JP5523721B2 - Aqueous ink composition, ink set, and image forming method - Google Patents

Description

  The present invention relates to an aqueous ink composition, an ink set, and an image forming method.

  The ink jet recording method performs recording by ejecting ink droplets from a large number of nozzles formed on an ink jet head, and the noise during the recording operation is low, the running cost is low, and various recording media are used. On the other hand, it is widely used because it can record high-quality images.

  By the way, carbon black pigment is used for black ink in inkjet ink, but water-soluble dye is central in color ink, and weather resistance (for example, light resistance, ozone resistance, water resistance) is improved. Is required. In particular, when considering application to the printing field, improvement in weather resistance is particularly important. The pigment is inherently high in fastness due to its high crystallinity, and has excellent light resistance and water resistance compared to dyes. However, there are problems such as dischargeability due to clogging of the nozzle part, storage stability such as coagulation sedimentation, and further fixing of printed matter such as abrasion resistance and glossiness due to particles remaining on the surface of the recording medium. It is left.

  Self-water dispersibility obtained by copolymerizing an unsaturated monomer having an aliphatic hydrocarbon group having 14 to 20 carbon atoms, a benzyl methacrylate monomer, and a styrene monomer as a fixability improving technique An aqueous inkjet recording liquid that uses a copolymer resin in the form of a hydrosol or an emulsion in an aqueous inkjet recording liquid is disclosed (for example, see Patent Document 1). This recording liquid has good storage stability, maintains a high printing density and printing quality even when it is given quick drying by osmotic drying, and is also excellent in friction resistance and water resistance.

  Also known is an ink for inkjet recording comprising a low MFT resin emulsion having a minimum film-forming temperature (MFT) of 60 to 100 ° C. and a high Tg resin emulsion having a glass transition temperature (Tg) of 140 to 200 ° C. In addition, it is said to be excellent in ejection property, fixing property, and the like (see, for example, Patent Document 2).

  Furthermore, as a method for producing a polymer particle dispersion (latex), a hydrophobic vinyl monomer mixture containing an α, β-unsaturated carboxylic acid is polymerized in an organic solvent, and the resulting polymer-containing solution is used as an organic solvent. In the presence of a vinyl-based aqueous emulsion polymer obtained by removing water and then adding water and a basic substance, a method of emulsion polymerization to form an emulsion is known (see, for example, Patent Document 3). .

JP 2002-88285 A JP-A-8-283636 JP 2006-249282 A

  However, although the aqueous dispersion-containing ink described in Patent Document 1 has an effect of improving the fixability, it may be difficult to obtain a stable aqueous dispersion. Even when a stable aqueous dispersion is obtained, the viscosity of the aqueous dispersion may be high, and for example, it is difficult to apply to an inkjet ink.

  In the ink for ink jet recording described in Patent Document 2, it is essential to heat the ink simultaneously with the application to the recording medium, and when the MFT contains a low MFT resin of less than 60 ° C., the blocking property is deteriorated. ing. Further, regarding the emulsion described in Patent Document 2, there is no description regarding the production method, and it is not difficult to imagine that the ejection properties and ink stability are inferior.

  Further, the emulsion obtained by the production method described in Patent Document 3 has a problem that when applied to an inkjet ink, the Tg of the polymer particles is low and the blocking resistance of the image is poor.

  The present invention provides an aqueous ink composition that is excellent in ink stability and capable of suppressing the occurrence of blocking in a recording medium on which an image is formed, an ink set including the aqueous ink composition, and an image forming method. Is an issue.

Specific means for solving the above problems are as follows.
<1> Water-insoluble colored particles containing a colorant, two or more kinds of polymers, at least one polymer having a carboxyl group , and a structural unit having a cyclic aliphatic group, and having a glass transition temperature of 120 ° C. or higher A water-based ink composition comprising: composite particles containing at least one polymer.
<2> The aqueous ink composition according to <1>, wherein the structural unit having a cyclic aliphatic group is a structural unit derived from a (meth) acrylic monomer having a cyclic aliphatic group.
<3> The cycloaliphatic group is a cyclopentyl group, a cyclohexyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a decahydronaphthalenyl group, a per <1> or <1 which is at least one selected from the group consisting of a hydrofluorenyl group, a tricyclo [5.2.1.0 ^2,6 ] decanyl group, and a bicyclo [4.3.0] nonanyl group 2> The water-based ink composition described in 2>.
< 4 > The water-based ink composition according to any one of <1> to <3>, wherein the composite particles have a property of aggregating due to a change in pH environment.
< 5 > The aqueous ink composition according to any one of <1> to <4>, wherein the composite particles include two kinds of polymers having an absolute value of a difference in glass transition temperature of 40 ° C. or more.

< 6 > The aqueous ink composition according to any one of <1> to < 5 >, wherein the composite particle is obtained by emulsion polymerization of a monomer in the presence of an aqueous solution or emulsion of a carboxyl group-containing polymer.
< 7 > The aqueous ink composition according to < 6 >, wherein the aqueous solution or emulsion of the carboxyl group-containing polymer further contains a basic compound.
< 8 > The composite particle according to any one of <1> to < 7 >, wherein the composite particle includes a first polymer having an acid value of 30 or more and 500 or less and a second polymer having an acid value of less than 30. Water-based ink composition.

< 9 > An ink set comprising the aqueous ink composition according to any one of <1> to < 8 >, and a treatment liquid capable of forming an aggregate by contact with the aqueous ink composition.
< 10 > A step of applying the water-based ink composition according to any one of <1> to < 8 > to a recording medium, and heat-fixing the recording medium to which the water-based ink composition has been applied to form an image. Forming an image.
<11> the <1> to treatment liquid capable of forming an aggregate upon contact with the aqueous ink composition according to any one of <8>, further comprising the step of applying to a recording medium the <10 > The image forming method described in the above.

  According to the present invention, there are provided an aqueous ink composition that is excellent in ink stability and can suppress the occurrence of blocking in a recording medium on which an image is formed, an ink set including the aqueous ink composition, and an image forming method. can do.

<Water-based ink composition>
The aqueous ink composition of the present invention (hereinafter sometimes simply referred to as “ink composition”) includes water-insoluble colored particles and composite particles containing two or more kinds of polymers, and the composite particles are And at least one polymer having a carboxyl group and at least one polymer having a glass transition temperature (Tg) of 120 ° C. or higher. By adopting such a configuration, it is possible to form an image having excellent ink stability and excellent fixability (rubbing resistance) and blocking resistance.

  The water-based ink composition of the present invention can be used not only for monochromatic image formation but also for full-color image formation. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone. Further, red, green, blue, and white inks other than yellow, magenta, and cyan color inks, and so-called special color inks (for example, colorless) in the printing field can be used.

  In the aqueous ink composition of the present invention, since the composite particles contain a polymer having a high glass transition temperature (Tg), for example, the interaction between the formed image ink films is weakened, and the mutual adhesive strength of the image is reduced. To do. As a result, it can be considered that blocking resistance is improved.

In the present invention, the glass transition temperature (Tg) of at least one of the two or more kinds of polymers contained in the composite particles is 120 ° C. or higher, preferably 130 ° C. or higher, preferably 130 ° C. or higher and 300 ° C. The following is more preferable.
When the composite particles do not contain a polymer having a glass transition temperature of 120 ° C. or higher, the blocking resistance of the formed image may be lowered.

In addition, at least one of the two or more kinds of polymers included in the composite particles has a carboxyl group. When the composite particles do not contain a polymer having a carboxyl group, the stability of the ink composition may be lowered.
In addition, the glass transition temperature (Tg) of the carboxyl group-containing polymer contained in the composite particles may be 120 ° C. or higher, or may be lower than 120 ° C.

In the present invention, the composite particles preferably include two kinds of polymers having an absolute value of a difference in glass transition temperature of 40 ° C. or higher, and an absolute value of the difference in glass transition temperature of 40 ° C. or higher and 200 ° C. or lower. It is more preferable to include seed polymers, and it is further preferable to include two kinds of polymers having an absolute value of a difference in glass transition temperature of 50 ° C. or higher and 200 ° C. or lower. By including two types of polymers having a glass transition temperature difference of 40 ° C. or more, the film property of the formed image is improved, and it becomes possible to more effectively achieve both blocking resistance and abrasion resistance. .
Furthermore, the composite particles in the present invention preferably include two types of polymers having a glass transition temperature of 130 ° C. or higher and an absolute value of a difference in glass transition temperature of 40 ° C. or higher and 200 ° C. or lower. More preferably, the glass transition temperature of at least one polymer is 130 ° C. or higher and 300 ° C. or lower, and the absolute value of the difference in glass transition temperature is 50 ° C. or higher and 200 ° C. or lower.

In the present invention, the glass transition temperature of the polymer can be appropriately controlled by a commonly used method. For example, the glass transition temperature of the polymer is desired by appropriately selecting the type of polymerizable group of the monomer constituting the polymer, the type and composition ratio of the substituent on the monomer, the molecular weight of the polymer molecule constituting the polymer particle, etc. Can be controlled within the range.
In the present invention, the glass transition temperature is a value (hereinafter referred to as “measurement Tg”) measured under normal measurement conditions using a differential scanning calorimeter (DSC) EXSTAR 6220 manufactured by SII Nanotechnology. Mean). In the present invention, the composite particle is composed of two or more kinds of polymers, and the glass transition temperature of each polymer corresponds to two or more peaks observed by DSC measurement.

However, when the polymer is decomposed, or when the glass transition temperatures of two or more polymers are close to each other and it is difficult to measure each glass transition temperature Tg, it is calculated by the following method. The calculated Tg is the glass transition temperature in the present invention.
The calculation Tg is calculated by the following formula.
(Formula) 1 / Tg = Σ (X _i / Tg _i )
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. X _i is the weight fraction of the i-th monomer (ΣX _i = 1), and Tg _i is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature value (Tg _i ) of each monomer can be referred to the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)). .

  The composite particle in the present invention is not particularly limited as long as it contains at least one polymer having two or more kinds of polymers and having a carboxyl group and at least one kind of polymer having a glass transition temperature of 120 ° C. or more. Any polymer can be included. The polymer constituting the composite particles may be a vinyl polymer or a condensation polymer (epoxy resin, polyester, polyurethane, polyamide, cellulose, polyether, polyurea, polyimide, polycarbonate, etc.). Among these, from the viewpoint of the dispersion stability of the composite particles, at least one type is preferably a vinyl polymer, and more preferably two or more types are vinyl polymers.

Preferable examples of the vinyl polymer and the monomer constituting the vinyl polymer in the present invention include those described in JP-A Nos. 2001-181549 and 2002-88294. In addition, radical transfer of vinyl monomers using dissociable groups (or substituents that can be induced to dissociable groups), polymerization initiators, and iniferters, or dissociable groups on either initiators or terminators A vinyl polymer in which a dissociable group is introduced at the end of a polymer chain by ionic polymerization using a compound having (or a substituent that can be derived from a dissociable group) can also be used.
Moreover, as a suitable example of the monomer which comprises a condensation type polymer and a condensation type polymer, what is described in Unexamined-Japanese-Patent No. 2001-247787 can be mentioned.

  The composite particles in the present invention preferably contain a polymer containing at least one structural unit having a cycloaliphatic group from the viewpoint of blocking properties and abrasion resistance of the formed image. The structural unit having a cycloaliphatic group may be derived from a monomer having a cycloaliphatic group or may be introduced into a polymer by a polymer reaction. The structural unit having a cycloaliphatic group in the present invention is preferably derived from a monomer having a cycloaliphatic group, and preferably derived from a (meth) acrylic monomer having a cycloaliphatic group. More preferred.

In the present invention, a (meth) acrylic monomer having a cycloaliphatic group (hereinafter sometimes referred to as “alicyclic (meth) acrylate”) is derived from a structural site derived from (meth) acrylic acid and an alcohol. And a structure containing at least one cyclic aliphatic group that is unsubstituted or substituted at the structure derived from the alcohol. The cyclic aliphatic group may be a structural site derived from alcohol itself, or may be bonded to a structural site derived from alcohol via a linking group.
Note that “(meth) acrylate” means methacrylate or acrylate.

The cyclic aliphatic group is not particularly limited as long as it contains a cyclic non-aromatic hydrocarbon group, and is a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or higher polycyclic hydrocarbon. Groups.
Examples of the cycloaliphatic group include 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 decane group, and the like. Examples thereof include a hydronaphthalenyl group, a perhydrofluorenyl group, a tricyclo [5.2.1.0 ^2,6 ] decanyl group, and a bicyclo [4.3.0] nonane.

The cycloaliphatic group may further have a substituent. Examples of the substituent include alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, hydroxyl groups, primary amino groups, secondary amino groups, tertiary amino groups, alkyl or arylcarbonyl groups, and cyano groups. Is mentioned.
Further, the cyclic aliphatic group may further form a condensed ring.
As a cycloaliphatic group in this invention, it is preferable that carbon number of a cycloaliphatic group part is 5-20 from a viscosity or a soluble viewpoint.

  Examples of the linking group that connects the cyclic aliphatic group and the structural part derived from the alcohol include alkyl groups, alkenyl groups, alkylene groups, aralkyl groups, alkoxy groups, mono- or oligoethylene glycol groups having 1 to 20 carbon atoms, Suitable examples include mono- or oligopropylene glycol groups.

Specific examples of the alicyclic (meth) acrylate in the present invention are shown below, but the present invention is not limited thereto.
Monocyclic (meth) acrylates include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, and cyclononyl. Examples thereof include cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in cycloalkyl groups such as (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 can be used alone or in admixture of two or more.

  Among these, from the viewpoints of dispersion stability, fixing property, and blocking resistance of the composite particles, at least one kind of bicyclic (meth) acrylate or tricyclic or higher polycyclic (meth) acrylate may be used. Preferably, it is at least one selected from isobornyl (meth) acrylate, adamantyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.

Moreover, it is preferable that the composite particle in this invention has the characteristic to aggregate by the change of pH environment. By having such characteristics, it is possible to achieve both the stability over time and the high-speed recording property of the ink composition. For example, when the composite particles contain at least one polymer having a dissociable group, the composite particles can be configured to aggregate due to a change in pH environment. In the present invention, the dissociable group is preferably an anionic group, and more preferably a carboxyl group. When the composite particles include a polymer having a carboxyl group, a high aggregation rate can be achieved, and the stability of the ink composition with time can be increased.
Further, the composite particles can form, for example, aggregates by incorporating water-insoluble colored particles during aggregation. Aggregates containing composite particles and water-insoluble colored particles can be suitably used for image formation, for example.

The composite particles contained in the ink composition of the present invention include at least one first polymer having an acid value (KOHmg / g) of 30 or more and 500 or less, and a second polymer having an acid value of less than 30. It is preferable that at least one of these is included. With such a configuration, the temporal stability and high-speed recording property of the ink composition can be achieved more effectively.
The first polymer is not particularly limited as long as it contains an anionic group so that the acid value is 30 or more and 500 or less. Examples of the anionic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. From the viewpoint of stability and aggregation, a carboxyl group is preferable. That is, the first polymer is preferably a carboxyl group-containing polymer.

<Carboxyl group-containing polymer>
The composite particles in the present invention contain at least one carboxyl group-containing polymer. The carboxyl group-containing polymer may be used alone or in combination of two or more different in structure, copolymerization ratio, molecular weight and the like.
The carboxyl group-containing polymer is not particularly limited as long as it has a carboxyl group, but preferably functions as an emulsifier component. The carboxyl group-containing polymer that functions as an emulsifier component forms micelles in which the emulsified component containing an ethylenically unsaturated monomer that constitutes a water-insoluble polymer described later that can be a component of the composite particle is a droplet, Polymerization can be initiated with the radical polymerization initiator incorporated in the micelle. That is, it is preferable that the carboxyl group-containing polymer can provide a polymerization site in water to an ethylenically unsaturated monomer that is insoluble or hardly soluble in water.
The carboxyl group-containing polymer may be used alone or in combination of two or more different in structure, copolymerization ratio, molecular weight and the like.

In general, an emulsifier in emulsion polymerization plays a role of emulsifying a hydrophobic component in an aqueous medium. Therefore, it is preferable to have a hydrophilic partial structure and a hydrophobic partial structure. Therefore, the carboxyl group-containing polymer in the present invention preferably has a carboxyl group as a hydrophilic partial structure and further has a hydrophobic partial structure.
Examples of the hydrophobic partial structure include aromatic groups, aralkyl groups, and alkyl groups. Among them, the hydrophobic part preferably contains at least one selected from an aromatic group, an aralkyl group, and an alkyl group having 4 or more carbon atoms.

The main chain structure of the carboxyl group-containing polymer is not particularly limited and may be, for example, a vinyl polymer or a condensation polymer, but is preferably a vinyl polymer.
The carboxyl group-containing polymer can be composed of, for example, an ethylenically unsaturated monomer having a carboxyl group and other monomers.
Examples of the ethylenically unsaturated monomer having a carboxyl group that is a copolymerization component of a carboxyl group-containing polymer include (meth) acrylic acid, (anhydrous) itaconic acid, and (anhydrous) maleic acid.

Examples of monomers other than the ethylenically unsaturated monomer having a carboxyl group that can constitute a carboxyl group-containing polymer include an ethylenically unsaturated monomer having a hydrophobic group and an ethylenically unsaturated monomer having a nonionic hydrophilic group. Etc.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate and other alkyl (meth) acrylates; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Ethylenically unsaturated monomers having hydroxyl groups such as butyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; aralkyl (meth) such as benzyl (meth) acrylate Acrylate; dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; aromatic monomers such as styrene and methylstyrene; alicyclic (meth) acrylates described above; N-hydroxymethyl (meth) acrylamide, N N-hydroxyalkyl (meth) acrylamides such as hydroxyethyl (meth) acrylamide and N-hydroxybutyl (meth) acrylamide; N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (n- , Iso) butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-alkoxyalkyl such as N- (n-, iso) butoxyethyl (meth) acrylamide Examples include (meth) acrylamides such as ru (meth) acrylamide.

  The carboxyl group-containing polymer in the present invention includes (meth) acrylic acid, alicyclic (meth) acrylate, aromatic monomer, aralkyl (meth) acrylate, and dialkyl from the viewpoints of emulsion polymerization stability and Tg control. It is preferably composed of at least one selected from aminoalkyl (meth) acrylate and alkyl (meth) acrylate. (Meth) acrylic acid, aromatic monomer, alicyclic (meth) acrylate, and alkyl ( More preferably, it comprises at least one selected from (meth) acrylate, and (meth) acrylic acid, alkyl (meth) acrylate, at least one selected from aromatic monomers and alicyclic (meth) acrylates, More preferably consisting of

  The acid value (KOHmg / g) of the carboxyl group-containing polymer in the present invention is a viewpoint of promoting the aggregation reaction by a change in pH environment (for example, contact with an acidic treatment liquid described later) and a viewpoint of stabilization of emulsion polymerization. Therefore, it is preferably 30 or more and 500 or less. More preferably, it is 30 or more and 400 or less, More preferably, it is 30 or more and 300 or less. When the acid value is 30 or more, the emulsifying power in radical polymerization is improved, and emulsion polymerization can be performed more stably. Moreover, aggregation reactivity can be improved more because an acid value is 500 or less.

The molecular weight range of the carboxyl group-containing polymer is preferably 1000 to 200,000 in terms of weight average molecular weight, more preferably 2000 to 150,000, and still more preferably 3000 to 70000. By setting the weight average molecular weight to 1000 or more, polymerization stability is further improved, and aggregation during polymerization can be more effectively suppressed. Moreover, when the weight average molecular weight is 200,000 or less, it is possible to suppress the viscosity of the aqueous solution or emulsion of the carboxyl group-containing polymer from becoming too high, and the emulsion polymer can be more uniformly performed. It is possible to more effectively suppress the deterioration of ejection properties when the aqueous ink composition is configured.
The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  The carboxyl group-containing polymer in the present invention can be obtained, for example, by a usual method such as solution polymerization in a solvent, and can also be synthesized by polymerization in an aqueous medium or bulk polymerization.

When carrying out emulsion polymerization using a carboxyl group-containing polymer obtained by solution polymerization as an emulsifier, it is preferable to remove the organic solvent used when preparing the carboxyl group-containing polymer. By reducing the ratio of the organic solvent, the polymerization conversion rate becomes better, and the physical properties of the coating film become better.
As a method for removing the organic solvent, for example, a solvent removal method using a normal decompression method can be used.

  Specific examples of the carboxyl group-containing polymer are exemplified compounds C-01 to C-10, but the present invention is not limited thereto. In addition, the parenthesis represents the mass ratio of the copolymerization component.

C-01: Styrene / butyl acrylate / acrylic acid polymer (48/27/25)
C-02: Methyl methacrylate / ethyl acrylate / methacrylic acid polymer (60/30/10)
C-03: benzyl methacrylate / ethyl acrylate / methacrylic acid / dimethylaminoethyl methacrylate polymer (60/30/4/6)
C-04: methyl methacrylate / isobornyl methacrylate / methacrylic acid polymer (55/37/8)
C-05: Styrene / butyl methacrylate / methacrylic acid / dimethylaminoethyl methacrylate polymer (55/24/15/6)
C-06: Styrene / t-butyl metallate / acrylic acid polymer (53/27/20)
C-07: benzyl methacrylate / butyl methacrylate / methacrylic acid polymer (55/30/15)
C-08: benzyl methacrylate / cyclohexyl methacrylate / methacrylic acid / dimethylaminoethyl acrylate polymer (70/15/10/5)
C-09: benzyl methacrylate / dodecyl methacrylate / N-vinyl pyrrolidone polymer / acrylic acid (50/25/5/20)
C-10: benzyl methacrylate / methyl methacrylate / hydroxyethyl methacrylate / acrylic acid polymer (55/15/10/20)

<Water-insoluble polymer>
The composite particles in the present invention preferably contain at least one water-insoluble polymer in addition to the carboxyl group-containing polymer. One kind of water-insoluble polymer may be used alone, or two or more kinds having different structures, copolymerization ratios, molecular weights and the like may be mixed and used.
The water-insoluble polymer may be a vinyl polymer or a condensation polymer, but is preferably a vinyl polymer. Examples of the monomer that constitutes the vinyl polymer and the monomer that constitutes the condensation polymer include the monomers in the carboxyl group-containing polymer described above.

The water-insoluble polymer in the present invention preferably contains at least one structural unit having a cycloaliphatic group from the viewpoint of blocking resistance, and includes at least one structural unit derived from an alicyclic (meth) acrylate. It is preferable to include. The structural unit having a cycloaliphatic group in the water-insoluble polymer is the same as described above, and the preferred embodiment is also the same.
Although there is no restriction | limiting in particular in the content rate of the structural unit which has a cycloaliphatic group in a water-insoluble polymer, From a viewpoint of blocking resistance, it is preferable that it is 30 mass% or more, and it is more preferable that it is 50 mass% or more. preferable.

  The water-insoluble polymer preferably includes a structural unit having a cyclic aliphatic group, but may further include other structural units as necessary. Other structural units that can constitute the water-insoluble polymer include hydrophilic structural units (preferably structural units having a carboxyl group), structural units derived from aromatic monomers, and derived from alkyl (meth) acrylates. And the like. Specific examples of the aromatic monomer and the alkyl (meth) acrylate are as described above.

The acid value (KOHmg / g) of the water-insoluble polymer in the present invention is not particularly limited, but it is less than 30 from the viewpoint of promoting the aggregation reaction due to a change in pH environment (for example, contact with an acidic treatment solution). Preferably, it is 20 or less, more preferably 10 or less.
The preferred molecular weight range of the water-insoluble polymer is the same as the preferred range mentioned in the description of the carboxyl group-containing polymer.

  The water-insoluble polymer in the present invention includes a structural unit having a cycloaliphatic group and has an acid value of less than 30 from the viewpoint of blocking resistance and aggregability, and the structural unit having a cycloaliphatic group is 30. More preferably, the acid value is 20% or less, more preferably 50% by mass or more of the structural unit having a cycloaliphatic group, and the acid value is 10 or less.

  The glass transition temperature (Tg) of the water-insoluble polymer is not particularly limited, but is preferably 120 ° C or higher, more preferably 130 ° C or higher, from 130 to 300 ° C from the viewpoint of blocking resistance. More preferably.

  Specific examples of the water-insoluble polymer are exemplified compounds B-01 to B-06, but the present invention is not limited to these. In addition, the parenthesis represents the mass ratio of the copolymerization component.

B-01: Isobornyl methacrylate polymer (100)
B-02: Methyl methacrylate / isobornyl methacrylate polymer (40/60)
B-03: Methyl methacrylate / isobornyl methacrylate / benzyl methacrylate polymer (30/65/5)
B-04: Methyl methacrylate / dicyclopentanyl methacrylate / methacrylic acid polymer (40/50/10)
B-05: Methyl methacrylate / isobornyl methacrylate polymer (20/80)
-B-06: Methyl methacrylate / isobornyl methacrylate / methacrylic acid polymer (30/66/4)

  When the composite particle in the present invention contains a carboxyl group-containing polymer and a water-insoluble polymer, the content thereof is not particularly limited, but from the viewpoint of abrasion resistance, blocking resistance and dispersion stability, carboxyl group-containing The content of the polymer is 5 to 80% by mass, the content of the water-insoluble polymer is preferably 20 to 95% by mass, the content of the carboxyl group-containing polymer is 5 to 70% by mass, More preferably, the content of the insoluble polymer is 30 to 95% by mass. Further, the content ratio of the carboxyl group-containing polymer to the water-insoluble polymer in the composite particles (carboxyl group-containing polymer / water-insoluble polymer) is not particularly limited, but from the viewpoint of abrasion resistance, blocking resistance and dispersion stability, It is preferably 1/20 to 5/1, and more preferably 1/10 to 2/1.

-Manufacturing method of composite particles-
As a method for producing composite particles in the present invention, a known method can be used without any particular limitation, and examples thereof include 1) emulsion polymerization, 2) emulsion dispersion and the like.
In the present invention, from the viewpoint of blocking resistance and aggregation properties, the water-insoluble polymer is subjected to emulsion polymerization or emulsion dispersion of the monomer constituting the water-insoluble polymer in the presence of the aqueous solution or emulsion of the carboxyl group-containing polymer. It is preferable that it is a manufacturing method including the process of obtaining the aqueous dispersion of the composite particle containing this.

In the present invention, it is preferable to use a carboxyl group-containing polymer as an emulsifier or dispersant, but a carboxylate emulsifier can be further used in combination as long as the effects of the present invention are not impaired.
The carboxylate emulsifier that can be used in the present invention is not particularly limited as long as it is an emulsifier having a carboxyl group in the molecule. For example, beef tallow fatty acid soap, coconut oil fatty acid soap, rosin acid soap, various purified fatty acid soaps such as stearate and oleate, alkenyl succinate, and N-acyl sarcosine salts such as sodium N-lauroyl sarcosine Is mentioned. Among them, alkenyl succinate is preferable from the viewpoint of stability against shearing force. Moreover, as a suitable example of a reactive carboxylate emulsifier, what is described in Unexamined-Japanese-Patent No. 9-302007 etc. can be mentioned.

-Basic compounds-
In the present invention, the aqueous solution or emulsion of the carboxyl group-containing copolymer preferably further contains a basic compound. By further containing a basic compound, part or all of the carboxyl groups in the carboxyl group-containing copolymer can be neutralized, and the aqueous solution or emulsion of the carboxyl group-containing copolymer can be made more stable. Thus, emulsion formation using this can be performed more efficiently.

Examples of the basic compound used in the present invention include organic amine compounds, ammonia, alkali metal hydroxides, and the like. Examples of organic amine compounds include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethyl-ethanolamine, N, N-diethyl-ethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, N-methyldiethanolamine, N-ethyldiethanolanine, monoisopropanolamine, di Examples include isopropanolamine and triisopropanolamine. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
These basic compounds are preferably used in an amount of 20 to 300 mol% with respect to 100 mol% of the carboxyl groups in the carboxyl group-containing copolymer.

-1) Emulsion polymerization
In the emulsion polymerization, for example, a monomer that constitutes a water-insoluble polymer in an aqueous medium (for example, water), a polymerization initiator, an emulsifier (preferably, the carboxyl group-containing polymer), and, if necessary, a water-soluble polymerization chain transfer. It can be carried out by polymerizing an emulsion prepared by adding an agent or the like.

The polymerization initiator is not particularly limited, and is an inorganic persulfate (for example, potassium persulfate, sodium persulfate, ammonium persulfate, etc.), an azo-based initiator (for example, 2,2′-azobis (2-amidinopropane). ) Dihydrochloride, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], etc.), organic peroxides (eg peroxypivalic acid-t-butyl, t-butylhydro) Peroxide) and the like. These can be used alone or in combination of two or more.
Among these, it is preferable to use an azo-based initiator and an organic peroxide from the viewpoint of cohesiveness of the composite particles.
The amount of the polymerization initiator used in the present invention is usually 0.01 to 2% by mass, preferably 0.2 to 1% by mass, based on all monomers.

  The amount of the carboxyl group-containing polymer used as an emulsifier in the present invention is preferably 2 to 300% by mass, and 5 to 100% by mass with respect to the total monomers, from the viewpoint of cohesiveness of the composite particles. Is more preferable. When the amount of the carboxyl group-containing polymer used is 2% by mass or more, the monomer can be emulsified more efficiently. Moreover, the aggregation property of the composite particle obtained can be made more favorable because it is 300 mass% or less.

  Examples of the water-soluble polymerization chain transfer agent include mercaptans such as n-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and disulfides such as tetramethylthiuram disulfide and tetraethylthiuram disulfide. , Halogenated derivatives such as carbon tetrachloride, carbon tetrabromide, 2-ethylhexyl thioglycolate, α-methylstyrene dimer, and sodium phosphinate as a water-soluble chain transfer agent, one or two of these The above can be used.

-2) Emulsification dispersion-
As the emulsification dispersion in the present invention, a known emulsification dispersion method can be used without particular limitation. For example, a forced emulsification method in which a polymer solution or a molten polymer is emulsified and dispersed in an aqueous medium containing an emulsifier, the emulsifier is dissolved in the polymer solution and the aqueous medium is added, or the aqueous medium solution of the emulsifier is gradually added to the polymer solution. Any method of phase inversion emulsification that is added and phase inversion may be used.
As the polymer in the polymer solution and the molten polymer, the water-insoluble polymer can be used. Moreover, about the emulsifier, the said carboxyl group-containing polymer can be used preferably, The addition amount is also the same.

  In the present invention, from the viewpoint of dispersion stability and aggregation of the composite particles, the composite particles are formed by emulsion polymerization of the monomer constituting the water-insoluble polymer in the presence of an aqueous solution or emulsion of the carboxyl group-containing polymer. It is preferable.

The volume average particle size of the composite particles in the present invention is not particularly limited, but is preferably in the range of 1 to 400 nm, more preferably 3 to 200 nm, and further preferably 5 to 100 nm. Aggregation characteristics are improved when the volume average particle diameter is 1 nm or more. Further, by setting the volume average particle diameter to 400 nm or less, ink droplet ejection properties are improved.
Further, the particle size distribution of the composite particles is not particularly limited, and may be any having a wide particle size distribution or a monodispersed particle size distribution. Further, two or more kinds of composite particles may be mixed and used.
The volume average particle size and particle size distribution of the composite particles can be measured using, for example, a dynamic light scattering method.

The content of the composite particles in the aqueous ink composition of the present invention is preferably 1 to 30% by mass, and 5 to 15% by mass with respect to the aqueous ink composition from the viewpoint of image glossiness and the like. More preferably.
The content ratio of the water-insoluble colored particles to the composite particles (water-insoluble colored particles / water-insoluble particles) in the water-based ink composition of the present invention is 1 / 0.5 to 1 from the viewpoint of image scratch resistance. / 10 is preferable, and 1/1 to 1/4 is more preferable.

[Water-insoluble colored particles]
The water-insoluble colored particles in the present invention contain at least one colorant, and can contain other components as necessary. As the colorant, known dyes, pigments and the like can be used without particular limitation. Among these, from the viewpoint of ink colorability, a colorant that is almost insoluble or hardly soluble in water is preferable. Specific examples include various pigments, disperse dyes, oil-soluble dyes, dyes forming J aggregates, and the like, and pigments are more preferable.
In the present invention, the water-insoluble pigment itself or the pigment surface-treated with a dispersant can be used as water-insoluble colored particles.

There is no restriction | limiting in particular as a pigment in this invention, A conventionally well-known organic and inorganic pigment can be used. For example, polycyclic pigments such as azo lakes, azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, basic Examples include dye lakes such as dye-type lakes and acid dye-type lakes, organic pigments such as nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments, and inorganic pigments such as titanium oxide, iron oxide, and carbon black. Any pigment not described in the color index can be used as long as it can be dispersed in the aqueous phase. Further, it is of course possible to use a pigment obtained by surface-treating the above pigment with a surfactant, a polymer dispersing agent or the like, or graft carbon. Among the above pigments, it is particularly preferable to use an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, or a carbon black pigment.
Specific examples of the pigment that can be used in the present invention include pigments described in paragraph numbers [0142] to [0145] of JP-A-2007-100071.

-Dispersant-
When the colorant in the present invention is a pigment, it is preferably dispersed in an aqueous solvent by a dispersant. The dispersant may be a polymer dispersant or a low molecular surfactant type dispersant. The polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.
The low molecular surfactant type dispersant (hereinafter sometimes referred to as “low molecular dispersant”) may be added for the purpose of stably dispersing the organic pigment in an aqueous solvent while keeping the ink at a low viscosity. it can. The low molecular dispersant herein is a low molecular dispersant having a molecular weight of 2000 or less. Moreover, 100-2000 are preferable and, as for the molecular weight of a low molecular dispersing agent, 200-2000 are more preferable.

  The low molecular weight dispersant has a structure including a hydrophilic group and a hydrophobic group. In addition, the hydrophilic group and the hydrophobic group may be independently contained in one molecule or more, and may have a plurality of types of hydrophilic groups and hydrophobic groups. In addition, a linking group for linking a hydrophilic group and a hydrophobic group can be appropriately included.

Examples of the hydrophilic group include an anionic group, a cationic group, a nonionic group, and a betaine type combining these.
The anionic group is not particularly limited as long as it has a negative charge, but may be a phosphate group, phosphonic acid group, phosphinic acid group, sulfuric acid group, sulfonic acid group, sulfinic acid group or carboxylic acid group. Preferably, it is a phosphoric acid group or a carboxylic acid group, more preferably a carboxylic acid group.

The cationic group is not particularly limited as long as it has a positive charge, but is preferably an organic cationic substituent, more preferably a cationic group containing nitrogen or phosphorus, and nitrogen. More preferably, it is a cationic group. Among these, a pyridinium cation or an ammonium cation is particularly preferable.
The nonionic group is not particularly limited as long as it has no negative or positive charge. For example, a polyalkylene oxide, polyglycerin, a part of sugar unit, etc. are mentioned.

In the present invention, the hydrophilic group is preferably an anionic group from the viewpoint of dispersion stability and aggregation of the pigment.
Moreover, when a low molecular weight dispersing agent has an anionic hydrophilic group, it is preferable that the pKa is 3 or more from a viewpoint of making it contact with an acidic process liquid and promoting aggregation reaction. The pKa of the low molecular dispersant in the present invention is determined experimentally from a titration curve by titrating a solution of 1 mol / L of the low molecular dispersant in tetrahydrofuran-water = 3: 2 (V / V) solution with an acid or alkaline aqueous solution. It is the calculated value.
Theoretically, if the pKa of the low molecular dispersant is 3 or more, 50% or more of the anionic groups are in a non-dissociated state when in contact with a treatment solution having a pH of about 3. Accordingly, the water solubility of the low molecular weight dispersant is remarkably lowered, and an agglomeration reaction occurs. That is, the aggregation reactivity is improved. From this viewpoint, it is preferable that the low molecular dispersant has a carboxylic acid group as an anionic group.

  On the other hand, the hydrophobic group may have any structure such as hydrocarbon-based, fluorocarbon-based, and silicone-based, but is particularly preferably hydrocarbon-based. Further, these hydrophobic groups may have a linear structure or a branched structure. The hydrophobic group may have a single chain structure or two or more chain structures, and may have a plurality of types of hydrophobic groups in the case of a structure having two or more chains.

  The hydrophobic group is preferably a hydrocarbon group having 2 to 24 carbon atoms, more preferably a hydrocarbon group having 4 to 24 carbon atoms, and further preferably a hydrocarbon group having 6 to 20 carbon atoms.

  Among the polymer dispersants in the present invention, a hydrophilic polymer compound can be used as the water-soluble dispersant. For example, natural hydrophilic polymer compounds include plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, seaweeds such as alginic acid, carrageenan and agar. Examples include molecules, animal polymers such as gelatin, casein, albumin and collagen, and microorganism polymers such as xanthene gum and dextran.

  Examples of hydrophilic polymer compounds chemically modified from natural products include fibrin polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium starch glycolate, sodium starch phosphate, etc. And seaweed polymers such as alginic acid propylene glycol ester.

  Synthetic water-soluble polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, acrylic polymers such as polyacrylamide, polyacrylic acid or alkali metal salts thereof, and water-soluble styrene acrylic resins. Resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalene sulfonic acid formalin condensate, quaternary ammonium, amino group, etc. And a polymer compound having a cationic functional group salt in the side chain.

  Among these, from the viewpoint of pigment dispersion stability and aggregation, a polymer compound containing a carboxyl group is preferable. For example, an acrylic resin such as a water-soluble styrene acrylic resin, a water-soluble styrene maleic resin, and a water-soluble vinyl naphthalene. High molecular compounds containing a carboxyl group such as an acrylic resin and a water-soluble vinyl naphthalene maleic resin are particularly preferred.

  As the water-insoluble dispersant among the polymer dispersants, a polymer having both a hydrophobic part and a hydrophilic part can be used. For example, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, polyethylene glycol ( Examples thereof include a meth) acrylate- (meth) acrylic acid copolymer and a styrene-maleic acid copolymer.

The weight average molecular weight of the polymer dispersant in the present invention is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, still more preferably 5,000 to 80,000, and particularly preferably 10,000. 000-60,000.
In addition, a weight average molecular weight can be measured by a gel permeation chromatograph (GPC), for example.

  Further, the mixing mass ratio of the pigment and the dispersant (pigment: 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. Preferably it is 1: 0.125 to 1: 1.5.

In the present invention, when a dye is used as the colorant, a water-insoluble carrier can be used as a water-insoluble colored particle. As the dye, known dyes can be used without particular limitation. For example, the dyes described in JP-A-2001-115066, JP-A-2001-335714, JP-A-2002-249677 and the like can be used in the present invention. It can be used suitably. The carrier is not particularly limited as long as it is insoluble in water or hardly soluble in water, and inorganic materials, organic materials, and composite materials thereof can be used. Specifically, the carriers described in JP-A-2001-181549, JP-A-2007-169418, etc. can be suitably used in the present invention.
The carrier holding the dye (water-insoluble colored particles) can be used as an aqueous dispersion using a dispersant. As the dispersant, the above-described dispersants can be suitably used.

  The water-insoluble colored particles in the present invention preferably contain a pigment and a dispersant, more preferably contain an organic pigment and a polymer dispersant, from the viewpoint of light resistance and quality of the image, and the organic pigment and the carboxyl group. It is particularly preferable to include a polymer dispersant.

In the present invention, the average particle size of the water-insoluble colored particles is preferably 10 to 200 nm, more preferably 10 to 150 nm, and still more preferably 10 to 100 nm. When the average particle size is 200 nm or less, the color reproducibility is good, and in the case of the ink jet method, the droplet ejection characteristics are good. Moreover, light resistance becomes favorable because an average particle diameter is 10 nm or more.
The particle size distribution of the water-insoluble colored 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 colored particles having a monodisperse particle size distribution may be mixed and used.
The average particle size and particle size distribution of the water-insoluble colored particles can be measured using, for example, a light scattering method.

In the present invention, the water-insoluble colored particles may be used alone or in combination of two or more.
Further, the content of the water-insoluble colored particles is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, and more preferably 5 to 20% by mass with respect to the aqueous ink composition from the viewpoint of image density. % Is more preferable, and 5 to 15% by mass is particularly preferable.

-Water-soluble organic solvent-
The water-based ink composition of the present invention contains water as a solvent, but can further contain a water-soluble organic solvent. The water-soluble organic solvent can be contained, for example, as a drying inhibitor or a penetration accelerator.
The anti-drying agent can effectively prevent nozzle clogging that may occur due to drying of ink at the ink ejection port, particularly when the aqueous ink composition of the present invention is applied to an image recording method using an ink jet method. .

  The drying inhibitor is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples of the drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, Polyvalent alcohols typified by acetylene glycol derivatives, glycerin, trimethylolpropane, etc., polyvalent alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether Lower alkyl ethers of alcohols, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyls Sulfoxide, sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are preferred as the drying inhibitor. Moreover, said drying inhibitor may be used independently or may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  Further, the penetration accelerator is preferably used for the purpose of allowing the ink to penetrate better into the recording medium (printing paper). Specific examples of penetration enhancers include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. Etc. can be used suitably. These penetration enhancers exhibit a sufficient effect when contained in the ink composition in an amount of 5 to 30% by mass. Further, it is preferable that the penetration enhancer is used within a range of an addition amount that does not cause bleeding of prints and paper loss (print through).

In addition to the above, 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 (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, Cyclohexanol, benzyl alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, Thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) Tellurium, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine) Ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N -Methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone).
In addition, a water-soluble organic solvent may be used independently and may use 2 or more types together.

-Other additives-
Examples of other additives in the present invention include, for example, antifading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, antifungal agents, pH adjusters, surface tension adjusters, antifoaming agents, and viscosity adjusters. Well-known additives, such as an agent, a dispersing agent, a dispersion stabilizer, a rust preventive agent, and a chelating agent, are mentioned. These various additives may be added directly after the aqueous ink composition is prepared, or may be added when the aqueous ink composition is prepared.

  Examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, cinnamic acid compounds, triazine compounds, Research Disclosure No. 1; The compounds described in No. 24239, and compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds can also be used.

  As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like.

Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the water-based ink composition in an amount of 0.02 to 1.00% by mass.
As the pH adjuster, a neutralizer (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the aqueous ink composition, the pH adjuster is preferably added so that the aqueous ink composition has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. .

Examples of the surface tension adjusting agent include nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants, and the like.
The addition amount of the surface tension adjusting agent is preferably an addition amount for adjusting the surface tension of the water-based ink composition to 20 to 60 mN / m in order to achieve good droplet ejection by the ink jet method, and is adjusted to 20 to 45 mN / m. The addition amount to be adjusted is more preferable, and the addition amount adjusted to 25 to 40 mN / m is more preferable. On the other hand, when ink is applied by a method other than the inkjet method, a range of 20 to 60 mN / m is preferable, and a range of 30 to 50 mN / m is more preferable.
The surface tension (25 ° C.) of the water-based ink composition can be measured using, for example, a plate method.

Specific examples of surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensation in hydrocarbons Products, anionic surfactants such as polyoxyethylene alkyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxy Nonionic surfactants such as ethylene alkylamine, glycerin fatty acid ester and oxyethyleneoxypropylene block copolymer are preferred. In addition, SURFYNOLS (Air Products & Chemicals) and Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which are acetylene-based polyoxyethylene oxide surfactants, are also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred.
Furthermore, pages (37) to (38) of JP-A-59-157636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.
Further, fluorine (fluorinated alkyl type) surfactants, silicone type surfactants and the like described in JP-A Nos. 2003-322926, 2004-325707, and 2004-309806 are disclosed. By using, the abrasion resistance can be improved.
These surface tension modifiers can also be used as antifoaming agents, and fluorine compounds, silicone compounds, chelating agents represented by EDTA, and the like can also be used.

The viscosity of the aqueous ink composition of the present invention is preferably in the range of 1 to 30 mPa · s, and in the range of 1 to 20 mPa · s, from the viewpoint of droplet ejection stability and agglomeration speed when ink is applied by an inkjet method. Is more preferable, the range of 2 to 15 mPa · s is more preferable, and the range of 2 to 10 mPa · s is particularly preferable.
In addition, when ink is applied by a method other than the inkjet method, a range of 1 to 40 mPa · s is preferable, and a range of 5 to 20 mPa · s is more preferable.
The viscosity (20 ° C.) of the water-based ink composition can be measured using, for example, a Brookfield viscometer.

<Ink set>
The ink set of the present invention includes at least one of the above-described aqueous ink composition of the present invention and at least one treatment liquid capable of forming an aggregate by contacting with the aqueous ink composition. It is a thing.
The details of the water-based ink composition are as described above.

  In the present invention, the composite particles constituting the water-based ink composition contain a polymer having a carboxyl group and a polymer having a glass transition temperature of 120 ° C. or higher, whereby blocking resistance and abrasion resistance of an image formed are formed. And become better. Furthermore, the composite particles contain the first polymer having an acid value of 30 or more and 500 or less and the second polymer having an acid value of less than 30 so that the formation of aggregates by contact with the treatment liquid is more effective. Promoted.

-Treatment liquid-
The treatment liquid in the present invention is configured to be able to form an aggregate by contacting with the above-described aqueous ink composition. Specifically, the treatment liquid preferably includes at least an aggregating component capable of aggregating dispersed particles such as coloring material particles (pigments, etc.) in the ink composition to form an agglomerate. It can comprise using the component of. By using the treatment liquid together with the water-based ink composition, for example, ink jet recording can be speeded up, and an image with excellent density and resolution can be obtained (for example, reproducibility of fine lines and fine portions) even at high speed recording. .

(Aggregating component)
The treatment liquid can contain at least one aggregation component capable of forming an aggregate upon contact with the ink composition. When the water-based ink composition applied to the recording medium comes into contact with the aggregation component in the treatment liquid, aggregation of pigments and the like stably dispersed in the ink composition is promoted.

Examples of the treatment liquid include a liquid capable of generating an aggregate by changing the pH of the ink composition. At this time, the pH (25 ° C. ± 1 ° C.) of the treatment liquid is preferably 1 to 6, more preferably 1.2 to 5, more preferably 1.5 from the viewpoint of the aggregation rate of the ink composition. More preferably, it is ~ 4. In this case, the pH (25 ± 1 ° C.) of the ink composition used in the ejection process is preferably 7.5 to 9.5 (more preferably 8.0 to 9.0).
Among these, in the present invention, from the viewpoint of image density, resolution, and speedup of inkjet recording, the pH (25 ° C.) of the ink composition is 7.5 or more, and the pH (25 ° C.) of the treatment liquid is. The case of 1.5-3 is preferable.
The aggregating components can be used alone or in combination of two or more.

  The treatment liquid can be configured using at least one acidic compound as an aggregation component. As the acidic compound, a compound having a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxyl group, or a salt thereof (for example, a polyvalent metal salt) may be used. it can. Among these, from the viewpoint of the aggregation rate of the ink composition, a compound having a phosphate group or a carboxyl group is more preferable, and a compound having a carboxyl group is still more preferable.

  Compounds having a carboxyl group include polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric 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, or salts thereof (for example, polyvalent metal salts), etc. It is preferable to be selected from among These compounds may be used alone or in combination of two or more.

The treatment liquid in the present invention can be configured to further contain an aqueous solvent (for example, water) in addition to the acidic compound and the like.
As content in the processing liquid of an acidic compound, it is preferable that it is 5-95 mass% with respect to the total mass of a processing liquid from a viewpoint of the aggregation effect, and it is more preferable that it is 10-80 mass%. More preferably, it is 15-50 mass%, Most preferably, it is 18-30%.

  Examples of the treatment liquid include a treatment liquid containing at least one polyvalent metal salt as an aggregating component. Thereby, high-speed cohesion can be improved. Examples of the polyvalent metal salt include salts of alkaline earth metals belonging to the second group of the periodic table (for example, magnesium and calcium), transition metals belonging to the third group of the periodic table (for example, lanthanum salts), and thirteenth of the periodic table. Examples thereof include salts of cations from the genus (for example, aluminum) and salts of lanthanides (for example, neodymium). As the metal salt, carboxylate (formic acid, acetic acid, benzoate, etc.), nitrate, chloride, and thiocyanate are suitable. Among them, preferred are calcium salts or magnesium salts of carboxylic acids (formic acid, acetic acid, benzoates, etc.), calcium salts or magnesium salts of nitric acid, calcium chloride, magnesium chloride, and calcium salts or magnesium salts of thiocyanic acid.

  The content of the metal salt in the treatment liquid is preferably 1 to 10% by mass, more preferably 1.5 to 7% by mass, and still more preferably 2 to 6% by mass from the viewpoint of the aggregation effect. It is.

  Moreover, a process liquid can be comprised using at least 1 sort (s) of a cationic organic compound as an aggregation component. Examples of the cationic organic compound include poly (vinyl pyridine) salt, polyalkylaminoethyl acrylate, polyalkylaminoethyl methacrylate, poly (vinyl imidazole), polyethyleneimine, polybiguanide, polyguanide, and polyallylamine and derivatives thereof. Mention may be made of cationic polymers.

  The weight average molecular weight of the cationic polymer is preferably smaller in terms of the viscosity of the treatment liquid. When the treatment liquid is applied to the recording medium by an ink jet method, the range of 1,000 to 500,000 is preferable, the range of 1,500 to 200,000 is more preferable, and still more preferably 2,000 to 100,000. Range. When the weight average molecular weight is 1000 or more, it is advantageous from the viewpoint of the aggregation rate, and when it is 500,000 or less, it is advantageous from the viewpoint of ejection reliability. However, this is not the case when the treatment liquid is applied to the recording medium by a method other than inkjet.

Furthermore, as the cationic organic compound, for example, a primary, secondary, or tertiary amine salt type compound is preferable. Examples of the amine salt type compounds include compounds such as hydrochloride or acetate (for example, laurylamine, cocoamine, stearylamine, rosinamine), quaternary ammonium salt type compounds (for example, lauryltrimethylammonium chloride, cetyltrimethyl). Ammonium chloride, lauryldimethylbenzylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, etc.), pyridinium salt type compounds (eg, cetylpyridinium chloride, cetylpyridinium bromide, etc.), imidazoline type cationic compounds (eg, 2-heptadecenyl- Hydroxyethyl imidazoline etc.), ethylene oxide adducts of higher alkylamines (eg dihydroxyethyl stearylamine etc.), etc. And cationic compounds, for example, amino acid type amphoteric _{surfactants, R-NH-CH 2 CH} 2 -COOH type compounds (R represents an alkyl group), carboxylic acid salt type amphoteric surfactants (e.g., Stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, etc.), amphoteric surfactants exhibiting a cationic property in a desired pH region, such as amphoteric surfactants such as sulfate ester type, sulfonic acid type, and phosphate ester type.
Of these, divalent or higher cationic organic compounds are preferred.

  As content in the processing liquid of a cationic organic compound, 1-50 mass% is preferable from a viewpoint of the aggregation effect, More preferably, it is 2-30 mass%.

  Among the above, the aggregating component is preferably a divalent or higher carboxylic acid or a divalent or higher cationic organic compound from the viewpoint of aggregability and image scratch resistance.

(Other ingredients)
The treatment liquid in the present invention can generally contain a water-soluble organic solvent in addition to the aggregating component, and can be constituted using other various additives within a range not impairing the effects of the present invention. The details of the water-soluble organic solvent are the same as those in the ink composition described above.

  Examples of the other additives include a drying inhibitor (wetting agent), an antifading agent, an emulsion stabilizer, a penetration accelerator, an ultraviolet absorber, an antiseptic, an antifungal agent, a pH adjuster, a surface tension adjuster, Known additives such as antifoaming agents, viscosity modifiers, dispersants, dispersion stabilizers, rust preventives, chelating agents are listed, and specific examples of other additives included in the ink composition described above The listed ones are applicable.

The viscosity of the treatment liquid is preferably in the range of 1 to 30 mPa · s, more preferably in the range of 1 to 20 mPa · s, still more preferably in the range of 2 to 15 mPa · s, from the viewpoint of the aggregation rate of the ink composition. The range of 10 mPa · s is particularly preferable.
The viscosity is measured under a condition of 20 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).

The surface tension of the treatment liquid is preferably 20 to 60 mN / m, more preferably 20 to 45 mN / m, and more preferably 25 to 40 mN / m from the viewpoint of the aggregation rate of the ink composition. More preferably.
The surface tension is measured under conditions of 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

<Image forming method>
The image forming method of the present invention includes an ink application step of applying the aqueous ink composition to a recording medium, and a heat fixing step of forming an image by heat-fixing the recording medium applied with the aqueous ink composition. However, if necessary, other steps can be further provided.
Examples of other steps include a treatment liquid application step for applying a treatment liquid capable of forming an aggregate by contact with the aqueous ink composition to the recording medium, and a heat drying step.

  In the present invention, the water-based ink composition includes water-insoluble colored particles and composite particles, and the composite particles include at least one polymer having a carboxyl group and at least one polymer having a glass transition temperature of 120 ° C. or higher. , It is possible to form an image having both rubbing resistance and blocking resistance.

-Ink application process-
In the ink application step, the aqueous ink composition of the present invention described above is applied to a recording medium to form an image. In this step, a water-based ink composition can be selectively applied on the recording medium, and a desired visible image can be formed. Examples of the application method of the water-based ink composition include an ink jet method, a copying method, and a printing method. Among these, from the viewpoint of downsizing the recording apparatus and high-speed recording properties, a step of applying the aqueous ink composition by an ink jet method is preferable.
The details of each component in the water-based ink composition of the present invention and the details such as preferred embodiments are as described above.

  Specifically, the image recording using the ink-jet method is performed by supplying energy to obtain a desired recording medium, that is, plain paper, resin-coated paper, for example, JP-A-8-169172 and JP-A-8-27693. Publication No. 2-276670, No. 7-276789, No. 9-323475, No. JP-A-62-238783, JP-A-10-153898, No. 10-217473, No. 10- No. 235995, No. 10-337947, No. 10-217597, No. 10-337947, etc. Liquid composition for ink jet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. This can be done by discharging objects. As a preferable ink jet recording method for the present invention, the method described in paragraph Nos. 0093 to 0105 of JP-A No. 2003-306623 can be applied.

The inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. )) Any method may be used.
The ink jet method includes a method of ejecting many 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.

In addition, an ink jet head used in the ink jet method may be an on-demand method or a continuous method. In addition, as a discharge method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion method (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.) and a discharge type (for example, a spark jet type). However, any discharge method may be used.
There are no particular restrictions on the ink nozzles used when recording by the ink jet method, and they can be appropriately selected according to the purpose.

  As an inkjet head, a short serial head is used, and a shuttle system that performs recording while scanning the head in the width direction of the recording medium, and a line head in which recording elements are arranged corresponding to the entire area of one side of the recording medium There is a line system using. In the line system, an image can be recorded on the entire surface of the recording medium by scanning the recording medium 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 not necessary. Further, since complicated scanning control of the carriage movement and the recording medium is not required, and only the recording medium is moved, the recording speed can be increased as compared with the shuttle system. The ink jet recording method of the present invention can be applied to any of these, but generally, when applied to a line system that does not use a dummy jet, the effect of improving ejection accuracy and image scratch resistance is great.

  Furthermore, in the ink application process in the present invention, in the case of the line method, not only one type of ink composition is used but also two or more types of ink compositions are used, and an ink composition (nth color ( n ≧ 1), for example, the second color), and the ink composition (n + 1th color, for example, the third color) to be ejected subsequently is preferably set to 1 second or less for the ejection (droplet ejection) interval to perform recording. be able to. In the present invention, an ejection interval of 1 second or less in the line method prevents bleeding and color mixing between ink droplets, and has excellent scratch resistance under high-speed recording higher than that of the prior art, and occurrence of blocking. A suppressed image can be obtained. In addition, an image having excellent hue and drawability (reproducibility of fine lines and fine portions in the image) can be obtained.

  The amount of ink droplets ejected from the inkjet head is preferably 0.5 to 6 pl (picoliter), more preferably 1 to 5 pl, and still more preferably 2 to 4 pl from the viewpoint of obtaining a high-definition image. .

[Heat fixing process]
The ink jet recording method of the present invention has a heating and fixing step of heating and fixing an ink image formed by applying an ink composition by bringing a heating surface into contact with the ink composition after the ink applying step. By performing the heat fixing process, the image on the recording medium is fixed, and the resistance against image abrasion can be further improved. Moreover, it can suppress effectively that the image formed by using the water-based ink composition of this invention is transcribe | transferred to the said heating surface.

  The heating is preferably performed at a temperature equal to or higher than at least one glass transition temperature (Tg) of the polymer contained in the composite particles in the image. Since it is heated to Tg or more, it becomes a film and the image is strengthened. The heating temperature is preferably a temperature range of Tg + 10 ° C. or higher. Specifically, the heating temperature is preferably in the range of 40 to 150 ° C, more preferably in the range of 50 ° C to 100 ° C, and still more preferably in the range of 60 ° C to 90 ° C.

  The pressure at the time of pressurizing with heating is preferably in the range of 0.1 to 3.0 MPa, more preferably in the range of 0.1 to 1.0 MPa, and still more preferably 0.1 in terms of surface smoothing. It is the range of -0.5MPa.

  The method of heating is not particularly limited, but a non-contact drying method such as 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, etc. Preferably, it can be mentioned. The heating and pressing method is not particularly limited. For example, a method of pressing a hot plate against the image forming surface of a recording medium, a pair of heating and pressing rollers, a pair of heating and pressing belts, or a recording medium Using a heating and pressing device equipped with a heating and pressing belt arranged on the image recording surface side and a holding roller arranged on the opposite side, heat fixing by bringing them into contact, such as a method of passing a pair of rollers, etc. The method to perform is mentioned suitably.

  In the case of heating and pressing, a preferable nip time is 1 to 10 seconds, more preferably 2 to 1 second, and further preferably 4 to 100 milliseconds. Moreover, a preferable nip width is 0.1 mm to 100 mm, more preferably 0.5 mm to 50 mm, and still more preferably 1 to 10 mm.

  The heat and pressure roller may be a metal metal roller, or a metal core bar provided with a coating layer made of an elastic body and, if necessary, a surface layer (also referred to as a release layer). Good. The latter metal core can be formed of, for example, a cylindrical body made of iron, aluminum, SUS, or the like, and the surface of the metal core is preferably at least partially covered with a coating layer. The coating layer is particularly preferably formed of a silicone resin or fluororesin having releasability. Further, it is preferable that a heating element is built in one core metal of the heat and pressure roller, and heat treatment and pressure treatment are performed simultaneously or necessary by passing a recording medium between the rollers. Accordingly, the recording medium may be sandwiched and heated using two heating rollers. As the heating element, for example, a halogen lamp heater, a ceramic heater, a nichrome wire or the like is preferable.

  As a belt base material constituting the heat and pressure belt used in the heat and pressure apparatus, seamless nickel brass is preferable, and the thickness of the base material is preferably 10 to 100 μm. Further, as the material of the belt base material, aluminum, iron, polyethylene or the like can be used in addition to nickel. When silicone resin or fluororesin is provided, the thickness of the layer formed using these resins is preferably 1 to 50 μm, more preferably 10 to 30 μm.

  Further, in order to realize the pressure (nip pressure), for example, an elastic member such as a spring having tension so that a desired nip pressure can be obtained in consideration of the nip gap at both ends of a roller such as a heat and pressure roller. Select and install.

  The conveyance speed of the recording medium when using a heat and pressure roller or a heat and pressure belt is preferably in the range of 200 to 700 mm / second, more preferably 300 to 650 mm / second, and still more preferably 400 to 600 mm / second. It is.

[Processing liquid application process]
The image forming method of the present invention preferably includes a treatment liquid application step in addition to the ink application step and the heat fixing step from the viewpoint of high-speed image formation.
In the treatment liquid application step, a treatment liquid capable of forming an aggregate by contact with the ink composition is applied to the recording medium, and the treatment liquid is brought into contact with the ink composition to form an aggregate containing water-insoluble colored particles. This forms an image. In this case, dispersed particles such as composite particles and water-insoluble colored particles in the ink composition aggregate to fix the image on the recording medium. The details and preferred embodiments of each component in the treatment liquid are as described above.

  The treatment liquid can be applied by applying a known method such as a coating method, an ink jet method, or an immersion method. As a coating method, a known coating method using a bar coater, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater or the like can be used. The details of the inkjet method are as described above.

The treatment liquid application step may be provided either before or after the ink application step using the ink composition.
In the present invention, an embodiment in which the ink application step is provided after the treatment liquid is applied in the treatment liquid application step is preferable. That is, before applying the ink composition to the recording medium, a treatment liquid for aggregating water-insoluble colored particles in the ink composition is applied in advance, and then contacted with the treatment liquid applied on the recording medium. Thus, an embodiment in which an ink composition is applied to form an image is preferable. Thereby, inkjet recording can be speeded up, and an image with high density and resolution can be obtained even at high speed recording.

The application amount of the treatment liquid is not particularly limited as long as the ink composition can be aggregated. / M ² or more. Especially, the quantity from which the provision amount of an aggregation component will be 0.1-1.0 g / m < ² > is preferable, More preferably, it is 0.2-0.8 g / m < ² >. When the amount of the aggregating component is 0.1 g / m ² or more, the agglomeration reaction proceeds favorably, and when it is 1.0 g / m ² or less, the glossiness is not excessively increased.

  In the present invention, an ink application step is provided after the treatment liquid application step, and the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied on the recording medium and before the ink composition is applied. It is preferable to further provide a heat drying step. By heating and drying the treatment liquid in advance before the ink application step, ink colorability such as bleeding prevention is improved, and a visible image with good color density and hue can be recorded.

  Heating and drying can be performed by known heating means such as a heater, air blowing means using air blowing such as a dryer, or a combination of these. As the heating method, for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, or an infrared heater was used. The heating method etc. are mentioned, You may heat combining these two or more.

-Recording media-
The inkjet recording method of the present invention records an image on a recording medium.
The recording medium is not particularly limited, and general printing paper mainly composed of cellulose, such as so-called high-quality paper, coated paper, and art paper, used for general offset printing and the like can be used. General printing paper mainly composed of cellulose is relatively slow in ink absorption and drying in image recording by a general ink jet method using water-based ink, and color material movement is likely to occur after droplet ejection, and image quality is likely to deteriorate. However, according to the ink jet recording method of the present invention, it is possible to record a high-quality image excellent in color density and hue by suppressing the movement of the color material.

  As the recording medium, commercially available media can be used. For example, “OK Prince fine quality” manufactured by Oji Paper Co., Ltd., “Shiorai” manufactured by Nippon Paper Industries Co., Ltd., and Nippon Paper Industries ( Fine coated paper such as “New NPI fine quality” manufactured by Co., Ltd., “OK Everlight Coat” manufactured by Oji Paper Co., Ltd., and “Aurora S” manufactured by Nippon Paper Industries Co., Ltd., Oji Lightweight coated paper (A3) such as “OK Coat L” manufactured by Paper Industries Co., Ltd. and “Aurora L” manufactured by Nippon Paper Industries Co., Ltd. “OK Top Coat +” manufactured by Oji Paper Co., Ltd. and Nippon Paper Industries Co., Ltd. ) Coated paper (A2, B2) such as “Aurora Coat” manufactured by Oji Paper Co., Ltd. Art paper (A1) such as “OK Kanfuji +” manufactured by Oji Paper Co., Ltd. and “Tokuhishi Art” manufactured by Mitsubishi Paper Industries Co., Ltd. Is mentioned. It is also possible to use various photographic papers for ink jet recording.

Among these, from the viewpoint of obtaining a high-quality image having a large color material movement suppression effect and better color density and hue than before, the water absorption coefficient Ka is preferably 0.05 to 0.5. a recording medium mL ^/ m 2 ^{· ms 1/2,} more preferably recording medium 0.1~0.4mL ^/ m 2 ^{· ms 1/2,} more preferably 0.2-0.3 ml / It is a recording medium of m ² · ms ^1/2 .

  The water absorption coefficient Ka is synonymous with that described in JAPAN TAPPI paper pulp test method No. 51: 2000 (issued by Japan Paper Pulp Technology Association). It is calculated from the difference in the amount of water transferred between the contact time of 100 ms and the contact time of 900 ms using KM500Win (manufactured by Kumagai Riki Co., Ltd.).

  Among the recording media, so-called coated paper used for general offset printing is preferable. The coated paper is obtained by applying a coating material to the surface of high-quality paper, neutral paper, or the like that is mainly surface-treated with cellulose as a main component and is not surface-treated. The coated paper tends to cause quality problems such as image gloss and scratch resistance in image formation by ordinary aqueous inkjet, but in the inkjet recording method of the present invention, gloss unevenness is suppressed and gloss and resistance are reduced. An image having good rubbing properties can be obtained. In particular, it is preferable to use a coated paper having a base paper and a coat layer containing kaolin and / or calcium bicarbonate. More specifically, art paper, coated paper, lightweight coated paper, or finely coated paper is more preferable.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

[Preparation of carboxyl group-containing polymer]
-Synthesis Example 1
In a 5-liter three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 400.0 g of isopropanol was charged and heated to 75 ° C. under a nitrogen stream. While maintaining the temperature in the reaction vessel at 75 ° C., 192.0 g of styrene, 108.0 g of n-butyl acrylate, 100.0 g of acrylic acid, 80.0 g of isopropanol, and “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) 1 A mixed solution consisting of .6 g was added dropwise at a constant speed so that the addition was completed in 2 hours. After completion of the dropwise addition, a solution consisting of 1.6 g of “V-601” and 80.0 g of isopropanol was added, stirred at 75 ° C. for 2 hours, and then a solution consisting of 0.8 g of “V-601” and 40.0 g of isopropanol was added. After stirring at 75 ° C. for 2 hours, the temperature was raised to 85 ° C., and stirring was further continued for 2 hours. The weight average molecular weight (Mw) of the obtained copolymer was 48000 (calculated in terms of polystyrene by gel permeation chromatography (GPC), the columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)), The acid value was 195 (mgKOH / g).
Next, after adding 105.3 g of triethylamine and stirring for 10 minutes, 1800 g of distilled water was added to disperse in water. Thereafter, a total of 680 g of isopropanol and distilled water was distilled off under reduced pressure at a temperature in the reaction vessel of 70 ° C., and water of a carboxyl group-containing polymer (aqueous acrylic copolymer) (C-01) having a solid content concentration of 19.1% was obtained. A dispersion was obtained. Table 1 shows the physical properties of the obtained carboxyl group-containing polymer (C-01).

-Synthesis Example 2-
Into a 1 liter three-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 65 g of Joncryl 67 (styrene acrylic resin manufactured by BASF) was weighed, 65 g of methyl ethyl ketone, 65 g of isopropanol, 1 mol / L. 190.58 g of NaOH was added, and the temperature in the reaction vessel was raised to 87 ° C. Next, 93 g of distilled water was added dropwise at a rate of 6 ml / min to disperse in water. Thereafter, the temperature in the reaction vessel was kept at 87 ° C. for 1 hour, 91 ° C. for 1 hour, and 95 ° C. for 30 minutes under atmospheric pressure, and then the pressure in the reaction vessel was reduced, and isopropanol, methyl ethyl ketone, and distilled water totaled 195. 5 g was distilled off to obtain an aqueous dispersion of a carboxyl group-containing copolymer (Jcr67) having a solid content concentration of 22.3%. Table 1 shows the physical properties of the obtained carboxyl group-containing copolymer (Jcr67).

-Synthesis Example 3-
In the synthesis of the aqueous dispersion (Jcr67) of Synthesis Example 2, Compound Example (Jcr67) was used except that Jonkrill 611 and Jonkrill 690 (both styrene acrylic resins manufactured by BASF) were used instead of Jonkrill 67. In the same manner as in the above synthesis, aqueous dispersions of carboxyl group-containing copolymers (Jcr611) and (Jcr690) were obtained. Table 1 shows the physical properties of the obtained carboxyl group-containing copolymers (Jcr611) and (Jcr690).

-Synthesis Example 4-
In the synthesis of Synthesis Example 1 (C-01), instead of 192.0 g of styrene, 108.0 g of n-butyl acrylate, and 100 g of acrylic acid, structures shown in the following compound examples (C-03) and (C-04) The amount of the monomer and the amount of the monomer were changed so that the ratio by weight was changed, and the addition amount of triethylamine was changed so that the degree of neutralization was the same with that of the compound example (C-01). In the same manner as in the synthesis, aqueous dispersions of carboxyl group-containing copolymers (C-03) and (C-04) were obtained. Table 1 shows the physical properties of the obtained carboxyl group-containing polymers (C-03) and (C-04). The weight average molecular weights (Mw) of the carboxyl group-containing copolymers (C-03) and (C-04) were 38000 and 44000, respectively. In addition, the number of each structural unit of the following compound example represents mass ratio.

[Preparation of composite particles]
-Synthesis Example 5-
A 1 liter three-necked flask equipped with a stirrer and a reflux condenser is charged with 62.8 g of C-1 obtained in Synthesis Example 1, 12.4 g of distilled water and 0.5 g of triethylamine, and heated to 70 ° C. under a nitrogen stream. Stir. Thereto was added an aqueous solution composed of 0.4 g of 2,2′-azobis (2-amidinopropane) dihydrochloride and 80 g of distilled water, stirred for 30 minutes, and then a monomer solution composed of 60 g of isobornyl methacrylate was added for 2 hours. Was dropped at a constant speed so that the dropping was completed. After completion of the dropwise addition, an aqueous solution consisting of 0.2 g of 2,2′-azobis (2-amidinopropane) dihydrochloride and 20 g of distilled water was added, stirred at 70 ° C. for 4 hours, then heated to 85 ° C. and further heated Stirring was continued for 2 hours. The reaction solution was cooled and filtered to obtain 236 g of an aqueous dispersion of composite particles (PL-01) containing a carboxyl group-containing polymer (C-01) and a water-insoluble polymer (B-01). The solid content concentration of the obtained aqueous dispersion was 30.5%, the volume average particle size of the composite particles was 56 nm (particle size was measured with Microtrac UPA EX-150 (manufactured by Nikkiso Co., Ltd.)), weight average molecular weight (Mw) was 183,000. Table 1 shows the physical properties of the obtained water-insoluble polymer (B-01) and composite particles (PL-01).

-Synthesis Example 6
Instead of the carboxyl group-containing copolymer (C-01), styrene 192.0 g, n-butyl acrylate 108.0 g, and acrylic acid 100 g in the synthesis of (B-01) in Synthesis Example 5, the carboxyls shown in Table 1 were used. Using the group-containing polymer, the monomer type and the charged amount were changed so that the structures and weight ratios shown in the following compound examples (B-02), (B-04) and (B-06) were obtained, and accordingly Composite particles containing a carboxyl group-containing polymer and a water-insoluble polymer in the same manner as in the synthesis of Compound Example (B-01) except that the addition amount of triethylamine was changed so that the degree of neutralization was the same ( An aqueous dispersion of PL-02) to (PL-11) was obtained. Table 1 shows the physical properties of the obtained water-insoluble polymer and composite particles.

<Comparative Example 1>
A carboxyl group-containing polymer (CH-01) was prepared according to Synthesis Example 1 of paragraph No. [0055] of JP-A-2006-249282, and then a water-insoluble polymer was prepared according to Example 1 of paragraph No. [0061] of the publication. Composite particles (PLH-01) containing (BH-01) were obtained. Table 1 shows the physical properties of CH-01, BH-01, and PLH-01.

<Comparative example 2>
In a 1-liter three-necked flask equipped with a stirrer and a reflux condenser, 8.1 g of Pionein A-43s (manufactured by Takemoto Yushi Co., Ltd.) and 236.0 g of distilled water were added and heated and stirred at 70 ° C. under a nitrogen stream. After adding 10 g of isobornyl methacrylate, 1.0 g of ammonium persulfate and 40 g of distilled water and stirring for 30 minutes, a monomer solution consisting of 190 g of isobornyl methacrylate was added dropwise at a constant speed so that the addition was completed in 2 hours. After completion of the dropwise addition, an aqueous solution consisting of 0.5 g of ammonium persulfate and 20 g of distilled water was added and stirred at 70 ° C. for 4 hours, then heated to 85 ° C. and stirred for another 2 hours. The reaction solution was cooled and filtered to obtain 505 g of an emulsion polymerization latex PLH-02 of a water-insoluble polymer (B-01). The physical properties of the obtained PLH-02 are shown in Table 1.

<Comparative Example 3>
Instead of the carboxyl group-containing copolymer (C-01), styrene 192.0 g, n-butyl acrylate 108.0 g, and acrylic acid 100 g in the synthesis of (B-01) in Synthesis Example 5, the carboxyls shown in Table 1 were used. Using the group-containing polymer, the monomer type and the charge amount were changed so that the structure and weight ratio shown in the following compound example (BH-03) were obtained, and the neutralization degree was adjusted to be the same accordingly. An aqueous dispersion of composite particles (PLH-03) containing a carboxyl group-containing polymer and a water-insoluble polymer was obtained in the same manner as in the synthesis of Compound Example (B-01) except that the amount added was changed. Table 1 shows the physical properties of the obtained water-insoluble polymer and composite particles.

Abbreviations in Table 1 are as follows.
Jcr67: John Krill 67 (styrene acrylic resin manufactured by BASF)
Jcr611: Joncrill 611 (styrene acrylic resin manufactured by BASF)
Jcr690: Jongkrill 690 (styrene acrylic resin manufactured by BASF)

The particle diameters in Table 1 are volume average particle diameters measured using a dynamic light scattering method within 24 hours after preparing an aqueous dispersion. Microtrac UPA EX-150 (manufactured by Nikkiso Co., Ltd.) ) Using a conventional method. The acid value is a value determined by the method described in JIS standard (JIS K0070: 1992) for the carboxyl group-containing polymer, and the acid value of the composite particle (method described in the JIS standard) for the water-insoluble polymer. And the acid value difference between the carboxyl group-containing polymer. The glass transition temperature (Tg) is a value obtained by measuring the polymer solid content with a differential scanning calorimeter (DSC) EXSTAR 6220 manufactured by SII Nanotechnology. Measurement conditions were as follows: a sample amount of 5 mg was sealed in an aluminum pan, and the peak top value of DDSC in the measurement data at the second temperature increase in the following temperature profile was set as the Tg of each polymer in a nitrogen atmosphere.
-Temperature profile-
30 ° C to -50 ° C (cooled at 50 ° C / min)
−50 ° C. → 230 ° C. (temperature rise at 20 ° C./min)
230 ° C → -50 ° C (cooled at 50 ° C / min)
−50 ° C. → 230 ° C. (temperature rise at 20 ° C./min)

The aqueous dispersion of composite particles obtained above was evaluated for stability as follows.
Each 10 mL of the aqueous dispersion was sealed in a 15 mL glass bottle and allowed to stand at 60 ° C. for 14 days, and then the average particle size was measured. The rate of change of the average particle size before and after being left [(average particle size after being left-average particle size before being left) / average particle size before being left] was calculated and evaluated according to the following evaluation criteria. The results are shown in Table 1.
The measurement before standing was performed within 24 hours at room temperature after preparing the aqueous dispersion of composite particles.

~Evaluation criteria~
A: The change rate of the average particle diameter was less than 10%.
Δ: The change rate of the average particle diameter was 10% or more and less than 50%.
X: The change rate of the average particle diameter was 50% or more.

<Example 3>
[Preparation of water-based ink composition]
<< Preparation of Cyan Ink C-1 >>
(Preparation of cyan dispersion as water-insoluble colored particles)
In a reaction vessel, 6 parts of styrene, 11 parts of stearyl methacrylate, 4 parts of styrene macromer AS-6 (manufactured by Toagosei Co., Ltd.), 5 parts of Blenmer PP-500 (manufactured by NOF Corporation), 5 parts of methacrylic acid, 2-mercaptoethanol A mixed solution of 0.05 part and 24 parts of methyl ethyl ketone was prepared.
On the other hand, 14 parts of styrene, 24 parts of stearyl methacrylate, 9 parts of styrene macromer AS-6 (manufactured by Toa Gosei), 9 parts of Blenmer PP-500 (manufactured by NOF Corporation), 10 parts of methacrylic acid, 2-mercaptoethanol A mixed solution consisting of 13 parts, 56 parts of methyl ethyl ketone and 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was prepared and placed in a dropping funnel.

  Next, under a nitrogen atmosphere, the mixed solution in the reaction vessel was heated to 75 ° C. while stirring, and the mixed solution in the dropping funnel was gradually dropped over 1 hour. After 2 hours from the end of dropping, a solution prepared by dissolving 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 12 parts of methyl ethyl ketone was added dropwise over 3 hours, and further at 75 ° C. for 2 hours, Aging was performed at 80 ° C. for 2 hours to obtain a polymer dispersant solution.

  A part of the obtained polymer dispersant solution was isolated by removing the solvent, the obtained solid content was diluted to 0.1% with tetrahydrofuran, and the weight average molecular weight was measured by GPC. As a result, the isolated solid had a polystyrene equivalent weight average molecular weight of 25,000.

  Moreover, 5.0 g of the obtained polymer dispersant solution in terms of solid content, 10.0 g of cyan pigment pigment blue 15: 3 (manufactured by Dainichi Seika), 40.0 g of methyl ethyl ketone, 8.0 g of 1 mol / L sodium hydroxide, Ion-exchanged water 82.0 g and 0.1 mm zirconia beads 300 g were supplied to the vessel and dispersed with a ready mill disperser (manufactured by Imex) at 1000 rpm for 6 hours. The obtained dispersion was concentrated under reduced pressure using an evaporator until methyl ethyl ketone could be sufficiently distilled off, and concentrated until the pigment concentration became 10%, and a cyan dispersion C1 as water-insoluble colored particles was prepared. The resulting cyan dispersion C1 had a volume average particle size of 77 nm.

  Then, using cyan dispersion C1 as water-insoluble colored particles and PL-01 as an aqueous dispersion of composite particles, each component was mixed so as to have the following ink composition, and then coarse particles were removed with a 5 μm filter. Cyan ink C-1 was prepared as a water-based ink composition.

<Ink composition of cyan ink C-1>
・ Cyan pigment (Pigment Blue 15: 3, manufactured by Dainichi Seika) 4%
・ The above polymer dispersant (in terms of solid content) 2%
・ PL-01 (solid content conversion) 8%
・ Diethylene glycol monoethyl ether: 10%
(Water-soluble solvent, manufactured by Wako Pure Chemical Industries)
・ Sanix GP250: 5%
(Water-soluble solvent, manufactured by Sanyo Chemical Industries, Ltd.)
・ Orphine E1010 (Nisshin Chemical)… 1%
・ Ion-exchanged water: added so that the total is 100%

<< Preparation of Cyan Inks C-2 to C-10, CH-1 to CH-4 >>
In the same manner as in the cyan ink C-1, except that the aqueous dispersion of composite particles shown in Table 2 below was used instead of the aqueous dispersion PL-01 of the composite particles in the cyan ink C-1, Cyan inks C-2 to 10 and CH-1 to 3 were prepared as ink compositions, respectively. For CH-3, a cyan ink was prepared without using an aqueous dispersion of composite particles.
Table 2 shows the physical property values of the cyan ink obtained above immediately after preparation (within 24 hours).

In Table 2, the term of viscosity is described according to the following evaluation criteria.
~Evaluation criteria~
○: Less than 6.5 mPa · s Δ ... 6.5 mPa · s or more and less than 10 mPa · s ×… 10 mPa · s or more

[Preparation of treatment liquid (1)]
Each component was mixed so that it might become the following composition, and the process liquid (1) was prepared. The physical properties of the treatment liquid (1) were a viscosity of 2.6 mPa · s, a surface tension of 37.3 mN / m, and a pH of 1.6 (25 ° C.).
-Composition of treatment liquid (1)-
Malonic acid: 15.0%
(Divalent carboxylic acid, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Diethylene glycol monomethyl ether: 20.0%
(Wako Pure Chemical Industries, Ltd.)
-N-oleoyl-N-methyl taurine sodium: 1.0%
(Surfactant)
・ Ion exchange water: 64.0%

[Evaluation]
Each cyan ink prepared as described above (hereinafter sometimes simply referred to as “ink”) was subjected to an ink stability test over time, a droplet ejection test, and an image fixability test. The ink aging stability test is an evaluation of the stability of the particle size and viscosity before ink is ejected, that is, when the ink is stored in the ink storage tank (or cartridge). When discharging from the droplet ejection nozzle of the ink jet apparatus, problems such as clogging of the droplet ejection nozzle occur. Further, the droplet ejection test is an evaluation relating to the ejection directionality. When the ink viscosity is high, the nozzles are clogged, resulting in a directionality defect.

(Ink stability test over time)
10 mL of each ink was sealed in a 15 mL glass bottle, and the average particle size and viscosity were measured after (1) leaving at 60 ° C. for 14 days and (2) leaving at 40 ° C. for 3 months. Change rate of average particle size before and after standing [(average particle size after leaving-average particle size before leaving) / average particle size before leaving] and change rate of viscosity [(viscosity after leaving-before leaving) Viscosity) / viscosity before standing] was calculated. The evaluation criteria are as follows.
The measurement before standing was performed within 24 hours at room temperature after the ink composition was prepared.
~Evaluation criteria~
A: The change rate of the average particle diameter or the change rate of the viscosity was less than 5%.
Δ: The change rate of the average particle diameter or the change rate of the viscosity was 5% or more and less than 10%.
X: The change rate of the average particle diameter or the change rate of the viscosity was 10% or more.
And evaluation of x was judged to be unusable. The results are shown in Table 3.

(Drip droplet stability test)
The droplet ejection stability test was conducted as follows. Using a GELJET G717 printer head manufactured by Ricoh, droplets were ejected onto Tokuhishi Double-sided Art N (Mitsubishi Paper Co., Ltd.) so that the resolution was 1200 × 600 dpi and the ink ejection amount was 12 pL. The droplet ejection stability was evaluated by observing the state after 5 hours of continuous hitting. Table 3 shows the droplet ejection stability test results. The evaluation criteria for the droplet ejection stability test in Table 3 are as follows. In addition, it was judged that evaluation of x was unusable.
~Evaluation criteria~
○: No discharge failure and no direction failure.
○ △: There was no ejection failure and a little direction failure occurred.
Δ: Almost no ejection failure and some direction failure occurred.
×: There were many ejection failures.

<Image formation and evaluation>
A GELJET GX5000 printer head (manufactured by Ricoh) was prepared, and the storage tank connected thereto was refilled with the cyan ink obtained above. Tokishi Art Double Sided N (Mitsubishi Paper Co., Ltd.) as a recording medium is fixed on a stage that can move in a predetermined linear direction at 500 mm / second, and the stage temperature is kept at 30 ° C. The treated liquid (1) was applied with a bar coater to a thickness of about 1.2 μm, and was dried at 50 ° C. for 2 seconds immediately after the application.
Thereafter, the GELJET GX5000 printer head is fixedly arranged so that the direction of the line head in which the nozzles are arranged (main scanning direction) is inclined by 75.7 degrees with respect to the direction orthogonal to the moving direction of the stage (sub-scanning direction). Then, while the recording medium was moved at a constant speed in the sub-scanning direction, the ink was ejected by a line method under an ink droplet amount of 2.4 pL, an ejection frequency of 24 kHz, and a resolution of 1200 dpi × 1200 dpi, and a solid cyan image was printed.
Immediately after printing, the film was dried at 60 ° C. for 3 seconds, passed between a pair of fixing rollers heated to 60 ° C., and subjected to heat fixing treatment with a nip pressure of 0.25 MPa and a nip width of 4 mm, thereby obtaining an evaluation sample. .

(Evaluation of blocking resistance)
Two pieces of the obtained evaluation sample are cut into a size of 3.5 cm × 4 cm, and the evaluation sample is placed on a 10 cm × 10 cm acrylic plate (thickness 7 mm) so that the marking screens face each other. A 10 cm × 10 cm acrylic plate (thickness 7 mm) is placed on top of 10 unprinted special Rhibishi art double-sided N (manufactured by Mitsubishi Paper Industries Co., Ltd.). It was allowed to stand for 12 hours under an environmental condition of% RH.
After standing, a weight of 1 kg was placed on the uppermost acrylic plate and left for another 24 hours (corresponding to a load of 700 kg / m ² ).
Furthermore, after storing for 2 hours under an environmental condition of 25 ° C. and 50% RH, the unprinted special rhizo art (unprinted paper) superimposed on the evaluation sample was peeled off. The ease of peeling at this time and the adhesion after peeling were visually observed and evaluated according to the following evaluation criteria.
~Evaluation criteria~
○: It did not adhere to the seal screen.
X: Adhesion occurred on the stamp screen, and adhesion of paper could be confirmed visually.

(Rubbing resistance evaluation)
Oji Paper Co., Ltd. OK top coat + (recording medium) was fixed on a stage operating at 500 mm / second, and the treatment liquid (1) was applied to a thickness of about 1.2 μm with a wire bar coater. Immediately after that, it was dried at 50 ° C. for 2 seconds. After that, solid printing of cyan ink with a resolution of 1200 x 1200 dpi, droplet ejection amount of 2.4 pL, and line system with a GELJET GX5000 printer head manufactured by Ricoh and fixed obliquely (75.5 degrees) with respect to the scanning direction did. Immediately after printing, the film was dried at 60 ° C. for 3 seconds, passed between a pair of fixing rollers heated to 60 ° C., and subjected to heat fixing treatment with a nip pressure of 0.25 MPa and a nip width of 4 mm, to obtain a print sample.
About the above printing sample, Oji Paper Co., Ltd. OK Top Coat + was wrapped around a paperweight (weight 470 g, size 15 mm × 30 mm × 120 mm, equivalent to load 260 kg / m ² ). The image was visually observed for peeling and evaluated according to the following evaluation criteria.
In addition, when the image peeling was not confirmed by 3 reciprocations, it rubbed to 6 reciprocations.
~Evaluation criteria~
A: Image peeling was not visible even after 6 reciprocations.
○: Image peeling was not visible on the surface of the print sample after 3 reciprocating rubs, but could be confirmed with 6 reciprocating rubs.
X: Image peeling was visually recognized on the surface of the print sample after three reciprocations.

As can be seen from Table 3, the ink of the present invention is excellent in stability over time. On the other hand, cyan inks CH-1 and CH-2, which are inks having low dispersion stability and high ink viscosity, tend to increase in viscosity and particle size over time. In addition, since all of the inks of the present invention have low ink viscosity, ejection failure does not occur and excellent droplet ejection stability, whereas cyan inks CH-1 and CH- having high ink viscosity and low dispersion stability. The droplet ejection stability of 2 was low. In addition, the cyan inks C-1 to C to 11 containing the composite particle aqueous dispersion of the present invention contained in the ink composition had good fixability, but had a low Tg and two types of composite particles. The cyan ink CH-1 having a small difference in Tg is inferior in both blocking properties and abrasion resistance. Cyan ink CH-2 containing an aqueous dispersion of particles that are not complexed with a carboxyl group-containing polymer is excellent in blocking properties because of high Tg, but is inferior in abrasion resistance. Note that the fixability of cyan ink CH-3, which does not contain an aqueous dispersion in the ink composition, is greatly inferior.
As described above, by using an ink composition containing an aqueous dispersion of composite particles according to the present invention, an ink having high unprecedented ink stability, stable ejection properties, good blocking resistance and abrasion resistance It can be seen that the composition could be provided.

Claims (11)

Water-insoluble colored particles containing a colorant;
A composite particle comprising two or more polymers, at least one polymer having a carboxyl group , and at least one polymer having a structural unit having a cycloaliphatic group and having a glass transition temperature of 120 ° C. or higher;
A water-based ink composition containing The water-based ink composition according to claim 1, wherein the structural unit having a cyclic aliphatic group is a structural unit derived from a (meth) acrylic monomer having a cyclic aliphatic group. The cycloaliphatic group includes a cyclopentyl group, a cyclohexyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a decahydronaphthalenyl group, a perhydrofluorene group. Nyl group, tricyclo [5.2.1.0 ^2,6 The aqueous ink composition according to claim 1 or 2, which is at least one selected from the group consisting of a decanyl group and a bicyclo [4.3.0] nonanyl group. The water-based ink composition according to any one of claims 1 to 3, wherein the composite particles have a property of aggregating due to a change in pH environment. The water-based ink composition according to any one of claims 1 to 4, wherein the composite particles include two kinds of polymers having an absolute value of a difference in glass transition temperature of 40 ° C or higher. The aqueous ink composition according to claim 1 , wherein the composite particles are obtained by emulsion polymerization of monomers in the presence of an aqueous solution or emulsion of a carboxyl group-containing polymer. The aqueous ink composition according to claim 6 , wherein the aqueous solution or emulsion of the carboxyl group-containing polymer further contains a basic compound. The aqueous ink composition according to any one of claims 1 to 7 , wherein the composite particles include a first polymer having an acid value of 30 or more and 500 or less and a second polymer having an acid value of less than 30. object. An ink set comprising: the aqueous ink composition according to any one of claims 1 to 8 ; and a treatment liquid capable of forming an aggregate by contact with the aqueous ink composition. Applying the water-based ink composition according to any one of claims 1 to 8 to a recording medium;
Forming an image by heating and fixing the recording medium to which the water-based ink composition has been applied. The image according to claim 10 , further comprising a step of applying a treatment liquid capable of forming an aggregate by contact with the aqueous ink composition according to claim 1 to a recording medium. Forming method.