow ink”) contains a yellow pigment having a structure represented by the following general formula (3) and water, and the content of the yellow pigment is the above. It is 1 to 10% by mass in the total amount of the water-based inkjet yellow ink.
  • R 1 , R 2 and R 3 are independently hydrogen atoms, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an anilide group and a carbamoyl group, respectively.
  • R 4 is either a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a group having a structure represented by the following general formula (2).
  • R 5 is any one of a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an amino group, or a nitro group.
  • R 6 and R 7 are independently any of a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an amino group, or a nitro group.
  • R 6 and R 7 are bonded to each other to form an imidazolidinone ring.
  • the part marked with * is a bond.
  • R 8 , R 9 , R 10 and R 11 are independently hydrogen atom, chlorine atom, alkyl group having 1 to 2 carbon atoms, and alkoxy having 1 to 2 carbon atoms, respectively. It is either a group or an amino group.
  • x is 1 or 2, and when x is 1, R 12 is either a hydrogen atom, a chlorine atom, or a nitro group, and when x is 2, R 12 is a direct bond. be.
  • a secondary color is formed by contacting two types of water-based inks having different hues on a recording medium.
  • a poorly permeable base material or a non-permeable base material is used as the recording medium
  • the printing medium is used.
  • the inks of the above will come into contact with each other in a wet state.
  • the colorants in the ink are aggregated, the colorants having different hues are bound to each other by interaction, and the distribution of the colorants is biased in the ink droplets, resulting in uneven shading.
  • Phenomena such as deterioration of color development and color reproducibility may occur.
  • the ink set containing the magenta ink and the yellow ink according to the embodiment of the present invention has the color development property in the red color region without using the secondary color ink (red ink) as conventionally used. It is possible to obtain a printed matter having excellent color reproducibility and no unevenness in shading.
  • the magenta ink contained in the ink set of the embodiment of the present invention is excellent in storage stability and dispersion stability (details will be described later), so that the magenta ink is the magenta ink even when it comes into contact with other inks. It is considered that the dispersed state of the naphthol-based mixed crystal pigment in the medium is stably maintained.
  • the naphthol-based mixed crystal pigment and the yellow pigment represented by the general formula (3) have relatively similar molecular structures, and thus affect the dispersed state of each other at the time of mixing. It is difficult to give each other, and the presence of the basic organic compound (B) having a specific pKa value makes it difficult to form a strong intramolecular interaction between each other. As a result, it is considered that the dispersion state of each other is not adversely affected during mixing, and the distribution of the pigment in the ink droplets is unlikely to be biased.
  • an ink set consisting of an ink containing a magenta pigment or a yellow pigment that does not have the above-mentioned structure
  • a printed matter that satisfies either color development and color reproducibility and image quality quality, but both. Difficult to meet.
  • a naphthol pigment other than a mixed crystal pigment is used as the magenta pigment
  • a quinacridone mixed crystal pigment is used as the magenta pigment
  • the red color region depends on the selection of the yellow ink to be combined as the ink set.
  • the printed matter is inferior in color reproducibility.
  • magenta pigment when a diketopyrrolopyrrole pigment is used as the magenta pigment, it is very difficult to achieve both the dispersion stability of the magenta ink containing the diketopyrrolopyrrole pigment and the image quality.
  • a yellow pigment C.I. I.
  • Pigment Yellow 185 isoindoline pigment
  • magenta ink containing a naphthol mixed crystal pigment when Pigment Yellow 185 (isoindoline pigment) is used and combined with magenta ink containing a naphthol mixed crystal pigment, the saturation of the red color region is inferior, and the color reproducibility and image quality of the color region are deteriorated. ..
  • a naphthol-based mixed crystal pigment having a specific structure and a basic organic compound having a specific pKa value are used in combination, and magenta in which the boiling point of the organic solvent to be used in combination is specified.
  • magenta ink and / or the yellow ink included in the ink set according to the embodiment of the present invention will be described in detail.
  • magenta ink forming the ink set of the embodiment of the present invention contains a magenta pigment (A) as a colorant, and the magenta pigment (A) has two or more kinds of structures represented by the above general formula (1).
  • a mixed crystal pigment (A-1) containing a pigment having a above hereinafter, also simply referred to as “naphthol-based mixed crystal pigment (A-1)”) is included.
  • naphthol pigments have excellent color development properties, but also have poor dispersion stability due to their molecular structure. Further, the mixed crystal pigment has improved optical properties such as color development and color reproducibility as compared with the case where each pigment forming the mixed crystal pigment is used alone, but the dispersion stability may be deteriorated.
  • a mixed crystal pigment containing two or more kinds of naphthol pigments hereinafter, also referred to as “naphthol mixed crystal pigment” in the present specification
  • has the above-mentioned poor dispersion stability which is a characteristic of the mixed crystal pigment.
  • the structure of the naphthol-based pigment forming the mixed crystal pigment is defined, and as will be described later, it is used in combination with the basic organic compound (B) having a specific pKa value, and further.
  • the basic organic compound (B) having a specific pKa value By limiting the amount of high-boiling organic solvent in magenta ink, while suppressing the above phenomenon, excellent optical characteristics, which are the characteristics of naphthol-based mixed crystal pigments, are exhibited, and dispersion stability and ejection stability are improved. In addition, it is possible to produce a printed matter having excellent color development and color reproducibility.
  • mixed crystal refers to a material in which two or more compounds are fused with each other to form a uniform solid phase as a whole, and is also called a solid solution. On the other hand, it is clearly distinguished from a mixture in which the two or more compounds are simply mixed.
  • the pigment forms a mixed crystal can be easily verified by X-ray diffraction analysis or the like.
  • the obtained X-ray diffraction pattern is a pattern in which the X-ray diffraction patterns of each pigment are superimposed, and the intensity of each diffraction peak is the compounding ratio of each pigment.
  • the intensity of each diffraction peak is the compounding ratio of each pigment.
  • an X-ray diffraction pattern different from the case where the plurality of pigments are simply mixed can be obtained. Specifically, phenomena such as the acquisition of a new diffraction peak, the intensity of each diffraction peak not depending on the blending ratio of the pigment, and the increase in the half-value width of the diffraction peak can be seen.
  • the naphthol-based mixed crystal pigment can be produced, for example, by the method described in JP-A-2005-107147 and JP-A-2010-195907.
  • the pigment forming the naphthol-based mixed crystal pigment (A-1) may contain a pigment other than the pigment having the structure represented by the general formula (1).
  • the naphthol-based mixed crystal pigment (A-1) comprises two or more pigments having a structure represented by the general formula (1) from the viewpoint of color development and color reproducibility of the printed matter. It is preferably a mixed crystal pigment.
  • R 1 is a methoxy group and R 2 is hydrogen from the viewpoint of color development and dispersion stability.
  • a compound which is an atom and R 3 is an anilide group is preferable, and the naphthol-based pigment forming the naphthol-based mixed crystal pigment has R 1 as a methoxy group, R 2 as a hydrogen atom, and R 3 in the above general formula (1). It is particularly preferable that the compound consists only of a compound which is an anilide group.
  • R 1 is a methoxy group
  • R 2 is a hydrogen atom
  • R 3 is an anilides group in the general formula (1), C.I. I. Pigment Red 31, 32, 146, 147, 150, 176, 269 and the like.
  • C.I. I. Pigment Red 150 has a structure represented by the above general formula (1), and in the general formula (1), R 1 is a methoxy group, R 2 is a hydrogen atom, and R 3 is anilides. It is particularly preferable to use a mixed crystal pigment composed of a compound as a group.
  • a naphthol-based mixed crystal pigment (A-1) is used as a component of C.I. I.
  • Pigment Red 150 is included, the above-mentioned C.I. I.
  • C.I. I is included, the above-mentioned C.I. I.
  • From the viewpoint of coloring power C.I. I. It is particularly preferred to select one or more selected from the group consisting of Pigment Red 31, 32, 146, 147, and 269.
  • C.I. I As a naphthol-based mixed crystal pigment (A-1), C.I. I.
  • the blending amount of Pigment Red 150 is preferably 0.1 to 99 mol%, more preferably 10 to 80 mol%, and 20 to 70 mol% in the naphthol-based mixed crystal pigment (A-1). It is particularly preferable to have. By keeping the blending amount within the above range, it is possible to achieve both coloring power (particularly, color development property when printed on a permeable substrate), dispersion stability, and ejection stability.
  • the content of the naphthol-based mixed crystal pigment (A-1) contained in the magenta ink is the total amount of the magenta ink. It is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, and particularly preferably 2 to 8% by mass.
  • magenta pigment (A) is a pigment other than the naphthol-based mixed crystal pigment (A-1) from the viewpoint of obtaining a printed matter having excellent color development and color reproducibility regardless of the recording medium used. (Hereinafter, also referred to as "other pigments for magenta ink”) may be used in combination.
  • magenta ink pigments orange pigments, magenta pigments, violet pigments and the like can be suitably used, and magenta pigments and / or violet pigments are included from the viewpoint of obtaining a printed matter having excellent color reproducibility in the red region. Is particularly suitable.
  • a magenta pigment and / or a violet pigment is used as a pigment for magenta ink other than the naphthol-based mixed crystal pigment (A-1)
  • the blending amount thereof is the naphthol-based mixed crystal pigment (A-1). It is preferably 10 to 100% by mass, and particularly preferably 20 to 70% by mass, based on the total amount of the mixture.
  • C.I. I. One or more selected from the group consisting of Pigment Orange 36, 38, 43, 60, 62, 64, and 72 can be preferably used.
  • magenta pigments that can be used together with the naphthol-based mixed crystal pigment (A-1) include naphthol-based pigments (excluding those that are mixed-crystal pigments), quinacridone-based pigments, and diketopyrrolopyrrole-based pigments. Be done.
  • the naphthol-based pigment the pigments listed above as specific examples of the naphthol-based pigment forming the naphthol-based mixed crystal pigment (A-1), and as the quinacridone-based pigment, C.I. I. Pigment Red 122, 202, 207, 209, etc., as a diketopyrrolopyrrole pigment, C.I. I. Pigment Red 254, 255 and the like.
  • the naphthol-based pigment (however, since the dispersed state of the naphthol-based mixed crystal pigment (A-1) is not easily destroyed and the color reproducibility when mixed with the naphthol-based mixed crystal pigment (A-1) is excellent.
  • a mixed crystal pigment) or a quinacridone-based pigment can be preferably used, for example, C.I. I.
  • One or more selected from the group consisting of Pigment Red 31, 32, 122, 146, 147, 150, 176, 185, 202, 209, 282, and 269 can be preferably used.
  • C.I. I. Pigment Violet 19, 23, 29, 30, 37, 40, 42, 43, 50 and the like C.I. I.
  • One or more selected from the group consisting of Pigment Violet 19, 23, 32, and 42 can be preferably used.
  • magenta ink pigments exemplified and selected above, benzimidazolone pigments, quinacridone pigments, naphthol pigments (excluding mixed crystal pigments), diketopyrrolopyrrole pigments, and One or more selected from the group consisting of dioxazine pigments is preferably selected. Since each of the pigments has a structure similar to that of the naphthol-based mixed crystal pigment (A-1), it is difficult to destroy the dispersed state of the naphthol-based mixed crystal pigment (A-1) and the dispersion stability is excellent. This is because the magenta ink can be obtained. These pigments are also suitable from the viewpoint of color reproducibility of printed matter. Above all, it is more preferable to use a quinacridone pigment and / or a naphthol pigment (however, the naphthol pigment is excluded from a mixed crystal pigment) in combination.
  • the blending amount of the quinacridone pigment or the naphthol pigment is determined. It is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, based on 100% by mass of the naphthol-based mixed crystal pigment (A-1). Within the above range, the dispersion stability is improved, and the color development and color reproducibility of the printed matter are improved regardless of the recording medium.
  • the yellow ink contained in the ink set of the embodiment of the present invention is a yellow ink having a structure represented by the above general formula (3) (hereinafter, also referred to as “azo yellow pigment”) as a colorant.
  • the total amount contains 1 to 10% by mass.
  • azo yellow pigment a mixed crystal pigment may be used, or a pigment other than the mixed crystal pigment may be used.
  • C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 49, 65, 73, 74, 168, 169 and the like
  • C.I. I. Pigment Yellow 12, 13, 14, 17, 55, 83, 87, 124, 127, 170, 171 and the like respectively.
  • C.I. I. Pigment Yellow preferably comprises one or more selected from the group consisting of 12, 13, 14, 74, and 83.
  • C.I. I. Pigment Yellow preferably comprises one or more selected from the group consisting of 12, 14, and 74.
  • the yellow ink may contain only one type of the above azo yellow pigment, or may contain two or more types in combination. When two or more kinds are used in combination, for example, a mixed crystal pigment as disclosed in JP-A-2007-527458 may be used.
  • the total amount of the azo yellow pigment contained in the yellow ink is 1 to 10% by mass, more preferably 1.5 to 9.5% by mass, based on the total amount of the yellow ink. Further, considering the storage stability and dispersion stability of the yellow ink and the ejection stability from the inkjet head, it is particularly preferably 2 to 8% by mass, and 3 to 5.5% by mass. Most preferred.
  • C.I. I. Pigment Red 150 and C.I. I. Pigment Red 31, 32, 146, 147, and C.I. I. Pigment Yellow Combinations with one or more azo yellow pigments selected from the group consisting of 12, 13, 14, 74, and 83 can be mentioned.
  • the yellow ink is used in combination with a pigment other than the yellow pigment having the structure represented by the general formula (3) (hereinafter, also referred to as “other yellow pigment”). You may.
  • the content of the azo yellow pigment is preferably 50% by mass or more with respect to the total amount of the pigment used. It is more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more. The content of the azo yellow pigment may be 100% by mass with respect to the total amount of the pigment used.
  • the above pigments may be used alone or in combination of two or more. Further, when two or more kinds are used in combination, a mixed crystal pigment may be used. Further, when two or more kinds of pigments are not in a mixed crystal state, that is, they have different crystal structures, the two or more kinds of pigments may be mixed and dispersed from the beginning by a method described later or the like. The pigment dispersions dispersed separately may be mixed later.
  • the total amount of the yellow pigment contained in the yellow ink is preferably 1 to 10% by mass in the total amount of the yellow ink. It is more preferably 5.5 to 9.5% by mass.
  • the magenta ink contained in the ink set of the embodiment of the present invention contains the basic organic compound (B) having a pKa value of 9.5 or less at 25 ° C. in an amount of 0.1 to 1.25% by mass based on the total amount of the magenta ink. It contains, preferably 0.1 to 1.0% by mass.
  • the "basic organic solvent (B)" in the present specification also includes a solvent that satisfies the above pKa value among the water-soluble organic solvents described later. Even if the compound is not a water-soluble organic solvent, the compound is included in the basic organic compound (B) if the above pKa value condition is satisfied.
  • the dispersed state of the pigment is maintained by the charge repulsion generated between the pigment particles, and the storage stability and the dispersion stability are 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 basic organic compounds are strongly basic, and by using these compounds in combination with the naphthol-based mixed crystal pigment (A-1), the naphthol-based mixed crystal pigment (A-) is used.
  • the dispersion stability of 1) may be deteriorated, and the discharge stability may be deteriorated accordingly.
  • the present inventors add to the above phenomenon, especially in a red-colored printed matter. It has been found that deterioration of color reproducibility and image quality (unevenness of shading), and discoloration and / or fading over time may occur.
  • the basic organic compound (B) having a pKa value of 9.5 or less the color reproducibility and image quality are excellent, and discoloration and discoloration occur with time, especially in the red color region.
  • magenta ink with excellent dispersion stability can be obtained.
  • the acid dissociation constant (pKa value) is moderately small and the organic compound suppresses the damage to the naphthol-based mixed crystal pigment (A-1). Conceivable.
  • magenta ink when the magenta ink is mixed with the yellow ink containing the azo yellow pigment described above, it is basic so as to suppress the contact between the naphthol-based mixed crystal pigment (A-1) molecule and the azo yellow pigment molecule. It is believed that the organic compound (B) migrates and prevents the formation of strong intermolecular interactions between the two.
  • the pKa value of the basic organic compound (B) is preferably 8.5 or less.
  • the lower limit of the pKa value of the basic organic compound (B) is not particularly limited, but is preferably 3 or more, more preferably 4.5 or more, and particularly preferably 6.5 or more.
  • the basic organic compound (B) preferably contains amino alcohols (alkanolamines) and has a small pKa value from the viewpoint of high solubility in an aqueous medium and safety to the human body. It is particularly preferred to include triethanolamine. 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. As an example of the case where two or more kinds are used in combination, a basic organic compound having a pKa value of 8.5 or less (for example, triethanolamine) and a basic organic compound having a pKa value of more than 8.5 (for example, 1-amino-) 2-Propanol and / or diisopropanolamine) in combination.
  • pKa can be measured by a known method. Specifically, it is a value measured in a 25 ° C. environment by a potentiometric titration method using water as a solvent using a potentiometric titration device AT-710S manufactured by Kyoto Electronics Industry Co., Ltd.
  • the molecular weight of the basic organic compound (B) contained in the magenta ink is preferably 500 or less, more preferably 300 or less, and particularly preferably 200 or less.
  • the molecular weight is preferably 50 or more, more preferably 75 or more, and particularly preferably 100 or more.
  • the content of the basic organic compound (B) in the magenta ink is 0.1 to 1.25% by mass in the total amount of the magenta ink. If it is 0.1% by mass or more, it is easy to secure long-term storage stability, and even when water volatilizes on the inkjet head nozzle, the naphthol-based mixed crystal pigment contained in magenta ink ( Since the dispersed state of A-1) is not destroyed, a printed matter having excellent color reproducibility and image quality can be obtained in the red color region, and deterioration of the printed matter due to nozzle omission or the like can be prevented. .. Further, by adding 1.25% by mass or less, it is possible to prevent discoloration and discoloration of the printed matter over time.
  • the content of the basic organic compound (B) is 0.1 to 1.0% by mass in the total amount of magenta ink. preferable.
  • the magenta ink contains the "pigment dispersion resin and / or the binder resin" having an acid group as an arbitrary component, and the pKa is used as the "pigment dispersion resin and / or the binder resin" having an acid group.
  • the basic organic compound satisfying the pKa used for neutralization (hereinafter, "basic organic compound (hereinafter,” basic organic compound (hereinafter, “basic organic compound”) b2) ”may also be included in the basic organic compound (B).
  • the basic organic compound (b2) forms an intramolecular interaction with the "pigment dispersion resin and / or binder resin” having an acid group. Therefore, in some embodiments, the amount obtained by subtracting the amount of the basic organic compound (b2) from the total amount of the basic organic compound (B) contained in the magenta ink is 0.1 to 1.0% by mass. Is preferable.
  • the basic organic compound (B) other than the basic organic compound (b2) may be referred to as a basic organic compound (b1).
  • the basic organic compound (b1) and the basic organic compound (b2) may be the same compound or different compounds from each other.
  • the basic organic compound (b1) and the basic organic compound (b2) are preferably amino alcohols (alkanolamines), and more preferably triethanolamine.
  • they are different compounds as a combination of the basic organic compound (b1) and the basic organic compound (b2), for example, a basic organic compound having a pKa value of 8.5 or less and a basic organic compound having a pKa of more than 8.5 are basic. Combinations with organic compounds; combinations of triethanolamine with basic organic compounds other than triethanolamine, and the like.
  • the basic organic compound may contain a basic organic compound having a pKa value of more than 9.5, but as described above, the basic organic compound having a pKa value of more than 9.5 is the present invention. Since the effect of the embodiment may be hindered, it is preferable that the blending amount is small. Specifically, when the basic organic compound contains a basic organic compound having a pKa value of more than 9.5, the content of the basic organic compound having a pKa value of more than 9.5 is the total amount of magenta ink. Of the above, it is preferably more than 0% by mass and 0.5% by mass or less, and more preferably more than 0% by mass and 0.25% by mass or less.
  • the total content of the basic organic compound (the total content of the basic organic compound (B) and the basic organic compound having a pKa value of more than 9.5) is 0.1 to 0.1 in the total amount of magenta ink. It is preferably 2.0% by mass, more preferably 0.1 to 1.5% by mass, and even more preferably 0.1 to 1.25% by mass. As a specific example, the content of the basic organic compound (B) is 0.1 to 1.0% by mass in the total amount of magenta ink, and the total content of the basic organic compounds (basic organic compound (basic organic compound ()). Examples thereof include magenta ink having a total content of B) and a basic organic compound having a pKa value of more than 9.5) of 1.5% by mass or less.
  • the azo yellow pigment contained in the yellow ink also tends to deteriorate in dispersion stability when a basic organic compound showing strong basicity is added, like the naphthol-based mixed crystal pigment (A-1).
  • a basic organic compound showing strong basicity like the naphthol-based mixed crystal pigment (A-1).
  • the yellow ink also contains the basic organic compound (B) having a pKa value of 9.5 or less at 25 ° C.
  • the suitable pKa value, suitable molecular weight, specific example, blending amount, etc. of the basic organic compound (B) contained in the yellow ink are the same as those of the magenta ink described above. That is, it is preferable that the yellow ink contains amino alcohols (for example, triethanolamine) as the basic organic compound (B) in an amount of 0.1 to 1.25% by mass based on the total amount of the yellow ink.
  • amino alcohols for example, triethanolamine
  • the magenta ink has a boiling point of 240 ° C. or higher at 1 atm, and the content of the organic solvent (hereinafter, also referred to as “high boiling point organic solvent”) is 8% by mass or less (0% by mass) in the total amount of the magenta ink. May be).
  • the "organic solvent” in the present specification includes, in addition to the water-soluble organic solvent described later, a solvent that is not the water-soluble organic solvent (however, a solvent that is liquid at 25 ° C. and 1 atm). do.
  • the high boiling point organic solvent tends to remain in the printed matter after printing, which may deteriorate image quality such as uneven shading.
  • the high boiling point organic solvent may permeate and diffuse inside the recording medium together with the naphthol-based mixed crystal pigment (A-1), which may lead to a decrease in concentration. be.
  • the high boiling point organic solvent generally has high hygroscopicity, when the printed matter is stored for a long period of time, the high boiling point organic solvent may absorb moisture in the atmosphere.
  • the boiling point of the basic organic compound (B) used is high, it is considered that a part of the basic organic compound (B) also remains in the printed matter. In that case, the basic organic compound (B) elutes in the water absorbed by the high boiling point organic solvent and diffuses into the printed matter, damaging the naphthol-based mixed crystal pigment (A-1) contained in the magenta ink. Can be considered.
  • the phenomenon is suppressed by setting the content of the high boiling point organic solvent in the magenta ink to a certain amount or less.
  • it is more preferably 3% by mass or less, and particularly preferably 1.5% by mass or less in the total amount of magenta ink.
  • the boiling point at 1 atm can be measured by using a thermal analyzer such as DSC (Differential Scanning Calorimetry).
  • the amount of the high boiling point organic solvent is small. This is because the magenta ink and the yellow ink are mixed on the recording medium when the red-colored printed matter is produced by using the ink set of the embodiment of the present invention.
  • the suitable blending amount of the high boiling point organic solvent contained in the yellow ink is the same as that of the magenta ink described above.
  • the ink contained in the ink set of the embodiment of the present invention preferably contains a water-soluble organic solvent.
  • an alcohol solvent, a glycol ether solvent, a polyalkylene glycol solvent and the like can be preferably used as the water-soluble organic solvent.
  • water-soluble organic solvent refers to a solvent having a solubility in water of 5 g / 100 gH 2 O or more and a liquid at 25 ° C. and 1 atm. Further, among the above-mentioned basic organic compounds (B), the solvent satisfying the above-mentioned solubility condition is also included in the water-soluble organic solvent.
  • the water-soluble organic solvent used in the embodiment of the present invention preferably has a weighted average boiling point of 100 to 235 ° C., more preferably 120 to 210 ° C., and 120 to 195 ° C. at 1 atm. It is particularly preferable to have. Further, considering the image quality for a non-permeable substrate such as a plastic substrate, 120 to 180 ° C. is particularly preferable.
  • the weighted average value of the boiling point of the water-soluble organic solvent under 1 atm is 100 ° C. or higher, the ejection stability from the inkjet head is improved, and the color development and color reproducibility when printed on a penetrating substrate are improved. Is improved.
  • the weighted average value of the boiling point when the weighted average value of the boiling point is 235 ° C. or less, the image quality is good without causing drying failure on the recording medium and preventing the remaining water-soluble organic solvent from causing bleeding between ink droplets. In addition, the adhesion to impermeable substrates such as plastic substrates and the scratch resistance of printed matter are improved.
  • the weighted average value of the boiling point shall include the water-soluble organic solvent having a boiling point of 240 ° C. or higher under 1 atm. When there are two or more types of water-soluble organic solvents contained in the water-based inkjet ink, the weighted average value of the boiling points under 1 atm is the boiling point at 1 atm calculated for each water-soluble organic solvent.
  • the blending amount of the water-soluble organic solvent having a boiling point of 100 to 220 ° C. under 1 atm is 50% by mass with respect to the total amount of the water-soluble organic solvent in the ink.
  • the above is preferable, 70% by mass or more is more preferable, and 85% by mass or more is particularly preferable.
  • water-soluble organic solvent preferably used in the embodiment of 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
  • glycol ether-based solvents 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, diethylene glycol monoisopropyl ether, Diethylene glycol monoisobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether.
  • Tetraethylene glycol dimethyl ether Tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol methyl ethyl ether.
  • Tetraethylene glycol butylmethyl ether propylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol dimethyl ether, tripropylene glycol dimethyl ether, etc.
  • Diethylene glycol, dipropylene glycol, etc. are used as polyalkylene glycol solvents.
  • 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.
  • cyclic amide solvent 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone and the like can be used.
  • cyclic carbamate solvent 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone and the like can be used. Each is listed, but not limited to these.
  • the water-soluble organic solvent used in the embodiment of the present invention can obtain a printed matter having excellent image quality and drying property, has excellent compatibility with a binder resin and a surfactant described later, and further, the water-soluble organic solvent.
  • a water-soluble organic solvent having one or two hydroxyl groups is preferably selected from the viewpoint of obtaining an ink having a low viscosity and excellent ejection stability.
  • a water-soluble organic solvent having two hydroxyl groups that is, a diol-based solvent is used from the viewpoint that the dispersion stability of the naphthol-based mixed crystal pigment (A-1) is unlikely to be adversely affected.
  • the diol-based solvents it is preferable to use at least one kind of alkanediol having 2 to 5 carbon atoms, more preferably an alkanediol having 3 to 4 carbon atoms, and particularly preferably an alkanediol having 3 carbon atoms. be.
  • the content of the water-soluble organic solvent used in the embodiment of the present invention is preferably 1 to 30% by mass with respect to the total amount of the ink. Further, from the viewpoint of ensuring ejection stability on the inkjet head and obtaining a printed matter having excellent adhesion, drying property and image quality even with a non-permeable substrate, the content is 3 to 27% by mass. More preferably, it is particularly preferably 5 to 25% by mass.
  • ⁇ Pigment dispersion resin> As a method for stably dispersing and holding the pigment contained in each ink contained in the ink set of the embodiment of the present invention, (1) at least a part of the pigment surface is covered with a pigment dispersion resin. Methods, (2) A method of adsorbing a water-soluble and / or water-dispersible surfactant on the pigment surface, (3) A hydrophilic functional group is chemically or physically introduced on the pigment surface, and a dispersed resin or a surfactant is used. Examples thereof include a method of dispersing in ink without an agent (self-dispersing pigment).
  • the method (1) above that is, the method using a pigment dispersion resin is preferably selected.
  • the covering ability of the pigment-dispersed resin to the pigment and the charge of the pigment-dispersed resin can be easily adjusted by selecting and examining the composition and molecular weight of the polymerizable monomer forming the resin.
  • the type of the pigment dispersion resin is not particularly limited, and for example, (meth) acrylic resin, styrene (meth) acrylic resin, (anhydrous) maleic acid resin, styrene (anhydrous) maleic acid resin, olefin (anhydrous) maleic acid resin, and the like.
  • Urethane resin, ester resin (polycondensate of polyvalent carboxylic acid and polyhydric alcohol) and the like can be used, but the present invention is not limited thereto.
  • a resin of the same type as the binder resin described later it is preferable to use a resin of the same type as the binder resin described later.
  • (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.
  • the "water-insoluble resin” refers to a resin in which the 1% by mass water mixture of the target pigment dispersion resin at 25 ° C. is not transparent to the naked eye.
  • a water-soluble resin When a water-soluble resin is 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 By setting the acid value within the above range, it is possible to maintain the dispersion stability of the pigment, and it is possible to stably eject the pigment from the inkjet head. In addition, it becomes possible to maintain the ejection stability on the inkjet head. Further, it is preferable from the viewpoint that the solubility of the pigment dispersion resin in water can be ensured and the viscosity of the pigment dispersion liquid can be suppressed by making the interaction between the pigment dispersion resins suitable.
  • 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 further preferably 10 to 80 mgKOH / g. preferable.
  • 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 using AT-610 manufactured by Kyoto Electronics Industry Co., Ltd. according to JIS K2501.
  • 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 aromatic group contained in the naphthol-based mixed crystal pigment (A-1) or the azo yellow pigment and the aromatic ring structure contained in the pigment dispersion resin interact with each other to cause the naphthol.
  • the ability of the pigment-dispersed resin to adsorb to the system-based mixed crystal pigment (A-1) or the azo yellow pigment is significantly improved.
  • the aromatic group 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 content of the monomer containing an aromatic ring is preferably 5 to 75% by mass with respect to the total amount of the pigment dispersion resin, and is 5 to 65. It is more preferably 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. This is because by setting the number of carbon atoms of the alkyl group to 8 to 36, it is possible to reduce the viscosity of the pigment dispersion liquid, improve the dispersion stability, and realize the ejection stability.
  • 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 ethylhexyl group (C8), lauryl group (C12), myristyl group (C14), cetyl group (C16), stearyl group (C18), araquil group (C20), behenyl group (C22), Lignoceryl group (C24), cellotoyl group (C26), montanyl group (C28), meliscil group (C30), dotriacontanyl group (C32), tetratriacontanyl group (C34), hexatriacontanyl group (C36) And so on.
  • the content of the monomer containing an alkyl chain having 8 to 36 carbon atoms is 5 to 60% by mass 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 10 to 55% by mass, more preferably 15 to 50% 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 of the ink, 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 solvents such as triethylamine, monoethanolamine, diethanolamine, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, and aminomethylpropanol, aqueous ammonia, and water.
  • organic amine solvents such as triethylamine, monoethanolamine, diethanolamine, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, and aminomethylpropanol, aqueous ammonia, and water.
  • examples include, but are not limited to, alkali metal hydroxides such as lithium oxide, sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate. ..
  • 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 500,000, 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 applied to ink.
  • the weight average molecular weight is 1,000 or more, the pigment dispersion resin is difficult to dissolve in the water-soluble organic solvent added to the ink, so that the adsorption of the pigment dispersion resin to the pigment is strengthened and the dispersion stability is increased. 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 blending amount of the pigment dispersion resin is preferably 1 to 100% by mass with respect to the blending amount of the pigment.
  • the ratio of the pigment to the pigment dispersion resin is more preferably 2 to 50% by mass, and particularly preferably 4 to 45% by mass.
  • ⁇ Dispersion aid> Of the above-mentioned dispersion methods (1) or (2), from the viewpoint of significantly improving the dispersion stability and ejection stability of the pigment and also improving the color reproducibility of the printed matter by enabling fine dispersion of the pigment.
  • 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 or the surfactant 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 disuazo dye, a polyazo dye, an anthraquinone dye, an isoindolinone dye, and an isoindoline dye.
  • the above-mentioned "dye” is a general term for pigments and dyes.
  • the blending amount thereof is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the blending amount of the pigment. Especially preferable.
  • the addition ratio to the pigment becomes a sufficient amount, and the dispersion stability, the ejection stability and the color reproducibility of the printed matter are improved.
  • the content is 10% by mass or less, the pigment miniaturization does not proceed more than necessary, so that the dispersion stability is improved and the deterioration of the light resistance of the printed matter can be prevented.
  • Each ink contained in the ink set of the embodiment of the present invention preferably contains a binder resin in order to improve scratch resistance, color development, and color reproducibility of the printed matter.
  • each ink may contain a pigment-dispersed resin, but when the resin contained in each ink is a water-soluble resin, which of the pigment-dispersed resin and the binder resin corresponds to the resin.
  • Shall be distinguished by the adsorption rate for the pigment. That is, a resin having an adsorption rate with respect to the pigment of 50% by mass or more with respect to the total amount to be blended is determined to be a pigment dispersion resin, and a resin having an adsorption rate of less than 50% by mass is determined to be a binder resin.
  • a water-based ink diluted with water is subjected to a centrifugal separation 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.
  • a centrifugal separation treatment for example, at 30,000 rpm for 4 hours
  • a water-soluble resin and resin fine particles are generally known, and in the embodiment of the present invention, either one may be selected and used, or both may be combined. You may use it.
  • the resin fine particles have a higher molecular weight than the water-soluble resin, can improve the scratch resistance of the printed matter, and are also excellent in the image quality of the printed matter. Further, when printing on a permeable substrate, the voids on the surface of the recording medium can be effectively filled, so that the color development and color reproducibility of the printed matter are improved.
  • an ink using a water-soluble resin as a binder resin has excellent ejection stability.
  • water-soluble resin refers to a resin other than the above-mentioned water-insoluble resin, that is, a resin in which a 1% by mass water mixture of the target resin at 25 ° C. is transparent to the naked eye. ..
  • Each ink included in the ink set of the embodiment of the present invention preferably contains a binder resin having an acid value of 1 to 80 mgKOH / g as the binder resin. Further, by ensuring the dispersion stability of the naphthol-based mixed crystal pigment (A-1) and rapidly moving to the gas-liquid interface, a printed matter having excellent image quality can be obtained, and further, the permeability of uncoated paper or the like can be obtained.
  • the binder resin contained in magenta ink is contained in the magenta ink from the viewpoint of producing a printed matter having excellent color development and color reproducibility by rapidly moving so as to fill the voids on the surface of the base material.
  • the acid value is preferably 3 to 60 mgKOH / g, and particularly preferably 5 to 40 mgKOH / g.
  • the acid value of the binder resin can be measured in the same manner as the acid value of the pigment-dispersed resin.
  • the glass transition temperature of the binder resin contained in each ink can be selected, for example, as follows according to the required characteristics. Specifically, it improves ejection stability and scratch resistance of printed matter, and is also excellent in drying property and blocking resistance (a phenomenon in which a print layer sticks to another recording medium when a recording medium after printing is stacked).
  • the glass transition temperature is preferably 60 to 140 ° C, more preferably 70 to 135 ° C, and particularly preferably 80 to 130 ° C.
  • the glass transition temperature is preferably ⁇ 120 to 45 ° C., preferably ⁇ 80, from the viewpoint of image quality and adhesion. It is more preferably about 25 ° C, and particularly preferably ⁇ 60 to 15 ° C.
  • 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
  • binder resin used in the embodiment of the present invention include (meth) acrylic resin, styrene (meth) acrylic resin, urethane resin, urethane / (meth) acrylic composite resin, styrene butadiene resin, vinyl chloride resin, and styrene (anhydrous).
  • examples thereof include maleic acid resin, ester resin, and polyolefin resin.
  • the binder resin is (meth) acrylic resin, styrene (meth) acrylic resin, urethane resin, urethane / (meth) acrylic composite resin, and polyolefin.
  • urethane resin urethane / (meth) acrylic composite resin, and polyolefin resin have a low glass transition temperature, so they are preferably selected from the viewpoint of adhesion to impermeable substrates such as plastic substrates and image quality. Will be done.
  • a binder resin a polyolefin resin and (meth ) It is preferable to include one or more resins selected from an acrylic resin, a styrene (meth) acrylic resin, a urethane resin, and a urethane / (meth) acrylic composite resin.
  • the amine value of the naphthol-based mixed crystal pigment (A-1) or the azo yellow pigment is Am (PA) [mgKOH / g], and the naphthol-based mixed crystal pigment (A-1).
  • the content of the azo yellow pigment in the total amount of ink is C (PA) [mass%]
  • the acid value of the olefin resin fine particles is Av (RO) [mgKOH / g]
  • the content of the olefin resin fine particles in the total amount of ink is C (RO) [mass%]
  • the acid value / amine value ratio represented by the following formula (4) is preferably 0.5 ⁇ 10 -4 to 15 ⁇ 10 -4. , 1.5 ⁇ 10 -4 to 10 ⁇ 10 -4 are particularly preferable.
  • the acid group present in the olefin resin fine particles and the naphthol-based mixed crystal pigment (A-1) or the azo yellow pigment having an amine structure interact with each other, and the naphthol-based mixed pigment is formed. It is considered that the presence of the olefin resin fine particles around the crystal pigment (A-1) or the azo yellow pigment can prevent the aggregation of the naphthol-based mixed crystal pigment (A-1) or the azo yellow pigment.
  • the above binder 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.
  • a water-soluble resin When a water-soluble resin is used as the binder resin in the embodiment of the present invention, its weight average molecular weight ensures stability of ejection from the inkjet nozzle, and has excellent adhesion and scratch resistance to various recording media. From the viewpoint of obtaining a printed matter having a It is more preferably 000, and even more preferably 10,000 to 40,000.
  • the weight average molecular weight of the resin 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 GPC measuring device (HLC-8120GPC manufactured by Tosoh Corporation) equipped with a TSKgel column manufactured by Tosoh Corporation and a THF as a developing solvent. Can be mentioned.
  • the content of the binder resin with respect to the total amount of the ink is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and further preferably 4 to 10% by mass in terms of solid content.
  • the content of the binder resin having an acid value of 1 to 80 mgKOH / g is preferably 20 to 100% by mass, more preferably 35 to 100% by mass, based on the total amount of the binder resin in the ink. Particularly preferably, it is 50 to 100% by mass.
  • ⁇ Surfactant> it is preferable to contain one or more surfactants from the viewpoint of obtaining an ink having excellent ejection stability, image quality of printed matter, drying property and the like. Further, it is preferable to use a nonionic surfactant as the surfactant. Generally, various nonionic surfactants are known, such as acetylenediol-based, acetylene alcohol-based, siloxane-based, acrylic-based, fluorine-based, and polyoxyalkylene-based, depending on the intended use.
  • the ink of is one or more nonionic surfactants selected from the group consisting of acetylene diol-based surfactants, siloxane-based surfactants, and polyoxyalkylene-based surfactants represented by the following general formula (3). It is preferable to contain an acetylene diol-based and / or a siloxane-based surfactant, and it is particularly preferable to contain a siloxane-based surfactant.
  • the acetylene diol-based surfactant and the siloxane-based surfactant are naphthol-based mixed crystal pigments (A-1) present in the ink droplets after landing on the recording medium.
  • the interface is rapidly oriented to the gas-liquid interface and the recording medium-droplet interface without being affected by.
  • the wettability of magenta ink can be improved and the ink droplets can be quickly smoothed even on a non-permeable substrate.
  • bleeding and uneven shading between droplets can be realized. It is possible to obtain a printed matter having excellent image quality with a small amount of ink.
  • magenta is used when printing on a penetrating base material such as uncoated paper.
  • a printed matter having excellent color development and color reproducibility can be obtained without causing excessive penetration and diffusion of ink.
  • a water-based ink having excellent ejection stability in addition to the improvement of the above-mentioned characteristics can be obtained. Therefore, at least in magenta ink, an acetylene diol-based surfactant and a siloxane-based ink can be obtained. It is preferable to use it in combination with a surfactant.
  • Suitable acetylene diol-based surfactants include, for example, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 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, Examples include, but are not limited to, 10-diols and their ethylene oxide and / or propylene oxide adducts.
  • siloxane-based surfactant for example, a 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.
  • examples include surfactants. Specifically, 8032ADDITIVE, FZ-2104, FZ-2120, FZ-2122, FZ-2162, FZ-2164, FZ-2166, FZ-2404, FZ-7001, FZ-7002, manufactured by Toray Dow Corning Co., Ltd.
  • examples of the polyoxyalkylene-based surfactant that can be preferably used include compounds represented by the following general formula (5).
  • 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.
  • surfactants exemplified above those having a hydrophilic ethylene oxide group are particularly preferably selected.
  • a surfactant having an HLB value of 0 to 5 is used. It is particularly preferable to include a surfactant having an HLB value of 0 to 4.
  • a surfactant having an HLB value of 0 to 5 (preferably 0 to 4) from the viewpoint of obtaining a printed matter having excellent color development and color reproducibility on a permeable base material such as uncoated paper. It is preferable to use in combination with a surfactant having an HLB value of 6 to 18 (preferably 7 to 18, particularly preferably 8 to 16).
  • HLB value is preferably 13 or less, and more preferably 10 or less.
  • 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.
  • the acetylenediol-based surfactant and the polyoxyalkylene-based surfactant are used.
  • the Griffin method is a method of calculating an HLB value using the following formula (6) 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, after dissolving 0.5 g of a surfactant in 5 mL of ethanol, the solution is titrated with a 2 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 (7).
  • the content of the surfactant 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.
  • each ink it is preferable to use ion-exchanged water (deionized water) instead of general water containing various ions.
  • the content thereof is preferably in the range of 20 to 90% by mass based on the total mass of the ink.
  • additives such as defoaming agents, thickeners, preservatives, infrared absorbers, and ultraviolet absorbers are appropriately added in order to obtain inks having desired physical property values as needed. be able to.
  • addition amount of these additives 0.01 to 10% by mass or less is preferable in the total amount of the ink.
  • each ink contains substantially no polymerizable monomer.
  • substantially not contained means that the ink is not intentionally added, and does not exclude a small amount of contamination or generation during manufacturing and storage of the ink.
  • the content of the polymerizable monomer is preferably 1% by mass, and particularly preferably 0.5% by mass or less, based on the total amount of the ink.
  • the ink composed of the above-mentioned components can be produced by a known method.
  • the pigment dispersion liquid and the constituent materials of the ink (basic organic compound, water-soluble organic) are used.
  • a manufacturing method of mixing is preferably selected.
  • An example of an ink manufacturing method will be described below, but as described above, the manufacturing method is not limited to the following.
  • Pigment Dispersion Liquid 1-1
  • Method of Dispersion Treatment Using Pigment Dispersion Resin which is a Water-Soluble Resin
  • a water-soluble resin is used as the pigment dispersion resin
  • the pigment dispersion resin water, and if necessary.
  • To prepare a pigment-dispersed resin aqueous solution by mixing and stirring with a water-soluble organic solvent.
  • a pigment and, if necessary, a dispersion aid, additional water, and a (additional) water-soluble organic solvent are added to the pigment-dispersed resin aqueous solution, mixed and stirred (premixed), and then a disperser is used. Perform distributed processing. Then, if necessary, centrifugation, filtration, and adjustment of the solid content are performed to obtain a pigment dispersion liquid.
  • pigment dispersion resin which is a water-insoluble resin
  • an organic solvent such as methyl ethyl ketone
  • a pigment-dispersed resin solution is prepared by dissolving the pigment-dispersed resin in a solution and neutralizing the pigment-dispersed resin, if necessary.
  • a pigment, water, a dispersion aid, a water-soluble organic solvent, and an additional organic solvent, if necessary are added, mixed and stirred (premixed), and then dispersed using a disperser. Perform processing. Then, the organic solvent is distilled off by vacuum distillation, and if necessary, centrifugation, filtration, and adjustment of the solid content are performed to obtain a pigment dispersion liquid.
  • the disperser used in the dispersion treatment of the pigment may be any generally used disperser, and for example, a ball mill, a roll mill, a sand mill, etc.
  • examples include bead mills and nanomizers.
  • 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, and the material of the pulverized media is changed.
  • a combination of methods can be mentioned.
  • the diameter of the pulverized media of the disperser is preferably 0.1 to 3 mm.
  • glass, zircon, zirconia and titania are preferably used as the material of the crushing media.
  • the method of grinding and kneading shown below can also be preferably used.
  • the pigment, pigment dispersion resin, water-soluble organic solvent, inorganic salt, and if necessary, a dispersion aid are kneaded by a kneader, and then water is added to the obtained mixture, and the mixture and stirring are performed.
  • the inorganic salt and, if necessary, the water-soluble organic solvent are removed by centrifugation, filtration, and washing, and the solid content is further adjusted to obtain a pigment dispersion liquid.
  • the kneader used in the above method (1-3) may be any disperser that is generally used, but a high-viscosity mixture can be kneaded to form a pigment dispersion liquid containing fine pigments.
  • a kneader or a remix is preferably used because a printed matter having excellent quality, 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 constituent materials of the ink (basic organic compound, water-soluble organic solvent, binder resin, surfactant, water, etc.) are added, and the mixture is stirred and mixed. 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 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 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 inks contained in the ink set of the embodiment of the present invention each have a static surface tension of 18 to 18 to 25 ° C. from the viewpoint that the ink can be stably ejected and a printed matter having excellent image quality can be obtained. It is preferably 35 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 inks contained in the ink set of the embodiment of the present invention are each based on the maximum foam pressure method.
  • the dynamic surface tension at 10 ms is preferably 26-36 mN / m, more preferably 28-36 mN / m, and particularly preferably 30-36 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 ink set of the embodiment of the present invention can obtain a printed matter having excellent color reproducibility.
  • the magenta ink preferably has a hue angle ⁇ H ° measured by the following method in the range of 330 to 360 °, and is also a yellow ink.
  • the hue angle ⁇ H ° is preferably in the range of 70 to 105 °.
  • the hue angle ⁇ H ° of the ink is measured by applying a wet film thickness of 6 ⁇ m on a recording medium and drying the coated product.
  • K control coater K202 manufactured by Matsuo Sangyo Co., Ltd., wire bar No. After applying the ink using No. 1, it is dried in an oven at 80 ° C. for 1 minute or more to prepare a coated product. Then, using i1Pro2 manufactured by X-rite, measurement was performed under the conditions of light source D50, viewing angle 2 ° and CIE color system, and the obtained a * and b * values were used to ⁇ H ° tan -1.
  • the spectral reflectance of the coated product of magenta ink is 10% or less in the wavelength region of 480 to 580 nm because a printed matter having excellent image density and excellent color reproducibility in the red region can be obtained. It is preferable that the spectral reflectance of the coated product of the yellow ink is 10% or less in the wavelength region of 380 to 480 nm.
  • the spectral reflectance of the printed matter is calculated by the method specified in ISO 5-3: 2009. Specifically, it can be measured using i1Pro2 manufactured by X-rite in the same manner as the above-mentioned hue angle ⁇ H °.
  • the measurement should be performed using a pigment dispersion produced by the same method as the magenta pigment dispersion 1 or the yellow pigment dispersion 1 of the examples described later. Is preferable.
  • a specific method for measuring the hue angle after diluting the pigment dispersion with water so that the pigment concentration becomes 3% by mass, recording is performed by the same method as for the ink coating product having a wet thickness of 6 ⁇ m. Apply on the medium. Then, the hue angle and the spectral reflectance of the obtained coated material are measured by the method described above.
  • the ink set of the embodiment of the present invention may include inks other than magenta ink and yellow ink (also referred to as "inks of other colors" in the present specification) from the viewpoint of obtaining a printed matter having excellent color reproducibility. Above all, it is preferable to include cyan ink and / or violet ink and black ink as the inks of the other colors.
  • Cyan ink contains cyan pigment and water.
  • the cyan pigment contained in the cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15: 3, 15: 4, 15: 6, 16, 22, 60 and the like.
  • the total content of the pigments listed above is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass in the total amount of the pigments contained in the cyan ink. % Or more, and particularly preferably 95% by mass or more.
  • the total content of the pigments listed above may be 100% by mass with respect to the total amount of the pigments used.
  • magenta ink having a hue angle ⁇ Hm ° of the coated object of 0 to 45 ° there are three types of ink, yellow ink, magenta ink, and cyan ink, which are the embodiments of the embodiment of the present invention. From the viewpoint of producing printed matter having excellent color reproducibility even with an ink set containing chromatic color ink consisting only of ink, C.I. I. It is preferable to use a cyan ink containing one or more selected from the group consisting of Pigment Blue 15: 6 and 60.
  • the content of the cyan pigment contained in the cyan ink is preferably 0.1 to 10% by mass, preferably 1 to 9.5% by mass, based on the total amount of the cyan ink. It is more preferable to have.
  • the cyan ink may contain a water-soluble organic solvent, a pigment dispersion resin, a dispersion aid, a binder resin, a surfactant, a basic organic compound, and other components in addition to the cyan pigment and water.
  • a water-soluble organic solvent e.g., a water-soluble organic solvent, a pigment dispersion resin, a dispersion aid, a binder resin, a surfactant, a basic organic compound, and other components in addition to the cyan pigment and water.
  • a pigment dispersion resin e.g., a pigment dispersion aid
  • a binder resin e.g., a surfactant, a basic organic compound, and other components in addition to the cyan pigment and water.
  • Violet ink contains violet pigment and water.
  • the violet pigment contained in the violet ink include C.I. I. Pigment Violet 1, 3, 23, 27, 32, 36, 37, 38 and the like.
  • the total content of the pigments listed above is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass in the total amount of the pigments contained in the violet ink. % Or more, and particularly preferably 95% by mass or more.
  • the total content of the pigments listed above may be 100% by mass with respect to the total amount of the pigments used.
  • the ink set containing the magenta ink and the yellow ink according to the embodiment of the present invention has the viewpoint of producing a printed matter having excellent color reproducibility.
  • the content of the violet pigment contained in the violet ink is preferably 0.1 to 10% by mass, preferably 1 to 9.5% by mass, based on the total amount of the violet ink. It is more preferable to have.
  • Violet ink may contain a water-soluble organic solvent, a pigment dispersion resin, a dispersion aid, a binder resin, a surfactant, a basic organic compound, and other components in addition to the violet pigment and water.
  • a pigment dispersion resin e.g., a pigment dispersion resin
  • a dispersion aid e.g., a pigment dispersion aid
  • a binder resin e.g., a surfactant, a basic organic compound, and other components in addition to the violet pigment and water.
  • cyan ink and violet ink are distinguished by the color index name of the pigment mainly contained in the ink. That is, C.I. I.
  • the ink containing the pigment blue pigment is cyan ink, and the main component is C.I. I.
  • Ink containing pigment violet pigment is referred to as violet ink.
  • the hue angle ⁇ H ° of the ink coated product with a wet film thickness of 6 ⁇ m produced in the same manner as in the case of the above yellow ink is 200 ° or more and less than 260 °.
  • Cyan ink is used as an ink, and violet ink is used as an ink having a temperature of 260 ° or more and less than 330 °.
  • the main component C.I. I. Pigment blue pigment and / or C.I. I. Even if the ink contains a pigment violet pigment, if the hue angle ⁇ H ° of the ink-coated product is less than 200 °, it is assumed to be a green ink described later, and the ⁇ H ° is 330 ° or more. In this case, it shall be the magenta ink described above.
  • the main component refers to the pigment having the highest content based on the total amount of the pigment.
  • red ink, orange ink, green ink, brown ink and the like can be further combined.
  • the pigment contained in the red ink may be, for example, C.I. I. Pigment Red 177, 254, 255, and C.I. I.
  • One or more selected from the group consisting of Pigment Orange 73 is preferably used.
  • the pigment contained in the orange ink may be, for example, C.I. I. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 62, 64, 67, 71, 72 and C.I. I.
  • Pigment Red 17, 49: 2,112, 149, 178, 188 and 264 is preferably used.
  • the pigment contained in the green ink may be, for example, C.I. I.
  • One or more selected from the group consisting of Pigment Greens 7, 36 and 58 is preferably used.
  • light-colored inks such as light yellow ink, light cyan ink, light magenta ink, and light black (gray) ink, which are inks having a low pigment concentration
  • light-colored inks such as light yellow ink, light cyan ink, light magenta ink, and light black (gray) ink, which are inks having a low pigment concentration
  • light magenta ink or light yellow ink it is preferable to use the pigment used in magenta ink and yellow ink.
  • Black ink> It is also possible to include black ink in the ink set. By using black ink together, it is possible to obtain a higher-definition image that is excellent in character expression and contrast expression.
  • black pigment contained in the black ink examples include organic pigments such as aniline black, lumogen black and azomethin black, and inorganic pigments such as carbon black and iron oxide. Further, a plurality of color pigments such as the above-mentioned magenta pigment, yellow pigment, and cyan pigment can be used as a composite black.
  • the carbon black pigment carbon black produced by the furnace method or the channel method is suitable.
  • the primary particle size is 11 to 40 m ⁇ m (nm)
  • the specific surface area by the BET method is 50 to 400 m 2 / g
  • the volatile content is 0.5 to 10% by mass
  • the pH value is 2 to.
  • Those having characteristics such as 10 are suitable. Examples of commercially available products having such characteristics include No.
  • the amount of the black pigment contained in the black ink is preferably 0.1 to 10% by mass, more preferably 1 to 9.5% by mass, based on the total amount of the black ink.
  • the ink set can also contain white ink.
  • white ink By using white ink together, a printed matter having good visibility can be formed on a transparent recording medium or a recording medium having low brightness.
  • magenta ink and yellow ink according to the embodiment of the present invention, it is possible to obtain clear and high-definition printed matter even on the above-mentioned recording medium as in the case of recording on a white medium. Become.
  • White pigments that can be used for white ink include inorganic white pigments and organic white pigments.
  • examples of the inorganic white pigment include alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, fine powder silicic acid, silicas such as synthetic silicates, calcium silicate and alumina.
  • alkaline earth metal sulfates such as barium sulfate
  • alkaline earth metal carbonates such as calcium carbonate
  • fine powder silicic acid fine powder silicic acid
  • silicas such as synthetic silicates, calcium silicate and alumina.
  • Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. Titanium oxide is most preferable from the viewpoint of hiding power and coloring power.
  • the average particle size of the white pigment is preferably 50 to 500 nm. By keeping the average particle size within the above range, it is possible to achieve both concealment, storage stability, and ejection stability. It is more preferably 100 to 400 nm.
  • the amount of the white pigment contained in the white ink is preferably 3 to 50% by mass, more preferably 5 to 30% by mass, based on the total amount of the white ink.
  • the ink set of the embodiment of the present invention is used in a recording method of ejecting ink from an inkjet head and applying it onto a recording medium.
  • the pass method in the inkjet recording method includes 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 water-based inkjet ink according to the embodiment 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.
  • the amount of droplets of each ink ejected from the inkjet head is 0.2 to 30 picolitres, respectively, from the viewpoint of greatly reducing the drying load and improving color reproducibility and other image quality. It is preferably 1 to 20 picolitres, and more preferably 1 to 20 picolitres.
  • drying mechanism for drying the ink on the recording medium after applying each ink contained in the ink set of the embodiment of the present invention onto the recording medium by an inkjet printing method.
  • drying method used in the drying mechanism include a heat drying method, a hot air drying method, an infrared ray (for example, an infrared ray having a wavelength of 700 to 2500 nm), a microwave drying method, and a drum drying method.
  • the drying temperature is set to 35 to 100 ° C. from the viewpoint of preventing the liquid component in the ink from suddenly boiling and obtaining a printed matter having excellent color reproducibility and image quality. It is preferable that the hot air temperature is 50 to 250 ° C., respectively, when the hot air drying method is adopted. From the same viewpoint, when the infrared drying method is adopted, it is preferable that 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.
  • the above-mentioned drying method may be used alone, in succession, or in combination at the same time.
  • the heat 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.
  • “semi-drying” means partial drying, and means a state in which the ink on the recording medium is partially dried but not completely dried. Specifically, the total amount of volatile components (water and water-soluble organic solvent) present in the ink after semi-drying is 10 to 80% by mass with respect to the total amount of volatile components present in the ink before semi-drying. Refers to the state of.
  • the recording medium for printing the ink set according to the embodiment of the present invention is not particularly limited, and any known material such as a permeable base material, a non-permeable base material, and a non-permeable base material can be arbitrarily used. can.
  • the ink set of the embodiment of the present invention can obtain a printed matter having excellent image quality, color development and color reproducibility.
  • 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 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-permeable base material”, which 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 “persistent base material”, and a recording medium having a value of 10 g / m 2 or more is referred to as a “permeable base material”.
  • 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.
  • permeable base materials examples include non-coated paper such as stencil paper, medium quality paper, woodfree paper and recycled paper, cotton, synthetic fiber woven fabric, silk, linen, non-woven fabric and other fabrics, 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 color development and image quality.
  • non-permeable or impervious substrates include plastic substrates such as polyvinyl chloride, polyethylene terephthalate (PET), polypropylene, polyethylene, nylon, polystyrene, polyvinyl alcohol, coated paper, art paper, etc.
  • plastic substrates such as polyvinyl chloride, polyethylene terephthalate (PET), polypropylene, polyethylene, nylon, polystyrene, polyvinyl alcohol, coated paper, art paper, etc.
  • 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 kinds 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 inkjet recording method of the embodiment of the present invention may be a roll shape or a sheet-fed shape.
  • the recording media listed above can be improved.
  • the printed matter produced by using the ink set of the embodiment of the present invention may be coated on the printed surface, if necessary.
  • Specific examples of the coating treatment include coating or printing of the coating composition, laminating processing by a dry laminating method, a solvent-free laminating method, an extrusion laminating method, or the like, and any of them may be selected. Both may be combined.
  • the coating or printing method includes a method of printing in a non-contact manner with a recording medium such as inkjet printing and a recording medium.
  • a method of printing by abutting the coating composition on the surface may be adopted.
  • the coating composition is a substantially colorant excluding the pigment from the water-based inkjet ink of the embodiment of the present invention. It is preferable to use ink that does not contain components (clear ink).
  • naphthol-based mixed crystal pigment 1 As a base component, 23.4 parts of 3-amino-4-methoxybenzanilide was added to 364.4 parts of water, and the suspension was prepared by stirring well, and then ice was added to adjust the liquid temperature to 5 ° C. bottom. Then, 39.7 parts of 35% hydrochloric acid was added to the suspension, and the mixture was stirred for 1 hour. Then, an aqueous solution prepared by dissolving 7.1 parts of sodium nitrite in 22 parts of water was added, and the mixture was stirred for 1 hour to diazotize.
  • sulfamic acid 1 part was added to the reaction mixture to eliminate nitrite, and then an aqueous solution consisting of 20.7 parts of sodium acetate, 1.8 parts of acetic acid and 165 parts of water was added to obtain a diazonium aqueous solution.
  • aqueous solution consisting of 20.7 parts of sodium acetate, 1.8 parts of acetic acid and 165 parts of water was added to obtain a diazonium aqueous solution.
  • 18.0 parts of 3-hydroxy-2-naphthamide and 2.0 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide were added as coupler components in a 25% aqueous sodium hydroxide solution.
  • An aqueous coupler solution was prepared by adding to 31.8 parts and 414 parts of water and stirring well to completely dissolve the mixture.
  • the coupler aqueous solution is added to the diazonium aqueous solution prepared above and stirred for 1 hour to complete the reaction, and then the mixture slurry is heat-treated to 70 ° C., further filtered and washed with water to obtain a naphthol-based mixed crystal pigment.
  • a press cake of a pigment composition was obtained. Further, this press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain a naphthol-based mixed crystal pigment 1.
  • the naphthol-based mixed crystal pigments 2 to 13 were produced in the same manner as the above-mentioned naphthol-based mixed crystal pigment 1 except that the base component and the coupler component were changed as shown in Table 1.
  • TM-40 3-amino-4methoxybenzanilide
  • TM-20 3-amino-4methoxybenzamide
  • 2M-5NA 2-methoxy-5-nitroaniline
  • Bonamide 3-hydroxy-2-naphthamide ⁇
  • AS 3-Hydroxy-N-phenyl-2-naphthamide ⁇
  • Naphthol AS-BS 3-Hydroxy-3'-nitro-2-naphthanilides ⁇
  • Naphthol AS-LC N- (4-chloro-2,5-dimethoxyphenyl) ) -3-Hydroxy-2-naphthamide-Naphthol
  • AS-BI 5- (2-Hydroxy-3-naphthoylamino) -1H-benzoimidazole-2 (3H) -on-Naphthol
  • AS-CA N- (5) -Chloro-2-methoxyphenyl) -3-hydroxy-2
  • the inside of the reaction vessel is heated to 110 ° C., and a mixture of 30 parts of acrylic acid, 35 parts of styrene, 35 parts of lauryl methacrylate as a polymerizable monomer, and 6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator is added.
  • the mixture was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was carried out at 110 ° C.
  • magenta pigment dispersion liquid 1 20 parts of naphthol-based mixed crystal pigment 1, 20 parts of an aqueous solution of a pigment dispersion resin (solid content 30%), and 60 parts of water are sequentially put into a mixing container equipped with a stirrer, and then premixed. Was done. Then, the magenta pigment dispersion 1 (pigment concentration 20%) was obtained by performing the main dispersion using a dynomill having a volume of 0.6 L filled with 1800 g of zirconia beads having a diameter of 0.5 mm.
  • aqueous solution means a solution containing an aqueous solvent and a component dispersed and / or dissolved in the aqueous solvent.
  • magenta pigment dispersions 2 to 13 both having a pigment concentration of 20% were produced in the same manner as the magenta pigment dispersion 1 except that the naphthol-based mixed crystal pigments 2 to 13 were used as the pigment. Further, magenta pigment dispersions 14 to 18 (all having a pigment concentration of 20%) were obtained in the same manner as in the magenta pigment dispersion 1 except that the pigments shown below were used.
  • -Magenta Pigment Dispersion 14 Toshiki Red 150TR (CI Pigment Red 150 manufactured by Tokyo Color Materials Co., Ltd.)
  • Magenta Pigment Dispersion Liquid 15 Toshiki Red 269N (CI Pigment Red 269 manufactured by Tokyo Color Materials Co., Ltd.)
  • Magenta Pigment Dispersion 16 Toshiki Red 31N (CI Pigment Red 31 manufactured by Tokyo Color Materials Co., Ltd.)
  • -Magenta pigment dispersion 18 FASTGEN SUPER MAGENTA RY (quinacridone solid solution manufactured by DIC Corporation)
  • azo yellow mixed crystal pigment 1 According to the method described in Example 6 of JP-A-2007-527458, C.I. I. Pigment Yellow 74 and C.I. I. A mixed crystal pigment containing Pigment Yellow 73 (hereinafter referred to as "azo yellow mixed crystal pigment 1") was produced.
  • Yellow pigment dispersions 1 to 9 (both having a pigment concentration of 20%) were produced in the same manner as the magenta pigment dispersion 1 except that the yellow pigments shown below were used.
  • -Yellow pigment dispersion 1 SYMULER FAST YELLOW GFCONC (C.I.
  • -Yellow pigment dispersion liquid 2 SYMULER FAST YELLOW 4090G (manufactured by DIC, CI Pigment Yellow 14)
  • -Yellow pigment dispersion liquid 3 HANSA YELLOW 5GX01 (manufactured by Clariant, CI Pigment Yellow 74)
  • -Yellow pigment dispersion liquid 4 Irgazin Yellow L 1030 (CI Pigment Yellow 109, manufactured by BASF).
  • -Yellow Pigment Dispersion Solution 5 Irgazin Yellow D 1999 (BASF, CI Pigment Yellow 110)
  • -Yellow Pigment Dispersion Solution 6 Pariotrol Yellow D 0960 (manufactured by BASF, CI Pigment Yellow 138)
  • -Yellow pigment dispersion 7 Pariotrol Yellow D 1819 (manufactured by BASF, CI Pigment Yellow 139)
  • -Yellow pigment dispersion 8 Pariotrol Yellow D 1155 (manufactured by BASF, CI Pigment Yellow 185)
  • -Yellow pigment dispersion liquid 9 Azo-yellow mixed crystal pigment 1 produced above.
  • binder resin 1 styrene (meth) acrylic water-soluble resin
  • 93.4 parts of butanol 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 110 ° C., and 5 parts of methacrylic acid, 30 parts of styrene, 30 parts of methyl methacrylate, 30 parts of butyl acrylate, 5 parts of stearyl methacrylate as a polymerizable monomer, and V-601 as a polymerization initiator (A mixture of 6 parts (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was carried out at 110 ° C. for 3 hours, 0.6 part of V-601 was added, and the reaction was further continued at 110 ° C. for 1 hour.
  • binder resin 2 ((meth) acrylic resin fine particles)>
  • 20 parts of toluene 20 parts of toluene, 7.5 parts of methacrylic acid and 7.5 parts of methyl methacrylate as a polymerizable monomer, and 2,2'-as a polymerization initiator.
  • 0.9 part of azobisisobutyronitrile and 3.6 parts of 2- (dodecylthiocarbonothio oilthio) -isobutyric acid were charged and replaced with nitrogen gas.
  • the inside of the reaction vessel was heated to 75 ° C. and a polymerization reaction was carried out for 3 hours to obtain a copolymer (A block) composed of methacrylic acid and methyl methacrylate.
  • the mixed solution is heated to distill off toluene, and then water is used to adjust the solid content to 30%, whereby the aqueous dispersion of the binder resin 2 which is the (meth) acrylic resin fine particles ( Solid content 30%) was obtained.
  • the weight average molecular weight of the binder resin 2 measured by the method described above was 19,500, the acid value was 46, and the glass transition temperature was 42 ° C.
  • binder resin 3 (olefin resin fine particles)> Except for using high wax 4052E manufactured by Mitsui Chemicals Co., Ltd. as the polyethylene oxide wax, the same method as described in paragraph No. 0103 of JP-A-2019-14237 is used with the oxide polyolefin resin fine particles having an acid value of 20 mgKOH / g. An aqueous dispersion of the binder resin 3 (solid content 26%) was produced.
  • Magenta pigment dispersion 1 (pigment concentration 20%) 20 parts ⁇ Aqueous solution of binder resin 1 (solid content 30%) 16.7 parts ⁇ 1,2-propanediol 15 parts ⁇ Surfinol 420 1 part ⁇ Triethanolamine 1 Part ⁇ Proxel GXL 0.05 part ⁇ Ion-exchanged water 46.25 part
  • water-based inkjet magenta inks 2 to 39 were produced by the same method as the water-based inkjet magenta ink 1 except that the materials shown in Table 3 below were used. Further, water-based inkjet yellow inks 1 to 15 were obtained by the same method as the water-based inkjet magenta ink 1 except that the materials shown in Table 4 below were used.
  • ⁇ Evaluation 1 Evaluation of dispersion stability> The average secondary particle size (D50) of the pigments in the water-based inkjet magenta inks 1 to 39 produced above was measured at 25 ° C. using Nanotrack UPAEX-150 manufactured by Microtrac Bell. This ink was stored in a thermostat at 70 ° C., accelerated over time for a predetermined period, and then D50 was measured again at 25 ° C. to confirm changes before and after time to evaluate the dispersion stability.
  • the evaluation criteria are as follows, and the evaluation criteria values 2 to 3 are set as the practical range. 3: The rate of change in D50 after storage for 2 weeks was less than ⁇ 5%.
  • the rate of change in D50 after storage for 1: 1 week was less than ⁇ 5%, but the rate of change in viscosity after storage for 2 weeks was ⁇ 5%.
  • the rate of change in D50 after storage for 1: 1 week was ⁇ 5% or more.
  • ⁇ Evaluation 2 Evaluation of discharge stability> An inkjet head KJ4B-QA (manufactured by Kyocera Corporation, design resolution 600 dpi) was installed on a conveyor capable of transporting a recording medium, and the water-based inkjet magenta inks 1 to 39 produced above were filled therein. 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.
  • a patch having a total printing rate of 80% is an image in which the printing rate of magenta ink is 40% and the printing rate of yellow ink is 40%.
  • the gradation patch image was put into a 70 ° C. air oven within 10 seconds after printing and dried for 1 minute to obtain a printed matter for image quality evaluation. Then, the image quality of the coated paper was evaluated by visually observing the presence or absence of shading unevenness of the obtained printed matter for image quality evaluation.
  • the evaluation criteria were as follows, and the evaluation criteria values 2 to 3 were set as the practical area. 3: No unevenness in shading was observed at any printing rate. 2: Uneven shading was observed in patches with a total printing rate of 120% or less. However, some patches with a total printing rate of 140% or more showed uneven shading. 1: Even patches with a total printing rate of 120% showed uneven shading.
  • the red color gamut was evaluated by measuring the obtained hue and the saturation C of the printed matter for color gamut evaluation.
  • the light source is D50
  • the viewing angle is 2 °
  • the density status is ISO Status T
  • the density white standard is the absolute value
  • the a * value and b * value are measured, and the following formula (8) ) To calculate the saturation C.
  • the evaluation criteria for red color gamut evaluation are as follows, and the evaluation criteria values 2 to 4 are set as the practical range 4: Saturation C is 100 or more 3: Saturation C is 98 or more and less than 100 2: Saturation C is 96 or more and less than 98 1: Saturation C is less than 96
  • ⁇ Evaluation 7 Evaluation of fading of printed matter>
  • the L * value, a * value and b * value of the hue and color gamut evaluation printed matter produced in evaluation 4 were measured with the same equipment and conditions as in evaluation 4.
  • the solid image is allowed to stand indoors and under a fluorescent lamp for 24 hours, then L *, a * and b * are measured in the same manner, and the color difference ⁇ E is calculated by the following formula (9) to obtain a printed matter.
  • the fading was evaluated.
  • ⁇ L *, ⁇ a *, and ⁇ b * are the differences between the L * value, the a * value, and the b * value before and after being left for 24 hours, respectively.
  • the evaluation criteria for evaluating the fading of printed matter are as follows, and the evaluation reference values 2 to 3 are set as the practical range. 3: ⁇ E is less than 2 2: ⁇ E is 2 or more and less than 3 1: ⁇ E is 3 or more

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

Abstract

Ensemble d'encres jet d'encre comprenant : une encre jet d'encre aqueuse magenta qui contient un pigment cristallin mixte à base de naphtol spécifique, un solvant organique, un composé organique basique et de l'eau ; et une encre jet d'encre aqueuse jaune qui contient un pigment jaune spécifique et de l'eau. Le composé organique basique qui présente une valeur de pKa inférieure ou égale à 9,5 à 25 °C représente 0,1 à 1,25 % en masse de la quantité totale de l'encre jet d'encre aqueuse magenta ; et le solvant organique qui présente un point d'ébullition au moins égal à 240 °C sous 1 atm ne représente pas plus de 8 % en masse de la quantité totale de l'encre jet d'encre aqueuse magenta.
PCT/JP2021/011635 2020-05-26 2021-03-22 Ensemble d'encres jet d'encre aqueuses et procédé de production d'un article imprimé WO2021240970A1 (fr)

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JP6979152B1 (ja) * 2021-03-23 2021-12-08 東洋インキＳｃホールディングス株式会社 水性インクジェットインキセット、及び、印刷物の製造方法

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JP2004189992A (ja) * 2002-12-13 2004-07-08 Dainichiseika Color & Chem Mfg Co Ltd インクジェット記録用ベンズイミダゾロン系モノアゾ顔料組成物およびその製造方法ならびにインクジェット記録液組成物
JP2004269607A (ja) * 2003-03-06 2004-09-30 Dainichiseika Color & Chem Mfg Co Ltd インクジェットインキ用アゾ顔料およびその製造方法、ならびにインクジェットインキおよびその製造方法
JP2005060708A (ja) * 2003-08-16 2005-03-10 Dystar Textilfarben Gmbh & Co Deutscheland Kg 繊維反応性アゾ染料の染料混合物、それらの調製、及びそれらの使用
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JP2010195907A (ja) * 2009-02-25 2010-09-09 Toyo Ink Mfg Co Ltd 顔料組成物および、それを用いたインクジェットインキ
WO2011105243A1 (fr) * 2010-02-26 2011-09-01 日本ゼオン株式会社 Toner magenta
JP2015183156A (ja) * 2014-03-26 2015-10-22 東洋インキＳｃホールディングス株式会社 顔料組成物およびその製造方法
JP2018528988A (ja) * 2015-06-25 2018-10-04 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 印刷材料中での新規ナフトールａｓ顔料混合物の使用

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JP2004510012A (ja) * 2000-09-21 2004-04-02 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド アゾオレンジ顔料組成物
JP2004189992A (ja) * 2002-12-13 2004-07-08 Dainichiseika Color & Chem Mfg Co Ltd インクジェット記録用ベンズイミダゾロン系モノアゾ顔料組成物およびその製造方法ならびにインクジェット記録液組成物
JP2004269607A (ja) * 2003-03-06 2004-09-30 Dainichiseika Color & Chem Mfg Co Ltd インクジェットインキ用アゾ顔料およびその製造方法、ならびにインクジェットインキおよびその製造方法
JP2005060708A (ja) * 2003-08-16 2005-03-10 Dystar Textilfarben Gmbh & Co Deutscheland Kg 繊維反応性アゾ染料の染料混合物、それらの調製、及びそれらの使用
JP2007502875A (ja) * 2003-08-19 2007-02-15 クラリアント・プロダクテ（ドイチユラント）ゲー・エム・ベー・ハー Ｃｉピグメントレッド１７０誘導体を含有する混晶
JP2005107147A (ja) * 2003-09-30 2005-04-21 Canon Inc 乾式トナー及び画像形成方法
JP2010195907A (ja) * 2009-02-25 2010-09-09 Toyo Ink Mfg Co Ltd 顔料組成物および、それを用いたインクジェットインキ
WO2011105243A1 (fr) * 2010-02-26 2011-09-01 日本ゼオン株式会社 Toner magenta
JP2015183156A (ja) * 2014-03-26 2015-10-22 東洋インキＳｃホールディングス株式会社 顔料組成物およびその製造方法
JP2018528988A (ja) * 2015-06-25 2018-10-04 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 印刷材料中での新規ナフトールａｓ顔料混合物の使用

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