JP2021183385A - Ink set and recording device - Google Patents

Abstract

To perform recording without impairing glossy feeling while suppressing occurrence of bleeding in a form using ink containing resin emulsion.SOLUTION: In a first type of ink containing a pigment, a second type of ink not containing a pigment and containing a reactive component of a polyvalent metal salt, and a third type of ink containing resin emulsion, an acid value of a dissociable group contained in the first type of ink is smaller than an acid value of a dissociable group of the resin emulsion contained in the third type of ink.SELECTED DRAWING: None

Description

The present invention relates to an ink set and a recording device.

A recording device for recording an image on a recording medium by ejecting ink while scanning the recording head relative to the recording medium in the scanning direction is known. In recent years, such recording devices have come to record recorded materials for various purposes, and various types of ink are used accordingly.

In Patent Document 1, an ink containing a pigment and a resin emulsion is used, and when the ink is landed on a recording medium, heat is applied to the ink to form a film on the surface of the recording medium to fix the resin emulsion. How to do it is disclosed. The document describes that the filming of the resin emulsion described above makes it possible to record an image having excellent durability.

On the other hand, in the recording device as described above, different types of ink droplets applied to the recording medium are attracted to each other, causing bleeding between the ink droplets, which may deteriorate the image quality. On the other hand, Patent Document 2 discloses that a solution containing a polyvalent metal salt is applied onto a recording medium, and then an ink containing a carboxyl group is applied. According to the same document, it is described that the occurrence of the above-mentioned bleeding can be reduced because the insoluble substance is formed by the contact between the polyvalent metal salt and the carboxyl group on the recording medium.

Japanese Unexamined Patent Publication No. 2005-220352 Japanese Unexamined Patent Publication No. 5-202328

However, as a result of the studies by the inventors, it has been found that there are the following problems in the system using the ink containing the pigment and the resin emulsion as described in Patent Document 1. That is, it was found that when a solution capable of reacting with the pigment (hereinafter, also referred to as a reaction solution) is used to reduce bleeding, it may be difficult to obtain sufficient image quality.

The reason for the deterioration of image quality will be described below.

First, the solid content of the ink may increase. While ordinary ink contains only pigments, the ink described in Patent Document 1 contains a relatively large amount of resin emulsion in addition to pigments. Therefore, the solid content (pigment, resin emulsion) contained in one drop of ink applied to the recording medium increases, and there is a possibility that the solid content (pigment, resin emulsion) will be clogged when the ejection operation from the ejection port is attempted. The above-mentioned clogging can be reduced by increasing the diameter of the ejection port and increasing the ejection amount from one ejection port, but this causes a large drop of ink, resulting in a decrease in fineness and gloss. It will occur.

In addition, the addition of an unnecessary resin emulsion may hinder the formation of a high-quality image. In particular, when recording a recorded object to be exhibited outdoors, the resin emulsion can be coated by heating with an ink containing a pigment and a resin emulsion, and recording with excellent water resistance and scratch resistance can be performed. .. However, even when recording a recorded material (photographic image, document, etc.) that is intended to be viewed indoors, not for outdoor exhibition, the resin emulsion is applied, and it is difficult to obtain a glossy feeling. .. As described above, there is a concern that the glossiness may be impaired by using the ink containing the resin emulsion.

On the other hand, by containing the pigment and the resin emulsion in separate inks, deterioration of image quality due to the above-mentioned phenomenon can be suppressed to some extent. However, even in such a system, if the reactivity between the resin emulsion and the reaction solution is high, the glossiness may decrease. This is because when the resin emulsion reacts with the reaction liquid, agglutination of the resin emulsion occurs, the surface of the image cannot be uniformly covered, and the unevenness of the image surface becomes large.

The present invention has been made in view of the above problems, and an object thereof is to perform recording without impairing the glossiness while suppressing the occurrence of bleeding in a form using an ink containing a resin emulsion. be.

Therefore, the present invention is an ink set composed of first, second, and third types of inks of different types, and the first type of ink is a pigment dispersed with a water-soluble resin as a coloring material. The second type of ink does not contain a coloring material and contains a reactive component that reacts with the first type of ink, and the third type of ink contains a coloring material. The reactive component contained in the second type of ink is a polyvalent metal salt, which does not contain the above-mentioned ink and contains a resin emulsion dispersed by a dissociative functional group. The water-soluble resin contained in the first type of ink has an acid value higher than that of the resin emulsion dispersed by the dissociative functional group contained in the third type of ink. It is a feature.

According to the ink set according to the present invention, in the form of using an ink having a resin emulsion, it is possible to perform recording without impairing the glossiness while suppressing the occurrence of bleeding.

It is a perspective view of the recording apparatus applied in embodiment. It is a schematic diagram of the recording head applied in embodiment. It is a schematic diagram which shows the recording control system in an embodiment. It is a figure which shows the data processing process in an embodiment. It is a figure for demonstrating the multipath recording in an embodiment. It is a schematic diagram which shows the mask pattern in an embodiment. It is a schematic diagram which shows the mask pattern in an embodiment. It is a schematic diagram which shows the mask pattern in an embodiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(First Embodiment)
FIG. 1 shows the appearance of an inkjet recording device (hereinafter, also referred to as a recording device and a printer) according to the present embodiment. This is a so-called serial scanning type printer, which scans a recording head in the X direction (scanning direction) orthogonal to the Y direction (transporting direction) of the recording medium P and records an image.

The configuration of this inkjet recording apparatus and the outline of the operation at the time of recording will be described with reference to FIG. First, the recording medium P is conveyed in the Y direction from the spool 6 holding the recording medium P by a transfer roller driven via a gear by a transfer motor (not shown). On the other hand, the carriage unit 2 is reciprocally scanned (reciprocated) along the guide shaft 8 extending in the X direction by a carriage motor (not shown) at a predetermined transport position. Then, in the process of this scanning, the ejection operation is performed from the ejection port of the recording head (described later) that can be attached to the carriage unit 2 at the timing based on the position signal obtained by the encoder 7, and the ejection operation corresponds to the arrangement range of the ejection port. Record a constant bandwidth. In the present embodiment, the scanning speed is 40 inches per second, and the ejection operation is performed at a resolution of 600 dpi (1/600 inch). After that, the recording medium P is conveyed, and the next bandwidth is recorded. In addition, it is possible to scan at a speed of 40 inches per second or more.

A carriage belt can be used to transmit the driving force from the carriage motor to the carriage unit 2. However, instead of the carriage belt, for example, a lead screw that is rotationally driven by a carriage motor and extends in the X direction, and an engaging portion provided in the carriage unit 2 that engages with the groove of the lead screw, etc. It is also possible to use other drive methods.

The fed recording medium P is sandwiched and conveyed between the paper feed roller and the pinch roller, and is guided to the recording position (scanning area of the recording head) on the platen 4. Since the face surface of the recording head is capped in the normal hibernation state, the cap is opened prior to recording so that the recording head or the carriage unit 2 can be scanned. After that, when the data for one scan is accumulated in the buffer, the carriage unit 2 is scanned by the carriage motor and recording is performed as described above.

Further, a heating unit (not shown) for heating the clear emulsion ink described later to form a film is provided in the recording device. This heating unit may be provided on the upper side in the vertical direction with respect to the recording head and may be configured to heat the recording medium on which the image is recorded from above. Further, a heating portion may be provided on the lower side of the platen 4 in the vertical direction, and the recording medium on which the image is recorded may be heated from the lower side.

Here, in the recording apparatus of the present embodiment, so-called multipath recording is performed in which an image is recorded in a unit region (1 / n band) on the recording medium P by scanning the recording head a plurality of times (n times). be able to. This multipath recording will be described in detail later.

FIG. 2 shows the recording head 9 according to the present embodiment. The recording head 9 has a discharge port row (K) for discharging black ink (K) as ink containing a coloring material, a discharge port row 22C for discharging cyan ink (C), and a discharge port for discharging magenta ink (M). The row 22M is provided with a discharge port row 22Y for discharging yellow ink (Y). Since these black inks (K), cyan inks (C), magenta inks (M), and yellow inks (Y) each contain pigments as coloring materials, these inks are used as pigments for the sake of simplicity in the following description. Also called ink.

Further, the recording head 9 includes a discharge port row 22RCT for discharging a reaction liquid (RCT) containing no coloring material. This reaction liquid is a liquid for improving image quality by contacting with ink containing a coloring material, specifically, improving at least one quality of bleeding, glossiness, and graininess.

Further, the recording head 9 is provided with a discharge port row 22Em that discharges a clear emulsion ink (Em) that does not contain a coloring material and contains a resin emulsion. This clear emulsion ink is a liquid for forming a film by being applied on a recording medium and then being heated to improve at least one of scratch resistance, water resistance, and light resistance of an image.

In the recording head 9, these discharge port rows are arranged side by side in the order of the discharge port rows 22K, 22C, 22M, 22Y, 22Em, and 22RCT from the left side to the right side in the X direction. These ejection port rows 22K, 22C, 22M, 22Y, 22Em, and 22RCT are configured by 1280 ejection ports 30 for ejecting each ink being arranged in the Y direction (arrangement direction) at a density of 1200 dpi. There is. The amount of ink ejected from one ejection port 30 in the present embodiment at one time is about 4.5 pl.

These ejection port rows 22K, 22C, 22M, 22Y, 22Em, and 22RCT are connected to ink tanks (not shown) for storing corresponding inks, and ink is supplied. The recording head 9 and the ink tank used in the present embodiment may be integrally configured or may be separable from each other.

The detailed compositions of black ink (K), cyan ink (C), magenta ink (M), yellow ink (Y), clear emulsion ink (Em), and reaction solution (RCT) will be described later.

FIG. 3 is a block diagram showing a schematic configuration of a control system in the recording device 100 in the present embodiment. The main control unit 300 includes a CPU 301 that executes processing operations such as calculation, selection, discrimination, and control, and a recording operation, a ROM 302 that stores a control program and the like to be executed by the CPU 301, and a RAM 303 that is used as a buffer for recorded data. I have. It also has an input / output port 304 and the like. The memory 313 stores a mask pattern and the like, which will be described later. The input / output ports 304 are connected to drive circuits 305, 306, and 307 such as a transfer motor (LF motor) 309, a carriage motor (CR motor) 310, a recording head 9, and an actuator in the cutting unit. Further, the main control unit 300 is connected to the PC 312 which is a host computer via the interface circuit 311.

(Data processing process)
FIG. 4 is a flowchart of the recorded data generation process executed by the CPU 301 according to the control program in the present embodiment.

First, an image represented by information (0 to 255) of 8-bit 256 values for each color of red (R), green (G), and blue (B) input from the host computer PC 312 to the recording device 100 in step S1. Acquire data (brightness data).

Next, in step S2, the image data represented by R, G, and B is converted into multi-valued data represented by a plurality of types of inks (K, C, M, Y, Em, RCT) used for recording. By this color conversion process, a multi-value represented by 8-bit 256-value information (0 to 255) that determines the gradation of each ink of K, C, M, Y, Em, and RCT in each pixel group composed of a plurality of pixels. Data is generated.

Next, in step S3, the quantization of the multi-valued data represented by K, C, M, Y, Em, and RCT is executed. As a result, the quantized data (binary data) represented by the 1-bit binary information (0, 1) that determines the ejection or non-ejection of the K, C, M, Y, Em, and RCT inks for each pixel is obtained. Generate. Here, as the quantization process, the process can be performed according to various quantization methods such as an error diffusion method, a dither method, and an index method.

Then, in step S4, a distribution process is performed in which the quantized data is distributed to a plurality of scans with respect to the unit region of the recording head. By this distribution process, 1-bit binary information (0, 1) that determines whether K, C, M, Y, Em, and RCT inks are ejected or not ejected for each pixel in each of a plurality of scans with respect to a unit area of a recording medium. ) Is generated. This distribution process corresponds to a plurality of scans and is performed using a mask pattern that determines the permissible or non-permissible ink ejection for each pixel.

In the present embodiment, the ink is ejected from the recording head according to the recording data generated as described above.

Although the mode in which the CPU 301 in the recording device 100 executes all the processes of S1 to S4 is described here, other modes can also be used. For example, the PC 312 may execute all the processes of S1 to S4. Further, for example, the PC 312 may perform a part of the operation and the recording device 100 may execute the rest.

(Multipath recording method)
In the present embodiment, K, C, M, Y, Em, and RCT inks are used, and an image is recorded by so-called multi-pass recording in which a unit region on a recording medium is scanned and recorded a plurality of times. Here, in the present embodiment, in step S4, the same mask pattern is applied to each of the K, C, M, Y, Em, and RCT inks for recording. Therefore, in the present embodiment, the order of applying K, C, M, Y, Em, and RCT in a plurality of scans is not particularly limited. In this embodiment, the unit area is scanned 6 times to complete the recording.

FIG. 5 is a diagram for explaining the multipath recording method performed in the present embodiment. In the present embodiment, ink is ejected from each of the six ejection port groups A1 to A6 configured by dividing each ejection port row 22 in the Y direction in each of the six scans with respect to the unit region. Actually, the recording medium 3 is conveyed to the downstream side in the Y direction during scanning of the recording head 9, but for simplicity in FIG. 5, the recording head 9 is described so as to be moved to the upstream side in the Y direction during scanning. do.

First, in the first scan (first scan), the recording head 9 is scanned in a positional relationship in which the unit region 80 on the recording medium 3 and the discharge port group A1 in the discharge port row 22 face each other. Then, while scanning, ink is ejected from the ejection port group A1 to the unit region 80 according to the recording data corresponding to each type of ink generated in step S4. After the first scan is completed, the recording medium is conveyed in the Y direction by a distance corresponding to one ejection port group. After that, a second scan (second scan) is performed, and ink is ejected from the ejection port group A2 to the unit region 80. After that, the recording medium is conveyed and discharged from the recording head alternately, and the discharge from the discharge port groups A3 to A6 in the third to sixth scans with respect to the unit region 80 is executed. In this way, multipath recording for the unit area 80 is completed.

FIG. 6 is a diagram showing a mask pattern used in this embodiment. Here, among the mask patterns shown in FIG. 6, the pixels filled in black are pixels that allow ink ejection when ink ejection is defined by the quantization data (hereinafter, also referred to as recording allowable pixels). .. Pixels shown by white spots indicate pixels that do not allow ink ejection (hereinafter, also referred to as non-recording allowable pixels) even when ink ejection is defined by quantization data. Further, FIG. 6 shows mask patterns having a size of 4 pixels × 8 pixels, respectively, and by repeatedly applying these mask patterns in the X direction and the Y direction, all of the quantized data corresponding to each unit region. Is distributed.

The number of pixels existing in each of the six mask patterns shown in FIG. 6 is 4 pixels × 8 pixels = 32 pixels, and the total recording allowance in the 6 mask patterns is 48 pixels. When the ratio of the number of recording allowable pixels to the number of pixels in the mask pattern is referred to as the recording allowable rate, the total recording allowable rate of the mask patterns shown in FIG. 6 is 150 (= 48/32 × 100)%.

Here, looking at the mask patterns corresponding to each scan, the mask pattern corresponding to the first scan (discharge port group A1) and the mask pattern corresponding to the sixth scan (discharge port group A6) are 6 respectively. A record allowable pixel is arranged. Therefore, the recording tolerance of the mask pattern corresponding to the first and sixth scans is about 20% (= 6/32 × 100).

Further, in the mask pattern corresponding to the second scan (discharge port group A2) and the mask pattern corresponding to the fifth scan (discharge port group A5), eight recording allowable pixels are arranged respectively. Therefore, the recording allowance of the mask pattern corresponding to the second and fifth scans is about 25% (= 8/32 × 100).

Then, 10 recording allowable pixels are arranged in each of the mask pattern corresponding to the third scan (discharge port group A3) and the mask pattern corresponding to the fourth scan (discharge port group A4). Therefore, the recording allowance of the mask pattern corresponding to the third and fourth scans is about 30% (= 10/32 × 100).

As described above, in the present embodiment, the same mask pattern group shown in FIG. 6 is applied to the quantized data corresponding to each ink. Therefore, the order of applying the K, C, M, Y, Em, and RCT inks in the plurality of scans is not particularly controlled, and is a random order.

(Ink composition)
Next, the details of each ink constituting the ink set used in the present embodiment will be described. Hereinafter, the terms "part" and "%" are based on mass unless otherwise specified.

1. 1. Preparation conditions for each ink In each ink used in this embodiment, the reactive component contained in the reaction solution (RCT) is a polyvalent metal salt, and the ink is contained in the pigment ink (C, M, Y, K). The acid value of the water-soluble resin is larger than the acid value of the resin Em contained in the resin emulsion (Em) ink. It is prepared in this way.

Here, the acid value (Acid Value) in the present specification represents the number of mg of potassium hydroxide required to neutralize the dissociative functional group present in 1 g of the resin. Generally, it can be said that the larger the acid value, the larger the number of dissociative functional groups per unit amount of resin, and the higher the dispersion stability of the particles in the solution.

The reactive component of the reaction solution used in the present embodiment has a large amount capable of maintaining the dispersed state of the resin emulsion contained in the clear emulsion ink and destroying the dispersed state of the pigment contained in the pigment ink. It is preferably a metal salt.

In this embodiment, a resin emulsion and a pigment in the form of resin dispersion are used. More specifically, a water-soluble resin having a dissociative functional group is attached to the surface of each of the pigment and the resin emulsion. Then, in the present embodiment, the acid value between the dissociative functional group of the water-soluble resin adhering to the pigment and the dissociable functional group of the water-soluble resin adhering to the resin emulsion is prepared as follows. .. In the following description, the acid value of the dissociative functional group of the water-soluble resin adhering to the pigment is referred to as PigAV, and the acid value of the dissociative functional group of the water-soluble resin adhering to the resin emulsion is referred to as EmAV.

In the present embodiment, in order to reduce bleeding, the pigment contained in the pigment ink needs to react with the reactive component contained in the reaction solution.

Further, in order to prevent the pigment from being inadequately reacted due to the reaction of the resin emulsion with the reactive component, the resin emulsion needs to have higher stability than the pigment contained in the pigment ink.

To summarize the above points, each ink used in this embodiment needs to satisfy the condition of EmAV> PigAV. As a result, when the inks are applied and they come into contact with each other, the pigment is likely to precipitate and the resin emulsion is less likely to precipitate.

In view of the above points, in the present embodiment, the combination of the reactive component and the anionic group of the water-soluble resin of each of the pigment and the resin emulsion is selected.

Specifically, first, a polyvalent metal salt is used as the reactive component, and in particular, calcium methanesulfonate (hereinafter referred to as MSA-Ca) is used in this embodiment.

As described above, when a polyvalent metal salt is used, "salting out" or "coagulation" can be considered as the behavior of destroying the dispersed morphology of the dispersed particles.

Salting out is a phenomenon in which the hydrated state is destroyed by increasing the concentration of the polyvalent metal of the electrolyte around the fine particles hydrated with a functional group or the like, and the particles aggregate with each other. In other words, it can be said that the hydrated particles are destroyed in the hydrated state by a large amount of polyvalent metal ions and the particles are aggregated.

Further, coagulation is a phenomenon in which particles of an electrolyte substance are electrically attracted to a state in which particles are dispersed by electrostatic repulsion, the original dispersed state is destroyed, and the particles are aggregated. Is. In other words, it can be said to be a reaction in which electrostatically repulsive particles are reduced in repulsive force with a small amount of multivalent metal ions to aggregate the particles.

In the present embodiment, the pigment and the resin emulsion are dispersed and stabilized in a state of being hydrated with a dissociative functional group. Therefore, it can be inferred that the aggregation mechanism of these particles is salting out.

In salting out, the dispersion stability is determined by the number of functional groups that hydrate the dispersed particles using the dissociative functional groups. That is, particles having a large valence have high dispersion stability, and particles having a small valence have low dispersion stability. Therefore, in the present embodiment, it is possible to control the gloss by setting EmAV> PigAV.

2. 2. Composition of Each Ink The composition of each ink will be described in detail below.

The pigment ink (C, M, Y, K), the reaction solution (RCT), and the clear emulsion ink (Em) used in the present embodiment all contain a water-soluble organic solvent. The water-soluble organic solvent preferably has a boiling point of 150 ° C. or higher and 300 ° C. or lower because of the wettability and moisturizing property of the face surface of the recording head 9. In addition, from the viewpoint of the function of the film-forming auxiliary for the resin fine particles and the swelling solubility in the recording medium on which the resin layer is formed, ketone compounds such as acetone and cyclohexanone, and propylene glycol derivatives such as tetraethylene glycol dimethyl ether are particularly preferable. preferable. Heterocyclic compounds having a lactam structure typified by N-methyl-pyrrolidone and 2-pyrrolidone are also particularly preferable. From the viewpoint of discharge performance, the content of the water-soluble organic solvent is preferably 3 wt% or more and 30 wt% or less. Specifically, the water-soluble organic solvent has 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. Alcohols. Amides such as dimethylformamide and dimethylacetamide. Ketones or keto alcohols such as acetone and diacetone alcohol. Ethers such as tetrahydrofuran and dioxane. Polyalkylene glycols such as polyethylene glycol and polypropylene glycol. ethylene glycol. Alternatively, alkylene glycols containing 2 to 6 carbon atoms such as propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, and diethylene glycol. Lower alkyl ether acetate such as polyethylene glycol monomethyl ether acetate. Glycerin. Lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ethers, diethylene glycol methyl (or ethyl) ethers, and triethylene glycol monomethyl (or ethyl) ethers. Trimethylolpropane, trimethylolethane and other polyhydric alcohols. Examples thereof include N-methyl-2-pyrrolidone, 2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone. The water-soluble organic solvent as described above can be used alone or as a mixture. Further, it is desirable to use deionized water as the water. The content of the water-soluble organic solvent in the reaction solution (RCT) is not particularly limited. However, the pigment ink (C, M, Y, K) and the clear emulsion ink (Em) have a surfactant and a defoaming agent in addition to the above-mentioned components in order to have desired physical property values as needed. , Preservatives, antifungal agents and the like can be appropriately added.

Further, the pigment ink (C, M, Y, K), the reaction solution (RCT), and the clear emulsion ink (Em) used in the present embodiment all contain a surfactant. Surfactants are used as penetrants for the purpose of improving the permeability of the ink to a recording medium dedicated to inkjet. The larger the amount of the surfactant added, the stronger the property of lowering the surface tension of the ink, and the better the wettability and permeability of the ink to the recording medium. In the present embodiment, a small amount of acetylene glycol EO adduct or the like is added as a surfactant, and the surface tension of each ink is adjusted to 30 dyn / cm or less, and the difference in surface tension between the inks is adjusted to 2 dyn / cm or less. bottom. More specifically, the surface tensions of all the inks were adjusted to about 28 to 30 dyn / cm. A fully automatic tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the surface tension. The measuring instrument is not limited to the above-exemplified one as long as the surface tension of the ink can be measured.

Further, the pH of each ink of the present embodiment is stable on the alkaline side, and the value is 8.5 to 9.5. The pH of each ink is 7.0 or more and 10.0 or less from the viewpoint of preventing elution and deterioration of members in contact with each ink in the recording device and recording head, and deterioration of the solubility of the dispersed resin in the ink. Is preferable. For the pH measurement, a pH METER model F-52 manufactured by HORIBA, Ltd. was used. The measuring instrument is not limited to the above-exemplified one as long as it can measure the pH of the ink.

2-1. Pigment ink For the sake of simplicity, among the black ink (K), cyan ink (C), magenta ink (M), and yellow ink (Y) used in this embodiment, cyan ink (C) and magenta ink (M) It will be explained in detail.

2-1-1. Magenta ink ・ Preparation of dispersion First, using benzyl acrylate and methacrylic acid as raw materials, an AB type block polymer having an acid value of 300 and a number average molecular weight of 2500 was prepared by a conventional method, and further neutralized with an aqueous potassium hydroxide solution. A homogeneous 50% by mass polymer aqueous solution was prepared by diluting with ion-exchanged water.

100 g of the above polymer solution, C.I. I. Pigment Red 122 and 300 g of ion-exchanged water were mixed and mechanically stirred for 0.5 hours.

The mixture was then treated using a microfluidizer by passing the mixture 5 times into the interaction chamber at a liquid pressure of about 70 MPa.

Further, the dispersion obtained above was subjected to centrifugation (12,000 rpm, 20 minutes) to remove non-dispersions containing coarse particles to obtain a magenta dispersion. The obtained magenta dispersion had a pigment concentration of 10% by mass and a dispersant concentration of 5% by mass.

-Preparation of ink For the preparation of ink, the above magenta dispersion liquid is used, and the following components are added thereto to obtain a predetermined concentration. Then, after sufficiently mixing and stirring these components, pressure filtration is performed with a microfilter (manufactured by Fujifilm Co., Ltd.) having a pore size of 2.5 μm to obtain a pigment ink having a pigment concentration of 4% by mass and a dispersant concentration of 2% by mass. Prepared.

40 parts of the above magenta dispersion 2-pyrrolidone 5 parts 2-methyl 1,3 propanediol 15 parts Acetylene glycol EO adduct 0.5 parts (manufactured by Kawaken Fine Chemical Co., Ltd.) Ion-exchanged water balance

2-1-2. Cyan ink ・ Preparation of dispersion First, using benzyl acrylate and methacrylic acid as raw materials, an AB type block polymer having an acid value of 250 and a number average molecular weight of 3000 was prepared by a conventional method, and further neutralized with an aqueous potassium hydroxide solution. A homogeneous 50% by mass polymer aqueous solution was prepared by diluting with ion-exchanged water.

180 g of the above polymer solution, C.I. I. Pigment Blue 15: 3 was mixed with 100 g and ion-exchanged water was 220 g, and the mixture was mechanically stirred for 0.5 hours.

The mixture was then treated using a microfluidizer by passing the mixture 5 times into the interaction chamber at a liquid pressure of about 70 MPa.

Further, the dispersion obtained above was subjected to centrifugation (12,000 rpm, 20 minutes) to remove non-dispersions containing coarse particles to obtain a cyan dispersion. The obtained cyan dispersion had a pigment concentration of 10% by mass and a dispersant concentration of 10% by mass.

-Preparation of ink For the preparation of ink, the above-mentioned cyan dispersion is used, and the following components are added to the above-mentioned cyan dispersion liquid to obtain a predetermined concentration. Then, after sufficiently mixing and stirring these components, pressure filtration is performed with a microfilter (manufactured by Fujifilm Co., Ltd.) having a pore size of 2.5 μm to obtain a pigment ink having a pigment concentration of 2% by mass and a dispersant concentration of 2% by mass. Prepared.

20 parts of the above cyan dispersion 2-pyrrolidone 5 parts 2-methyl 1,3 propanediol 15 parts Acetylene glycol EO adduct 0.5 parts (manufactured by Kawaken Fine Chemical Co., Ltd.) Ion-exchanged water balance

2-2. Reaction solution The reaction solution used in the present embodiment contains a reactive component that reacts with the pigment contained in the ink and aggregates or gels the pigment. Specifically, this reactive component is a dispersion of the ink when mixed with an ink having a pigment stably dispersed or dissolved in an aqueous medium by the action of an ionic group on a recording medium or the like. It is a component that can destroy stability. Specifically, as described above, MSA-Ca is used in this embodiment.

It is not always necessary to use MSA-Ca, and in this embodiment, various polyvalent metal salts can be used as the reactive component of the reaction solution as long as they are water-soluble. Specific examples of the polyvalent metal salt include inorganic salts (calcium nitrate, magnesium chloride, etc.) and organic salts (calcium acetate, calcium lactate, magnesium citrate, etc.). The content of the polyvalent metal salt is preferably 0.1% by mass or more and 90.0% by mass or less, preferably 1.0% by mass or more and 70.0% by mass, based on the total mass of the composition contained in the reaction solution. It is more preferably mass% or less.

-Preparation of ink In this embodiment, as described above, glutaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as an organic acid, and the following components were mixed to prepare a reaction solution 1.

MSA-Ca 3 parts 2-Pyrrolidone 5 parts 2-Methyl 1,3 Propanediol 15 parts Acetylene glycol EO adduct 0.5 parts (manufactured by Kawaken Fine Chemicals Co., Ltd.) Ion-exchanged water balance

2-3. Clear Emulsion Ink The clear emulsion ink used in this embodiment does not contain a coloring material but contains a resin emulsion.

In the present embodiment, the "resin emulsion" means polymer fine particles existing in a state of being dispersed in water. Specific examples thereof include acrylic resin fine particles synthesized by emulsion polymerization of a monomer such as (meth) acrylic acid alkyl ester and (meth) acrylic acid alkyl amide. Examples thereof include styrene-acrylic resin fine particles synthesized by emulsion polymerization of a styrene monomer and (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl amide, or the like. Examples thereof include polyethylene resin fine particles, polypropylene resin fine particles, polyurethane resin fine particles, and styrene-butadiene resin fine particles. In addition, core-shell type resin fine particles having different polymer compositions between the core portion and the shell portion constituting the resin fine particles and acrylic fine particles synthesized in advance to control the particle size are used as seed particles and emulsion-polymerized around them. The obtained resin fine particles may be used. Further, hybrid type resin fine particles in which different resin fine particles such as acrylic resin fine particles and urethane resin fine particles are chemically bonded may be used.

Further, "polymer fine particles existing in a state of being dispersed in water" is a form of resin fine particles obtained by homopolymerizing or copolymerizing a plurality of types of monomers having a dissociative group, so-called self-dispersion type resin fine particle dispersion. It may be a body. Here, the dissociative group has a sulfonic acid group as described above. Examples of the monomer having this dissociative group include acrylic acid and methacrylic acid.

The dissociative group does not necessarily have to be a carboxylic acid group as long as the above-mentioned condition of EmAV> PigAV is satisfied, and for example, a phosphoric acid group, a sulfonic acid group and the like can be preferably used. The dissociative group concentration may be controlled by changing the monomer concentration so as to satisfy the above conditions.

The resin component constituting the resin fine particles is not particularly limited as long as it is a resin containing a dissociative group, and any commonly used natural or synthetic polymer, a polymer newly developed for the present invention, or the like can be used. Any resin component can be used without limitation. In particular, from the viewpoint that it can be generally used and the functional design of the resin fine particles can be easily performed, a polymer or copolymer of a monomer component having a radically polymerizable unsaturated bond, such as an acrylic resin and a styrene / acrylic resin, can be used. You can use coalescence.

Examples of the hydrophilic radically polymerizable unsaturated monomer (hereinafter referred to as a monomer) having a sulfonic acid group used in the present embodiment include the following. Examples thereof include styrene sulfonic acid, -2-propyl acrylamide sulfonic acid, ethyl -2-sulfonic acid acrylate, ethyl -2-sulfonic acid methacrylate, butyl acrylamide sulfonic acid and salts thereof.

Further, as the hydrophilic monomer, in addition to the above-mentioned monomer having a sulfonic acid group, carboxyl such as acrylic acid, methacrylic acid, crotonic acid, etaacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like. Monomers having a group and salts thereof can be mentioned. Monomers having a phosphonic acid group such as ethyl methacrylate-2-phosphonate and ethyl -2-phosphonate acrylate may be used together.

Examples of the monomer classified as a hydrophobic monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-propyl acrylate, -n-butyl acrylate, -t-butyl acrylate, and acrylic acid. Examples include benzyl and methyl methacrylate. Also included are ethyl methacrylate, isopropyl methacrylate, -n-propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -t-butyl methacrylate and tridecyl methacrylate. (Meta) acrylic acid esters such as benzyl methacrylate; styrene-based monomers such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene and the like can also be mentioned. .. Itaconic acid esters such as benzyl itaconic acid; maleic acid esters such as dimethyl maleate; fumaric acid esters such as dimethyl fumarate; acrylonitrile, methacrylonitrile, vinyl acetate and the like can also be mentioned. In addition, various publicly known or novel oligomers, macromonomers and the like can be used without limitation.

Since the radically polymerizable monomer used in the production method according to the present invention is a component constituting the resin fine particles having a sulfonic acid group through aqueous precipitation polymerization, it may be appropriately selected depending on the characteristics of the desired resin fine particles. Also in the present embodiment, any conventionally known radically polymerizable monomer or a radically polymerizable monomer newly developed for the present invention can be used.

In the present embodiment, in particular, the resin fine particles having a sulfonic acid group are obtained from a copolymer of a monomer component containing at least one kind of hydrophilic monomer having at least one kind of sulfonic acid and at least one kind of hydrophobic monomer among the above-mentioned fine particles of resin. It is preferable that the configuration is as follows. This is preferable in terms of obtaining a water-based inkjet recording ink having dispersion stability and suitable printing characteristics. That is, when producing the resin fine particles, for example, various characteristics of the resin fine particles are appropriately adjusted depending on many control factors such as the type and concentration of the polymerization initiator used, the type of the constituent monomers, the copolymerization ratio, and the like. It is possible to control.

The radical polymerization reaction conditions vary depending on the properties of the polymerization initiator, dispersant, and monomer used, but for example, the reaction temperature is 100 ° C. or lower, preferably 40 ° C. or higher and 80 ° C. or lower. The reaction time is 1 hour or more, preferably 6 hours or more and 30 hours or less. The stirring speed during the reaction is preferably 50 rpm or more and 500 rpm or less, preferably 150 rpm or more and 400 rpm or less.

In the above-mentioned steps, particularly when at least one kind of hydrophobic monomer and a hydrophilic monomer containing at least a sulfonic acid group are polymerized to obtain resin fine particles having a sulfonic acid group, the monomer component is preferably aqueous. It is desirable to drop into an aqueous dispersion containing a radical polymerization initiator. In order to uniformly obtain resin fine particles having a desired sulfonic acid group from a mixture of monomers having different properties such as a hydrophobic monomer and a hydrophilic monomer, the copolymerization ratio of the monomers having different properties should always be kept constant. Is desirable. When the mixture of the monomers is added into the polymerization system in excess of the amount of the monomers consumed in the polymerization reaction within a certain period of time, only a specific monomer species is polymerized in advance, and the remaining monomers are polymerized in advance. There is a tendency to polymerize after the resulting monomer is consumed. In this case, a large non-uniformity occurs in the properties of the resin fine particles having a sulfonic acid group to be produced.

A resin component having a large content of a hydrophilic monomer component may not be precipitated due to its high hydrophilicity, and resin fine particles having a sulfonic acid group may not be formed and may remain in the system as a water-soluble resin component. be. The above-mentioned method for synthesizing resin fine particles can be carried out by a known general method for synthesizing resin fine particles.

In the present embodiment, first, insoluble resin fine particles are dispersed in a water-soluble resin that functions as a dispersant to obtain an aqueous dispersion. The resin fine particles obtained by this step are resin fine particles having a sulfonic acid group, and are excellent in dispersion stability by themselves. Hereinafter, preferred embodiments of the above manufacturing method will be described in detail.

-Preparation of Ink In this embodiment, a specific method for dispersing resin fine particles will be described.

First, under a nitrogen atmosphere and heated to 70 ° C., the following three additive liquids were gradually added dropwise while stirring with a motor, and polymerization was carried out for 5 hours. Each additive solution is a mixed solution containing a hydrophobic monomer consisting of 28.5 parts of methyl methacrylate, a hydrophilic monomer consisting of 4.3 parts of sodium p-styrene sulfonate and 30 parts of water, and 0.05 part of potassium persulfate. It is a mixed solution containing 30 parts of water and a polymerization initiator.

The following components are mixed so that the obtained resin fine particles are 10% in the ink, and further pressure-filtered with a microfilter (manufactured by FUJIFILM Corporation) having a pore size of 2.5 μm to obtain a clear emulsion ink. bottom. The acid value of the clear emulsion ink of the present invention was adjusted to 100.

Resin fine particles 10 parts 2-Pyrrolidone 5 parts 2-Methyl 1,3 Propanediol 15 parts Acetylene glycol EO adduct 0.5 parts (manufactured by Kawaken Fine Chemical Co., Ltd.) Ion-exchanged water balance The acid value can be adjusted by adjusting the concentration of the resin containing the dissociative group. Furthermore, the acid value can be measured using the following method.

Weigh 10 g of pigment ink or clear emulsion ink and add pure water to make 100 mL. To this, a few drops of phenolphthalein reagent are added as an indicator and titrated with 0.1 mol / L potassium hydroxide solution until a pink color lasting for 30 seconds is exhibited. The acid value is calculated by the following formula from the amount of the potassium hydroxide solution required for titration.
(Acid value) = (0.1 mol / L potassium hydroxide solution amount: mL) x 56.1
The acid value of each ink was calculated by the above formula, and used as the acid value of the pigment ink and the acid value of the clear emulsion ink in the present invention. In the present invention, the values after the decimal point in the calculation are rounded down to the nearest whole number, and the ones place is rounded off.

The acid value calculated by the above method was adjusted to have the following values.

Pigment ink acid value: 80
EM solution 1 acid value: 100

3. 3. Preparation of Comparative Form The following comparative forms were prepared as two types of resin emulsion liquids (EM liquid 2).

In the EM solution 1, the acid value was adjusted to 100 as described above, but in the EM solution 2, the acid value was adjusted to 50. Then, the following components were mixed to prepare EM liquid 2.

(EM liquid 2)
Resin fine particles 10 parts 2-Pyrrolidone 5 parts 2-Methyl 1,3 Propanediol 15 parts Acetylene glycol EO adduct 0.5 parts (manufactured by Kawaken Fine Chemical Co., Ltd.) Ion-exchanged water balance EM solution 2 Acid value: 50

4. Reactivity of each ink As described above, in each ink used in the present embodiment, the pigment is prepared so as to react with the reactive component of the reaction solution, and the resin emulsion is prepared so as not to react with the reactive component.

The results of the experiment for evaluating the reactivity of each ink are described below.

Each of the above-mentioned reaction solutions 1, 2 and 3 is diluted 100-fold with pure water, and 0.25 g of each of the above-mentioned pigment and resin emulsion 3% aqueous solutions is added to a container having an inner diameter of 10 mm containing 5 g of the diluted solution. Dropped. Then, after allowing to stand for 60 minutes, the ratio of the height of the precipitate from the bottom surface of the container to the height from the bottom surface of the container to the gas-liquid surface was calculated. The higher the calculated value obtained by the above method, the higher the reactivity between the reactive component in the reaction solution and the pigment. In the present embodiment, the calculated value obtained as described above is expressed as a coagulation value of the pigment and the resin fine particles with respect to the reaction solution (simply "coagulation value of the pigment", "coagulation value of the resin emulsion"). As a result of obtaining the coagulation values of the pigment and the resin fine particles, when the coagulation value was smaller than 0.1, no reaction was observed. Therefore, in the present embodiment, the case where the coagulation value is smaller than 0.1 is evaluated as "not reactive", and the case where the coagulation value is larger than 0.1 is evaluated as "reactive".

(Table 1) shows the determination result of whether or not each of the pigment and the resin emulsion obtained as a result of calculating the coagulation value is reactive with each reaction liquid. (Table 1) shows ◯ when it is “reactive” and × when it is “not reactive”.

When the EM solution 2 which is a comparative example is used, as can be seen from (Table 1), not only the pigment but also the resin emulsion has reacted. On the other hand, when the EM solution 1 was used, the pigment reacted and the resin emulsion did not react.

The results of an experiment for evaluating the glossiness when recording is performed using each of the above-mentioned inks are described.

Using the magenta ink, reaction solution, EM solution 1 and EM solution 2 described above in (Table 2), a glossy vinyl chloride (KSM-VS2 gloss 170 μm / manufactured by Kimoto Co., Ltd.), which is a glossy non-absorbent recording medium, is used. The recorded result is shown. Here, 100% Duty of the pigment ink, 20% Duty of the reaction solution, and 50% Duty of the EM solution were ejected, and the bleeding and glossiness at that time were visually evaluated. In addition, the case where the ink is ejected once to all the pixels of the 1200 dpi unit included in a certain area is described as 100% Duty.

The "glossiness" was evaluated by the glossiness measured according to the method specified in JIS K 5600-4-7. For simplicity, the evaluation was performed by setting "high" when the recording surface and the recording medium show the same degree of glossiness by visual evaluation, and "low" when the glossiness of the printing surface (recording surface) decreases. ..

In "bleeding", two types of water-based color inks using pigments of different colors were ejected onto a recording medium, and the degree of bleeding at the boundary portion of adjacent images was quantitatively evaluated. In detail, the degree of bleeding between inks using pigments of different colors was visually observed at a distance of 30 cm from the recording surface, and the case where bleeding was recognizable was defined as "low", and the case where bleeding could not be recognized was defined as "high". The bleed length L for evaluating the degree of bleeding may be quantified using the personal image quality evaluation system Personal IAS (Quality Engineering Associate, Inc.) (ISO13660 compliant).

As can be seen from (Table 2), when the EM solution 2 is used, the glossiness is lowered. It is considered that this is because the resin emulsion tends to aggregate with respect to the reactive component, so that the reaction causes aggregation, and as a result, the image surface cannot be covered.

On the other hand, when the EM liquid 1 is used, since PigpAV <EmAV is satisfied as described above, the pigment is easily precipitated and the resin emulsion is difficult to precipitate. By controlling the cohesiveness in this way, it is possible to reduce bleeding and also suppress a decrease in glossiness.

(Second embodiment)
In the first embodiment described above, the same mask pattern group is used for each of the K, C, M, Y, Em, and RCT inks, and the order in which the inks are applied is not particularly limited, and a random order is described. bottom.

On the other hand, in the present embodiment, a mode is described in which different mask pattern groups are applied to the pigment ink, the reaction liquid, and the clear emulsion ink, and the order of applying the inks to the unit region is limited for recording.

The description of the same parts as those of the first embodiment described above will be omitted.

In the present embodiment, recording is completed by scanning 16 scans for a unit area.

FIG. 7 is a schematic diagram showing a mask pattern applied in the present embodiment. 7 (a), (b), (c), and (d) show a cyan ink ejection port row 22C, a magenta ink ejection port row 22M, a reaction liquid ejection port row 22RCT, and a clear emulsion ink ejection port. A group of mask patterns applied to the quantization data corresponding to each of the columns 22Em is shown.

As can be seen from FIG. 7A, the ejection port groups B1 to B16 in the cyan ink ejection port row 22C corresponding to the 1st to 16th scans are the ejection port groups corresponding to the intermediate 5th to 12th scans. Recordable pixels are arranged only in the mask patterns corresponding to B5 to B12. The recording allowable pixels are not arranged in the discharge port groups B1 to B4 corresponding to the first 1st to 4th scans and the discharge port groups B13 to B16 corresponding to the last 13th to 16th scans. Therefore, in the present embodiment, the cyan ink is ejected only in the 5th to 12th scans out of the 16 scans.

The same applies to the magenta ink ejection port row 22M. As shown in FIG. 7B, among the discharge port groups C1 to C16 corresponding to the 1st to 16th scans, the mask pattern corresponding to the discharge port groups C5 to C12 corresponding to the intermediate 5th to 12th scans. The recording allowable pixel is arranged only in. Therefore, the magenta ink is also ejected only in the 5th to 12th scans out of the 16 scans.

On the other hand, the reaction liquid discharge port row 22RCT corresponds to the discharge port groups D1 to D6 corresponding to the first 1st to 6th scans among the discharge port groups D1 to D16 corresponding to the 1st to 16th scans. Allowable recording pixels are arranged in the mask pattern. In the other mask patterns corresponding to the discharge port groups D7 to D16 corresponding to the 7th to 16th scans, the recording allowable pixels are not arranged. Therefore, the reaction solution is discharged only in the 1st to 6th scans out of the 16 scans.

The clear emulsion ink ejection port row 22Em is recorded in the mask pattern corresponding to the ejection port groups E11 to E16 corresponding to the last scan among the ejection port groups E1 to E16 corresponding to the 1st to 16th scans. Allowable pixels are arranged. In the other mask patterns corresponding to the ejection port groups E1 to E10 corresponding to the 1st to 10th scans, the recording allowable pixels are not arranged. Therefore, the clear emulsion ink is ejected only in the 11th to 16th scans out of the 16 scans, and is not ejected in the scans before the 10th scan.

Summarizing the above, in the present embodiment, the reaction solution is ejected in the first scan, the pigment ink (cyan ink, magenta ink) is ejected in the next scan, and the clear emulsion ink is ejected in the final scan.

Specifically, first, only the reaction solution is discharged in the 1st to 4th scans. In the 5th and 6th scans, the pigment ink is ejected together with the reaction solution. In the 7th to 10th scans, only the pigment ink is ejected. In the 11th and 12th scans, the clear emulsion ink is ejected together with the pigment ink. Then, in the 13th to 16th scans, only the clear emulsion ink is ejected.

In the present embodiment, the reaction liquid is applied onto the recording medium to some extent, and then the pigment ink is applied. Therefore, the pigment ink comes into contact with the reaction liquid immediately after being applied to the recording medium, so that the agglutination of the pigment starts immediately. As a result, the bleeding of the pigment ink can be suitably reduced.

On the other hand, the clear emulsion ink is applied onto the recording medium after a lapse of time (7th to 10th scans) after the reaction solution is applied. Therefore, when the clear emulsion ink is applied, the reaction solution has already lost its reactivity, and the clear emulsion ink does not aggregate.

Further, the clear emulsion ink is applied onto the recording medium after the pigment ink. Therefore, even if the unevenness of the image surface becomes large at the stage of applying the pigment ink, the surface layer of the image can be overcoated with the resin emulsion by finally applying the clear emulsion ink, and the glossiness can be improved.

As described above, using each of the inks described in the first embodiment, the reaction solution is used in the first scan of the plurality of scans, the pigment ink is used in the middle scan, and the clear emulsion ink is used in the last scan. Discharge in order. This makes it possible to obtain the effects of reducing bleeding and improving glossiness more remarkably than in the first embodiment.

Although the form in which the reaction solution and the pigment ink are applied in the 5th and 6th scans and the pigment ink and the clear emulsion ink are applied in the 11th and 12th scans is described here, other forms can also be used. be.

FIG. 8A shows a mask pattern applied to the reaction liquid discharge port row 22RCT in another form, and FIG. 8B shows a mask pattern applied to the clear emulsion ink discharge port row 22Em in other forms. ing. For the pigment ink, the mask patterns shown in FIGS. 7A and 7B are used.

When the mask patterns shown in FIGS. 7 (a), 7 (b), 8 (a), and (b) are used, only the reaction solution is used in the 1st to 4th scans, and only the pigment ink is used in the 5th to 12th scans. In the 13th to 16th scans, only the clear emulsion ink is ejected. Even in such a form, the effects of reducing bleeding and improving glossiness can be obtained.

(Other embodiments)
In general, the higher the concentration of the reactive component in the reaction solution, the higher the reaction rate. The decrease in reactivity due to the large acid value in the present invention can be considered to be the decrease in reaction rate. Therefore, since the pigment needs to react with the reactive component, it is preferable that the difference between the AV of the dissociative group of the water-soluble resin of the pigment and the AV of the EM solution is large. Specifically, the difference between the AV of the pigment and the AV of the EM solution is preferably 10 or more, and more preferably 20 or more.

Further, although the reaction liquid and the clear emulsion ink in each embodiment are described in such a manner that they do not contain any coloring material, they may contain some coloring material as long as they do not affect the image quality. In addition, in this specification, even if a slight amount of a color material is contained within a range that does not affect the image quality, it is included in the expression "does not contain a color material".

Further, although the recording device and the recording method using the recording device are described in each embodiment, the present invention can also be applied to an image processing device or an image processing method that generates data for performing the recording method described in each embodiment. .. Further, it can also be applied to a mode in which a program for performing the recording method described in each embodiment is prepared separately from the recording device.

Further, the present invention can be effectively applied to various image recording devices such as a so-called piezo type inkjet recording device that ejects ink by using a piezoelectric element, in addition to a thermal jet type inkjet recording device.

In addition, the "recording medium" includes not only paper used in general recording equipment, but also a wide range of materials such as cloth, plastic film, metal plate, glass, ceramics, wood, and leather that can accept ink. ..

9 Recording head 301 CPU
302 ROM

Claims (12)

An ink set consisting of first, second, and third types of ink of different types.
The first type of ink contains a pigment as a coloring material and a water-soluble resin having a dissociative group.
The second type of ink does not contain a coloring material and contains a polyvalent metal salt as a reactive component that reacts with the first type of ink.
The third type of ink contains a resin emulsion which does not contain a coloring material, has a dissociative group, and has a property of forming a film by heating.
An ink set characterized in that the acid value of the first type of ink is smaller than the acid value of the third type of ink. The ink set according to claim 1, wherein the polyvalent metal salt of the reactive component contained in the second type of ink is calcium methanesulfonate. The cohesiveness of the pigment contained in the first type of ink with respect to the second type of ink is the cohesiveness of the resin emulsion contained in the third type of ink with respect to the second type of ink. The ink set according to claim 1 or 2, wherein the ink set is higher than the property. The coagulation value of the pigment contained in the first type of ink with respect to the second type of ink is larger than 0.1.
The invention according to any one of claims 1 to 3, wherein the resin emulsion contained in the third type of ink has a coagulation value of less than 0.1 with respect to the second type of ink. Ink set. The ink according to any one of claims 1 to 4, wherein the difference between the acid value of the first type of ink and the acid value of the third type of ink is 20 or more. set. A recording head for ejecting the first, second, and third types of ink, which comprises the ink set according to any one of claims 1 to 5.
A recording device comprising: a control means for controlling the ejection of ink onto a recording medium from the recording head. The recording device according to claim 6, wherein the control means controls a recording operation so that the recording head is scanned a plurality of times with respect to a unit area on a recording medium to perform recording. The control means controls the recording operation so that the ratio of the second type of ink ejected in the previous scan of the plurality of scans is larger than that of the first type of ink. The recording device according to claim 7. The control means does not eject the first type of ink in the scan before the first scan among the plurality of scans, and the second type in the scan after the first scan. The recording device according to claim 8, wherein the recording operation is controlled so as not to eject ink. The control means controls the recording operation so that the ratio of the third type of ink ejected in the subsequent scan of the plurality of scans is larger than that of the first type of ink. The recording apparatus according to claim 8 or 9. The control means does not eject the third type of ink before the second scan of the plurality of scans, and ejects the first type of ink in the scans after the second scan. The recording device according to claim 10, wherein the recording operation is controlled so as not to discharge the ink. An ink set consisting of first, second, and third types of ink of different types.
The first type of ink contains a pigment as a coloring material and a water-soluble resin having a dissociative group.
The second type of ink does not contain a coloring material and contains a reactive component that reacts with the first type of ink.
The third kind of ink does not contain a coloring material and contains a resin emulsion having a dissociative group.
The reactivity of the reactive component contained in the second type of ink and the dissociative group of the water-soluble resin contained in the first type of ink is contained in the second type of ink. An ink set characterized by having a higher reactivity than the dissociative group of the resin emulsion contained in the reactive component and the third kind of ink.

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