JP6868216B2 - Ink, ink container, inkjet recording method, and inkjet recording device - Google Patents

Description

The present invention relates to ink, an ink container, an inkjet recording method, and an inkjet recording device.

The ink used in the inkjet recording method generally contains a wetting agent composed of a high boiling point organic solvent in order to maintain moisturizing properties, and beading and bleeding may occur depending on the blending amount and the type of recording medium. May occur.

As a method of suppressing the beading, there is a method of improving the permeability of the ink to the recording medium. For example, a method of suppressing beating by using an ink containing a highly permeable organic solvent has been proposed (see, for example, Patent Document 1).
Further, a method has been proposed in which the permeability of the ink is adjusted by adjusting the viscosity according to the content of the organic solvent to suppress beading (see, for example, Patent Document 2).
Further, a method of suppressing beading by adjusting the penetration rate of ink into a recording medium evaluated by the Bristow method has been proposed (see, for example, Patent Document 3).

On the other hand, there is a method of preventing the ink droplets from coalescing with each other and suppressing the beating by gelling the ink droplets on the recording medium in the process of evaporation, penetration, and diffusion after the ink droplets land. For example, by containing glycol ethers or 1,2-alkanediols having 4 or more carbon atoms, the formation of a pseudo-crosslinked state of the water-soluble resin and the water-dispersed polymer particles during ink drying is promoted, and beading is performed. A method of suppressing has been proposed (see, for example, Patent Document 4).
Further, a method of suppressing beading by containing an aqueous gelling agent containing a carboxylic acid having a molecular weight of 1,000 or less or a salt thereof has been proposed (see, for example, Patent Document 5).

An object of the present invention is to provide an ink capable of suppressing beading even for a low-permeability recording medium without causing a decrease in image density and deterioration of ink ejection property.

The ink of the present invention as a means for solving the above-mentioned problems is
Ink containing resin
Storage elastic modulus G by dynamic viscoelasticity measurement method at 25 ° C. when the resin is contained in an amount of 4.0% by mass or more and 10.0% by mass or less and concentrated until the solid content of the ink reaches 20% by mass. The ratio (G'/ G ") of'to loss elastic modulus G'is 1.0 or more and 2.0 or less.
The absorption coefficient Kα of the ink according to the Bristow method for a low-permeability recording medium at 25 ° C. is 0.06 mL · m- ² · ms- ^{1 / 2} or more and 0.12 mL · m- ² · ms- ^{1 / 2} or less.

According to the present invention, it is possible to provide an ink capable of suppressing beading even for a low-permeability recording medium without causing a decrease in image density and a deterioration in ink ejection property.

FIG. 1 is a perspective explanatory view showing an example of an inkjet recording device. FIG. 2 is a perspective explanatory view showing an example of a main tank in an inkjet recording device. FIG. 3 is a graph showing a graph for obtaining the absorption coefficient of ink by the Bristow method with respect to a recording medium. FIG. 4 is a graph showing the measurement results of the storage elastic modulus G'and the loss elastic modulus G'of the ink obtained in Example 1.

The ink of the present invention is an ink containing a resin, which is obtained by containing the resin in an amount of 4.0% by mass or more and 10.0% by mass or less and concentrating the ink until the solid content of the ink reaches 20% by mass. The ratio (G'/ G ") of the storage elastic modulus G'and the loss elastic modulus G" by the dynamic viscoelasticity measurement method at 25 ° C. is 1.0 or more and 2.0 or less, and 25 of the ink by the Bristow method. The absorption coefficient Kα for a low-permeability recording medium at ° C. is 0.06 mL · m- ² · ms- ^{1 / 2} or more and 0.12 mL · m- ² · ms- ^{1 / 2} or less.

The conventional method for improving the permeability of ink to a recording medium has a limit as a beating countermeasure, and there is a possibility that the image density may be lowered by increasing the permeability too much. In addition, the method of gelling ink droplets on a recording medium has a limited effect of suppressing beading, especially for a low-permeability recording medium having low permeability, and ink ejection is caused by excessively promoting gelation. There is concern about sexual deterioration.
Here, the beading means that the ink droplets cannot be completely absorbed inside the recording medium between the time when the ink droplets land on the surface of the recording medium and the time when the next ink droplets land on the surface of the recording medium during inkjet recording. This is a phenomenon in which the coloring material in the ink is partially agglomerated and uneven density is formed by mixing with the ink droplets that remain in the liquid state and land afterwards.

The ink contains a resin, and the ratio (G) of the storage elastic modulus G'and the loss elastic modulus G'by the dynamic viscoelasticity measurement method at 25 ° C. when the solid content is concentrated to 20% by mass. '/ G') is 1.0 or more and 2.0 or less, preferably 1.5 or more and 2.0 or less. At this time, it is important that the resin content is 4.0% by mass or more and 10.0% by mass or less, and 5.0% by mass or more and 10.0% by mass or less is preferable. As shown in FIG. 4, the ink containing the resin has low viscoelasticity because collision / coalescence of solids in the ink has not started in a state where the solid content concentration is low, but evaporation / penetration / In the process of concentrating the ink on the recording medium due to diffusion, collisions and coalescence of resins occur in the ink droplets on the recording medium, and the viscoelasticity value begins to increase sharply when the solid content is around 20% by mass. .. The ratio of the storage elastic modulus G'and the loss elastic modulus G'at this time differs depending on the ink, but contains the resin in an amount of 4.0% by mass or more and 10.0% by mass or less, and the ratio (G'/ G'). Is 1.0 or more, that is, by using an ink having a storage elastic modulus G'equal to or higher than the loss elastic modulus G', the ink droplets gel and it becomes difficult for the ink droplets to easily coalesce with each other. The beading can be suppressed. The behavior of the viscoelastic change during concentration can be controlled by the plasticizing force of the organic solvent used with respect to the resin. In addition, when the resin is contained in an amount of more than 10.0% by mass, or When the ratio (G'/ G ") exceeds 2.0, the ink solidifies as it evaporates and the ejection stability decreases, but the resin is contained in an amount of 10.0% by mass or less and the ratio (G'/ G") is increased. By setting G'/ G ") to 2.0 or less, the discharge stability is not impaired.

The Hansen solubility parameter (hSP value) is one index of the affinity between materials. Among these, the Hansen solubility parameter (hSP value) δh, which is related to the hydrogen bonding force with the strongest intermolecular force, can be treated as an index of plasticization force, and those with similar Hansen solubility parameters (hSP values) can be treated. High affinity. In order to make the ratio (G'/ G ") of the storage elastic modulus G'and the loss elastic modulus G'" 1.0 or more and 2.0 or less, it is necessary to increase the plasticizing power of the organic solvent with respect to the resin. .. The resin has a relatively small δh as compared with an organic solvent or the like. Therefore, by selecting an organic solvent in which δh does not become too high as the organic solvent, the ratio (G'/ G ") of the storage elastic modulus G'and the loss elastic modulus G'is set to 1.0 or more. It can be 0 or less.

Further, the storage elastic modulus G'at 25 ° C. when the ink is concentrated to a solid content of 20% by mass is preferably 10 Pa or more and 20 Pa or less, and more preferably 15 Pa or more and 20 Pa or less. As the viscoelastic property when the solid content is 20% by mass, not only the ratio of the storage elastic modulus G'and the loss elastic modulus G'but also the magnitude of the numerical value of the storage elastic modulus G'is important. When the storage elastic modulus G'is 10 Pa or more, a gel having a lower fluidity can be produced at an early stage, so that the effect of preventing the coalescence of ink droplets is improved, which leads to further suppression of beading. Can be controlled by the plasticizing force of the organic solvent used with respect to the resin, as in the case of the above ratio (G'/ G "). Further, if the storage elastic modulus G'exceeds 20 Pa, the ink tends to solidify with evaporation and the ejection stability may decrease, but if it is 20 Pa or less, the ejection stability is not impaired.

Here, the storage elastic modulus G'and the loss elastic modulus G'when the ink is concentrated to a solid content of 20% by mass can be measured under the following measurement conditions.
〔Measurement condition〕
・ Equipment: AR2000 (manufactured by TA Instruments Co., Ltd.)
・ Geometry: 40mm 1 ° cone plate ・ Geometry gap: 300μm
・ Measurement frequency: 1Hz
・ Measurement temperature: 25 ° C
・ Analysis software: TA DATA ANALYSIS
(Made by TA Instruments Co., Ltd.)

The concentration of the ink can be carried out on a hot plate at 80 ° C. with the ink placed in a beaker and stirred. The solid content of the ink can be calculated from the mass change before and after drying when the concentrated ink is placed in an aluminum cup and dried at 150 ° C. for 4 hours.
80 ° C. is a condition close to the concentration mechanism of the actual machine, and it has been confirmed that there is no significant difference in the “concentration-viscoelasticity” relationship between concentration in the temperature range of 80 ° C. to 100 ° C.

The absorption coefficient Kα of the ink by the Bristow method for a low-permeability recording medium at 25 ° C. is 0.06 mL · m- ² · ms- ^{1 / 2} or more and 0.12 mL · m- ² · ms- ^{1 / 2} or less. , 0.08 mL · m- ² · ms- ^{1 / 2} or more, preferably 0.12 mL · m- ² · ms- ^{1 / 2} or less.
When the absorption coefficient Kα is 0.06 mL · m- ² · ms- ^{1 / 2} or more, the penetration rate of the ink into the low permeability recording medium becomes high, and the concentration rate of the ink droplets on the low permeability recording medium becomes high. Becomes faster. As a result, the viscoelasticity of the ink droplets can be greatly increased, that is, the time until gelation can be shortened, and the ink droplets on the low-permeability recording medium are fixed before they coalesce to bead. Can be suppressed. Further, if the absorption coefficient Kα exceeds 0.12 mL · m- ² · ms- ^{1 /} 2, the image density will decrease, but if it is 0.12 mL · m- ² · ms- ^{1 / 2} or less, the image will be reduced. Prevents a decrease in concentration.
The absorption coefficient Kα can be, for example, 0.06 mL · m- ² · ms- ^{1 / 2} or more and 0.12 mL · m- ² · ms- ^{1 / 2} or less by controlling the surface tension of the ink. ..

The absorption coefficient Kα can be determined using a dynamic permeability tester based on a method called the Bristow method (J. TAPPI No. 51-87).
The dynamic permeability tester is a device that scans a head containing a fixed amount of liquid sample on a paper surface at a variable speed and measures the scanned length (trace length) before the fixed amount of ink is used up. , The faster the penetration, the shorter the trace length. At this time, the contact time T is defined by the contact time represented by the following formula from the slit width bmm of the head and the moving speed vmm / s of the test piece.
Contact time T (ms) = slit width b (mm) x 1000 / paper moving speed v (mm / s)
Further, the amount of liquid added to the head is X (μL), the length of the transition trace (trace length) left by the liquid until the transfer to the paper surface is completed is L (mm), and the slit length w (mm) of the head. Then, the transfer amount V of the liquid is defined by the following equation.
Liquid transfer amount V (mL / m ² )
= X (μL) x 1000 / (L (mm) x slit length w (mm))
When the trace length L is measured for the moving speed v of the test piece at a plurality of levels and the transfer amount is plotted against the square root of the contact time, the graph shown in FIG. 3 is obtained, and the following equation is obtained. Be done.
V = Vr + Kα (T-Tw) ^1/2
Vr: Roughness index (mL / m ² )
Kα: Absorption coefficient (mL / m ² · ms ^1/2 )
T: Absorption time (ms)
Tw: Wet time (ms)
The absorption coefficient Kα is obtained from the above equation.
Here, the roughness index Vr is completely irrelevant to the permeation of the liquid, and is due to the unevenness of the surface and the like. The absorption coefficient Kα is an index showing the speed of absorption, and is related to the contact angle between the liquid and the paper, the capillary radius of the paper surface, the viscosity of the liquid, and the surface tension. The wetting time Tw is observed when the contact angle between the liquid and the paper is large, and is the time from when the liquid wets the surface of the paper fiber to when absorption starts.

In the present invention, the absorption coefficient Kα of the low-permeability recording medium for the ink can be calculated based on the following conditions. The low-permeability recording medium will be described later.
[Measurement condition]
・ Equipment: Dynamic permeability tester (Model S, manufactured by Toyo Seiki Seisakusho Co., Ltd.)
・ Slit length: 18 mm
・ Slit width: 0.5 mm
-Amount of liquid added to the head: 20 μL
-Paper movement speed: 0.35 mm / s, 1.15 mm / s, 2.5 mm / s (3 levels)
-Low permeability recording medium: Lumiart Gloss 90gsm (manufactured by STORA ENSO)
・ Measurement temperature: 25 ° C
In the present invention, the absorption coefficient Kα refers to a value measured using a recording medium having “Lumiatogloss 90 gsm” or a pure water transfer characteristic similar to this as a low permeability recording medium.
The Lumiart Gloss 90 gsm (manufactured by STORA ENSO) is a pure water having a contact time of 100 ms measured by a dynamic scanning liquid absorbent meter (dynamic scanning liquid absorbent meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.)) at 25 ° C. The transfer amount of pure water is 2.3 mL / m ² and the transfer amount of pure water at a contact time of 400 ms is 4.4 mL / m ² .

Further, the ink of the present invention contains a plurality of organic solvents, and among the plurality of organic solvents, the Hansen solubility parameter (hSP value) of the organic solvent contained most in terms of mass has a δh of 3.0 (cal / cm). ³ ) ^{It is preferably 1/2} or more and 9.5 (cal / cm ³ ) ^1/2 or less, and 3.0 (cal / cm ³ ) ^1/2 or more and 8.0 (cal / cm ³ ) ^1/2. The following is more preferable.

Here, the Hansen solubility parameter is a solubility parameter introduced by Hildebrand divided into three components, a dispersion term δd, a polar term δp, and a hydrogen bond term δh. The dispersion term δd indicates the effect due to the non-polar interaction, the polar term δp indicates the effect due to the dipole moment, and the hydrogen bond term δh indicates the effect due to the hydrogen bond force. The numerical value of the Hansen solubility parameter used in the present invention can be quoted or calculated from HSPiP (Ver3.1), which is a database of Hansen solubility parameters and calculation software.

By setting δh of the Hansen solubility parameter (hSP value) of the organic solvent to 3.0 (cal / cm ³ ) ^1/2 or more and 9.5 (cal / cm ³ ) ^1/2 or less, the organic substance with respect to the resin is used. The plasticizing power of the solvent is increased, the film-forming property of the ink droplets on the low-permeability recording medium is improved, and the film-forming is completed at an early stage. This leads to further suppression of beading.

The content of the organic solvent in which the Hansen solubility parameter (hSP value) δh in the ink is 3.0 (cal / cm ³ ) ^1/2 or more and 9.5 (cal / cm ³ ) ^{1/2 or less suppresses beading.} From the viewpoint of discharge stability, it is preferably 15% by mass or more and 40% by mass or less, and more preferably 20% by mass or more and 40% by mass or less.

The surface tension of the ink at 25 ° C. is preferably 20.0 mN / m or more and 27.0 mN / m or less, and more preferably 20.0 mN / m or more and 25.0 mN / m or less.
By using an ink having a surface tension of 27.0 mN / m or less at 25 ° C., beading can be further suppressed.
It is known that the permeability of ink to a recording medium follows the following Lucas-Washburn equation.
l / t = (rγcosθ / 2η) ^1/2
Here, in the above formula, l is the permeation distance, t is the time, r is the pore diameter on the surface of the recording medium, θ is the contact angle, γ is the surface tension of the ink, and η is the viscosity of the ink.
The penetration rate of the ink is proportional to the 1/2 power of the term γcosθ of the wettability between the ink and the recording medium. When the surface tension of the ink is reduced, the wettability between the recording medium and the ink is improved and the value of the contact angle θ is reduced to 0 °, so that the value of cos θ approaches the maximum value. As a result, the numerical value of the wettability term γcosθ becomes large and the permeation rate is improved. Therefore, by reducing the surface tension of the ink, the penetration rate of the ink is improved and beading can be suppressed.
The surface tension of the ink can be controlled, for example, by selecting a surfactant. The penetrability of the ink can be improved by using a surfactant having a low HLB (hydrophilicity / lipophilicity ratio) and significantly lowering the surface tension of the ink.
The method for measuring the surface tension is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include various methods such as the Wilhelmy method, the ring ring method, the suspension method, and the maximum foam pressure method. In the present invention, the surface tension was measured by the Wilhelmy method. For example, it can be measured using a high-performance tensiometer (DY-500, manufactured by Kyowa Interface Science Co., Ltd.).

The viscosity of the ink at 25 ° C. is preferably 6.0 Pa · s or more and 10.0 mPa · s or less, and more preferably 7.0 mPa · s or more and 9.0 mPa · s or less.
By using the ink having a viscosity at 25 ° C. of 10.0 mPa · s or less, beading can be further suppressed. As shown in the Lucas-Washburn equation, the ink penetration rate l / t is proportional to the -1 / 2th power of the ink viscosity η. That is, by lowering the viscosity of the ink, the penetration rate of the ink is improved and beading can be suppressed.
The viscosity can be measured using, for example, a rotary viscometer (RE-80L, manufactured by Toki Sangyo Co., Ltd.).
As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.

The particle size (D50) of the solid content of the ink is preferably 90 nm or more and 120 nm or less, and more preferably 100 nm or more and 120 nm or less.
By using an ink having a solid content particle size (D50) of 90 nm or more and 120 nm or less, it is possible to prevent the pores on the outermost surface of the low-penetration recording medium from being blocked, and high penetration into the low-penetration recording medium. It can have sex and can suppress beading.

The ratio of the particle size (D50) to the particle size (D90) of the solid content of the ink is preferably 0.60 or more and 1.00 or less, and more preferably 0.70 or more and 1.00 or less.
The current state of ink penetration into a low-penetration recording medium can be regarded as a cake filtration phenomenon of the solid content component of the ink due to the pores on the outermost surface of the low-penetration recording medium. It is preferable that the particle size distribution is narrow. Therefore, by using an ink in which the ratio of the particle size (D50) to the particle size (D90) of the solid content is 0.6 or more and 1.0 or less, it is possible to have high permeability even to a low penetration recording medium. It can suppress beading.

Further, it is preferable that the particle size (D50) of the solid content of the ink is 1.5 times or more and 2.2 times or less with respect to the median value of the pore diameter distribution on the outermost surface of the permeation recording medium. More preferably, it is 7 times or more and 2.1 times or less.
By using an ink in which the particle size (D50) of the solid content of the ink is 1.5 times or more and 2.2 times or less with respect to the median value of the pore size distribution on the outermost surface of the permeation recording medium, the permeation is further reduced. It is possible to prevent the pores on the outermost surface of the recording medium from being blocked, to have high permeability to a low-penetration recording medium, and to suppress beading.

The particle size (D50) and the particle size (D90) of the solid content can be measured, for example, by using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.). In this case, the particle size (D50) and the particle size (D90) of the solid content are the particle size based on the volume, and the volume percentages with respect to all the particles are 50% and 90% when integrated from the small particle size side. Indicates the particle size.

For the pore distribution on the outermost surface of the low-penetration recording medium, for example, the low-penetration recording medium was observed with a scanning electron microscope (super-engineering resolution field emission scanning electron microscope SU8230, manufactured by Hitachi High-Technologies Corporation). It can be measured by calculating the equivalent circle diameter of the pore portion from the observation result using image analysis software (LMeye, manufactured by Lasertech).

The pH of the ink is preferably 7 to 12, more preferably 8 to 11, from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

The ink of the present invention can suppress beading even on a low-permeability recording medium without causing a decrease in image density and deterioration of ink ejection property.

<Low permeability recording medium>
The ink of the present invention preferably uses a low-permeability recording medium as the recording medium.
The low-permeability recording medium preferably has a support and a coating layer on at least one surface of the support, and may further have another layer if necessary. .. The surface having the coating layer is the printing surface.
In the present invention, the low-permeability recording medium means that on the printed surface, the amount of pure water transferred to the low-permeability recording medium at a contact time of 100 ms measured by a dynamic scanning liquid absorber at 25 ° C. is 2 mL / m. ² or more and 35 mL / m ² or less.
If the transfer amount of pure water at the contact time of 100 ms is too small, beading may easily occur, and if it is too large, the ink dot diameter after recording may be too small than the desired diameter.
Further, at 25 ° C., the amount of pure water transferred to the low-permeability recording medium at a contact time of 400 ms measured by a dynamic scanning liquid absorbent is 3 mL / m ² or more and 40 mL / m ² or less.
If the amount of transfer at the contact time of 400 ms is too small, the drying property is insufficient, so that spur marks may easily occur, and if it is too large, the gloss of the image portion after drying tends to be low. There is.

Here, the dynamic scanning absorber (DSA, Paper Technology Cooperative Magazine, Vol. 48, May 1994, pp. 88-92, Shigenori Kukan) has a liquid absorption amount in an extremely short time. It is a device that can accurately measure.
The dynamic scanning liquid absorption meter directly reads the speed of liquid absorption from the movement of the meniscus in the capillary, makes the sample disk-shaped, and scans the liquid absorption head spirally on the sample, and scans the speed according to a preset pattern. The measurement is automated by a method in which the number of points required for one sample is automatically changed.
The liquid supply head to the paper sample is connected to the capillary via a Teflon® tube, and the position of the meniscus in the capillary is automatically read by an optical sensor.
Specifically, the transfer amount of pure water or ink was measured using a dynamic scanning liquid absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.).
The transfer amount at the contact time of 100 ms and the contact time of 400 ms can be obtained by interpolation from the measured values of the transfer amounts at the contact times in the vicinity of each contact time.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper mainly composed of wood fibers and sheet-like substances such as non-woven fabric mainly composed of wood fibers and synthetic fibers. ..
The paper is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, wood pulp, used paper pulp and the like are used.
Examples of the wood pulp include hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), NBSP, LBSP, GP, TMP and the like.
The raw materials for the recycled paper pulp are fine white, ruled white, cream white, card, special white, medium white, imitation, fair white, Kent, and white, which are shown in the used paper standard quality standard table of the Recycled Paper Recycling Promotion Center. Examples include art, special cuts, special cuts, newspapers, and magazines.
Specifically, information-related paper such as non-coated computer paper, heat-sensitive paper, pressure-sensitive paper, and other printer paper; OA waste paper such as PPC paper; art paper, coated paper, finely coated paper, matte paper, and the like. Paper; high-quality paper, high-quality color, notebook, letter paper, wrapping paper, fancy paper, medium-quality paper, newspaper paper, stencil paper, super hanging paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, etc. Used paper and paperboard, such as chemical pulp paper and high-yield pulp-containing paper. These may be used alone or in combination of two or more.

The recycled paper pulp is generally produced from a combination of the following four steps.
(1) For disassembly, used paper is treated with a pulper with mechanical force and chemicals to loosen it into fibers, and the printing ink is peeled from the fibers.
(2) Dust removal removes foreign matter (plastic, etc.) and dust contained in used paper with a screen, cleaner, or the like.
(3) For deinking, the printing ink peeled off from the fiber using a surfactant is removed from the system by a flotation method or a cleaning method.
(4) Bleaching enhances the whiteness of fibers by using an oxidizing action or a reducing action.
When the used paper pulp is mixed, the mixing ratio of the used paper pulp in the total pulp is preferably 40% or less from the viewpoint of curl countermeasures after recording.

As the internal filler used for the support, for example, a conventionally known pigment as a white pigment is used.
Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, and silica soil. White inorganic pigments such as calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, lithopone, zeolite, magnesium carbonate, magnesium hydroxide, etc .; styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins , Organic pigments such as melamine resin, and the like. These may be used alone or in combination of two or more.

Examples of the internal sizing agent used when making the support include a neutral rosin-based sizing agent used for neutral paper making, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resin. Examples include system sizing agents. These may be used alone or in combination of two or more. Among these, a neutral rosin sizing agent and alkenyl succinic anhydride are preferable.
The alkyl ketene dimer requires a small amount to be added because of its high size effect, but it is not preferable from the viewpoint of transportability during inkjet recording because the friction coefficient on the surface of the recording paper (recording medium) is lowered and it becomes slippery. In some cases.

-Coating layer-
The coating layer contains a pigment and a binder (binding agent), and further contains a surfactant and other components, if necessary. As the pigment, an inorganic pigment or a combination of an inorganic pigment and an organic pigment can be used.

Examples of the inorganic pigment include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and the like. Examples include zinc hydroxide and chlorite.
Among these, kaolin is particularly preferable because it has excellent gloss development and can have a texture close to that of paper for offset printing. The kaolin includes delaminated kaolin, calcined kaolin, engineered kaolin by surface modification, etc., but in consideration of gloss development, a particle size distribution in which the particle size is 2 μm or less is 80% by mass or more. It is preferable that the kaolin contained in the kaolin accounts for 50% by mass or more of the total kaolin.
The amount of kaolin added is preferably 50 parts by mass or more with respect to 100 parts by mass of the binder. If the amount added is less than 50 parts by mass, a sufficient effect on glossiness may not be obtained. The upper limit of the addition amount is not particularly limited, but in consideration of the fluidity of kaolin, particularly the thickening under a high shearing force, 90 parts by mass or less is more preferable from the viewpoint of coating suitability.

Examples of the organic pigment include water-soluble dispersions such as styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. Two or more of these organic pigments may be mixed.

The amount of the organic pigment added is preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total pigment in the coating layer. Since the organic pigment is excellent in gloss development and its specific gravity is smaller than that of the inorganic pigment, it is possible to obtain a coating layer having a bulky, high gloss and good surface coating property. If the amount added is less than 2 parts by mass, the effect may be lost, and if it exceeds 20 parts by mass, the fluidity of the coating liquid deteriorates, leading to a decrease in coating operability. It is not economical in terms of cost. The organic pigment has a solid type, a hollow type, a donut type and the like in its form, but the average particle size (D50) is set in consideration of the balance between gloss development, surface coating property and fluidity of the coating liquid. A hollow type having a porosity of 40% or more is preferably adopted, preferably 0.2 μm to 3.0 μm.

As the binder, it is preferable to use an aqueous resin. As the water-based resin, at least one of a water-soluble resin and a water-dispersible resin is preferably used. The water-soluble resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a modified product of polyvinyl alcohol such as polyvinyl alcohol, anion-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and acetal-modified polyvinyl alcohol; Polyurethane; polyvinylpyrrolidone and a copolymer of polyvinylpyrrolidone and vinyl acetate, a copolymer of vinylpyrrolidone and dimethylaminoethyl / methacrylic acid, a quaternized polymer of vinylpyrrolidone and dimethylaminoethyl / methacrylic acid, and vinylpyrrolidone. Modified products of polyvinylpyrrolidone such as copolymers of methacrylicamidopropyl trimethylammonium chloride; celluloses such as carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose; Modified products of cellulose such as cationized hydroxyethyl cellulose; polyester, polyacrylic acid (ester) , Melamine resin, or synthetic resins such as polyester and polyurethane copolymers; poly (meth) acrylic acid, poly (meth) acrylamide, oxidized starch, phosphoric acid esterified starch, self-modified starch, cationized starch , Or various modified starches, polyethylene oxide, sodium polyacrylate, sodium alginate, and the like. These may be used alone or in combination of two or more. Among these, polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol, polyester, polyurethane, and a copolymer of polyester and polyurethane are particularly preferable from the viewpoint of ink absorbency.

The water-dispersible resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polystyrene, styrene- (meth) acrylic acid ester copolymer weight. Combined, (meth) acrylic acid ester-based polymer, vinyl acetate- (meth) acrylic acid (ester) copolymer, styrene-butadiene copolymer, ethylene-propylene copolymer, polyvinyl ether, silicone-acrylic acid-based copolymer Coalescence, etc.
Further, it may contain a cross-linking agent such as methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, or isocyanate, or may be a copolymer containing a unit such as N-methylolacrylamide having self-crosslinking property. It is also possible to use a plurality of these water-based resins at the same time.

The amount of the aqueous resin added is preferably 2 parts by mass to 100 parts by mass, and more preferably 3 parts by mass to 50 parts by mass with respect to 100 parts by mass of the pigment. The amount of the aqueous resin added is determined so that the liquid absorption characteristics of the recording medium fall within a desired range.

When a water-dispersible coloring material is used as the color material of the ink, the cationic organic compound does not necessarily have to be blended in the coating layer, but the cationic organic compound may be blended in the coating layer.
The cationic organic compound blended in the coating layer is not particularly limited, and can be appropriately selected and used depending on the intended purpose. Examples of the cationic organic compound to be blended in the coating layer include direct dyes in water-soluble inks and sulfonic acid groups, carboxyl groups, amino groups and the like in acid dyes to form insoluble salts1 Examples thereof include monomers, oligomers and polymers of primary to tertiary amines and quaternary ammonium salts. Among these, oligomers or polymers are preferable.

Examples of the cationic organic compound include dimethylamine / epichlorohydrin polycondensate, dimethylamine / ammonia / epichlorohydrin condensate, poly (trimethylaminoethyl methacrylate / methylsulfate), diallylamine hydrochloride / acrylamide copolymer, and poly. (Diallylamine hydrochloride / sulfur dioxide), polyallylamine hydrochloride, poly (allylamine hydrochloride / diallylamine hydrochloride), acrylamide / diallylamine copolymer, polyvinylamine copolymer, dicyandiamide, dicyandiamide / ammonium chloride / urea / formaldehyde condensate , Polyalkylene polyamine / disiandiamide ammonium salt condensate, dimethyldiallylammonium chloride, polydiallylmethylamine hydrochloride, poly (diallyldimethylammonium chloride), poly (diallyldimethylammonium chloride / sulfur dioxide), poly (diallyldimethylammonium chloride / diallylamine) Hydrochloride derivatives), acrylamide / diallyldimethylammonium chloride copolymers, acrylate / acrylamide / diallylamine hydrochloride copolymers, ethyleneimine derivatives such as polyethyleneimine and acrylicamine polymers, polyethyleneimine alkylene oxide modified products, etc. Be done. These may be used alone or in combination of two or more.

Among these, low molecular weight cationic organic compounds such as dimethylamine / epichlorohydrin polycondensate and polyallylamine hydrochloride and other relatively high molecular weight cationic organic compounds such as poly (diallyldimethylammonium chloride) are used. It is preferable to use them in combination. When used in combination, the image density is improved and feathering is further reduced as compared with the case of single use.

The cationic equivalent of the cationic organic compound by the colloid titration method (using polyvinyl sulfate potassium or toluidine blue) is preferably 3 meq / g to 8 meq / g. If the cation equivalent is in this range, good results can be obtained in the range of the dry adhesion amount. Here, in the measurement of the cationic equivalent by the colloid titration method, the cationic organic compound is diluted with distilled water so as to have a solid content of 0.1% by mass, and the pH is not adjusted.

The dry adhesion amount of the cationic organic compound ^{is preferably 0.3 g / m 2} or more and 2.0 g / m ² or less.
When the dry adhesion amount of the cationic organic compound is 0.3 g / m ² or more, the image density is improved and the effect of reducing feathering can be obtained.

The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants and the like can be selected. Can be mentioned. Among these, nonionic surfactants are preferable.
By adding the surfactant, the water resistance of the image is improved, the image density is increased, and the bleeding is improved.
Examples of the nonionic surfactant include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, and higher aliphatic amine ethylene oxide adducts. Fatty Acid Amid Ethylene Oxide Additives, Fats and Oils Ethylene Oxide Additives, Polypropylene Glycol Ethylene Oxide Additives, Gglycerol Fatite Esters, Pentaerythritol Fatite Esters, Solbitol and Sorbitane Fatite Esters, Sucrose Fatty Acid Esters, Alcohol Alcohol Examples thereof include ether and fatty acid amides of alkanolamines. These may be used alone or in combination of two or more.

The polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose. As for the ethylene oxide adduct, it is also effective to replace a part of ethylene oxide with an alkylene oxide such as propylene oxide or butylene oxide as long as the water solubility can be maintained.
The substitution rate is preferably 50% or less.
The HLB (hydrophilic / lipophilic ratio) of the nonionic surfactant is preferably 4 to 15, more preferably 7 to 13.
The amount of the surfactant added is preferably 0 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the cationic organic compound.
Other components can be added to the coating layer as needed, as long as the object and effect of the present invention are not impaired.
Examples of the other components include additives such as alumina powder, pH adjusters, preservatives, and antioxidants.

The method for forming the coating layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the coating layer liquid can be impregnated or applied onto the support.
The impregnation or coating method of the coating layer liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a conventional size press, a gate roll size press, a film transfer size press, a blade coater, and a rod coater. , Air knife coater, curtain coater, etc. can be applied with various coating machines, but from the viewpoint of cost, the conventional size press, gate roll size press, film transfer size press, etc. installed in the paper machine can be used. It may be impregnated or adhered and finished on-machine.
The amount of the coating layer liquid adhered is not particularly limited and can be appropriately selected depending on the intended purpose. The solid content ^{is preferably 0.5 g / m 2} or more and 20 g / m ² or less, and 1 g / m ² or more. More preferably, it is 15 g / m ^{2 or less.}
After the impregnation or coating, it may be dried if necessary, and the drying temperature in this case is not particularly limited and may be appropriately selected depending on the intended purpose, but is 100 ° C. or higher and 250 ° C. or lower. preferable.

The low-permeability recording medium may further form a back layer on the back surface of the support, between the support and the coating layer, and between the support and the back layer, and may form other layers on the coating layer. A protective layer can also be provided. Each of these layers may be a single layer or a plurality of layers.
The low-permeability recording medium may be an inkjet recording medium, an electrophotographic recording coated paper, a commercially available offset printing coated paper, a gravure printing coated paper, or the like, as long as the liquid absorption property is within the above range. Good.

The ink of the present invention contains a resin, but can also contain an organic solvent, water, a coloring material, an additive, and the like.

<Ink>
Hereinafter, the organic solvent, water, coloring material, resin, additive, etc. used for the ink will be described.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. For example, polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds and the like can be mentioned.
Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-Pentanediol, 1,5-Pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, other hydroxyl group compounds such as 3-hydroxymethyl-3-ethyloxetane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Polyhydric alcohol alkyl ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2. Nitrogen-containing heterocyclic compounds such as −pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N -Methylformamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and other amides, monoethanolamine, diethanolamine, triethylamine and other amines , Diolsulfoxide, Sulfolane, Sulfur-containing compounds such as thiodiethanol, propylene carbonate, ethylene carbonate and the like.

Among these, the largest number of organic solvents contained in ink from the viewpoint of enhancing the plasticizing power of the organic solvent with respect to the resin, promoting gelation of ink droplets on the low-permeability recording medium, and suppressing beading. As the organic solvent contained, it is preferable to use an organic solvent having a Hansen solubility parameter (hSP value) of δh of 3.0 (cal / cm ³ ) ^1/2 or more and 9.5 (cal / cm ³ ) ^{1/2 or less.} .. Specifically, 1,2-butanediol (δh: 9.4 (cal / cm ³ ) ^1/2 , 3-hydroxymethyl-3-ethyloxetane (δh: 6.0 (cal / cm ³ ) ^{1 /) 2} ), Diethylene glycol monomethyl ether (δh: 6.2 (cal / cm ³ ) ^1/2 ), Diethylene glycol monobutyl ether (δh: 5.2 (cal / cm ³ ) ^1/2 ), propylene glycol monoethyl ether (δh) : 4.2 (cal / cm ³ ) ^1/2 ), propylene glycol monobutyl ether (δh: 5.1 (cal / cm ³ ) ^1/2 ), dipropylene glycol monomethyl ether (δh: 4.9 (cal / cal /) cm ³ ) ^1/2 ), 2-methyl-2,4-pentanediol (δh: 7.9 (cal / cm ³ ) ^1/2 ), 3-methoxy-N, N-dimethylpropionamide (δh:) 5.1 (cal / cm ³ ) ^1/2 ), 3-butoxy-N, N-dimethylpropionamide (δh: 4.6 (cal / cm ³ ) ^1/2 ).
Further, from the viewpoint of showing good drying property and improving the concentration rate of ink, it is preferable to use an organic solvent having a boiling point of 250 ° C. or lower, but even when an organic solvent having a boiling point of 250 ° C. or higher is used, 3% by mass is used. By setting the following, it is possible to reduce the deterioration of the ink concentration rate.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers: Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether can be mentioned.

A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve the permeability of ink when paper is used as a recording medium.

The content of the organic solvent in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 60% by mass or less from the viewpoint of ink drying property and ejection reliability. More preferably, it is 20% by mass or more and 60% by mass or less.

<Water>
The content of water in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of ink drying property and ejection reliability, it is preferably 10% by mass or more and 90% by mass or less, and 20% by mass. % To 60% by mass is more preferable.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Moreover, you may use a mixed crystal.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by known methods such as contact method, furnace method, and thermal method. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of pigments for black include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, or copper and iron (CI pigment black 11). , Metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmin 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Magenta), 104, 105, 106, 108 ( Cadmium Red), 112, 114, 122 (Quinacridone Magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As the dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52,80,82,249,254,289, C.I. I. Acid Blue 9,45,249, C.I. I. Acid Black 1,2,24,94, C.I. I. Hood Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1,2,15,71,86,87,98,165,199,202, C.I. I. Dilekdo Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3, 4, 35 can be mentioned.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass, from the viewpoint of improving image density, good fixability and ejection stability. It is as follows.

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin coating pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effects of the present invention are not impaired. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low molecular weight dispersant and a high molecular weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonate Na formalin condensate can also be suitably used as a dispersant.
One type of dispersant may be used alone, or two or more types may be used in combination.

<Pigment dispersion>
It is possible to obtain ink by mixing a material such as water or an organic solvent with a coloring material. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. A disperser may be used for dispersion.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1 mass is used. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
If necessary, the pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifuge, or the like.

<Resin>
The type of resin contained in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, etc. Examples thereof include resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.
The form of addition of these resins is not particularly limited, but the following are preferable.
(1) Form of addition as resin fine particles (2) Form of addition as polymer emulsion containing water-insoluble or sparingly water-soluble coloring material (3) Form of addition as microcapsules coated with pigment

In the form (1), it is possible to obtain an ink by mixing it with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which resin particles are dispersed in water. As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used. Further, these may be used alone or in combination of two or more kinds of resin particles.
The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is particularly preferable.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The glass transition temperature of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good film-forming property, it is preferably −60 ° C. or higher and 10 ° C. or lower, preferably −40 ° C. More than 0 ° C. or lower is particularly preferable.
The glass transition temperature of the resin particles can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation).

In the form of (2) above, the polymer emulsion containing a coloring material means at least one in which a pigment is encapsulated in polymer fine particles and one in which a pigment is adsorbed on the surface of the polymer fine particles.
For example, those described in JP-A-2001-139894 can be mentioned.
In this case, it is not necessary that all the pigments are enclosed or adsorbed in the polymer fine particles, and the pigments may be dispersed in the emulsion as long as the effects of the present invention are not impaired.
The above-mentioned "water-insoluble or sparingly water-soluble" means that the coloring material does not dissolve more than 10 parts by mass with respect to 100 parts by mass of water at 20 ° C.
Further, the above-mentioned "dissolve" means that no separation or sedimentation of the coloring material is visually observed on the surface layer or the lower layer of the aqueous solution.

The polymer that forms the polymer emulsion containing the coloring material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, vinyl-based polymer, polyester-based polymer, polyurethane-based polymer, JP-A-2000-53897. Examples thereof include polymers disclosed in Japanese Patent Application Laid-Open No. 2001-139894.
Among these, vinyl-based polymers and polyester-based polymers are particularly preferable.

The volume average particle size of the polymer fine particles (colored fine particles) containing the coloring material is preferably 0.01 μm to 0.16 μm in the ink.

In the form (3), the pigment is coated with a hydrophilic and water-insoluble resin, and the pigment is made hydrophilic by the resin layer on the surface of the pigment so that the pigment is dispersed in water, for example. Examples thereof include those described in JP-A-2002-67473.

<Additives>
If necessary, a surfactant, a defoaming agent, an antiseptic / antifungal agent, a rust preventive, a pH adjuster, or the like may be added to the ink.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose.
Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, and side chain double-ended modified polydimethylsiloxane. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. A polyoxyalkylene ether polymer compound is particularly preferable because it has a low foaming property. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counterions of the salts in these fluorine-based surfactants are Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside agent include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and polyoxyethylene alkyl ether sulfate salt.
These may be used alone or in combination of two or more.

（但し、一般式（Ｓ−１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ−３５１Ａ、ＫＦ−３５２、ＫＦ−３５３Ａ、ＫＦ−３５５Ａ、ＫＦ−６１５Ａ、ＫＦ−６１８、ＫＦ−６４２、ＫＦ−６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ−ＳＳ−５６０２、ＳＳ−１９０６ＥＸ（日本エマルジョン株式会社）、ＳＨ８４００、Ｌ−７７、ＦＺ−２１０５、ＦＺ−２１１８、ＦＺ−２１２３、ＦＺ−２１５４、ＦＺ−２１６１、ＦＺ−２１６２、ＦＺ−２１６３、ＦＺ−２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ−３３、ＢＹＫ−３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as modifying groups exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the general formula (S-1) is dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)
Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-351A, KF-352, KF-353A, KF-355A, KF-615A, KF-618, KF-642. , KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (Nippon Emulsion Co., Ltd.), SH8400, L-77, FZ-2105, FZ-2118, FZ-2123, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) And so on.

The polyether-modified silicone-based surfactant is added for the purpose of lowering the surface tension of the ink in order to improve the permeability and increase the absorption coefficient Kα. On the other hand, since the polyether-modified silicone-based surfactant inhibits the coalescence of ink solids, adding a high concentration of the polyether-modified silicone-based surfactant reduces the storage elastic modulus G'when the ink is concentrated. It ends up. Therefore, it is preferable that the surface tension of the ink is significantly reduced by adding a low concentration.
Among the polyether-modified silicone-based surfactants, KF-351A, KF-352, KF-353A, KF-355A, KF-615A (Shin-Etsu Chemical Co., Ltd.), SH8400, L-77, FZ-2118, FZ-2123, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), TSF4452, TSF4453 (Toshiba Silicone Co., Ltd.) are particularly preferable.

上記一般式（Ｆ−１）で表される化合物において、水溶性を付与するためにｍは０〜１０の整数が好ましく、ｎは０〜４０の整数が好ましい。
一般式（Ｆ−２）
Ｃ_nＦ_2n+1−ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂−Ｏ−(ＣＨ₂ＣＨ₂Ｏ)_a−Ｙ
上記一般式（Ｆ−２）で表される化合物において、ＹはＨ、又はＣ_mＦ_2m+1でｍは１〜６の整数、又はＣＨ₂ＣＨ(ＯＨ)ＣＨ₂−Ｃ_mＦ_2m+1でｍは４〜６の整数、又はＣ_pＨ_2p+1でｐは１〜１９の整数である。ｎは１〜６の整数である。ａは４〜１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ−１１１、Ｓ−１１２、Ｓ−１１３、Ｓ−１２１、Ｓ−１３１、Ｓ−１３２、Ｓ−１４１、Ｓ−１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ−９３、ＦＣ−９５、ＦＣ−９８、ＦＣ−１２９、ＦＣ−１３５、ＦＣ−１７０Ｃ、ＦＣ−４３０、ＦＣ−４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ−４４４、Ｆ−４７０、Ｆ−１４０５、Ｆ−４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ−１００、ＦＳＮ、ＦＳＯ−１００、ＦＳＯ、ＦＳ−３０、ＦＳ−３００、ＦＳ−３１００、ＵＲ（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ−１３６Ａ，ＰＦ−１５６Ａ、ＰＦ−１５１Ｎ、ＰＦ−１５４、ＰＦ−１５９（オムノバ社製）、ユニダインＤＳＮ−４０３Ｎ（ダイキン工業株式会社製）などが挙げられる。 As the fluorine-based surfactant, a compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine is more preferable.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain.
Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has low foaming property, and is particularly a fluorine-based compound represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.

In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10, and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
C _n F _{2n + 1} −CH ₂ CH (OH) CH ₂ −O− (CH ₂ CH ₂ O) _a −Y
In the compound represented by the above general formula (F-2), Y is H, or C _m F _{2 m + 1} , and m is an integer of 1 to 6, or CH ₂ CH (OH) CH _2- C _m F _{2 m +. At 1} , m is an integer of 4 to 6, or C _p H _{2p + 1} and p is an integer of 1 to 19. n is an integer of 1-6. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant. Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-444, F -470, F-1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-30, FS-300, FS-3100, UR (all manufactured by The Chemours Company); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.) ), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omniova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) and the like.

The fluorine-based surfactant is added for the purpose of lowering the surface tension of the ink in order to improve the permeability and increase the absorption coefficient Kα. On the other hand, since the fluorine-based surfactant inhibits the coalescence of ink solids, the storage elastic modulus G'at the time of ink concentration decreases when the fluorine-based surfactant is added at a high concentration. Therefore, it is preferable that the surface tension of the ink is significantly reduced by adding a low concentration. Among the fluorine-based surfactants, Megafuck F-444 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Zonyl FSO, FS-3100 (manufactured by The Chemours Co., Ltd.), Unidyne DSN-403N (Daikin Industries, Ltd.) (Manufactured) is particularly preferable.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of preventing a decrease in the storage elastic modulus G'when the ink is concentrated, it is 0.001% by mass. It is preferably 2% by mass or less, and more preferably 0.05% by mass or more and 2% by mass or less.

<Defoamer>
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

<Preservatives and fungicides>
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<Rust inhibitor>
The rust preventive is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

<pH adjuster>
The pH adjusting agent is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

<Recorded material>
The ink recording material of the present invention comprises an image formed by using the ink of the present invention on a recording medium.
It can be recorded by an inkjet recording device and an inkjet recording method to obtain a recorded material.

(Ink container)
The ink container of the present invention comprises an ink accommodating portion for accommodating the ink of the present invention, and further comprises other members appropriately selected as necessary.
The ink container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. For example, an ink container formed of an aluminum laminate film, a resin film, or the like. Those having at least such as, etc. are preferably mentioned.

(Recording device, recording method)
The inkjet recording method of the present invention is an inkjet recording method in which the ink of the present invention is used as the ink in the inkjet recording method in which ink is ejected from a nozzle of a recording head and applied to a recording medium for recording.
The recording medium comprises a support and a coating layer on at least one surface of the support, and the coating of the recording medium of pure water at a contact time of 100 ms measured by a dynamic scanning liquid absorbent meter. The amount of transfer of pure water to the surface having the coating layer at a contact time of 400 ms is 3 mL / m ^{2 and the} amount of transfer to the surface having the layer is 2 mL / m ² or more and 35 mL / m ^{2 or less.} It is preferably 40 mL / m ^{2 or more.}
The inkjet recording apparatus of the present invention has the ink container of the present invention, a recording head for ejecting ink droplets, and further has other members as needed.

The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method of recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, and other devices called pretreatment devices and posttreatment devices. ..
The recording device and recording method may include a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the print surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form a three-dimensional image are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous line printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of a main tank which is an ink container. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanical unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage section 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided behind the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

This recording device can include not only a portion that ejects ink, but also a device called a pretreatment device, a posttreatment device, and the like.
As one aspect of the pretreatment apparatus and the posttreatment apparatus, it has a pretreatment liquid and a posttreatment liquid as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is an embodiment in which a liquid accommodating portion and a liquid discharge head are added, and a pretreatment liquid or a posttreatment liquid is discharged by an inkjet recording method.
As another aspect of the pretreatment device and the posttreatment device, there is a mode in which a pretreatment device and a posttreatment device by, for example, a blade coating method, a roll coating method, and a spray coating method are provided other than the inkjet recording method.

The method of using the ink is not limited to the inkjet recording method, and can be widely used. In addition to the inkjet recording method, examples thereof include a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spray coating method.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

(Manufacturing Example 1)
-Polymer emulsion type cyan pigment-
After sufficiently substituting nitrogen gas in a 1 L flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas introduction tube, a reflux tube, and a dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, and 12.0 g of lauryl methacrylate , 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toa Synthetic Co., Ltd., trade name: AS-6), and 0.4 g of mercaptoethanol were mixed and heated to 65 ° C.
Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyl ethyl methacrylate 60.0 g, styrene macromer (manufactured by Toa Synthetic Co., Ltd., trade name: AS-6). A mixed solution of 36.0 g, 3.6 g of mercaptoethanol, 2.4 g of azobismethylvaleronitrile, and 18 g of methyl ethyl ketone was added dropwise into the flask over 2.5 hours.
After completion of the dropwise addition, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was added dropwise to the flask over 0.5 hours.
After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added, and the mixture was further aged for 1 hour.
After completion of the reaction, 364 g of methyl ethyl ketone was added into the flask to prepare 800 g of a polymer solution having a concentration of 50% by mass.
Next, 46 g of the obtained polymer solution, C.I. I. After sufficiently stirring 33 g of Pigment Blue 15: 3 (manufactured by Dainichiseika Kogyo Co., Ltd.), 13.6 g of a 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water, a roll mill was used. Kneaded.
The obtained paste was put into 200 g of pure water, stirred sufficiently, methyl ethyl ketone and water were distilled off using an evaporator, and then glycerin was added to add pigment 10.9% by mass and resin 7.5% by mass. , And a polymer emulsion type cyan pigment (solid content concentration 18.4% by mass) of Production Example 1 containing 9.1% by mass of glycerin was prepared.

(Manufacturing Example 2)
-Polymer emulsion type yellow pigment-
In Production Example 1, C.I. I. Pigment Blue 15: 3 (manufactured by Dainichiseika Kogyo Co., Ltd.) I. A polymer emulsion type yellow pigment of Production Example 2 was produced in the same manner as in Production Example 1 except that it was changed to Pigment Yellow 74 (manufactured by Dainichiseika Kogyo Co., Ltd.). Further, this polymer emulsion type yellow pigment contains 13.0% by mass of pigment, 7.5% by mass of resin, and 9.1% by mass of glycerin (solid content concentration 20.5% by mass).

(Manufacturing Example 3)
-Preparation of acrylic silicone particle dispersion-
After sufficient nitrogen gas replacement in a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube, and dropping funnel, Latemul S-180 (reactive emulsifier with unsaturated carbon, Kao shares) 8.0 g (100% by mass of the component) manufactured by the company and 350 g of ion-exchanged water were added and mixed, and the temperature was raised to 65 ° C.
After the temperature was raised, 3.0 g of the reaction initiator t-butyl peroxobenzoate and 1.0 g of sodium isoascorbate were added, and after 5 minutes, 45 g of methyl methacrylate, 160 g of diethylhexyl methacrylate, 5 g of acrylic acid, and methacrylic acid were added. 45 g of butyl, 30 g of cyclohexyl methacrylate, 15 g of vinyltriethoxysilane, 8.0 g of Latemul S-180 (reactive emulsifier having unsaturated carbon, manufactured by Kao Co., Ltd., 100% by mass of components), and 340 g of ion-exchanged water are mixed. The dropping was carried out over 3 hours.
Then, after heat aging at 80 ° C. for 2 hours, the mixture was cooled to room temperature (25 ° C.) and the pH was adjusted to 7 to 8 with sodium hydroxide.
Next, ethanol was distilled off using an evaporator, and the water content was adjusted to prepare 730 g of the acrylic silicone fine particle dispersion solution of Production Example 3 having a solid content concentration of 40% by mass.
The volume average particle size of the acrylic silicone fine particles in the obtained acrylic silicone fine particle dispersion was 140 nm, and the glass transition temperature was -3.36 ° C.

(Manufacturing Example 4)
-Preparation of polyurethane resin emulsion-
In an autoclave reactor equipped with a stirrer and jacket, 500 g of Mn500 amorphous polycarbonate diol [Duranol T5651, manufactured by Asahi Kasei Chemicals], 45.8 g of dimethylol propionic acid, 358 g of isophorone diisocyanate (IPDI), 29.4 g of triethylamine and 650 g of acetone were added. , Prepared while introducing nitrogen. Then, the mixture was heated to 80 ° C. and subjected to a urethanization reaction over 5 hours to produce a prepolymer.
After returning the system to 40 ° C., the temperature was maintained. After confirming the NCO% present in the system, water was slowly added, and the mixture was heated and stirred for 30 minutes, then an extender (isophorone diamine (IPDA)) was added, and the mixture was heated and stirred for 3 to 6 hours. Finally, the organic solvent was removed to obtain a polyurethane resin emulsion of Production Example 4 having a solid content concentration of 31% by mass.
The volume average particle size of the polyurethane resin in the obtained polyurethane resin emulsion was 106 nm, and the glass transition temperature was -22.02 ° C.

(Example 1)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 2)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-3-Hydroxymethyl-3-ethyloxetane as an organic solvent (δh: 6.0 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.03% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 3)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 25.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.03% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 4)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-3-Hydroxymethyl-3-ethyloxetane as an organic solvent (δh: 6.0 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 5)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-3-Hydroxymethyl-3-ethyloxetane as an organic solvent (δh: 6.0 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 1.5% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 6)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-3-Hydroxymethyl-3-ethyloxetane as an organic solvent (δh: 6.0 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
-Fluorine-based surfactant (Mega Fvck F-444, manufactured by DIC Corporation)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 7)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
-Fluorine-based surfactant (Mega Fvck F-444, manufactured by DIC Corporation)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 8)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type yellow pigment of Production Example 2 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 9)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type yellow pigment of Production Example 2 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-3-Hydroxymethyl-3-ethyloxetane as an organic solvent (δh: 6.0 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
-Fluorine-based surfactant (Mega Fvck F-444, manufactured by DIC Corporation)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 10)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type yellow pigment of Production Example 2 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 6% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 11)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type yellow pigment of Production Example 2 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 18% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 12)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
-Polyurethane resin emulsion of Production Example 4: 19.35% by mass
-Propylene glycol monobutyl ether as an organic solvent (δh: 5.1 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
-Fluorine-based surfactant (Mega Fvck F-444, manufactured by DIC Corporation)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 13)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
-Polyurethane resin emulsion of Production Example 4: 15.48% by mass
-2-Methyl-2,4-pentandial as an organic solvent (δh: 7.9 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Example 14)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
-Polyurethane resin emulsion of Production Example 4: 15.48% by mass
-Diethylene glycol monomethyl ether as an organic solvent (δh: 6.2 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
-Fluorine-based surfactant (Mega Fvck F-444, manufactured by DIC Corporation)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 1)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
・ Glycerin as an organic solvent ・ ・ ・ 11.17% by mass
-1,3-Butanediol as an organic solvent (δh: 10.4 (cal / cm ³ ) ^1/2 )
... 13.95% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
-Fluorine-based surfactant (FS-300, manufactured by The Chemours Company)
・ ・ ・ 2.5% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 2)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
-Propylene glycol as an organic solvent (δh: 11.4 (cal / cm ³ ) ^1/2 )
... 27.9% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
・ ・ ・ 5.9% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.03% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 3)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-Propylene glycol as an organic solvent (δh: 11.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.03% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 4)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-Ethylene glycol as an organic solvent (δh: 12.7 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.03% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 5)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-3-Hydroxymethyl-3-ethyloxetane as an organic solvent (δh: 6.0 (cal / cm ³ ) ^1/2 ) ・ ・ ・ 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
-Fluorine-based surfactant (FS-30, manufactured by The Chemours Company)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 6)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 28.0% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 20% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 7)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 28.0% by mass
-Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 25% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.3% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 8)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type cyan pigment of Production Example 1 ... 30.55% by mass
-Propylene glycol as an organic solvent (δh: 11.4 (cal / cm ³ ) ^1/2 )
... 14.2% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
・ ・ ・ 3.8% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 1.5% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 9)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type yellow pigment of Production Example 2 ... 30.55% by mass
・ Acrylic silicone emulsion of Production Example 3 ・ ・ ・ 15% by mass
-Propylene glycol as an organic solvent (δh: 11.4 (cal / cm ³ ) ^1/2 )
... 28.6% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 0.03% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

(Comparative Example 10)
An ink having the following formulation was prepared, the pH was adjusted, and then filtration was performed with a membrane filter having an average pore size of 5 μm to prepare an ink.
<Ink prescription>
-Polymer emulsion type yellow pigment of Production Example 2 ... 30.55% by mass
-Propylene glycol as an organic solvent (δh: 11.4 (cal / cm ³ ) ^1/2 )
... 10.8% by mass
-1,2-Butanediol as an organic solvent (δh: 9.4 (cal / cm ³ ) ^1/2 )
... 2.4% by mass
-2-Ethyl-1,3-hexanediol as an organic solvent ・ ・ ・ 2% by mass
・ Fluorine-based surfactant (Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.)
・ ・ ・ 2.0% by mass
・ Antiseptic and antifungal agent (Proxel LV, manufactured by Avecia) ・ ・ ・ 0.05% by mass
・ PH adjuster (triethanolamine) ・ ・ ・ 0.3% by mass
-Silicone emulsion defoamer (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ ・ ・ 0.1% by mass
・ Water ・ ・ ・ Remaining amount (total: 100% by mass)

Next, the ink physical characteristics, beading, image density, and ejection stability of each of the produced inks were evaluated as follows. The results are shown in Tables 1 and 2.
Tables 1 and 2 show the Hansen solubility parameter (hSP value) δh of the organic solvent contained in the produced ink at the highest concentration.

<Measurement of storage elastic modulus G'and loss elastic modulus G'>
The storage elastic modulus G'and the loss elastic modulus G'when the ink was concentrated to a solid content of 20% by mass were measured under the following measurement conditions.
[Measurement condition]
・ Equipment: AR2000 (manufactured by TA Instruments Co., Ltd.)
・ Geometry: 40mm 1 ° cone plate ・ Geometry gap: 300μm
・ Measurement frequency: 1Hz
-Measurement temperature: 25 ° C-Analysis software: TA DATA ANALYSIS (manufactured by TA Instruments Co., Ltd.)
The concentration of the ink was carried out on a hot plate at 80 ° C. with the ink placed in a beaker and stirred. The solid content of the ink was calculated from the mass change before and after drying when the concentrated ink was placed in an aluminum cup and dried at 150 ° C. for 4 hours.
FIG. 4 shows the measurement results of the storage elastic modulus G'and the loss elastic modulus G'of the ink of Example 1.

<Absorption coefficient Kα>
The absorption coefficient Kα was determined using a dynamic permeability tester based on a method called the Bristow method (J. TAPPI No. 51-87).
The dynamic permeability tester is a device that scans a head containing a fixed amount of liquid sample on a paper surface at a variable speed and measures the scanned length (trace length) before the fixed amount of ink is used up. , The faster the penetration, the shorter the trace length. At this time, the contact time T is defined by the contact time represented by the following formula from the slit width bmm of the head and the moving speed vmm / s of the test piece.
Contact time T (ms)
= Slit width b (mm) x 1000 / Paper movement speed v (mm / s)
Further, the amount of liquid added to the head is X (μL), the length of the transition trace (trace length) left by the liquid until the transfer to the paper surface is completed is L (mm), and the slit length w (mm) of the head. Then, the transfer amount V of the liquid is defined by the following equation.
Liquid transfer amount V (mL / m ² )
= X (μL) x 1000 / (L (mm) x slit length w (mm))
When the trace length L was measured for the moving speed v of the test piece at a plurality of levels and the transfer amount was plotted against the square root of the contact time, the following equation was obtained.
V = Vr + Kα (T-Tw) ^1/2
Vr: Roughness index (mL / m ² )
Kα: Absorption coefficient (mL / m ² · ms ^1/2 )
T: Absorption time (ms)
Tw: Wet time (ms)
The absorption coefficient Kα was calculated from the above formula.
In the present invention, the absorption coefficient Kα [mL · m- ² · ms- ^{1 / 2} ] of the following low-permeability recording medium for the ink was calculated based on the following conditions.
[Measurement condition]
・ Equipment: Dynamic permeability tester (Model S, manufactured by Toyo Seiki Seisakusho Co., Ltd.)
・ Slit length: 18 mm
・ Slit width: 0.5 mm
-Amount of liquid added to the head: 20 μL
-Paper movement speed: 0.35 mm / s, 1.15 mm / s, 2.5 mm / s (3 levels)
-Low permeability recording medium: Lumiart Gloss 90gsm (manufactured by STORA ENSO)
・ Measurement temperature: 25 ° C
The Lumiart Gloss 90 gsm (manufactured by STORA ENSO) is pure at 25 ° C. with a contact time of 100 ms measured by a dynamic scanning liquid absorbent (dynamic scanning liquid absorbent (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The transfer amount of water is 2.3 mL / m ² , and the transfer amount of pure water at a contact time of 400 ms is 4.4 mL / m ² .

<Surface tension>
The surface tension of the ink was measured under the following conditions.
[Measurement condition]
・ Equipment: High-performance surface tensiometer (DY-500, manufactured by Kyowa Interface Science Co., Ltd.)
・ Temperature: 25 ℃
-Measurement method: Wilhelmy method

<Viscosity>
The viscosity was measured using a rotary viscometer (RE-80L, manufactured by Toki Sangyo Co., Ltd.).
As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.

<Solid content D50 and D90>
The solid contents D50 and D90 were measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.) after diluting the ink 300 times with pure water. In this case, the particle size (D50) and the particle size (D90) of the solid content refer to the volume-based particle size.

<Evaluation of beading>
A solid image is formed on a recording medium (Lumiart Gloss 90 gsm, manufactured by STORA ENSO) using an inkjet printer (IPSiO GXe-5500, manufactured by Ricoh Co., Ltd.) in an environment adjusted to 23 ° C. and 50% RH. Then, the degree of beading of the solid image was visually observed and evaluated according to the following criteria. The drive voltage of the piezo element was changed so that the amount of ink ejected was even, and the setting was made so that the same amount of ink adhered to the recording medium. As the print mode, the driver attached to the printer was used to modify the "glossy paper-clean" mode to "no color correction".
The recording medium used this time, Lumiart Gloss 90 gsm, manufactured by STORA ENSO, has a coating layer having a thickness of about 10 to 15 μm mainly composed of modified starch, styrene-butadiene copolymer, and calcium carbonate on both the front and back surfaces. Had had.
〔Evaluation criteria〕
⊚: Uniform printing without beading ○: Slight beading is observed △: Beading is observed in some places ×: Significant beading is observed × ×: Very severe Occurrence of beading is observed

<Evaluation of image density>
Inkjet printer (manufactured by Ricoh Co., Ltd., IPSiO GX5000) was filled with ink prepared at 23 ° C. and 50% RH environment, and 64point characters JIS X 0208 (1997), 2223 were prepared by Microsoft Word2000 (manufactured by Microsoft). The chart with the general symbol of is printed on a recording medium (Lumiart Gloss 90 gsm, manufactured by STORA ENSO), and the general symbol part of JIS X 0208 (1997) and 2223 on the printed surface is X-Rite 938 (manufactured by X-Rite). ), And judged according to the following evaluation criteria.
As the print mode, the driver attached to the printer was used to modify the "glossy paper-clean" mode to "no color correction".
〔Evaluation criteria〕
・ Cyan ○: 1.90 or more Δ: 1.80 or more and less than 1.90 ×: less than 1.80 ・ Yellow ○: 1.20 or more △: 1.10 or more and less than 1.20 ×: less than 1.10

<Evaluation of discharge stability>
After printing the printed matter, the printer was left in an environment of 40 ° C. for one day with the printer capped on the printer head. Whether or not the ejection state of the printer after being left to stand is restored to the initial ejection state was evaluated by the following number of cleaning operations.
◯: Printing was possible without cleaning operation Δ: Recovered by one operation ×: No recovery was observed by two or more operations

Aspects of the present invention are, for example, as follows.
<1> An ink containing a resin at 25 ° C. when the resin is contained in an amount of 4.0% by mass or more and 10.0% by mass or less and concentrated until the solid content of the ink reaches 20% by mass. The ratio (G'/ G ") of the storage elastic modulus G'and the loss elastic modulus G" by the dynamic viscoelasticity measurement method is 1.0 or more and 2.0 or less, and the ink is low at 25 ° C. by the Bristol method. An ink having an absorption coefficient Kα for a penetrating recording medium of 0.06 mL · m- ² · ms- ^{1 / 2} or more and 0.12 mL · m- ² · ms- ^{1 / 2} or less.
<2> The ink according to <1>, wherein the storage elastic modulus G'is 10 Pa or more and 20 Pa or less.
<3> The ink contains a plurality of organic solvents, and the Hansen solubility parameter (hSP value) δh of the organic solvent contained most in terms of mass among the plurality of organic solvents is 3.0 (cal / cm ³ ) ¹ The ink according to <1> or <2> above, which is ^{/ 2} or more and 9.5 (cal / cm ³ ) ^{1/2 or less.}
<4> The ink according to any one of <1> to <3>, wherein the surface tension at 25 ° C. is 20.0 mN / m or more and 27.0 mN / m or less.
<5> The ink according to any one of <1> to <4>, wherein the viscosity at 25 ° C. is 6.0 mPa · s or more and 10.0 mPa · s or less.
<6> The ink according to any one of <1> to <5>, wherein the solid content particle size (D50) is 90 nm or more and 120 nm or less.
<7> The ink according to any one of <1> to <6>, wherein the ratio of the particle size (D50) to the particle size (D90) of the solid content is 0.60 or more and 1.00 or less.
<8> An ink container having an ink accommodating portion for accommodating the ink according to any one of <1> to <7>.
<9> An inkjet recording method in which ink is ejected from a nozzle of a recording head and applied to a recording medium for recording, wherein the ink is the ink according to any one of <1> to <7>. Recording method.
<10> The recording medium comprises a support and a coating layer on at least one surface of the support, and pure water at a contact time of 100 ms measured by a dynamic scanning liquid absorbent meter at 25 ° C. The amount of transfer of the recording medium to the surface having the coating layer is 2 mL / m ² or more and 35 mL / m ² or less, and pure water at a contact time of 400 ms is transferred to the surface of the recording medium having the coating layer. The inkjet recording method according to <9> above, wherein the transfer amount is 3 mL / m ² or more and 40 mL / m ^{2 or less.}
<11> An inkjet recording apparatus having the ink container according to <8> and a recording head for ejecting ink droplets.

The ink according to any one of <1> to <7>, the ink container according to <8>, the inkjet recording method according to <9> or <10>, and the inkjet according to <11>. According to the recording device, the conventional problems can be solved and the object of the present invention can be achieved.

Japanese Unexamined Patent Publication No. 2011-063630 Japanese Unexamined Patent Publication No. 2008-101192 Japanese Unexamined Patent Publication No. 2004-174948 Japanese Unexamined Patent Publication No. 2010-047700 Japanese Unexamined Patent Publication No. 2009-280671

400 Image forming device 401 Exterior 401c Cover 404 Cartridge holder 410, 410k, 410c, 410m, 410y Main tank 411 Ink storage unit 413 Ink storage port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube L Ink storage container

Claims (11)

Ink containing resin
The resin is an acrylic silicone resin or a urethane resin.
Storage elastic modulus G by dynamic viscoelasticity measurement method at 25 ° C. when the resin is contained in an amount of 4.0% by mass or more and 10.0% by mass or less and concentrated until the solid content of the ink reaches 20% by mass. The ratio (G'/ G ") of'to loss elastic modulus G'is 1.0 or more and 2.0 or less.
An ink according to the Bristow method having an absorption coefficient Kα for a low-permeability recording medium at 25 ° C. of 0.06 mL · m- ² · ms- ^{1 / 2} or more and 0.12 mL · m- ² · ms- ^{1 / 2} or less. .. The ink according to claim 1, wherein the storage elastic modulus G'is 10 Pa or more and 20 Pa or less. The ink contains a plurality of organic solvents, and the Hansen solubility parameter (hSP value) δh of the organic solvent contained most in terms of mass among the plurality of organic solvents is 3.0 (cal / cm ³ ) ^1/2 or more. The ink according to claim 1 or 2, which is 9.5 (cal / cm ³ ) ^{1/2 or less.} The ink according to any one of claims 1 to 3, wherein the surface tension at 25 ° C. is 20.0 mN / m or more and 27.0 mN / m or less. The ink according to any one of claims 1 to 4, wherein the viscosity at 25 ° C. is 6.0 mPa · s or more and 10.0 mPa · s or less. The ink according to any one of claims 1 to 5, wherein the particle size (D50) of the solid content is 90 nm or more and 120 nm or less. The ink according to any one of claims 1 to 6, wherein the ratio of the particle size (D50) to the particle size (D90) of the solid content is 0.60 or more and 1.00 or less. An ink container having an ink accommodating portion for accommodating the ink according to any one of claims 1 to 7. An inkjet recording method in which ink is ejected from a nozzle of a recording head and applied to a recording medium for recording.
The inkjet recording method in which the ink is the ink according to any one of claims 1 to 7. The recording medium comprises a support and a coating layer on at least one surface of the support, and the recording medium of pure water at a contact time of 100 ms measured by a dynamic scanning liquid absorber at 25 ° C. The amount of transfer of pure water to the surface having the coating layer is 2 mL / m ² or more and 35 mL / m ² or less, and the amount of pure water transferred to the surface having the coating layer at a contact time of 400 ms. The inkjet recording method according to claim 9, wherein the content is 3 mL / m ² or more and 40 mL / m ^{2 or less.} An inkjet recording apparatus having the ink container according to claim 8 and a recording head for ejecting ink droplets.

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