WO2018179848A1 - Ensemble d'encre et procédé de formation d'image - Google Patents

Ensemble d'encre et procédé de formation d'image Download PDF

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Publication number
WO2018179848A1
WO2018179848A1 PCT/JP2018/003872 JP2018003872W WO2018179848A1 WO 2018179848 A1 WO2018179848 A1 WO 2018179848A1 JP 2018003872 W JP2018003872 W JP 2018003872W WO 2018179848 A1 WO2018179848 A1 WO 2018179848A1
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Prior art keywords
group
water
resin
acid
formula
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PCT/JP2018/003872
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English (en)
Japanese (ja)
Inventor
大島　康仁
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富士フイルム株式会社
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Publication of WO2018179848A1 publication Critical patent/WO2018179848A1/fr

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    • 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • 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
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

  • the present disclosure relates to an ink set and an image forming method.
  • the recording method using the ink jet method is widely used because a high-quality image can be recorded on a wide variety of substrates by ejecting ink in droplets from a number of nozzles provided in the ink jet head. It's being used.
  • Various forms of image forming methods using the inkjet method have been proposed. For example, an ink set using an ink containing a colorant and a pretreatment liquid containing a compound that aggregates the components in the ink is used. The method to use is known. In this method, for example, an image with excellent resolution can be formed by bringing the ink and the pretreatment liquid into contact with each other.
  • an overcoat liquid containing water-dispersible polyurethane, two kinds of specific compounds, and water is applied to the surface of the recording medium on which the inkjet ink is ejected (for example, Japanese Patent Application Laid-Open No. 2015-2015). No. 172124).
  • the resin contained in the clear ink printed on the image contains acrylic acid having a carboxy group. Components such as resin particles in the clear ink tend to aggregate due to the acid therein, and as a result, a high gloss image cannot be obtained.
  • an aqueous treatment liquid film is formed on an image recorded with pigment ink. The same liquid is used, and the flocculant contained in the aqueous treatment liquid is a polyvalent metal salt. Since the polyvalent metal salt has a weak cohesive force with respect to components such as resin particles in the ink as compared with the acid, the problem of reducing the glossiness of the image hardly occurs, but the sharpness of the image becomes insufficient.
  • overcoat liquids many commercial products marketed as overcoat liquids (so-called aqueous varnishes) have components such as resin particles dispersed and stabilized with carboxylic acid. Therefore, when an image is formed by utilizing the action of an acid contained as a flocculant in the pretreatment liquid, it is dispersed in the overcoat liquid by the action of the acid, as in the case of pigments dispersed and contained in the ink. Aggregation of components such as resin particles tends to occur. When aggregation occurs in the overcoat liquid, the overcoat liquid thickens. Thereby, when the overcoat liquid is applied, irregularities are generated on the surface of the coating film, and the gloss of the film is lowered.
  • the overcoat liquid described in JP-A-2015-172124 is also a resin particle having a carboxy group as a dispersion stabilizing group, as is apparent from the content of Japanese Patent No. 366047 described as a specific example of the production method (see FIG. That is, it is considered that a highly glossy film cannot be obtained due to the increase in viscosity due to aggregation of the resin particles.
  • Such a decrease in the glossiness of the film is a phenomenon that tends to occur in a non-curing aqueous overcoat liquid (so-called aqueous varnish). From the viewpoint of environmental suitability and safety in recent years, it is expected that a water-based overcoat solution that does not easily cause a thickening phenomenon due to aggregation is required.
  • the storage stability of the overcoat liquid is good, and the gloss is good when the image forming surface of the recording material on which an image is formed is overcoated using an acidic pretreatment liquid.
  • the present invention relates to providing an ink set capable of obtaining the characteristics.
  • Another embodiment of the present invention relates to providing an image forming method capable of obtaining good glossiness.
  • Means for solving the above problems include the following aspects. ⁇ 1> An ink composition containing a colorant and water, a pretreatment liquid containing an acid and water, and a resin particle having a group represented by the following formula (1) and having no carboxy group And an overcoat liquid containing water.
  • A represents an alkylene group having 2 or 3 carbon atoms
  • R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • m represents an integer of 3 to 40.
  • the ink set according to ⁇ 1> wherein the total content of the group represented by the formula (1) in the resin contained in the particles is 0.05 g or more and 0.50 g or less per 1 g of the resin.
  • the resin contained in the particles is at least one selected from the group consisting of at least one structural unit represented by the following formula (2), the following formula (3), and the following formula (4).
  • A represents an alkylene group having 2 or 3 carbon atoms
  • R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • R 1 represents a hydrogen atom or a methyl group
  • m represents an integer of 3 to 40.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents a hydrocarbon group having 1 to 20 carbon atoms.
  • ⁇ 4> The ink set according to ⁇ 3>, wherein m in the formula (2) represents an integer of 6 or more and 20 or less.
  • ⁇ 5> The ink set according to any one of ⁇ 1> to ⁇ 4>, wherein the particles include a nonionic surfactant having a group represented by the formula (1).
  • ⁇ 6> Forming an image by applying a pretreatment liquid containing acid and water to the recording material, and applying an ink composition containing a colorant and water to the application surface of the pretreatment liquid of the recording material And a resin particle having a group represented by the formula (1) and not having a carboxy group on at least a part of the recording material on which an image is formed, and over containing water. Applying the coating liquid.
  • the storage stability of the overcoat solution is good, and the image forming surface of the recording material on which an image is formed using an acidic pretreatment solution is good.
  • an ink set capable of obtaining high glossiness.
  • an image forming method capable of obtaining good glossiness is provided.
  • a numerical range indicated by using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the content of each component means the total content of the plurality of types of substances unless there is a specific notice when there are a plurality of types of substances corresponding to the respective components.
  • process is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • (meth) acryl is a term used in a concept including both acrylic and methacrylic.
  • An ink set of the present disclosure includes an ink composition containing a colorant and water, a pretreatment liquid containing an acid and water, a resin having a group represented by the formula (1) and having no carboxy group And an overcoat liquid containing water.
  • the ink set of the present disclosure has good storage stability of the overcoat liquid, and good gloss when the image forming surface of a recording material on which an image is formed is overcoated using an acidic pretreatment liquid Is obtained.
  • JP-A-2015-199780 and JP-A-2003-326829 disclose a technique for improving image abrasion or water resistance by providing a liquid containing resin particles dispersed on an image. ing.
  • a pretreatment liquid containing an aggregating agent for aggregating the pigment in the ink composition in addition to the ink composition containing the pigment or the like, it is brought into contact with the pretreatment liquid.
  • the ink composition After the ink composition is ejected and an image is formed, when the image is overcoated with a liquid containing components such as resin particles, the components in the overcoated liquid aggregate and thicken.
  • the effect of improving gloss may be reduced.
  • the aggregating agent contained in the aqueous treatment liquid is a polyvalent metal salt
  • the polyvalent metal salt has a weaker aggregating action of the dispersed component than the acid. It is expected that the viscosity increase due to the aggregation of the components in the liquid when the image is overcoated is small.
  • the overcoat liquid described in JP-A-2015-172124 also contains resin particles having a carboxy group as a dispersion stabilizing group (that is, water-dispersible polyurethane particles), and therefore, due to aggregation of the resin particles. It is thought that thickening occurs and a highly glossy film cannot be obtained. In general, in an overcoat liquid in which resin particles and the like are dispersed and contained, good storage stability is required.
  • an image formed using an acid-containing treatment liquid in an aqueous pretreatment liquid containing an acid (hereinafter also referred to as “acid-containing treatment liquid”) and an ink composition.
  • an aqueous overcoat solution containing resin particles having a specific group that is, a group represented by the formula (1)
  • the overcoat solution Even when the image forming surface of a recording material on which an image is formed is overcoated using the containing treatment liquid, good glossiness can be obtained.
  • the ink set of the present disclosure even when an image formed using an acid-containing processing liquid is overcoated, thickening due to aggregation of components in the overcoat liquid due to the action of an acid in the acid-containing processing liquid can be suppressed. Therefore, the occurrence of irregularities such as streaks that cause a decrease in gloss is effectively suppressed. As a result, it is considered that the effect of improving the glossiness of the image by performing the overcoat treatment is excellent.
  • the resin forming the resin particles contained in the overcoat liquid has a specific group (that is, a group represented by the formula (1)) and does not have a carboxy group, The overcoat solution has good storage stability.
  • the overcoat liquid will be described first, and then the ink composition and the pretreatment liquid will be described.
  • the overcoat liquid contains particles of a resin having a group represented by the formula (1) and not having a carboxy group, and water.
  • the overcoat liquid is an aqueous liquid.
  • the overcoat liquid contains a resin particle having a group represented by the formula (1) and not having a carboxy group, the storage stability is improved.
  • the overcoat liquid has an image forming surface formed by using a pretreatment liquid containing an acid by containing particles of a resin having a group represented by the formula (1) and not having a carboxy group. Even when the film is overcoated, good gloss can be obtained.
  • the overcoat liquid contains resin particles having a group represented by the formula (1) and not having a carboxy group.
  • the resin forming the particles is not particularly limited as long as it has a group represented by the formula (1) and does not have a carboxy group and can maintain the shape of the particles in an aqueous liquid.
  • the resin can be appropriately selected from known resins, and is preferably a water-insoluble or poorly water-soluble resin (hereinafter, the resin forming the particles is also referred to as “water-insoluble resin”).
  • water-insoluble or poorly water-soluble means that when the resin is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., the dissolved amount is 15 g or less. That means.
  • the dissolution amount is the dissolution amount when 100% neutralized with sodium hydroxide or acetic acid according to the type of the salt-forming group of the water-insoluble or poorly water-soluble resin.
  • A represents an alkylene group having 2 or 3 carbon atoms
  • R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • m represents an integer of 3 to 40.
  • the water-insoluble resin may have only one type represented by the formula (1), or may have two or more types.
  • a in Formula (1) represents an alkylene group having 2 or 3 carbon atoms. Specific examples of the alkylene group having 2 or 3 carbon atoms include —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, and —CH (CH 3 ) CH 2 —. From the viewpoint that the storage stability of the overcoat solution is better, A is preferably —CH 2 CH 2 —.
  • the alkylene group having 2 or 3 carbon atoms represented by A may be only one kind in the formula (1), or may be contained in two or more kinds.
  • m represents the total sum of repeating units represented by — (AO) — contained in two or more types.
  • AO repeating units represented by —
  • R in the formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, Octyl group, nonyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, norbornyl group, adamantyl group, etc.), aryl group having 6 to 20 carbon atoms (phenyl group, naphthyl group, 4-biphenyl) Group, 2-biphenyl group, etc.), and aralkyl groups having 7 to 20 carbon atoms (benzyl group, phenethyl group, 3-phenylpropyl
  • the hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, It is more preferably an alkyl group of 1 to 4, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • hydrocarbon groups may have a substituent.
  • Substituents include halogen atoms (chlorine atoms, fluorine atoms, bromine atoms, etc.), hydroxy groups, thiol groups, sulfo groups, cyano groups, epoxy groups, —OR 10 groups, —OCOR 10 groups, —COOR 10 groups, — COR 10 group, —N (R 10 ) (R 11 ) group, —NHCONHR 10 group, —NHCOOR 10 group, —Si (R 10 ) 3 group, —CONHR 10 group and the like can be mentioned. A plurality of these substituents may be substituted in the alkyl group.
  • R 10 and R 11 are each independently methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, propenyl, butenyl, hexenyl, octenyl, 2-hydroxy Ethyl group, 3-chloropropyl group, 2-cyanoethyl group, N, N-dimethylaminoethyl group, 2-bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxyethyl Group, 3-carboxypropyl group, benzyl group and the like. Note that when the hydrocarbon group having 1 to 20 carbon atoms has a substituent, the number of carbon atoms represents the total including the number of carbon atoms contained in the substituent.
  • M in Formula (1) represents an integer of 3 to 40. Preferably it represents an integer of 5 or more and 25 or less, more preferably an integer of 6 or more and 20 or less.
  • m is in the above range, the storage stability of the overcoat liquid is good, and the water resistance of the film formed from the overcoat liquid is good.
  • the total content of the group represented by the formula (1) in the water-insoluble resin contained in the particles is preferably 0.05 g or more and 0.50 g or less, and 0.10 g or more and 0 or less per 1 g of the water-insoluble resin. More preferably, it is not more than .40 g, more preferably not less than 0.20 g and not more than 0.30 g.
  • the total content of the group represented by the formula (1) in the water-insoluble resin is 0.05 g or more per 1 g of the water-insoluble resin, the storage stability of the overcoat liquid becomes better.
  • the total content of the group represented by the formula (1) in the water-insoluble resin is 0.50 g or less per 1 g of the water-insoluble resin, the water resistance of the film formed by the overcoat liquid becomes good.
  • the water-insoluble resin contained in the particles is a polymer having at least a structural unit derived from a monomer having a group represented by the formula (1) and not having a carboxy group.
  • the water-insoluble resin may contain only one type of structural unit derived from a monomer having a group represented by the formula (1) and not having a carboxy group, or may contain two or more types. May be.
  • the content of the structural unit having the group represented by the formula (1) in the water-insoluble resin contained in the particles is appropriately selected depending on the structure of the structural unit, but is 0.05 g or more per 1 g of the water-insoluble resin. 0.55 g or less is preferable, 0.10 g or more and 0.45 g or less is more preferable, and 0.20 g or more and 0.35 g or less is still more preferable.
  • the content of the structural unit having the group represented by the formula (1) in the water-insoluble resin is 0.05 g or more per 1 g of the water-insoluble resin, the storage stability of the overcoat liquid becomes better.
  • the content of the structural unit having the group represented by formula (1) in the water-insoluble resin is 0.55 g or less per 1 g of the water-insoluble resin, the water resistance of the film formed by the overcoat liquid is good. It becomes.
  • the water-insoluble resin contained in the particles is at least one selected from the group consisting of at least one structural unit represented by the following formula (2), the following formula (3), and the following formula (4). And a structural unit. According to such an aspect, the abrasion resistance and water resistance of the film formed from the overcoat liquid, and the storage stability of the overcoat liquid are further improved.
  • A represents an alkylene group having 2 or 3 carbon atoms
  • R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • R 1 represents a hydrogen atom or a methyl group
  • m represents an integer of 3 to 40.
  • a in Formula (2) is synonymous with A in Formula (1).
  • R in Formula (2) has the same meaning as R in Formula (1).
  • R 1 in formula (2) is preferably a methyl group.
  • M in the formula (2) has the same meaning as m in the formula (1).
  • the water-insoluble resin may contain only one type of structural unit represented by the formula (2), or may contain two or more types.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents a hydrocarbon group having 1 to 20 carbon atoms.
  • R 2 in Formula (3) is preferably a methyl group.
  • R 3 in the formula (3) represents a hydrocarbon group having 1 to 20 carbon atoms and is synonymous with the hydrocarbon group having 1 to 20 carbon atoms represented by R in the formula (1).
  • the water-insoluble resin may include only one type of the structural unit represented by the formula (3), or may include two or more types.
  • the water-insoluble resin contains at least one structural unit represented by the formula (2) and at least one structural unit represented by the formula (4).
  • the water-insoluble resin comprises at least one structural unit represented by the formula (2), at least one structural unit represented by the formula (3), and the formula (4).
  • at least one structural unit represented by: Formula (4) is a structural unit derived from styrene.
  • the water-insoluble resin is at least one structural unit represented by the formula (2), at least one structural unit represented by the formula (3), and at least one structural unit represented by the formula (4). And a structural unit represented by the formula (2), a structural unit represented by the formula (3), and a structural unit represented by the formula (4) in the water-insoluble resin.
  • the content ratio (content of structural unit represented by formula (2) / content of structural unit represented by formula (3) / content of structural unit represented by formula (4)) is based on mass. It is preferably 5 to 55/5 to 75/20 to 80, more preferably 10 to 45/10 to 60/25 to 70, and more preferably 20 to 35/15 to 45/30 to 60. Is more preferable.
  • the content of the structural unit represented by the formula (2) in the water-insoluble resin contained in the particles is preferably 0.05 g or more and 0.55 g or less, and 0.10 g or more and 0.45 g or less per 1 g of the water-insoluble resin. Is more preferable, and 0.20 g or more and 0.35 g or less is still more preferable.
  • the content of the structural unit represented by the formula (2) in the water-insoluble resin is 0.05 g or more per 1 g of the water-insoluble resin, the storage stability of the overcoat liquid becomes better.
  • the content of the structural unit represented by the formula (2) in the water-insoluble resin is 0.55 g or less per 1 g of the water-insoluble resin, the water resistance of the film formed by the overcoat liquid becomes better. .
  • the content of the structural unit represented by the formula (3) in the water-insoluble resin contained in the particles is arbitrary depending on the structure of R 3. However, it is preferably 0.05 g or more and 0.75 g or less, more preferably 0.10 g or more and 0.60 g or less, and still more preferably 0.15 g or more and 0.45 g or less per 1 g of water-insoluble resin.
  • the content of the structural unit represented by the formula (3) in the water-insoluble resin contained in the particles is within the above range, the water resistance of the film formed by the overcoat liquid becomes better.
  • the content of the structural unit represented by the formula (4) in the water-insoluble resin contained in the particles is 0 per 1 g of the water-insoluble resin. 20 g or more and 0.80 g or less is preferable, 0.25 g or more and 0.70 g or less is more preferable, and 0.30 g or more and 0.60 g or less is still more preferable.
  • the content of the structural unit represented by the formula (4) in the water-insoluble resin contained in the particles is within the above range, the gloss of the film formed by the overcoat liquid becomes better.
  • the content of the group represented by the formula (1) contained in the resin in the water-insoluble resin, the structural unit represented by the formula (2), the structural unit represented by the formula (3), and the formula ( The content of the structural unit represented by 4) is determined by the following method.
  • the overcoat solution is centrifuged using a test tube (product name: Amicon Ultra-15, molecular weight cut off 100 kDa, Merck) equipped with an ultrafiltration filter, and the water-insoluble resin particles are collected and completely dissolved in the solvent. Then, the structure is identified by nuclear magnetic resonance spectroscopy (NMR method). Based on the obtained results, the content of the group represented by the formula (1) contained in the resin, the structural unit represented by the formula (2), the structural unit represented by the formula (3), and the formula The content of the structural unit represented by (4) is calculated.
  • the water-insoluble resin contained in the particles may contain a constituent unit derived from another monomer other than the constituent units described above.
  • the structural unit derived from other monomers is not particularly limited, and examples thereof include ⁇ -methylstyrene, amide monomers (acrylamide, N- (2-hydroxyethyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, isopropylacrylamide, N- (2-hydroxymethyl) acrylamide, methacrylamide, etc.), vinyl cyanide monomers (acrylonitrile, methacrylonitrile, etc.), ethylenically unsaturated carboxylic acid hydroxyalkyl esters Monomers ( ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, etc.), dialkylaminoalkyl (meth) acrylamide hydrochlorides and tertiary salts such as sulfates (dimethylaminoethyl (meth) acryl
  • the water-insoluble resin contained in the particles does not have a carboxy group. If the water-insoluble resin contained in the particles has a carboxy group, the acid, which is an aggregating component contained in the pretreatment liquid described later, reacts with the water-insoluble resin to aggregate the particles, resulting in a decrease in gloss. Invite.
  • the water-insoluble resin contained in the particles does not have a carboxy group, so that the gloss of the formed film is good.
  • “having no carboxy group” means that the water-insoluble resin has substantially no carboxy group.
  • substantially does not have means that even when it has a carboxy group, it exhibits the same performance as when it does not.
  • the content of the carboxy group in the water-insoluble resin is, for example, 0.05 g or less, preferably 0. 03 g or less, more preferably 0.01 g or less.
  • the glass transition temperature (Tg) of the water-insoluble resin is preferably 40 ° C. or higher.
  • Tg is preferably 45 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 130 ° C. or lower, from the viewpoint that the heat resistance of the resin film to be formed is well maintained and the film can be satisfactorily formed. It is preferably 55 ° C. or higher and 110 ° C. or lower.
  • the Tg of the water-insoluble resin is a value measured by a differential scanning calorimetry (DSC).
  • DSC differential scanning calorimeter
  • EXSTAR 6220 manufactured by SII Nanotechnology Inc. can be used.
  • the weight average molecular weight (Mw) of the water-insoluble resin is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, still more preferably 10,000 to 300,000, From the viewpoint of viscosity, 20,000 to 70,000 is particularly preferable.
  • the weight average molecular weight of the water-insoluble resin is a value measured by gel permeation chromatography (GPC).
  • GPC uses HLC-8220GPC (Tosoh Corp.) as a measuring device, and three columns of TSKgel, Super Multipore HZ-H (4.6 mm ID ⁇ 15 cm, Tosoh Corp.) as columns.
  • eluent THF tetrahydrofuran
  • RI refractometer
  • the calibration curve is “standard sample TSK standard, polystyrene” of Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000” Prepared from 8 samples of “A-2500”, “A-1000”, and “n-propylbenzene”.
  • the particle of the water-insoluble resin contains a nonionic surfactant having a group represented by the formula (1), that is, a nonion having a group represented by the formula (1) on at least a part of the surface of the particle. It is preferable to have a surfactant.
  • the particles include at least a particulate water-insoluble resin and a nonionic surfactant having a group represented by the formula (1).
  • “including a nonionic surfactant having a group represented by the formula (1)” covers the surface of the water-insoluble resin with the nonionic surfactant having a group represented by the formula (1).
  • a mode in which a nonionic surfactant having a group represented by the formula (1) is contained in the water-insoluble resin.
  • nonionic surfactant having a group represented by the formula (1) a nonionic surfactant having a group represented by the formula (1) introduced into the liquid is described later.
  • the particles and the nonionic surfactant having the group represented by the formula (1) are taken out from another phase, or the particles and the formula ( This is determined by whether the nonionic surfactant having the group represented by 1) is simultaneously taken out from the same phase.
  • nonionic surfactant any conventionally known surfactant can be used without limitation as long as it has at least the group represented by the formula (1).
  • examples of the nonionic surfactant having a group represented by the formula (1) include compounds having a combination of a hydrophobic group and ethylene oxide and / or propylene oxide in the molecule. Specifically, alkyl (carbon number: 6 to 40) phenol-ethylene oxide condensate, aliphatic (carbon number: 6 to 40) first or second linear or branched alcohol and condensation product of ethylene oxide And those represented by the structure of R—O— (CH 2 CH 2 O) n—H (R and n are the same as R and n in formula (1)) are preferable.
  • nonionic surfactant having a group represented by the formula (1) commercially available products can be used.
  • examples of commercially available nonionic surfactants having a group represented by the formula (1) include Kao's Emulgen (registered trademark) series, Nippon Emulsifier's New Coal (registered trademark) series, Neugen (registered trademark) series of Daiichi Kogyo Seiyaku Co., Ltd., Adekator (registered trademark) series of ADEKA Corporation, New Pole (registered trademark) series, Sanyo Chemical Co., Ltd.
  • the total content of the group represented by the formula (1) in the nonionic surfactant contained in the particles is preferably 0.05 g or more and 0.50 g or less per 1 g of the water-insoluble resin forming the particles. 0.10 g or more and 0.40 g or less, more preferably 0.20 g or more and 0.30 g or less.
  • the total content of the group represented by the formula (1) in the nonionic surfactant is 0.05 g or more per 1 g of the water-insoluble resin forming the particles, the storage stability of the overcoat liquid is better. It becomes.
  • the total content of the group represented by the formula (1) in the nonionic surfactant is 0.50 g or less per 1 g of the water-insoluble resin, the water resistance of the film formed by the overcoat liquid is good. Become.
  • the content of the group represented by the formula (1) in the nonionic surfactant contained in the particles is determined by the following method.
  • the overcoat solution is centrifuged using a test tube (product name: Amicon Ultra-15, molecular weight cut off 100 kDa, Merck) equipped with an ultrafiltration filter, and the water-insoluble resin particles are collected and completely dissolved in the solvent. Then, the structure is identified by nuclear magnetic resonance spectroscopy (NMR method). Based on the obtained results, the content of the group represented by the formula (1) in the nonionic surfactant contained in the particles is calculated.
  • the water-insoluble resin particles may be used in the form of a dispersion in which the particles are dispersed in an aqueous medium (so-called aqueous dispersion called latex).
  • a dispersion in which water-insoluble resin particles are dispersed in an aqueous medium can be prepared by a conventionally known method. Examples of the production method include Method A and Method B shown below.
  • Method A A hydrophobic polymer is dissolved in a water-miscible organic solvent (acetone, methanol, etc.), and then added to water containing a nonionic surfactant having a group represented by the formula (1). The mixture is stirred to obtain an emulsified state. Next, the aqueous dispersion of water-insoluble resin particles dispersed with a nonionic surfactant having a group represented by the formula (1) is obtained by heating and / or reducing pressure and distilling off the organic solvent.
  • Method to obtain (so-called phase inversion emulsification method).
  • Method B A hydrophobic polymerizable monomer and a thermal polymerization initiator are added to water containing a nonionic surfactant having a group represented by the formula (1), and stirred to obtain an emulsified state. Next, polymerization is initiated in micelles by heat to obtain an aqueous dispersion of water-insoluble resin particles (so-called emulsion polymerization method).
  • the aqueous dispersion of water-insoluble resin particles is preferably prepared by Method B from the viewpoint of the abrasion resistance and water resistance of the film formed by the overcoat liquid and the storage stability of the overcoat liquid.
  • the average particle size of the water-insoluble resin particles is preferably 10 nm to 500 nm, more preferably 20 nm to 400 nm, and still more preferably 30 nm to 300 nm in terms of volume average particle size.
  • the particle size distribution of the water-insoluble resin particles is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. Further, two or more kinds of water-insoluble resin particles having a monodisperse particle size distribution may be mixed and used.
  • the average particle size and particle size distribution of the water-insoluble resin particles are determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution measuring device.
  • a nanotrack particle size distribution measuring apparatus for example, UPA-EX150 manufactured by Nikkiso Co., Ltd. can be used.
  • the overcoat liquid may contain only one kind of water-insoluble resin particles, or may contain two or more kinds.
  • the content of the resin particles in the overcoat liquid is not particularly limited, and is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 45% by mass with respect to the total mass of the overcoat liquid, 20 More preferred is from 40% by weight.
  • the content of the resin particles in the overcoat liquid is 10% by mass or more, the gloss of the film formed by the overcoat liquid becomes better.
  • the content of the resin particles in the overcoat liquid is 50% by mass or less, the storage stability of the overcoat liquid becomes better.
  • the overcoat liquid contains water.
  • the overcoat liquid is an aqueous liquid containing water as a main solvent.
  • water is the main solvent” means that the content of water exceeds 50% by mass with respect to the total mass of all solvents contained in the overcoat solution.
  • the content of water in the overcoat liquid is not particularly limited, and is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass with respect to the total mass of the overcoat liquid.
  • the overcoat liquid may contain components other than the above components.
  • examples of other components include organic solvents, surfactants, and waxes.
  • bead particles that are incompatible with the resin particles described above may be included.
  • Organic solvent- Organic solvents include alcohol (methanol, ethanol, propanol, isopropanol (IPA), butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohol (ethylene glycol) , Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), glycol derivatives (ethylene glycol monomethyl ether, ethylene glycol) Monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol), propylene glycol
  • the overcoat liquid may contain a surfactant.
  • the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants, and the like, and anionic surfactants are preferable.
  • anionic surfactant it can select from a well-known thing suitably, For example, a sulfate ester salt, a sulfonate, a phosphate, a fatty acid salt, a formalin condensate etc. are mentioned.
  • cations that form salts include ammonium ions, triethanolamine ions, metal cations, and the like. Among these, as the cation forming the salt, a monovalent metal cation is preferable, and sodium ion or potassium ion is particularly preferable.
  • the anionic surfactant preferably contains at least one selected from a sulfonate salt and a sulfate ester salt from the viewpoint that the effect of suppressing the decrease in the density of the solid image portion and the effect of suppressing the stripe unevenness are more excellent.
  • anionic surfactants sodium lauryl sulfate, linear sodium dodecylbenzene sulfonate, branched sodium dodecylbenzene sulfonate, or sulfosuccinic acid is preferable because the effect of improving the wettability of the surface of the recording material is easily exhibited. Acid-di-2-ethylhexyl sodium is preferred.
  • the content of the surfactant in the overcoat liquid is such that the surface tension of the overcoat liquid (25 ° C.) is 20 mN from the viewpoint of making the coated film uniform and improving the gloss. It is preferably an amount that can be adjusted to 40 mN / m or less, more preferably an amount that can be adjusted to 25 mN / m to 35 mN / m.
  • the overcoat liquid may contain a wax.
  • wax means a polymer compound having a melting point of 170 ° C. or less
  • wax particles means particles formed from the above wax.
  • the wax is distinguished from “resin” which is a polymer compound having no melting point or a melting point exceeding 170 ° C., and wax particles are distinguished from “resin particles”.
  • fusing point means the temperature of the endothermic peak top in DSC measurement using a differential scanning calorimeter (DSC: Differential scanning calorimetry).
  • DSC differential scanning calorimeter
  • EXSTAR 6220 of Hitachi High-Tech Science Co., Ltd. can be used.
  • the wax is preferably contained in the form of particles from the viewpoint of dispersion stability. That is, the wax is preferably contained in the form of wax particles.
  • the particles may be used in the form of a dispersion in which particles are dispersed in an aqueous medium (so-called aqueous dispersion called latex).
  • waxes examples include plant systems such as carnauba wax, candelix wax, beeswax, rice wax, lanolin, animal waxes, paraffin wax, microcrystalline wax, polyolefin wax (polyethylene wax, oxidized polyethylene wax, etc.), petrolatum, etc.
  • Natural wax or synthetic wax such as petroleum wax, montan wax, mineral wax such as ozokerite, synthetic wax such as carbon wax, Hoechst wax, stearamide, ⁇ -olefin / maleic anhydride copolymer, or a mixture thereof Is mentioned.
  • the wax is preferably at least one selected from carnauba wax and polyolefin wax, and polyethylene wax is particularly preferable from the viewpoint of image scratch resistance.
  • the wax is preferably added in the form of a dispersion, and can be included in the overcoat liquid, for example, as a dispersion such as an emulsion.
  • a solvent in the case of a dispersion water is preferable, but it is not limited to water.
  • a commonly used organic solvent can be appropriately selected and used during dispersion.
  • a commercially available product can be used as the wax.
  • Examples of commercially available waxes include Nopcoat PEM17 (San Nopco), Chemipearl (registered trademark) W4005 (Mitsui Chemicals), AQUACER (registered trademark) 515, AQUACER (registered trademark) 531 and AQUACER (registered trademark) 593. (Above, Big Chemie Japan Co., Ltd.), Cellosol 524 (Chukyo Yushi Co., Ltd.), etc.
  • the overcoat solution contains a wax
  • it may contain only one type of wax or two or more types.
  • the overcoat liquid may contain bead particles.
  • bead particles include particles such as acrylic resin beads, amino resin beads, polyolefin resin beads, alumina beads, and glass beads.
  • acrylic resin beads polymethyl methacrylate, polybutyl methacrylate, polymethacrylate, polystyrene having a refractive index of 1.40 to 1.60 and a true specific gravity of 1.01 to 1.50. And other resins (polymethyl methacrylate, polybutyl methacrylate, polymethacrylates, etc.).
  • Amino resin beads include melamine / formaldehyde condensate, benzoguanamine / formaldehyde condensate, melamine / benzoguanamine / formaldehyde having a refractive index of 1.50 to 1.80 and a true specific gravity of 1.30 to 1.80. Examples include condensates and silica-treated products of these condensates.
  • polyolefin resin beads examples include polyethylene resin beads and polypropylene resin beads having a refractive index of 1.30 to 1.60 and a true specific gravity of 0.90 to 1.80.
  • alumina beads examples include aluminum oxide having a refractive index of 1.50 to 1.90 and a true specific gravity of 3.80 to 4.00.
  • soda-lime glass having a refractive index of 1.40 to 2.30 and a true specific gravity of 2.40 to 4.60
  • titanium-barium glass low alkali glass, low alkali borosilicate Glass etc.
  • the beads to be used are incompatible with resin particles having a group represented by the above-described formula (1) and not having a carboxy group.
  • the overcoat liquid is formed of the overcoat liquid by including bead particles having a group represented by the above-described formula (1) and not compatible with resin particles not having a carboxy group.
  • the gloss of the film can be controlled.
  • the overcoat liquid contains bead particles, it may contain only one kind of bead particles or two or more kinds.
  • the content of the bead particles in the overcoat liquid is a ratio of the resin particle content to the bead particle content (resin particle content / The content of the bead particles) is preferably in the range of 20/1 to 1/3, and more preferably in the range of 2/1 to 1/2.
  • the gloss of the film formed by the overcoat liquid can be controlled to a desired gloss.
  • the adhesion of the film formed by the overcoat liquid tends to be insufficient.
  • the bead particles preferably have a refractive index of 1.4 or more and an average particle diameter of 0.5 ⁇ m to 30 ⁇ m.
  • the refractive index and the average particle diameter of the bead particles are within the above range, the bead particles do not diffuse light and the gloss control becomes easy.
  • the average particle diameter of the bead particles is 0.5 ⁇ m to 30 ⁇ m, the adhesion of the film formed by the overcoat liquid is improved.
  • the pH of the overcoat solution is preferably 5.0 to 10.0, more preferably 6.0 to 9.0, from the viewpoint of storage stability.
  • the pH of the overcoat solution is a value measured using a pH meter in a state where the temperature of the overcoat solution is adjusted to 25 ° C. in an environment of 25 ° C.
  • As the pH meter for example, WM-50EG manufactured by Toa DK Corporation can be used.
  • surface tension of an overcoat liquid there is no restriction
  • the surface tension of the overcoat liquid is a value measured under a condition of 25 ° C. by a plate method using a surface tension meter. As the surface tension meter, for example, Automatic Surface Tensiometer CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. can be used.
  • the surface tension of the overcoat liquid can be adjusted, for example, by adding a surfactant.
  • the ink composition contains a colorant and water, and preferably contains resin particles, and may further contain other components as necessary.
  • the ink composition includes a colorant.
  • the colorant is not particularly limited, and may be a pigment or a dye.
  • the colorant is preferably an anionic colorant, and more preferably a pigment, from the viewpoint of excellent cohesiveness when contacted with an aggregating component (that is, an acid) contained in a pretreatment liquid described later.
  • an aggregating component that is, an acid
  • anionic colorant refers to a carboxy group, a sulfo group, or a phosphate group in the structure (for example, in the structure of a dispersant when the colorant is coated with a dispersant described later).
  • a colorant having an anionic group such as
  • any of an organic pigment or an inorganic pigment may be sufficient.
  • the pigment is preferably insoluble or hardly soluble in water from the viewpoint of ink colorability.
  • Organic pigments include polycyclic pigments such as azo lakes, azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments.
  • Dye lakes such as basic dye type lakes and acid dye type lakes; nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments and the like.
  • inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black.
  • any pigment that is not described in the color index can be used as long as it is dispersible in water.
  • pigments surface-treated with a surfactant, a polymer dispersant, etc., graft carbon, etc. can also be used.
  • the pigment at least one selected from the group consisting of an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a carbon black pigment is preferable, and an anionic azo pigment, an anionic phthalocyanine pigment, and an anion More preferred is at least one selected from the group consisting of quinacridone pigments.
  • a form in which the pigment is dispersed by a dispersant is preferable.
  • a form in which the pigment is dispersed with the polymer dispersant that is, a form in which at least a part of the pigment is coated with the polymer dispersant is preferable.
  • a pigment at least partially coated with a polymer dispersant is referred to as a “resin-coated pigment”.
  • the dispersant may be a polymer dispersant or a low molecular surfactant type dispersant.
  • the polymer dispersant may be an uncrosslinked polymer dispersant (that is, a non-crosslinked polymer dispersant), or a polymer dispersant that is crosslinked by a crosslinking agent (that is, a crosslinked polymer dispersant). May be.
  • the non-crosslinked polymer dispersant may be a water-soluble non-crosslinked polymer dispersant or a water-insoluble non-crosslinked polymer dispersant.
  • the low molecular surfactant type dispersant the surfactant type dispersants described in paragraphs [0016] to [0020] of JP 2010-188661 A can be used.
  • hydrophilic polymer compounds can be used as the water-soluble non-crosslinked polymer dispersant.
  • water-soluble non-crosslinked polymer dispersant for example, natural hydrophilic polymer compounds described in paragraphs [0021] to [0022] of JP 2010-188661 A can be used.
  • a synthetic hydrophilic polymer compound can also be used as the water-soluble non-crosslinked polymer dispersant.
  • Synthetic hydrophilic polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, polyacrylamide, polyacrylic acid or alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resins, Water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, ⁇ -naphthalene sulfonic acid formalin condensate alkali metal salt, quaternary ammonium, cation such as amino group And a high molecular compound having a salt of a functional functional group in the side chain.
  • a polymer compound containing a carboxy group is preferable from the viewpoint of dispersion stability and aggregation of the pigment, for example, an acrylic resin such as a water-soluble styrene acrylic resin, High molecular compounds containing a carboxy group such as a water-soluble styrene maleic acid resin, a water-soluble vinyl naphthalene acrylic resin, and a water-soluble vinyl naphthalene maleic resin are particularly preferred.
  • a polymer having both a hydrophobic portion and a hydrophilic portion can be used as the water-insoluble dispersant.
  • the polymer having both a hydrophobic part and a hydrophilic part include a styrene- (meth) acrylic acid copolymer, a styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, and a (meth) acrylic acid ester.
  • -(Meth) acrylic acid copolymer polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymer, styrene-maleic acid copolymer and the like.
  • Styrene- (meth) acrylic acid copolymer (meth) acrylic acid ester- (meth) acrylic acid copolymer, polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymer, and styrene-maleic acid copolymer
  • the coalescence may be a binary copolymer or a ternary or higher copolymer.
  • (meth) acrylic acid ester- (meth) acrylic acid copolymer is preferable, and benzyl (meth) acrylate- (meth) acrylic acid-methyl (meth) acrylate ternary copolymer is preferable.
  • Polymers are particularly preferred.
  • (meth) acrylic acid refers to acrylic acid or methacrylic acid
  • (meth) acrylate refers to acrylate or methacrylate.
  • the copolymer may be a random copolymer, a block copolymer, or a graft copolymer.
  • the weight average molecular weight (Mw) of the non-crosslinked polymer dispersant is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, still more preferably 5,000 to 80,000. Particularly preferred is 10,000 to 60,000.
  • the weight average molecular weight (Mw) of the non-crosslinked polymer dispersant is a value measured by the same method as the measurement of the weight average molecular weight (Mw) of the water-insoluble resin contained in the overcoat liquid described above.
  • the acid value of the non-crosslinked polymer dispersant is not particularly limited, but is preferably larger than the acid value of a resin (preferably a self-dispersing resin) in resin particles described later from the viewpoint of cohesiveness.
  • the crosslinked polymer dispersant is formed by crosslinking a polymer (so-called uncrosslinked polymer) with a crosslinking agent.
  • the polymer is not particularly limited, and various polymers can be used. Among them, polyvinyls, polyurethanes, polyesters and the like that can function as a water-soluble dispersant are preferable, and polyvinyls are more preferable.
  • the polymer is preferably a copolymer obtained using a carboxy group-containing monomer as a copolymerization component. Examples of the carboxy group-containing monomer include (meth) acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid and the like. Among these, from the viewpoint of the crosslinkability and dispersion stability of the polymer, At least one monomer selected from (meth) acrylic acid and ⁇ -carboxyethyl acrylate is preferred.
  • the polymer Since the polymer is crosslinked by a crosslinking agent, it has a functional group that can be crosslinked by the crosslinking agent.
  • the crosslinkable functional group is not particularly limited, and examples thereof include a carboxy group or a salt thereof, an isocyanate group, and an epoxy group.
  • a carboxy group or a salt thereof is preferable from the viewpoint of improving dispersibility.
  • the acid value of the polymer is preferably 90 mgKOH / g or more, and more preferably 95 mgKOH / g or more, from the viewpoint of water solubility of the polymer. Furthermore, from the viewpoint of the dispersibility and dispersion stability of the pigment, it is preferably 100 mgKOH / g to 180 mgKOH / g, more preferably 100 mgKOH / g to 170 mgKOH / g, and 100 mgKOH / g to 160 mgKOH / g. More preferably it is.
  • the acid value of the polymer is a value measured by the method described in Japanese Industrial Standard (JIS K0070: 1992).
  • the weight average molecular weight (Mw) of the polymer is preferably 50,000 to 120,000, more preferably 60,000 to 120,000, still more preferably 60,000 to 100,000, and particularly preferably 60,000 to 90,000.
  • the weight average molecular weight (Mw) of a polymer is a value measured by the method similar to the measurement of the weight average molecular weight (Mw) of the water-insoluble resin contained in the above-mentioned overcoat liquid.
  • the polymer preferably further has at least one hydrophobic monomer as a copolymerization component.
  • the hydrophobic monomer include (meth) acrylate having an aromatic ring group such as alkyl (meth) acrylate having 1 to 20 carbon atoms, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate, styrene and derivatives thereof. It is done.
  • the copolymerization form of the polymer is not particularly limited, and the polymer may be a random polymer, a block polymer, or a graft polymer.
  • the method for synthesizing the polymer is not particularly limited, but for example, synthesis by random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.
  • the cross-linking agent is not particularly limited as long as it is a compound having two or more sites that react with the polymer, but has two or more epoxy groups from the viewpoint of excellent reactivity with a carboxy group. (I.e., bifunctional or higher functional epoxy compounds) are preferred.
  • the crosslinking agent include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and polypropylene glycol.
  • the crosslinking agent is preferably at least one selected from the group consisting of polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.
  • Examples of the method of coating the pigment with the crosslinked polymer dispersant include a method of dispersing the pigment using a water-soluble or water-insoluble polymer and then crosslinking the polymer with the crosslinking agent.
  • the mass ratio of pigment to dispersant is preferably in the range of 1: 0.06 to 1: 3, more preferably in the range of 1: 0.125 to 1: 2. 1: 0.125 to 1: 1.5 is more preferable.
  • the average particle diameter of the pigment (when the pigment is a resin-coated pigment, the average particle diameter of the resin-coated pigment; hereinafter the same) is preferably 10 nm to 200 nm, more preferably 10 nm to 150 nm, and more preferably 10 nm to 100 nm. Further preferred. When the average particle size is 200 nm or less, the color reproducibility is good and the droplet ejection characteristics when droplets are ejected by the ink jet method are good. When the average particle size is 10 nm or more, light resistance is improved.
  • the particle size distribution of the pigment is not particularly limited, and may be either a wide particle size distribution or a monodispersed particle size distribution.
  • Two or more pigments having a monodispersed particle size distribution may be mixed and used.
  • the average particle diameter and particle size distribution of a pigment are calculated
  • the nanotrack particle size distribution measuring apparatus for example, UPA-EX150 manufactured by Nikkiso Co., Ltd. can be used.
  • the dye is not particularly limited, and known dyes such as those described in JP-A Nos. 2001-115066, 2001-335714, and 2002-249677 can be suitably used.
  • a dye a dye held on a water-insoluble carrier may be used.
  • the carrier holding the dye (so-called water-insoluble colored particles) can be used as an aqueous dispersion using a dispersant.
  • the carrier can be used without particular limitation as long as it is insoluble in water or hardly soluble in water.
  • the carrier may be any of inorganic materials, organic materials, and composite materials thereof. Specifically, the carriers described in JP-A Nos. 2001-181549 and 2007-169418 can be preferably used.
  • the ink composition may contain only one colorant or two or more colorants.
  • the content of the colorant (particularly the pigment) in the ink composition is preferably 1% by mass to 25% by mass with respect to the total mass of the ink composition from the viewpoint of image density, and 2% by mass to 20% by mass. Is more preferable, and 2% by mass to 10% by mass is particularly preferable.
  • the ink composition contains water and is prepared as an aqueous composition.
  • water ion-exchanged water or the like can be used.
  • the content of water in the ink composition is not particularly limited, and is preferably 10% by mass to 99% by mass, more preferably 30% by mass to 80% by mass, and 50% by mass with respect to the total mass of the ink composition. More preferably, it is 80% by mass.
  • the ink composition preferably contains resin particles. Unlike the polymer dispersant described above (that is, the polymer dispersant covering at least a part of the pigment), the resin particles are particles that exist separately from the pigment. When the ink composition contains resin particles, the resin particles are preferably aggregated by contact with an aggregating component (that is, an acid) contained in a pretreatment liquid described later. In addition, the resin particles are preferably resin particles having an anionic dissociation group other than a sulfo group from the viewpoint of excellent cohesiveness when contacted with an aggregating component contained in a pretreatment liquid described later. Details of the resin particles having an anionic dissociation group other than the sulfo group will be described later.
  • Resin particles having a sulfo group as an anionic dissociation group are not preferable in that the dispersion stability of the resin particles themselves is greatly improved, so that they do not easily aggregate even if they come into contact with the aggregating component contained in the pretreatment liquid.
  • the resin particles are preferably water-insoluble or poorly water-soluble resin particles.
  • “non-water-soluble or sparingly water-soluble” means that the resin is dried at 105 ° C. for 2 hours and then 100 g of water at 25 ° C. When dissolved in, it means that the dissolved amount is 15 g or less. From the viewpoint of improving the continuous ejection property and ejection stability of the ink, the dissolution amount is preferably 10 g or less, more preferably 5 g or less, and even more preferably 1 g or less.
  • the dissolution amount is the dissolution amount when 100% neutralized with sodium hydroxide or acetic acid depending on the type of the salt-forming group of the water-insoluble or poorly water-soluble resin.
  • the resin particles include thermoplastic, thermosetting, or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, or fluorine resins, Polyvinyl resins such as vinyl chloride, vinyl acetate, polyvinyl alcohol, or polyvinyl butyral, polyester resins such as alkyd resins and phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd co-condensation resins, urea resins, urea resins, etc. Examples thereof include resin particles having an anionic group such as an amino material, a copolymer or a mixture thereof.
  • an anionic acrylic resin is, for example, an acrylic monomer having an anionic dissociative group other than a sulfo group (so-called anionic group-containing acrylic monomer) and an anionic dissociation as required. It can be obtained by polymerizing another monomer copolymerizable with a functional group-containing acrylic monomer in a solvent.
  • anionic dissociable group-containing acrylic monomer include an acrylic monomer having one or more groups selected from the group consisting of a carboxy group and a phosphonic acid group.
  • an acrylic monomer having a carboxy group (acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, etc. ) Is preferred, and at least one of acrylic acid and methacrylic acid is particularly preferred.
  • the resin particles are self-dispersing resin particles (so-called self-dispersing resin particles) from the viewpoint of ejection stability of the ink composition and liquid stability (particularly dispersion stability) of the system containing the colorant. It is preferable.
  • the “self-dispersing resin” as used in the present disclosure is a functional group (especially an acidic group or a hydrophilic group of a salt thereof) possessed by the polymer itself when dispersed by the phase inversion emulsification method in the absence of a surfactant. Refers to a water-insoluble polymer that can be dispersed in an aqueous medium.
  • the “dispersed state” means an emulsified state in which a water-insoluble polymer is dispersed in an aqueous medium (so-called emulsion), and a dispersed state in which the water-insoluble polymer is dispersed in a solid state. It includes both states (so-called suspension).
  • An “aqueous medium” refers to a medium containing water.
  • the aqueous medium may contain a hydrophilic organic solvent as necessary.
  • the aqueous medium preferably contains water and 0.2% by mass or less of a hydrophilic organic solvent with respect to water, and more preferably contains only water.
  • the self-dispersing resin is preferably self-dispersing resin particles that can be in a dispersed state in which a water-insoluble polymer is dispersed in a solid state from the viewpoint of aggregation speed and fixing property when contained in the ink composition.
  • Examples of a method for obtaining an emulsified state or a dispersed state of the self-dispersing resin that is, a method for preparing an aqueous dispersion of self-dispersing resin particles include a phase inversion emulsification method.
  • a phase inversion emulsification method for example, a self-dispersing resin is dissolved or dispersed in a solvent (for example, a water-soluble organic solvent) and then poured into water as it is without adding a surfactant.
  • Examples include a method of obtaining an aqueous dispersion in an emulsified state or a dispersed state after stirring and mixing in a state in which a salt-forming group (for example, acidic group) of the resin is neutralized and mixing, and removing the solvent.
  • a salt-forming group for example, acidic group
  • a stable emulsified state or dispersed state in the self-dispersing resin is a solution in which 30 g of a water-insoluble polymer is dissolved in 70 g of an organic solvent (for example, methyl ethyl ketone).
  • Mixing agent sodium hydroxide when the salt-forming group is anionic, acetic acid when the salt-forming group is cationic
  • 200 g of water stirring (apparatus: stirring device with stirring blades, Rotational speed: 200 rpm (revolutions per minute; the same applies hereinafter), stirring time: 30 minutes, stirring temperature: 25 ° C., and even after removing the organic solvent from the mixture, the emulsified state or dispersed state is 25 ° C.
  • the emulsified state or dispersed state is 25 ° C.
  • a state that exists stably for at least one week that is, a state in which precipitation cannot be visually confirmed).
  • the stability of the emulsified state or dispersed state in the self-dispersing resin can also be confirmed by an accelerated sedimentation test by centrifugation.
  • the stability by the accelerated sedimentation test by centrifugation is, for example, that the aqueous dispersion of resin particles obtained by the above method is adjusted to a solid content concentration of 25% by mass and then centrifuged at 12,000 rpm for 1 hour. It can be evaluated by measuring the solid content concentration of the supernatant after centrifugation. If the ratio of the solid content concentration after centrifugation to the solid content concentration before centrifugation is large (that is, a value close to 1), the resin particles will not settle due to centrifugation, that is, the aqueous dispersion of resin particles. It means that things are more stable.
  • the ratio of the solid content concentration before and after centrifugation is preferably 0.8 or more, more preferably 0.9 or more, and particularly preferably 0.95 or more.
  • the self-dispersing resin preferably has a water-soluble component content that exhibits water solubility in a dispersed state of 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. More preferably.
  • a water-soluble component content that exhibits water solubility in a dispersed state of 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. More preferably.
  • water-soluble component refers to a compound that is contained in a self-dispersing resin and that dissolves in water when the self-dispersing resin is in a dispersed state.
  • the water-soluble component is a water-soluble compound that is by-produced or mixed when the self-dispersing resin is produced.
  • the main chain skeleton of the water-insoluble polymer is not particularly limited, and examples thereof include vinyl polymers and condensation polymers (epoxy resins, polyesters, polyurethanes, polyamides, celluloses, polyethers, polyureas, polyimides, polycarbonates, etc.).
  • vinyl polymers and condensation polymers epoxy resins, polyesters, polyurethanes, polyamides, celluloses, polyethers, polyureas, polyimides, polycarbonates, etc.
  • a vinyl polymer is particularly preferable as the main chain skeleton of the water-insoluble polymer.
  • Preferable examples of the vinyl polymer and the monomer constituting the vinyl polymer include those described in JP-A Nos. 2001-181549 and 2002-88294. Further, a radical transfer of a vinyl monomer using a chain transfer agent having a dissociable group (or a substituent that can be derived to a dissociable group), a polymerization initiator, an iniferter, a dissociable group (either an initiator or a terminator) Alternatively, a vinyl polymer in which a dissociable group is introduced at the end of a polymer chain by ionic polymerization using a compound having a substituent that can be derived from a dissociable group can also be used. In addition, preferable examples of the condensation polymer and the monomer constituting the condensation polymer include those described in JP-A-2001-247787.
  • the resin particles preferably contain a water-insoluble polymer containing a hydrophilic structural unit and a structural unit derived from an aromatic group-containing monomer or a cyclic aliphatic group-containing monomer from the viewpoint of dispersion stability.
  • the “hydrophilic structural unit” is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and may be derived from one type of hydrophilic group-containing monomer, or two or more types It may be derived from a hydrophilic group-containing monomer.
  • the hydrophilic group is not particularly limited except for a sulfo group, and may be a dissociable group or a nonionic hydrophilic group.
  • the hydrophilic group is preferably a dissociable group, more preferably an anionic dissociative group, from the viewpoint of the stability of the formed emulsified state or dispersed state. That is, the resin particles are preferably resin particles having an anionic dissociation group.
  • the dissociable group include a carboxy group and a phosphate group. Among these, the dissociable group is preferably a carboxy group from the viewpoint of fixability when the ink composition is constituted.
  • the hydrophilic group-containing monomer is preferably a dissociable group-containing monomer from the viewpoint of dispersion stability and aggregability, and more preferably a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond. preferable.
  • the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.
  • the unsaturated carboxylic acid monomer examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, 2-methacryloyloxymethyl succinic acid and the like.
  • unsaturated phosphoric acid monomers include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloxyethyl phosphate, diphenyl-2-methacryloxyethyl phosphate, dibutyl-2-acryloxy Examples thereof include ethyl phosphate.
  • an unsaturated carboxylic acid monomer is preferable from the viewpoint of dispersion stability and ejection stability, and at least one of acrylic acid and methacrylic acid is more preferable.
  • the resin particles preferably contain a polymer having a carboxy group from the viewpoint of dispersion stability and agglomeration rate when in contact with the pretreatment liquid described later, and have a carboxy group and an acid value of 25 mgKOH / g to More preferably, it contains a polymer that is 100 mg KOH / g.
  • the acid value is more preferably from 25 mgKOH / g to 80 mgKOH / g, particularly from 30 mgKOH / g to 65 mgKOH, from the viewpoint of self-dispersibility and aggregation rate when contacting with the pretreatment liquid described later. preferable.
  • the acid value of the resin particles is 25 mgKOH / g or more, the dispersion stability is good, and when it is 100 mgKOH / g or less, the cohesiveness is improved.
  • the acid value of the resin particles is a value measured by the method described in Japanese Industrial Standard (JIS K0070: 1992).
  • the aromatic group-containing monomer is not particularly limited as long as it is a compound containing an aromatic group and a polymerizable group.
  • the aromatic group may be a group derived from an aromatic hydrocarbon or a group derived from an aromatic heterocycle.
  • the aromatic group is preferably an aromatic group derived from an aromatic hydrocarbon from the viewpoint of particle shape stability in an aqueous medium.
  • the polymerizable group may be a polycondensable polymerizable group or an addition polymerizable polymerizable group.
  • the polymerizable group is preferably an addition polymerizable polymerizable group from the viewpoint of particle shape stability in an aqueous medium, and more preferably a group containing an ethylenically unsaturated bond.
  • the aromatic group-containing monomer is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond.
  • One type of aromatic group-containing monomer may be used, or two or more types may be used in combination.
  • Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and a styrene monomer.
  • an aromatic group-containing (meth) acrylate monomer is preferable from the viewpoint of the balance between the hydrophilicity and hydrophobicity of the polymer chain and ink fixability, and phenoxyethyl (meth) acrylate, At least one selected from the group consisting of benzyl (meth) acrylate and phenyl (meth) acrylate is more preferable, and at least one selected from the group consisting of phenoxyethyl (meth) acrylate and benzyl (meth) acrylate is more preferable.
  • the cycloaliphatic group-containing monomer is preferably a monomer having a cycloaliphatic group derived from a cycloaliphatic hydrocarbon and an ethylenically unsaturated bond, and a cycloaliphatic group-containing (meth) acrylate monomer (hereinafter, “ More preferably, it is also referred to as “alicyclic (meth) acrylate”.
  • An alicyclic (meth) acrylate includes a component derived from (meth) acrylic acid and a component derived from alcohol, and the component derived from alcohol is unsubstituted or substituted with alicyclic carbonization. It has a structure containing at least one hydrogen group (cycloaliphatic group).
  • the alicyclic hydrocarbon group may be a constituent site derived from alcohol itself, or may be bonded to a constituent site derived from alcohol via a linking group.
  • the alicyclic hydrocarbon group is not particularly limited as long as it includes a cyclic non-aromatic hydrocarbon group, and may be a monocyclic hydrocarbon group or a bicyclic hydrocarbon group. It may be a tricyclic or more polycyclic hydrocarbon group.
  • the alicyclic hydrocarbon group includes a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a decahydro group.
  • the alicyclic hydrocarbon group may further have a substituent.
  • substituents include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, a hydroxyl group, a primary amino group, a secondary amino group, a tertiary amino group, an alkylcarbonyl group, an arylcarbonyl group, and a cyano group. It is done.
  • the alicyclic hydrocarbon group may further form a condensed ring.
  • the alicyclic hydrocarbon group preferably has 5 to 20 carbon atoms in the alicyclic hydrocarbon group portion from the viewpoint of viscosity and solubility.
  • alicyclic (meth) acrylate is not limited to these specific examples.
  • monocyclic (meth) acrylates include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth) acrylate.
  • cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in the cycloalkyl group such as cyclononyl (meth) acrylate and cyclodecyl (meth) acrylate.
  • examples of the bicyclic (meth) acrylate include isobornyl (meth) acrylate and norbornyl (meth) acrylate.
  • Examples of the tricyclic (meth) acrylate include adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These alicyclic (meth) acrylates may be used alone or in combination of two or more.
  • bicyclic (meth) acrylate and tricyclic or higher polycyclic (meth) It is preferably at least one selected from the group consisting of acrylates, and at least one selected from the group consisting of isobornyl (meth) acrylate, adamantyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. More preferred.
  • the resin used for forming the resin particles is preferably an acrylic resin containing a structural unit derived from a (meth) acrylate monomer, and a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate.
  • An acrylic resin containing is more preferable, it contains a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate, and its content is 10% by mass to 95% by mass Is preferred.
  • the content of the aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate is 10% by mass to 95% by mass, the stability of the emulsified state or the dispersed state is improved, and the ink viscosity is further increased. Can be suppressed.
  • the content of the aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate is stable in the dispersion state, and the particle shape stability in an aqueous medium due to the hydrophobic interaction between aromatic rings or alicyclic rings.
  • the content is more preferably 15% by mass to 90% by mass, further preferably 15% by mass to 80% by mass, and more preferably 25% by mass % To 70% by mass is particularly preferable.
  • the resin used for forming the resin particles can be configured to include, for example, a structural unit derived from an aromatic group-containing monomer or a cycloaliphatic group-containing monomer and a structural unit derived from a dissociable group-containing monomer. Other structural units may be further included as necessary.
  • the monomer that forms the other structural unit is not particularly limited as long as it is a monomer copolymerizable with an aromatic group-containing monomer and a dissociable group-containing monomer.
  • an alkyl group-containing monomer is preferable from the viewpoint of flexibility of the polymer skeleton and easy control of the glass transition temperature (Tg).
  • alkyl group-containing monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl.
  • Alkyl (meth) acrylates such as (meth) acrylate, hexyl (meth) acrylate, and ethylhexyl (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Ethylenically unsaturated monomers having a hydroxyl group such as hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; dimethylaminoethyl (meth) Dialkylaminoalkyl (meth) acrylates such as acrylate; N-hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide; N- Methoxymethyl (meth
  • the weight average molecular weight (Mw) of the water-insoluble polymer constituting the resin particles is preferably 3,000 to 200,000, more preferably 5,000 to 150,000, and 10,000 to 100,000. More preferably, it is 000.
  • the weight average molecular weight (Mw) of the water-insoluble polymer is a value measured by the same method as the measurement of the weight average molecular weight (Mw) of the water-insoluble resin contained in the overcoat liquid described above.
  • the water-insoluble polymer constituting the resin particle is a structural unit derived from an aromatic group-containing (meth) acrylate monomer (preferably a structural unit derived from phenoxyethyl (meth) acrylate and / or from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer. Or a structural unit derived from benzyl (meth) acrylate) or a cycloaliphatic group-containing monomer (preferably alicyclic (meth) acrylate), and a copolymerization ratio of 15% by mass to 80% by mass of the total mass of the resin particles. It is preferable to include.
  • the water-insoluble polymer has a copolymerization ratio of 15% by mass to 80% by mass of a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate monomer from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer.
  • % A structural unit derived from a carboxy group-containing monomer, and a structural unit derived from an alkyl group-containing monomer (preferably a structural unit derived from an alkyl ester of (meth) acrylic acid).
  • the water-insoluble polymer preferably has an acid value of 25 mgKOH / g to 100 mgKOH / g, a weight average molecular weight (Mw) of 3,000 to 200,000, and an acid value of 25 mgKOH / g to 95 mgKOH. More preferably, the weight average molecular weight (Mw) is 5,000 to 150,000.
  • the acid value of the water-insoluble polymer is a value measured by the method described in Japanese Industrial Standard (JIS K0070: 1992).
  • B-01 Phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/5)
  • B-02 Phenoxyethyl acrylate / benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (30/35/29/6)
  • B-03 Phenoxyethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (50/44/6)
  • B-04 Phenoxyethyl acrylate / methyl methacrylate / ethyl acrylate / acrylic acid copolymer (30/55/10/5)
  • B-05 benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (35/59/6)
  • B-06 Styrene / phenoxyethyl acrylate / methyl methacrylate / acrylic acid copo
  • the method for producing the water-insoluble polymer contained in the resin particles is not particularly limited.
  • a method for producing a water-insoluble polymer emulsion polymerization is carried out in the presence of a polymerizable surfactant to covalently bond the surfactant and the water-insoluble polymer, the hydrophilic group-containing monomer and the aromatic group-containing monomer.
  • a method of copolymerizing a monomer mixture containing an alicyclic group-containing monomer by a known polymerization method such as a solution polymerization method or a bulk polymerization method may be used.
  • the polymerization method is preferably a solution polymerization method, more preferably a solution polymerization method using an organic solvent, from the viewpoint of the aggregation rate and droplet ejection stability when an ink composition is used.
  • the resin particles include a polymer synthesized in an organic solvent from the viewpoint of aggregation rate, the polymer has an anionic group (preferably a carboxy group), and preferably has an acid value of 20 mgKOH / g to 100 mgKOH / g), and a part or all of anionic groups (preferably carboxy groups) of the polymer are preferably neutralized and prepared as a polymer dispersion having water as a continuous phase. That is, the production of the resin particles includes a step of synthesizing a polymer in an organic solvent, and a dispersion step of forming an aqueous dispersion in which at least a part of an anionic group (preferably a carboxy group) of the polymer is neutralized. It is preferable to provide it.
  • the dispersion step preferably includes the following step (1) and step (2).
  • Step (1) A step of stirring a mixture containing a polymer (that is, a water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium.
  • Step (2) A step of removing the organic solvent from the mixture.
  • Step (1) is a step in which a polymer (that is, a water-insoluble polymer) is first dissolved in an organic solvent, and then a neutralizing agent and an aqueous medium are gradually added and mixed, followed by stirring to obtain a dispersion. It is preferable. By adding a neutralizing agent and an aqueous medium to a water-insoluble polymer solution dissolved in an organic solvent, resin particles having a particle size with higher storage stability can be obtained without requiring strong shearing force. it can.
  • the stirring method of a mixture is not specifically limited, The stirring method using the mixing stirring apparatus generally used is mentioned. Moreover, you may stir a mixture using dispersers, such as an ultrasonic disperser and a high-pressure homogenizer, as needed.
  • step (2) the aqueous dispersion of resin particles is obtained by distilling off the organic solvent from the dispersion obtained in step (1) by a conventional method such as distillation under reduced pressure and phase-inversion into an aqueous system. Obtainable.
  • the organic solvent in the obtained aqueous dispersion is substantially removed, and the amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.
  • the organic solvent include alcohol solvents, ketone solvents, and ether solvents.
  • the organic solvent for example, the organic solvent exemplified in paragraph [0059] of JP 2010-188661 A can be used.
  • the neutralizing agent the neutralizing agents exemplified in paragraphs [0060] to [0061] of JP 2010-188661 A can be used.
  • the average particle size of the resin particles is preferably 10 nm to 400 nm, more preferably 10 nm to 200 nm, still more preferably 10 nm to 100 nm, and particularly preferably 10 nm to 50 nm.
  • the particle size distribution of the resin particles is not particularly limited, and may be either a wide particle size distribution or a monodispersed particle size distribution. Two or more kinds of resin particles having a monodisperse particle size distribution may be mixed and used.
  • the average particle diameter and particle size distribution of the resin particles are obtained by measuring the volume average particle diameter by a dynamic light scattering method using a nanotrack particle size distribution measuring apparatus.
  • a nanotrack particle size distribution measuring apparatus for example, UPA-EX150 manufactured by Nikkiso Co., Ltd. can be used.
  • the ink composition may contain only one type of resin particles (preferably self-dispersing resin particles), or may contain two or more types.
  • the content of the resin particles (preferably self-dispersing resin particles) in the ink composition is, for example, 1% by mass to 30% by mass with respect to the total mass of the ink composition from the viewpoint of glossiness of the image. Preferably, 3% by mass to 15% by mass is more preferable.
  • the ink composition may contain components other than the above components.
  • examples of other components include organic solvents, surfactants, and other additives.
  • the ink composition preferably further contains an organic solvent.
  • an organic solvent particularly a water-soluble organic solvent
  • the “water-soluble organic solvent” in the present disclosure refers to an organic solvent that dissolves 5 g or more in 100 g of water at 20 ° C.
  • a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
  • the water-soluble organic solvent suitable for preventing drying include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2 , 6-hexanetriol, acetylene glycol derivatives, polyhydric alcohols such as glycerin and trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, Lower alkyl ethers of polyhydric alcohols such as tripropylene glycol monomethyl (or ethyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imida Rijinon, hetero
  • water-soluble organic solvents suitable for promoting penetration include ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, tripropylene glycol monomethyl (or ethyl) ether, and 1,2-hexanediol. Examples include alcohol. These water-soluble organic solvents can exhibit good effects when contained in the ink composition in an amount of 5 to 30% by mass. In addition, these water-soluble organic solvents are preferably used within a range of addition amounts that do not cause printing, image bleeding, and paper loss (so-called print-through).
  • the water-soluble organic solvent can be used for adjusting the viscosity.
  • Specific examples of water-soluble organic solvents that can be used to adjust the viscosity include alcohols (methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol).
  • polyhydric alcohols ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol Etc.
  • glycol derivatives ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, triethylene glycol monomethyl ether, ethylene glycol di Acetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether,
  • the ink composition may contain only one type of organic solvent or two or more types of organic solvent.
  • the content of the organic solvent in the ink composition is preferably 10% by mass to 50% by mass with respect to the total mass of the ink composition.
  • the ink composition may further contain a surfactant.
  • a surfactant it may contain only one kind of surfactant or two or more kinds.
  • the surfactant examples include nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants and the like.
  • the surfactant an anionic surfactant or a nonionic surfactant is preferable from the viewpoint of aggregation rate.
  • the surfactant content in the ink composition is determined so that the surface tension of the ink composition (25 ° C.) is 25 mN / It is preferably an amount that can be adjusted to m or more and 40 mN / m or less, and more preferably an amount that can be adjusted to 27 mN / m to 37 mN / m.
  • Surfactants can also be used as antifoaming agents.
  • a fluorine compound, a silicone compound, a chelating agent such as ethylenediaminetetraacetic acid (EDTA), or the like can also be used.
  • the ink composition can further contain other additives in addition to the above components.
  • Other additives include, for example, antifading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, antiseptics, antifungal agents, pH adjusters, antifoaming agents, viscosity modifiers, dispersion stabilizers, and rust inhibitors.
  • Known additives such as agents and chelating agents are included. These various additives may be added directly after the ink composition is prepared, or may be added when the ink composition is prepared.
  • the pH adjuster a neutralizing agent (organic base, inorganic alkali, etc.) can be used.
  • the pH adjuster is preferably added so that the pH of the ink composition (25 ° C.) is 6 to 10, and the pH is 7 to 10. It is more preferable to add.
  • the pH of the ink composition is preferably 6 to 10 and more preferably 7 to 10 from the viewpoint of improving the storage stability of the ink composition.
  • the pH of the ink composition is a value measured using a pH meter in a state where the temperature of the ink composition is adjusted to 25 ° C. in an environment of 25 ° C.
  • As the pH meter for example, WM-50EG manufactured by Toa DK Corporation can be used.
  • the viscosity of the ink composition is preferably in the range of 1 mPa ⁇ s to 30 mPa ⁇ s, from the viewpoint of ejection stability when ejected by the ink jet method, and aggregation rate when using a pretreatment liquid described later.
  • the range of s to 20 mPa ⁇ s is more preferred, the range of 2 mPa ⁇ s to 15 mPa ⁇ s is still more preferred, and the range of 2 mPa ⁇ s to 10 mPa ⁇ s is particularly preferred.
  • the viscosity of the ink composition is measured at 25 ° C. using VISCOMETER TV-22 (Toki Sangyo Co., Ltd.).
  • the surface tension of the ink composition is not particularly limited and can be, for example, 20 mN / m or more. From the viewpoint of better droplet ejection by the inkjet method, it is preferably 23 mN / m to 40 mN / m, more preferably 26 mN / m to 37 mN / m.
  • the surface tension of the ink composition is a value measured at 25 ° C. by a plate method using a surface tension meter.
  • As the surface tension meter for example, Automatic Surface Tensiometer CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. can be used.
  • the surface tension of the ink composition can be adjusted, for example, by adding a surfactant.
  • the pretreatment liquid contains an acid and water, and may further contain other components as necessary.
  • the pretreatment liquid contains an acid.
  • the pretreatment liquid contains an acid as a compound (aggregating component) that aggregates at least the colorant contained in the ink composition.
  • the acid acts on at least the colorant which is a dispersed component in the ink composition. Since at least the colorant aggregates, a sharper image can be obtained.
  • Examples of the acid include organic acidic compounds and inorganic acidic compounds that can lower the pH of the ink composition.
  • an organic acidic compound For example, the compound which has a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfo group, a sulfinic acid group, a carboxy group etc. is mentioned.
  • the organic acidic compound a compound having a phosphate group or a carboxy group is preferable, and a compound having a carboxy group is more preferable from the viewpoint of the aggregation rate of the dispersion component (at least the colorant) in the ink composition.
  • Examples of the compound having a carboxy group include polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, Tartaric acid, phthalic acid, 4-methylphthalic acid, lactic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, these Examples thereof include salts (for example, polyvalent metal salts).
  • the compound having a carboxy group is preferably a divalent or higher carboxylic acid (polyvalent carboxylic acid) from the viewpoint of the aggregation rate of the dispersion component (at least the colorant) in the ink composition, and malonic acid, malic acid, maleic acid. More preferably at least one polycarboxylic acid selected from the group consisting of succinic acid, glutaric acid, fumaric acid, tartaric acid, 4-methylphthalic acid, and citric acid, and malonic acid, malic acid, tartaric acid, and citric acid. Particularly preferred is at least one selected from the group consisting of
  • the organic acidic compound preferably has a low pKa. Dispersion stability is reduced by bringing the surface charge of particles such as pigments and polymer particles in the ink composition stabilized by a weakly acidic functional group such as a carboxy group into contact with an organic acidic compound having a lower pKa. Can be reduced.
  • an acidic compound having a low pKa, a high solubility in water, and a valence of 2 or more is preferable, and a functional group (for example, carboxy group) that stabilizes the particles in the ink composition.
  • a divalent or trivalent acidic compound having a high buffer capacity in a pH range lower than the pKa of the group) is more preferable.
  • inorganic acidic compounds include phosphoric acid, phosphoric acid compounds, nitric acid, nitrous acid, sulfuric acid, hydrochloric acid and the like.
  • phosphoric acid and a phosphoric acid compound are preferable from the viewpoint of suppressing the roughness of the image and the aggregation rate of the dispersion component (at least the colorant) in the ink composition.
  • Phosphoric acid has a low water solubility (25 ° C.) of 0.0018 g / 100 g of water when calcium salt (that is, calcium phosphate) is used. Therefore, when the inorganic acidic compound contained in the pretreatment liquid is phosphoric acid, the calcium salt is not dissolved but immobilized, and the effect of suppressing the roughness generated on the surface of the image area is high. In particular, when a recording medium having a coating layer containing calcium carbonate is used as the recording medium, phosphoric acid is advantageous as the inorganic acidic compound contained in the pretreatment liquid.
  • Examples of the phosphoric acid compound include phosphorous acid, hypophosphorous acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, and salts thereof.
  • the pretreatment liquid may contain only one kind of acid, or may contain two or more kinds.
  • the acid content in the pretreatment liquid is preferably 5% by mass to 40% by mass and more preferably 10% by mass to 30% by mass with respect to the total mass of the pretreatment liquid.
  • the content of the acid as an aggregating component in the pretreatment liquid is 5% by mass or more, the roughness of the image is further suppressed.
  • the content of the acid that is an aggregating component in the pretreatment liquid is 40% by mass or less, the abrasion resistance of the image is further improved.
  • the content ratio of the organic acidic compound and the inorganic acidic compound in the pretreatment liquid is: From the viewpoint of the aggregation rate of the ink composition and the suppression of roughness of the image, 5 mol% to 50 mol% is preferable, 10 mol% to 40 mol% is more preferable, and 15 mol% to 35 mol% is still more preferable.
  • the pretreatment liquid contains water and is prepared as an aqueous composition.
  • water ion-exchanged water or the like can be used.
  • the content of water in the pretreatment liquid is not particularly limited, and is preferably 10% by mass to 99% by mass, more preferably 50% by mass to 90% by mass, and 60% by mass with respect to the total mass of the pretreatment liquid. More preferably, it is 80% by mass.
  • the pretreatment liquid may contain components other than the above components.
  • examples of other components include organic solvents, nitrogen-containing heterocyclic compounds, antifoaming agents, and other additives.
  • the pretreatment liquid preferably further contains an organic solvent.
  • a water-soluble organic solvent is preferable.
  • the water-soluble organic solvent include the same water-soluble organic solvents that can be contained in the ink composition described above.
  • polyalkylene glycol or a derivative thereof is preferable from the viewpoint of curling suppression. Diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, dipropylene glycol, tripropylene glycol monoalkyl ether, At least one selected from the group consisting of oxypropylene glyceryl ether and polyoxyethylene polyoxypropylene glycol is more preferable.
  • the pretreatment liquid may contain only one organic solvent or two or more organic solvents.
  • the content of the organic solvent in the pretreatment liquid is not particularly limited.
  • 1% by mass to 30% by mass is preferable, and 5% by mass to 15% by mass is more preferable.
  • the pretreatment liquid may further contain a nitrogen-containing heterocyclic compound.
  • the pretreatment liquid contains a nitrogen-containing heterocyclic compound, the abrasion resistance of the image is further improved.
  • a nitrogen-containing 5-membered ring structure or a nitrogen-containing 6-membered ring structure is preferable, and a nitrogen-containing 5-membered ring structure is more preferable.
  • a nitrogen-containing 5-membered ring structure and the nitrogen-containing 6-membered ring structure a 5-membered or 6-membered heterostructure containing at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom A ring structure is preferred.
  • the heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring.
  • Heterocycles include tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzothiazole, benzimidazole, pyrimidine, and triazaine. Examples include a den ring, a tetraazaindene ring, and a pentaazaindene ring.
  • the heterocycle may have a substituent.
  • Substituents include nitro groups, halogen atoms (chlorine atoms, bromine atoms, etc.), mercapto groups, cyano groups, substituted or unsubstituted alkyl groups (eg, methyl, ethyl, propyl, t-butyl, cyanoethyl groups, etc.) ), Aryl groups (eg, phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl, etc.), alkenyl groups (eg, allyl groups), aralkyl groups (eg, Benzyl, 4-methylbenzyl, phenethyl, etc.), sulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl,
  • nitrogen-containing heterocyclic compound examples include imidazole, benzimidazole, benzoindazole, benzotriazole, tetrazole, benzoxazole, benzothiazole, pyridine, quinoline, pyrimidine, piperidine, piperazine, quinoxaline, morpholine and the like.
  • nitrogen-containing heterocyclic compounds may have a substituent such as the above alkyl group, carboxy group, or sulfo group.
  • the nitrogen-containing 6-membered ring compound a compound having a triazine ring, a pyrimidine ring, a pyridine ring, a pyrroline ring, a piperidine ring, a pyridazine ring or a pyrazine ring is preferable, and a compound having a triazine ring or a pyrimidine ring is more preferable.
  • the nitrogen-containing 6-membered ring compound may have a substituent.
  • substituents examples include an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3), an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3), a hydroxyl group, a carboxy group, a mercapto group, and 1 carbon atom. And an alkoxyalkyl group having 6 to 6 (preferably 1 to 3), a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 3), and the like.
  • the nitrogen-containing 6-membered ring compound include triazine, methyltriazine, dimethyltriazine, hydroxyethyltriazine ring, pyrimidine, 4-methylpyrimidine, pyridine, pyrroline and the like.
  • the pretreatment liquid may contain an antifoaming agent.
  • the antifoaming agent include silicone compounds (that is, silicone antifoaming agents) and pluronic compounds (that is, pluronic antifoaming agents).
  • silicone compounds that is, silicone antifoaming agents
  • pluronic compounds that is, pluronic antifoaming agents
  • an antifoamer a silicone type antifoamer is preferable.
  • the silicone-based antifoaming agent a silicone-based antifoaming agent having a polysiloxane structure is preferable.
  • a defoaming agent As a defoaming agent, a commercially available product may be used.
  • examples of commercially available antifoaming agents include BYK-012, BYK-017, BYK-021, BYK-022, BYK-024, BYK-025, BYK-038, BYK-094 (above, BYK Chemie Japan, Inc. )), KS-537, KS-604, KM-72F (Shin-Etsu Chemical Co., Ltd.), TSA-739 (Momentive Performance Materials Japan GK), Olfin (registered trademark) AF104 (Nissin) Chemical Industry Co., Ltd.).
  • silicone-based antifoaming agents such as BYK-017, BYK-021, BYK-022, BYK-024, BYK-025, BYK-094, KS-537, KS-604, At least one selected from the group consisting of KM-72F and TSA-739 is preferred, and BYK-024 is particularly preferred from the viewpoint of ejection stability of the ink composition.
  • the content of the antifoaming agent in the pretreatment liquid is preferably 0.0001% by mass to 1% by mass, and 0.001% by mass with respect to the total mass of the pretreatment liquid. % To 0.1% by mass is more preferable.
  • the amount of the silicone oil is 0.005% by mass to 0.02% by mass.
  • the pretreatment liquid may contain water-insoluble resin particles.
  • the pretreatment liquid may contain water-insoluble resin particles.
  • water-insoluble resin particles By including the water-insoluble resin particles in the pretreatment liquid, most of the water-insoluble resin particles are unevenly distributed on the surface of the recording material after the pretreatment liquid is applied, and the wettability of the surface of the recording material is improved. .
  • an aggregating component ie, acid
  • the droplets are prevented from coalescing, and the droplet size becomes a desired size.
  • the pretreatment liquid contains water-insoluble resin particles, the occurrence of streak-like unevenness that tends to occur in the recorded image is suppressed. Furthermore, roughness in the image can also be suppressed.
  • “graininess” means that after the ink composition has landed on the recording material, the droplets coalesce, causing minute density unevenness in the image and pixel uniformity. A phenomenon that decreases.
  • the “water-insoluble” of the water-insoluble resin is synonymous with the “water-insoluble” of the resin (water-insoluble resin) in the “resin particles” contained in the above-described overcoat liquid. That is, it is synonymous with “water-insoluble or poorly water-soluble” defined in the above-mentioned section of the overcoat solution.
  • the water-insoluble resin in the water-insoluble resin particles includes a structural unit derived from a monomer containing at least one group selected from a sulfo group and a salt of the sulfo group, and a structural unit derived from a monomer containing an aromatic ring structure. It is preferable to have at least, and if necessary, it may further have structural units derived from other monomers.
  • Examples of the structural unit derived from a monomer having at least one group selected from a sulfo group and a salt of a sulfo group include acrylamide-2-methylpropanesulfonic acid, acrylamide-2-methylpropanesulfonic acid salt, styrene Examples include structural units derived from sulfonic acid, ⁇ -methylstyrene sulfonic acid, 3-sulfopropyl (meth) acrylate, and the like.
  • the counter ion in the salt is preferably Na ion, K ion, Li ion, or Al ion.
  • the structural unit derived from a monomer having at least one group selected from a sulfo group and a salt of a sulfo group a structural unit derived from acrylamide-2-methylpropanesulfonic acid is preferable.
  • a structural unit derived from a monomer containing an aromatic ring structure a structural unit derived from styrene is preferable.
  • a structural unit derived from another monomer a structural unit derived from an acrylate ester monomer is preferable.
  • the water-insoluble resin constituting the particles preferably has a weight average molecular weight (Mw) of 3,000 to 150,000.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the water-insoluble resin that can be contained in the pretreatment liquid is measured by the same method as the measurement of the weight average molecular weight (Mw) of the water-insoluble resin contained in the overcoat liquid described above. Value.
  • the glass transition temperature (Tg) of the water-insoluble resin constituting the particles is preferably 40 ° C. or higher and 120 ° C.
  • Tg of the water-insoluble resin is 40 ° C. or higher, the storage stability of the pretreatment liquid is good.
  • the Tg of the water-insoluble resin is 120 ° C. or less, the change in the texture of the recording material before and after the pretreatment liquid is applied is reduced.
  • the Tg of the water-insoluble resin is a value measured by the same method as the measurement of the Tg of the water-insoluble resin contained in the overcoat liquid described above.
  • the average particle size of the water-insoluble resin particles is preferably 10 nm to 300 nm, more preferably 15 nm to 150 nm in terms of volume average particle size.
  • the particle size distribution of the water-insoluble resin particles is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. Further, two or more kinds of water-insoluble resin particles having a monodisperse particle size distribution may be mixed and used.
  • the average particle size and particle size distribution of the water-insoluble resin particles are determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution measuring device.
  • a nanotrack particle size distribution measuring apparatus for example, UPA-EX150 manufactured by Nikkiso Co., Ltd. can be used.
  • the pretreatment liquid can further contain other additives in addition to the above components.
  • Other additives are the same as other additives in the ink composition described above.
  • the pH of the pretreatment liquid is preferably 7.0 or less, more preferably 0.5 to 3.5, and still more preferably 0.5 to 2.0 from the viewpoint of the aggregation rate of the ink composition.
  • the pH of the pretreatment liquid is a value measured using a pH meter in a state where the temperature of the pretreatment liquid is adjusted to 25 ° C in an environment of 25 ° C.
  • As the pH meter for example, WM-50EG manufactured by Toa DK Corporation can be used.
  • surface tension of a pretreatment liquid there is no restriction
  • the surface tension of the pretreatment liquid is a value measured at 25 ° C. by a plate method using a surface tension meter.
  • As the surface tension meter for example, Automatic Surface Tensiometer CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. can be used.
  • the surface tension of the pretreatment liquid can be adjusted, for example, by adding a surfactant.
  • the viscosity of the pretreatment liquid is preferably 1 mPa ⁇ s to 30 mPa ⁇ s, more preferably 1 mPa ⁇ s to 20 mPa ⁇ s, further preferably 2 mPa ⁇ s to 15 mPa ⁇ s, from the viewpoint of the aggregation rate of the ink composition. • s to 10 mPa ⁇ s is particularly preferable.
  • the viscosity of the pretreatment liquid is a value measured under the condition of 25 ° C. using VISCOMETER TV-22 (Toki Sangyo Co., Ltd.).
  • the ink set of the present disclosure includes at least one overcoat liquid described above, at least one ink composition described above, and a pretreatment liquid described above. As long as it contains at least one kind, another liquid may be included.
  • the image forming method of the present disclosure includes a step of applying a pretreatment liquid containing acid and water to a recording material (hereinafter also referred to as a “pretreatment step”), and a pretreatment liquid application surface of the recording material.
  • a step of forming an image by applying an ink composition containing a colorant and water (hereinafter also referred to as an “image forming step”), and at least a part of the recording material on which the image is formed.
  • a step of applying an overcoat solution containing the resin particles having a group represented by (1) and having no carboxy group, and water (hereinafter also referred to as “overcoat step”). Have.
  • the image forming method of the present disclosure may include processes other than the pretreatment process, the image forming process, and the overcoat process as necessary.
  • the above-described ink set is used for image formation, and the image is overcoated. Therefore, even when an image is formed using an acid-containing treatment liquid, the glossiness of the image forming surface is high. It becomes good.
  • each step in the image forming method of the present disclosure will be described.
  • the details of the ink composition, the pretreatment liquid, the ink composition, and the overcoat liquid, as well as the preferred embodiments, have been described in detail in the section of the ink set, and thus the description thereof is omitted here.
  • a substrate having a contact angle (water contact angle) of 70 ° or more when 3 seconds have passed since a water droplet was applied to the surface is suitable.
  • the recording material include paper base materials such as coated paper and synthetic paper, and polymer base materials such as polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • a paper base material is preferable and has a coating layer in that the effect of suppressing density reduction and streaky unevenness (and roughness in some cases) in the solid image portion appears remarkably.
  • a paper base material (so-called coated paper) is more preferable.
  • the contact angle with water on the surface of the recording material is determined according to the method described in Japanese Industrial Standard (JIS R3257) using a contact angle meter (product name: Dropmaster DM700, Kyowa Interface Science Co., Ltd.) Measured at room temperature and humidity.
  • JIS R3257 Japanese Industrial Standard
  • a contact angle meter product name: Dropmaster DM700, Kyowa Interface Science Co., Ltd.
  • the coated paper is one in which a coating layer containing an inorganic pigment or the like is provided on the surface of high-quality paper or neutral paper that is generally not surface-treated and mainly comprises cellulose as a support. Coated paper tends to cause uneven gloss in the image area, but effectively suppresses uneven gloss in the image area when the pretreatment liquid contains phosphoric acid or a phosphoric acid compound. Can do.
  • the coated paper is preferably art paper, coated paper, lightweight coated paper, or fine coated paper.
  • the inorganic pigment contained in the coating layer is not particularly limited, for example, silica, kaolin, clay, calcined clay, zinc oxide, tin oxide, magnesium sulfate, aluminum oxide, aluminum hydroxide, pseudoboehmite, calcium carbonate, It is preferably at least one selected from the group consisting of satin white, aluminum silicate, smectite, zeolite, magnesium silicate, magnesium carbonate, magnesium oxide, and diatomaceous earth, and at least selected from the group consisting of calcium carbonate, silica, and kaolin. One type is more preferable.
  • the recording material a commercially available product can be used.
  • Examples of commercially available recording materials include “Bon Ivory” from Oji Paper Co., Ltd., “MagnoStarGloss” from Sappi, “Carolina C2S” from International, “CartaIntegra” from Metsaboard, “VJFP series” from YUPO. Etc.
  • the application amount of the pretreatment liquid and the application amount of the ink composition are adjusted as necessary.
  • the amount of the pretreatment liquid applied may be changed in order to adjust the physical properties such as the viscoelasticity of the aggregate formed by mixing the pretreatment liquid and the ink composition according to the recording material.
  • a pretreatment liquid containing acid and water is applied to the recording material.
  • the pretreatment liquid can be applied by a known method such as a coating method, an ink jet method, or an immersion method.
  • the coating method include known coating methods using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater and the like. Details of the inkjet method will be described later.
  • the pretreatment process is provided before the image forming process using the ink composition. That is, before applying the ink composition onto the recording material, a pretreatment liquid for aggregating the dispersion components (colorant, etc.) in the ink composition is applied in advance, and then applied onto the recording material. The ink composition is applied so as to come into contact with the pretreatment liquid, and an image is formed. Thereby, inkjet recording can be speeded up, and a fine image with high density and resolution can be obtained even at high speed recording.
  • the pretreatment liquid on the recording material is preferably heat-dried after the pretreatment liquid is applied onto the recording material and before the ink composition is applied. Accordingly, bleeding is prevented, ink colorability is improved, and a visible image having good color density and hue can be recorded.
  • Heating and drying can be performed by a known heating means such as a heater, a blowing means using blowing air such as a dryer, or a combination of a known heating means and a blowing means.
  • a heating method for example, a method of applying heat with a heater or the like from the side opposite to the side to which the pretreatment liquid of the recording material is applied, or hot air or hot air is applied to the side of the recording material to which the pretreatment liquid has been applied.
  • the method or the method of heating using an infrared heater is mentioned. Heating may be performed by combining a plurality of these heating methods.
  • an image is formed by applying an ink composition containing a colorant and water to the application surface of the pretreatment liquid of the recording material.
  • the ink jet method is not particularly limited.
  • a charge control method that ejects ink using electrostatic attraction
  • a drop-on-demand method that uses vibration pressure of a piezoelectric element
  • an electric signal as an acoustic beam.
  • acoustic ink jet method that uses ink to irradiate ink and ejects ink using radiation pressure
  • thermal ink jet method bubble jet (registered trademark)) method that uses ink to form bubbles by heating ink Either may be sufficient.
  • the ink jet method in particular, the method described in Japanese Patent Application Laid-Open No.
  • the ink jet method for discharging can be used effectively.
  • the inkjet method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method using is included.
  • An ink jet head used in the ink jet method may be an on-demand method or a continuous method.
  • Discharge methods include electro-mechanical conversion methods (single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (thermal ink jet type, bubble jet ( (Registered trademark) type), electrostatic attraction method (electric field control type, slit jet type, etc.), discharge method (spark jet type, etc.), and any of these discharge methods may be used.
  • electro-mechanical conversion methods single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.
  • electro-thermal conversion methods thermal ink jet type, bubble jet ( (Registered trademark) type)
  • electrostatic attraction method electric field control type, slit jet type, etc.
  • discharge method spark jet type, etc.
  • an ink jet head As an ink jet head, a single serial head is used, and a shuttle system that performs recording while scanning the head in the width direction of the recording material, and recording elements are arranged corresponding to the entire area of one side of the recording material.
  • a line system using a line head In the line method, an image can be formed on the entire surface of the recording material by scanning the recording material in a direction orthogonal to the arrangement direction of the recording elements, and a carriage system such as a carriage for scanning a short head is unnecessary. Become. Further, since complicated scanning control of the carriage movement and the recording material is not required, and only the recording material moves, the recording speed can be increased as compared with the shuttle system.
  • the image forming step is preferably started within 10 seconds after the preprocessing step, and more preferably within 0.1 seconds to 10 seconds. Thereby, an image can be formed at high speed.
  • Start within 10 seconds after the pretreatment step means that the time from the application of the pretreatment liquid and the completion of drying to the first ink droplet landing on the recording material is within 10 seconds. means.
  • the amount of ink droplets to be applied is preferably 1.5 pL (picoliter) to 3.0 pL, and preferably 1.5 pL to 2. More preferably, it is 5 pL.
  • the amount of ink droplets can be adjusted by appropriately selecting the ejection conditions in the ink jet method according to the ink composition to be ejected.
  • the image forming method of the present disclosure may further include a heat fixing step of heat fixing the image recorded through the preprocessing step and the image forming step. According to the heat fixing step, the image on the recording material is fixed, and the abrasion resistance of the image is further improved.
  • the heating in the heat fixing step is preferably performed at a temperature equal to or higher than the minimum film-forming temperature (MFT) of the resin particles in the image.
  • MFT minimum film-forming temperature
  • the pressure at the time of pressurization is preferably 0.1 MPa to 3.0 MPa, more preferably 0.1 MPa to 1.0 MPa, and further preferably 0.1 MPa to 0.5 MPa in terms of surface smoothing. .
  • the heating method is not particularly limited, and for example, a method of heating with a heating element such as a nichrome wire heater, a method of supplying warm air or hot air, a method of heating with a halogen lamp, an infrared lamp, or the like, and drying without contact.
  • the method of making it suitable is.
  • the method of heating and pressing is not particularly limited. For example, a method of pressing a hot plate against the image forming surface of the recording material, a pair of heating and pressing rollers, a pair of heating and pressing belts, or an image of the recording material.
  • a heating and pressing apparatus having a heating and pressing belt arranged on the forming surface side and a holding roller arranged on the opposite side, heat fixing is performed by contacting them, such as a method of passing a pair of rollers. The method is preferred.
  • a preferable nip time is 1 to 10 seconds, more preferably 2 to 1 second, and further preferably 4 to 100 milliseconds.
  • the preferable nip width is 0.1 mm to 100 mm, more preferably 0.5 mm to 50 mm, and still more preferably 1 mm to 10 mm.
  • the heat and pressure roller may be a metal metal roller, a coating layer made of an elastic body around a metal core, and a surface layer (also referred to as a “release layer”) as necessary. May be provided.
  • the latter core metal can be formed of a cylindrical body made of, for example, iron, aluminum, or stainless steel (SUS), and the surface of the core metal is preferably at least partially covered with a coating layer.
  • the covering layer is particularly preferably formed of a silicone resin or fluororesin having releasability.
  • a heating element is built in one core metal of the heat and pressure roller, and the heat treatment and the pressure treatment are performed simultaneously by passing a recording material between the rollers, or If necessary, the recording material may be sandwiched and heated using two heating rollers.
  • a heating element a halogen lamp heater, a ceramic heater, a nichrome wire or the like is preferable.
  • the thickness of the base material is preferably 10 ⁇ m to 100 ⁇ m.
  • the material of the belt base material aluminum, iron, polyethylene or the like can be used in addition to nickel.
  • the thickness of the layer formed using these resins is preferably 1 ⁇ m to 50 ⁇ m, and more preferably 10 ⁇ m to 30 ⁇ m.
  • elastic members such as springs having tension are provided at both ends of the roller such as a heat pressure roller so that a desired nip pressure can be obtained in consideration of the nip gap. Select and install.
  • the recording material conveyance speed is preferably 200 mm / second to 700 mm / second, more preferably 300 mm / second to 650 mm / second, and 400 mm / second to 600 mm / second. Further preferred.
  • the recording material has a group represented by the formula (1) on at least a part on the side where the image is formed in the image forming process (and in some cases, the heat fixing process), and carboxy.
  • An overcoat liquid containing resin particles having no group and water is applied.
  • the overcoat liquid can be applied by a known method such as a coating method, an ink jet method, or an immersion method.
  • a coating method such as a coating method, an ink jet method, or an immersion method.
  • the coating method include the same as the known coating methods in the above-described pretreatment step.
  • the overcoat process is provided after the image forming process using the ink composition. That is, after a desired image is formed by applying the ink composition on the recording material, at least a part of the image forming surface including the image of the recording material (at least on the side where the image of the recording material is formed) Apply an overcoat solution to a part).
  • the overcoat may be applied only on the image forming surface, only on the image portion where the image is formed, only on the non-image portion where the image is not formed, or on the entire image forming surface. It is preferable that an overcoat is applied to the entire image forming surface. Thereby, the glossiness on the image forming surface of the recording material is effectively improved.
  • overcoat solution preferably, the coating weight
  • 2.0g / m 2 ⁇ 6.0g / m 2 are preferred, 3.0g / m 2 ⁇ 5.0g / m 2 Is more preferable.
  • the volume average particle diameter of resin (including water-insoluble resin) particles was measured by the following method. That is, after preparing a water dispersion whose volume average particle diameter of the resin particles is adjusted so that the solid content concentration of the water dispersion of the resin particles is 2% by mass, and adjusting the liquid temperature to 25 ° C. Measurement was performed by a dynamic light scattering method using a nanotrack particle size distribution measuring apparatus (product name: UPA-EX150, Nikkiso Co., Ltd.).
  • the mixture was further reacted for 3 hours, and then water was added to adjust the solid content concentration of the resin particles to 30% by mass to obtain an aqueous dispersion of resin particles A-1.
  • the volume average particle size of the resin particles A-1 in the obtained aqueous dispersion was 35 nm as measured by the method described above.
  • the weight average molecular weight (Mw) of the resin contained in the particles A-1 was 50,000 as measured by the method described above.
  • the total content of the group represented by the formula (1) in the resin contained in the particles A-1 was calculated and found to be 0.24 g per 1 g of resin.
  • Resin particles A-2 were prepared in the same manner as in the production of resin particles A-1, except that the raw material monomers used in the production of resin particles A-1 were changed as shown in Table 1 below.
  • An aqueous dispersion of ⁇ A-15 was obtained.
  • the volume average particle diameter of the resin particles A-2 to A-15 and the weight average molecular weight (Mw) of the resin contained in the particles A-2 to A-15 in the obtained aqueous dispersion are described above. Measured by the method. Further, the total content of the group represented by the formula (1) in the resins contained in the particles A-2 to A-15 was calculated. The results are shown in Table 1.
  • Resin particles R-1 were prepared in the same manner as in the production of resin particles A-1, except that the raw material monomers used in the production of resin particles A-1 were changed as shown in Table 1 below.
  • An aqueous dispersion of ⁇ R-3 was obtained.
  • the volume average particle diameter of the resin particles R-1 to R-3 and the weight average molecular weight (Mw) of the resin contained in the particles R-1 to R-3 in the obtained aqueous dispersion are described above. Measured by the method. Further, the total content of the group represented by the formula (1) in the resins contained in the particles R-1 to R-3 was calculated. The results are shown in Table 1.
  • resin particles in the present disclosure that is, resin particles having a group represented by the formula (1) and not having a carboxy group
  • resin particles those not corresponding to the resin particles in are referred to as “comparative resin particles”.
  • the numerical values described in the column of the raw material monomer in Table 1 indicate the amount of the raw material monomer used (unit: part by mass), and “-” means that the raw material monomer is not used.
  • composition -75% by weight of aqueous dispersion of resin particles A-1 obtained above ⁇ Wax dispersion 15% by mass (AQUACER (registered trademark) 531, BYK-Chemie) ⁇ Isopropyl alcohol (IPA) 3% by mass ⁇ Butyl carbitol 1% by mass ⁇ Sulfosuccinic acid-di-2-ethylhexyl sodium 1% by mass ⁇ Ion-exchanged water Total amount of 100% by mass
  • overcoat solutions 2-19- Other than changing the aqueous dispersion of resin particles A-1 to any of aqueous dispersions of resin particles A-2 to A-16 and R-1 to R-3 in the preparation of overcoat liquid 1
  • overcoat solutions 2 to 19 were prepared.
  • the pH values of the obtained overcoat solutions 2 to 19 were measured by the method described above, and all were within the range of 6.4 to 8.7. Further, the surface tensions of the overcoat liquids 2 to 19 were measured by the method described above, and all were within the range of 25.3 mN / m to 33.6 mN / m.
  • Each component shown to the following composition was mixed and the pretreatment liquid 1 was prepared. It was 0.8 when the pH of the obtained pretreatment liquid was measured by the above-mentioned method. Moreover, it was 32.8 mN / m when the surface tension of the pretreatment liquid was measured by the method described above.
  • composition ⁇ Diethylene glycol monoethyl ether 4% by mass ⁇ Tripropylene glycol monomethyl ether 4% by mass -Malonic acid (organic acid) 17.3% by mass Propane tricarboxylic acid (organic acid) 4.3% by mass ⁇ Phosphoric acid (inorganic acid) 4.3% by mass -5% by mass of the following water-insoluble resin particles C-1 ⁇ Benzotriazole 1% by mass ⁇ Antifoaming agent
  • the amount of silicone oil to be 0.01% by mass (Product name: TSA-739, solid content: 15% by mass, emulsion type silicone antifoaming agent, Momentive Performance Materials Japan GK) ⁇ Ion-exchanged water Total amount of 100% by mass
  • the weight average molecular weight (Mw) of the polymer dispersant P-1 was 44,600 as measured by the method described above. Furthermore, when the acid value of the polymer dispersant P-1 was measured by a method based on JIS standard (JIS K 0070: 1992), it was 65.2 mgKOH / g.
  • the methyl ethyl ketone was removed from the obtained dispersion at 55 ° C. under reduced pressure, and a part of the water was further removed. Then, using a high-speed centrifugal cooler 7550 (Kubota Co., Ltd.), 50 ml Centrifugation was performed for 30 minutes at a rotation speed of 8,000 rpm using a centrifuge tube. After centrifugation, the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and a dispersion (cyan pigment dispersion C) of resin-coated pigment particles (pigment coated with a polymer dispersant) having a pigment concentration of 10.2% by mass was obtained. The average particle diameter of the resin-coated pigment particles in the obtained cyan pigment dispersion C was 105 nm. The average particle size was measured by the method described above.
  • the copolymer contained in the obtained polymer solution had a weight average molecular weight (Mw) of 64,000 and an acid value of 38.9 mgKOH / g.
  • Mw weight average molecular weight
  • the acid value and the weight average molecular weight were measured by the methods described above.
  • an aqueous dispersion (emulsion) of resin particles (B-01) having a solid content concentration of 28.0% by mass was obtained.
  • Each structural unit in the resin of the resin particle (B-01) is shown below.
  • the number of each structural unit in the following formula represents “mass ratio”.
  • Each prepared ink composition was filtered through a polyvinylidene fluoride (PVDF) 5 ⁇ m filter (Millex SV, diameter: 25 mm, Millipore) connected to a plastic disposable syringe, and four inks (magenta ink M1, black) Ink 1 composed of ink K1, cyan ink C1, and yellow ink Y1) was obtained.
  • the pH of the obtained ink 1 was measured by the above-described method and found to be 8.2. Further, the viscosity of the ink 1 was measured by the above-described method and found to be 37.6 mPa ⁇ s.
  • Examples 1 to 16 and Comparative Examples 1 to 3> Using ink 1, pretreatment liquid 1, and overcoat liquids 1 to 19 prepared as described above, ink sets 1 to 19 shown in Table 4 below were produced. Images were formed and evaluated by the following procedures using the ink sets 1 to 19 prepared.
  • the pretreatment liquid 1 was applied onto the substrate using an application bar. The coating was performed with the coating amount of the pretreatment liquid 1 being 1.5 g / m 2 . Next, the pretreatment liquid 1 coated on the substrate was dried under the following conditions.
  • Image formation step Ink 1 (magenta ink M1, black ink K1, cyan ink C1, and yellow ink Y1) is ejected on the side of the base material on which the pretreatment liquid 1 has been applied, under the following conditions.
  • a multicolor image was formed. Specifically, ink of each color was applied (droplet ejected) on the pretreatment liquid-coated surface of the substrate coated with the pretreatment liquid 1 under the following conditions to form an image.
  • Head Head with 1,200 dpi (dots per inch) / 20 inch wide piezo full line heads for 4 colors
  • the ink 1 applied to the pretreatment liquid coating surface of the substrate was dried under the following conditions.
  • an overcoat solution (overcoat) is applied to the entire image forming surface of the substrate on which an image is formed using a roller coater (product name: Digi Coater POD, Toyotec Co., Ltd.). Any one of the coating liquids 1 to 19) was applied by the roller coater described above, so that the image forming surface of the substrate was post-treated to prepare an image sample.
  • the post-treatment was performed by coating the overcoat solution on the image forming surface of the substrate with a coating amount of 4.0 g / m 2 .
  • the overcoat solution coated on the image forming surface of the substrate was dried under the following conditions.
  • ⁇ Condition Temperature and heating method: Heating was performed from the surface of the substrate using an infrared heater so that the surface temperature of the substrate was 40 ° C. Conveying speed: 30m / min
  • Evaluation 1 Calculate the average value of the measured value in the direction parallel to the coating direction of the overcoat liquid and the measured value in the direction perpendicular to the coating direction of the overcoat solution as the gloss value, and use the calculated average value as the gloss value to evaluate the following: Evaluation was made according to criteria.
  • the average glossiness is 60 or more.
  • 4 Average glossiness is 50 or more and less than 60.
  • 3 The average glossiness was 40 or more and less than 50, and a highly glossy overcoat surface was obtained.
  • 2 The average glossiness is 30 or more and less than 40, and a high gloss overcoat surface is not obtained.
  • 1 The average value of glossiness was less than 30.
  • -Evaluation criteria- 5 The absolute value of the difference between the measured value p in the parallel direction and the measured value q in the vertical direction is 0 or more and less than 5.
  • 4 The absolute value of the difference between the measured value p in the parallel direction and the measured value q in the vertical direction is 5 or more and less than 10.
  • 3 The absolute value of the difference between the measured value p in the parallel direction and the measured value q in the vertical direction is 10 or more and less than 15, which is practically acceptable.
  • 2 The absolute value of the difference between the measured value p in the parallel direction and the measured value q in the vertical direction is 15 or more and less than 20, and the difference in gloss between the parallel direction and the vertical direction is clearly visually recognized and is not practically acceptable. It is. 1: The absolute value of the difference between the measured value p in the parallel direction and the measured value q in the vertical direction is 20 or more.
  • -Evaluation criteria- 5 The rubbed portion was not different from the rubbed portion, and no scratch was observed. 4: Although the surface of the rubbed portion is slightly scratched, there is no damage as an image and there is no practical problem. 3: The surface of the rubbed part was slightly peeled off and very fine scratches were observed, but this is not a problem in practical use. 2: The surface of the rubbed part is peeled off, scratches are conspicuous, and impede practically. 1: The image of the rubbed part is peeled off, and the white background of the coated paper is partially exposed, causing a practical problem.
  • -Evaluation criteria- 5 The part to which ion exchange water is attached is not different from the part to which ion exchange water is not attached, and no change is observed. 4: Although the trace part of the part of the part which ion-exchange water adhered adhered a little, there is no problem practically. 3: A trace was weakly attached to the entire surface of the portion to which the ion-exchanged water was adhered, but it was practically acceptable. 2: The mark is clearly attached to the portion where the ion exchange water is adhered, and it is practically hindered. 1: The overcoat of the part to which ion-exchange water adhered is lost, and it is unacceptable practically.
  • the ink sets of Examples 1 to 16 including an overcoat solution containing resin particles having a group represented by the formula (1) and not having a carboxy group were used.
  • the image sample prepared in this way had very good gloss.
  • grains of the resin which has group represented by Formula (1), and does not have a carboxy group was favorable in storage stability.
  • the image samples produced using the ink sets of Examples 1 to 16 also had good abrasion resistance and water resistance.
  • An image sample produced using the ink set of Comparative Example 3 having an overcoat solution containing resin particles having a group represented by the formula (1) but also having a carboxy group is an ink set of Example 1 or the like.
  • the gloss was remarkably inferior as compared with the image sample produced using.

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

Abstract

L'invention concerne un ensemble d'encre et une application associée, l'ensemble d'encre comprenant : une composition d'encre contenant un agent colorant et de l'eau ; un liquide de prétraitement contenant un acide et de l'eau ; et un liquide de revêtement contenant de l'eau et des particules d'une résine qui comporte un groupe représenté par la formule (1) et ne possède pas de groupe carboxy. Dans la formule (1), A représente un groupe alkylène ayant deux ou trois atomes de carbone, R représente un atome d'hydrogène ou un groupe hydrocarboné ayant 1 à 20 atomes de carbone, et m représente un nombre entier de 3 à 40.
PCT/JP2018/003872 2017-03-29 2018-02-05 Ensemble d'encre et procédé de formation d'image WO2018179848A1 (fr)

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JP2017066115A JP2020094080A (ja) 2017-03-29 2017-03-29 インクセット及び画像形成方法
JP2017-066115 2017-03-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210032485A1 (en) * 2019-07-31 2021-02-04 Seiko Epson Corporation Aqueous ink jet ink composition and an ink jet recording method
JPWO2021140772A1 (fr) * 2020-01-10 2021-07-15

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7175417B1 (ja) 2021-06-30 2022-11-18 株式会社Ｄｎｐファインケミカル オーバーコートインク及びこれを含むインクセット

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011177965A (ja) * 2010-02-26 2011-09-15 Hitachi Maxell Ltd クリア層形成用インク組成物及びその塗布方法並びにそれを用いた印刷物
JP2014094998A (ja) * 2012-11-07 2014-05-22 Ricoh Co Ltd インクジェット記録方法
JP2016172819A (ja) * 2015-03-17 2016-09-29 コニカミノルタ株式会社 活性光線硬化型インクジェットインク、画像形成方法およびインクセット
JP2016216670A (ja) * 2015-05-25 2016-12-22 株式会社リコー 水性インク用後処理液、画像記録セット、画像形成方法、画像形成装置、及び記録物
JP2017014372A (ja) * 2015-06-30 2017-01-19 セイコーエプソン株式会社 処理液組成物、インクジェット用インク組成物、及びインクセット
JP2017222833A (ja) * 2016-06-08 2017-12-21 株式会社リコー 被印刷物の表面処理用液体組成物、およびそれを用いたインクセット、記録方法、記録装置、収容容器、印刷物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011177965A (ja) * 2010-02-26 2011-09-15 Hitachi Maxell Ltd クリア層形成用インク組成物及びその塗布方法並びにそれを用いた印刷物
JP2014094998A (ja) * 2012-11-07 2014-05-22 Ricoh Co Ltd インクジェット記録方法
JP2016172819A (ja) * 2015-03-17 2016-09-29 コニカミノルタ株式会社 活性光線硬化型インクジェットインク、画像形成方法およびインクセット
JP2016216670A (ja) * 2015-05-25 2016-12-22 株式会社リコー 水性インク用後処理液、画像記録セット、画像形成方法、画像形成装置、及び記録物
JP2017014372A (ja) * 2015-06-30 2017-01-19 セイコーエプソン株式会社 処理液組成物、インクジェット用インク組成物、及びインクセット
JP2017222833A (ja) * 2016-06-08 2017-12-21 株式会社リコー 被印刷物の表面処理用液体組成物、およびそれを用いたインクセット、記録方法、記録装置、収容容器、印刷物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210032485A1 (en) * 2019-07-31 2021-02-04 Seiko Epson Corporation Aqueous ink jet ink composition and an ink jet recording method
JPWO2021140772A1 (fr) * 2020-01-10 2021-07-15
WO2021140772A1 (fr) * 2020-01-10 2021-07-15 富士フイルム株式会社 Procédé d'enregistrement d'image
CN114845881A (zh) * 2020-01-10 2022-08-02 富士胶片株式会社 图像记录方法
EP4088932A4 (fr) * 2020-01-10 2023-07-05 FUJIFILM Corporation Procédé d'enregistrement d'image
JP7408689B2 (ja) 2020-01-10 2024-01-05 富士フイルム株式会社 画像記録方法
CN114845881B (zh) * 2020-01-10 2024-02-20 富士胶片株式会社 图像记录方法

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