JP2020138454A - Method for manufacturing printed matter - Google Patents

Abstract

To improve image quality of a printed matter and fixability of an image onto the printed matter.SOLUTION: A method for manufacturing a printed matter includes: imparting one of a first pretreatment liquid and a second pretreatment liquid, the other of the first pretreatment liquid and the second pretreatment liquid and aqueous ink in this order to a recording region of a base material using an inkjet recording device; and discharging the first pretreat liquid and the second pretreatment liquid in a fixed order so as to be landed onto the base material, in which the first pretreatment liquid contains a coagulant, and the second pretreatment liquid contains no coagulant and a penetrant.SELECTED DRAWING: Figure 2

Description

One embodiment of the present invention relates to a method for producing a printed matter.

In the inkjet recording method, highly fluid inkjet ink is ejected as droplets from a fine nozzle, and an image is recorded on a base material placed facing the nozzle, enabling high-speed printing with low noise. Therefore, it has spread rapidly in recent years. As inks used in such inkjet recording methods, water-based inks containing water as a main solvent, ultraviolet curable inks (UV inks) containing a high content of polymerizable monomers as main components, and wax as main components are high. A so-called non-aqueous ink containing a non-aqueous solvent as a main solvent is known as well as a hot melt ink (solid ink) contained in a content. Non-aqueous inks can be classified into solvent inks (solvent-based inks) whose main solvent is a volatile organic solvent and oil-based inks (oil-based inks) whose main solvent is a low-volatile or non-volatile organic solvent.

Since water is used as the main solvent in the water-based ink, the load on the environment is small, and the solvent easily volatilizes, so that the printed matter is excellent in drying property. On the other hand, depending on the type of the base material, the water-based ink may not have sufficient permeability to the base material, and the fixability of the image may become a problem. There is also a method of adding a penetrant to the water-based ink to improve the permeability to the base material, but by increasing the permeability to the base material, the color material of the water-based ink is immersed in the portion other than the recording area. The image may be blurred due to smearing. Further, in a wide recording area such as a solid image or a photographic image, there is a problem that the image becomes uneven.

In order to prevent image bleeding due to the water-based ink, there is a method of treating the substrate with a pretreatment agent containing a coagulant and then applying the water-based ink. Since the color material of the water-based ink is aggregated on the base material by the coagulant applied on the base material, it is possible to prevent the color material from infiltrating into a portion other than the recording area of the base material.

In Patent Document 1 (Japanese Unexamined Patent Publication No. 2017-94672), in a liquid injection method in which a medium is coated with a pretreatment liquid and then ink is ejected onto the medium, a plurality of methods having different permeability are described depending on the type of medium. By changing the stacking order of the pretreatment liquid, the permeability and wet spreadability of the pretreatment liquid are stabilized regardless of the characteristics of the medium, and the reactivity of the pretreatment liquid and the ink is enhanced while the pretreatment liquid is wet. It is disclosed to improve the spreadability.
In Patent Document 1, each of the first pretreatment liquid and the second pretreatment liquid contains a reaction component such as a coagulant and a solution component, and the reaction component between the first pretreatment liquid and the second pretreatment liquid. Is the same, but the permeability is different. Further, in one form of Patent Document 1, a liquid injection device provided with a serial head is used to inject the first pretreatment liquid on the outward route and the second pretreatment liquid on the return route to inject two types of pretreatment liquids. Are layered and covered.

JP-A-2017-94672

According to Patent Document 1, a medium having high permeability is coated with a pretreatment liquid having high permeability and then coated with a pretreatment liquid having low permeability, so that the medium is permeable to be landed later. It is disclosed that the low pretreatment liquid does not permeate the medium but remains on the surface of the medium, improving the reactivity with the ink and the wet spreadability.
In order to further improve the fixability of the image on the base material, it is preferable that the water-based ink penetrates into the base material and the coloring material spreads inside the base material. Further, in order to prevent blurring of the image, it is preferable that the color material of the water-based ink does not penetrate into the portion other than the recording area inside the base material. As in the disclosure of Patent Document 1, the method of leaving the two types of pretreatment agents on the surface of the medium has a problem that both the fixability of the image and the blurring of the image are not improved.
One object of the present invention is to improve the image quality of a printed matter and the fixability of an image on the printed matter.

In one embodiment of the present invention, an inkjet recording device is used to use one of the first pretreatment liquid and the second pretreatment liquid, the other of the first pretreatment liquid and the second pretreatment liquid, and an aqueous solution. The first pretreatment liquid and the second pretreatment liquid are ejected so as to land on the base material in a certain order, and the ink is applied to the recording area of the base material in this order. The pretreatment liquid 1 is a method for producing a printed matter, which contains a coagulant, and the second pretreatment liquid does not contain a coagulant and contains a penetrant.

According to one embodiment of the present invention, it is possible to improve the image quality of the printed matter and the fixability of the image on the printed matter.

FIG. 1 is a top view schematically showing an example of a serial type recording head unit. FIG. 2 is a top view schematically showing another example of the serial type recording head unit. FIG. 3 is a top view schematically showing still another example of the serial type recording head unit. FIG. 4 is an explanatory diagram for explaining a conventional recording method using a serial type recording head unit.

Hereinafter, one embodiment of the present invention will be described in detail, but it goes without saying that the present invention is not limited to the following embodiments, and various modifications and changes may be made.

"Manufacturing method of printed matter"
As a method for producing a printed matter according to an embodiment of the present invention, one of a first pretreatment liquid and a second pretreatment liquid, the other of a first pretreatment liquid and a second pretreatment liquid, and a water-based ink are used. The first pretreatment liquid and the second pretreatment liquid are applied to the recording area of the base material in this order, and the first pretreatment liquid and the second pretreatment liquid are discharged so as to land on the base material in a certain order, and the first pretreatment liquid is aggregated. The second pretreatment liquid contains an agent, and is characterized in that it does not contain a coagulant and contains a penetrant.
According to this, the image quality of the printed matter and the fixability of the image on the printed matter can be improved.
In addition, the density on the back side of the printed matter can be increased, and it can be preferably applied to applications that require visibility from the back side of the printed matter.

By applying the first pretreatment liquid containing a coagulant and the second pretreatment liquid not containing a coagulant and containing a penetrant to the base material, and allowing the coagulant to penetrate into the inside of the base material. , It is possible to prevent the occurrence of blurring or unevenness of the image. In addition, since the coagulant penetrates into the base material together with the penetrant, the water-based ink permeates not only the surface portion of the base material but also the inside of the base material, and the color material of the water-based ink inside the base material. Aggregates, so that the fixability of the image can be improved.
Further, since the second pretreatment liquid does not contain the coagulant, the excessive coagulation of the ink by the coagulant is alleviated, the water-based ink permeates into the inside of the base material, and the coloring material is fixed while coagulating. Therefore, the visibility of the image from the back surface of the base material can be obtained. For example, it can be preferably used in applications such as advertising banners, flags, goodwill, etc., where visibility from the back surface of the printed surface is required.
Further, since the water-based ink penetrates into the inside of the base material, when the water-based ink contains a resin component, the anchor effect of the resin film can be obtained, and the fixability of the image can be further improved.

When the first pretreatment liquid and the second pretreatment liquid are applied to the base material by using an inkjet recording device provided with a serial recording head unit arranged in the main scanning direction, the first pass is the first on the outward path. When the pretreatment liquid and the second pretreatment liquid of No. 1 are discharged in this order, and the second pretreatment liquid and the first pretreatment liquid are discharged in this order in the second pass of the return route, in the transport direction of the base material, The order of applying the first pretreatment liquid and the second pretreatment liquid is switched for each line corresponding to the path. When the water-based ink is applied to the base material treated in this way, the permeability of the water-based ink to the base material differs for each line, so that the permeability of the water-based ink to the base material is hindered, and the above-mentioned effect is obtained. There is a problem that cannot be obtained. Therefore, the first pretreatment liquid, the second pretreatment liquid, and the water-based ink are applied to the recording area of the base material in a predetermined order, and the first pretreatment liquid, the second pretreatment liquid, and the second pretreatment liquid are applied over the entire recording area. It is preferable that the pretreatment liquid and the water-based ink are laminated in the same order.

The method for producing a printed matter according to one embodiment can preferably record an image on various substrates.
Examples of the base material include printing paper such as plain paper, coated paper, and special paper, cloth, wood base material, metal base material, glass base material, resin base material, and the like. Above all, it is possible to record an image with improved image quality and fixability on cloth.
Examples of the cloth include natural fibers such as cotton, silk, wool and hemp; chemical fibers such as polyester, acrylic, polyurethane, nylon, rayon, cupra and acetate; or blended fibers thereof. Further, the cloth may be a woven fabric, a knitted fabric, a non-woven fabric or the like.

"First pretreatment liquid"
The first pretreatment liquid preferably contains a flocculant. By applying the first pretreatment liquid containing a coagulant to the base material, it is possible to have an action of coagulating the color material of the water-based ink on the base material. Then, the first pretreatment liquid can prevent bleeding of the coloring material on the base material and reduce color unevenness of the printed matter. In addition, since the wet spread of the coloring material is prevented, the image density of the printed matter can be increased.
The first pretreatment liquid preferably contains a flocculant and water, and the main solvent is preferably water. Further, a water-soluble organic solvent may be used in addition to or in place of water.

The coagulant preferably has an action of coagulating the color material by lowering the dispersibility or solubility of the color material in the water-based ink. Specifically, a compound exhibiting ionicity or an acid can be used. In a general water-based ink, the color material itself or the dispersant of the color material adjusts the charge balance on the surface of the color material, and the color material is dispersed or dissolved in water. Therefore, it is considered that the addition of these compounds disrupts this charge balance and causes the coloring material to aggregate.
As the flocculant, for example, an organic acid, a polyvalent metal salt, a cationic resin or the like can be preferably used.

The organic acid is an organic compound showing acidity, and specifically, an organic compound having an acidic group such as a carboxy group, a phenolic hydroxy group, and a sulfo group can be preferably used. Of these, a carboxy group is preferable from the viewpoint of easily forming a hydrogen bond, which will be described later.
The organic acid can cause an interaction such as a hydrogen bond with the base material to further improve the adhesion to the base material. In addition, the organic acid can improve the adhesion with the components of the water-based ink on the base material by the interaction such as hydrogen bonding, and can further improve the fixability of the image.
Further, when the water-based ink contains a cross-linking agent, when the organic acid and the cross-linking agent come into contact with each other on the base material, the organic acid becomes insoluble, so that the water resistance of the image can be improved.
Examples of the organic acid include carboxylic acids such as formic acid, acetic acid and oxalic acid, hydroxycarboxylic acids such as lactic acid, glyceric acid, tartaric acid, citric acid and malic acid, ascorbic acid and sulfonic acid.

From the viewpoint of scratch resistance of the base material, and in particular, from the viewpoint of further enhancing the wet friction fastness of the cloth as the base material, it is preferable to use a liquid organic acid at 23 ° C. as the coagulant. By applying the flocculant to the surface of the cloth as a liquid, it is possible to make it less susceptible to friction due to its high permeability and smoothness of the printed surface. Further, when each pretreatment liquid is applied using an inkjet recording device, non-ejection of the recording head can be prevented for a long period of time by using a liquid organic acid as a coagulant.
Acetic acid, lactic acid, or a combination thereof can be preferably used as the organic acid liquid at 23 ° C., and lactic acid is more preferable.

The boiling point of the organic acid is preferably 120 ° C. or higher.
In an inkjet recording device, a recording head filled with water-based ink prints while moving on the upper part of a base material to which each pretreatment liquid is applied. By using an organic acid having a boiling point of 120 ° C. or higher, the organic acid is less likely to volatilize from the base material to which each pretreatment liquid is applied, so that the volatilized organic acid does not come into contact with the water-based ink in the nozzle portion of the recording head. Therefore, it is possible to prevent the deterioration of the water-based ink due to the organic acid at the nozzle portion. Therefore, it is possible to suppress defective ejection of water-based ink from the nozzle portion.

The above-mentioned organic acids may be used alone or in combination of two or more.
The organic acid is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total amount of the first pretreatment liquid.
The organic acid is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total amount of the first pretreatment liquid.

As the polyvalent metal salt, for example, a halide of a divalent or higher valent metal, a nitrate, a sulfate, an acetate, a fatty acid salt, a lactate, a chlorate or the like can be used. As the halide, chloride, bromide, iodide and the like are preferable. Examples of the divalent or higher metal include divalent alkaline earth metals such as Mg, Ca, Sr and Ba, divalent metals such as Ni, Zn, Cu and Fe (II), and Fe (III) and Al. Examples thereof include trivalent metals, and among them, alkaline earth metals are preferable.
More specifically, calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, copper nitrate, calcium acetate, magnesium acetate and the like can be mentioned.

The above-mentioned multivalent metal salts may be used alone or in combination of two or more.
The polyvalent metal salt is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total amount of the first pretreatment liquid.
The polyvalent metal salt is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total amount of the first pretreatment liquid.

The cationic resin may be either a cationic water-soluble resin or a cationic water-dispersible resin, and these may be used in combination.

Examples of the cationic water-soluble resin include polyethyleneimine (PEI), polyvinylamine, polyallylamine and salts thereof, polyvinylpyridine, and a copolymer of cationic acrylamide. More specifically, for example, polydiallyldimethylammonium chloride or the like can be used.

Commercially available products of cationic water-soluble resins include polydialyldimethylammonium chlorides such as Charol series "DC-303P and DC-902P (both trade names)" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and Uni made by Senka Co., Ltd. Sense series "FCA1000L, FPA100L (both trade names)", Osaka Organic Chemical Industry Co., Ltd. HC polymer series "1S, 1N, 1NS, 2, 2L (both trade names)" and the like can be mentioned.

Further, as the cationic water-soluble resin, a water-soluble resin having an amino group can be preferably used.
As the water-soluble resin having an amino group, for example, polyethyleneimine, polyvinylamine, polyallylamine and salts thereof, basic polymers such as polyvinylpyridine, or derivatives thereof can be used. Of these, polyethyleneimine or polyallylamine is preferable.

Examples of commercially available polyethyleneimine products include the Epomin series "SP-006, SP-012, SP-018, SP-200 (all trade names)" manufactured by Nippon Shokubai Co., Ltd .; "Lupasol FG" manufactured by BASF Japan Ltd. , Lupasol G20 Waterfree, Lupasol PR 8515 (all trade names) ”and the like.
Examples of commercially available polyallylamine products include "allylamine polymers PAA-01, PAA-03, PAA-05, and allylamine hydrochloride polymers PAA-HCL-01, PAA-" manufactured by Nitto Spinning Co., Ltd. HCL-03, PAA-HCL-05, PAA-SA (all trade names), which is an allylamine amide hydrochloride polymer, and the like can be mentioned.

The cationic water-dispersible resin is a positively charged resin particle in which the surface of the resin particle is positively charged, and is dispersed in the form of particles without being dissolved in water, and is an oil-in-water (O / W) type. It is possible to form an emulsion of. Like the self-emulsifying resin, the cationic functional group of the resin may be present on the surface of the particles, or the surface of the resin particles may be surface-treated such as by adhering a cationic dispersant. The cationic functional group is typically a primary, secondary or tertiary amino group, a pyridine group, an imidazole group, a benzimidazole group, a triazole group, a benzotriazole group, a pyrazole group, a benzopyrazole group and the like. Can be mentioned. Examples of the cationic dispersant include primary, secondary, tertiary or quaternary amino group-containing acrylic polymers, polyethyleneimine, cationic polyvinyl alcohol resins, and cationic water-soluble polybranched polyesteramide resins.
The amount of surface charge of the cationic water-dispersible resin particles can be evaluated with a particle charge meter. The amount of surface charge can be calculated by measuring the amount of anion or cation required to neutralize the sample. Specifically, the surface charge amount is preferably 20 to 500 μeq / g, more preferably 20 to 100 μeq / g. As the particle charge meter, a colloidal particle charge meter "Model CAS" manufactured by Nihon Rufuto Co., Ltd. can be used.

As the cationic water-dispersible resin, it is preferable to use a resin that forms a transparent coating film. Further, in the production of the treatment liquid, it can be blended as an oil-in-water resin emulsion.
Examples of the cationic water-dispersible resin include urethane resin, (meth) acrylic resin, styrene / (meth) acrylic resin, polyester resin, olefin resin, vinyl chloride resin, vinyl acetate resin, melamine resin, amide resin, and ethylene-. In vinyl chloride copolymer resin, styrene-maleic anhydride copolymer resin, vinyl acetate- (meth) acrylic copolymer resin, vinyl acetate-ethylene copolymer resin, and composite resins thereof, cations are added to these resins. A positive functional group may be introduced or surface-treated with a cationic dispersant or the like to give a positive surface charge. Here, "(meth) acrylic resin" indicates both an acrylic resin and a methacrylic resin (hereinafter, the same applies).

In the water-dispersible resin emulsion, the average particle size of the water-dispersible resin particles forming the emulsion (the average particle size measured by the dynamic light scattering method on a volume basis) prevents the texture of the substrate surface from changing. The average particle size of the water-dispersible resin particles is preferably 300 nm or less, more preferably 200 nm or less, preferably 10 μm or less in order to prevent the particles from falling off from the surface of the substrate, and more preferably 300 nm or less in order to be suitable for ejection in an inkjet recording device. , 150 nm or less is more preferable.
The average particle size of the water-dispersible resin particles is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, from the viewpoint of water scratch resistance of the ink.

Commercially available products of the cationic water-dispersible resin include, for example, "PINTRITE DP375" manufactured by Lubrizol, "Superflex 620, 650" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and "PP-15" manufactured by Meisei Chemical Works, Ltd. Examples include "PP-17", "Polysol AP-1350" manufactured by Showa Denko Co., Ltd., "Boncoat SFC-55" manufactured by DIC Corporation, and "Aquatex AC-3100" manufactured by Japan Coating Resin Co., Ltd.

The above-mentioned cationic resins may be used alone or in combination of two or more.
The amount of the cationic resin is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total amount of the first pretreatment liquid.
The amount of the cationic resin is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total amount of the first pretreatment liquid.

The above-mentioned flocculants may be used alone or in combination of two or more. When two or more kinds of coagulants are used, it is preferable to select two or more kinds of coagulants so as not to impair each other's action, and to adjust the blending ratio thereof. For example, it is preferable to use a combination of coagulants showing the same ionicity.
The total amount of the flocculant is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, based on the entire first pretreatment liquid. Thereby, by applying the first pretreatment liquid to the base material, the coagulant can be applied in an appropriate amount on the base material, and the color material of the water-based ink can be appropriately agglomerated on the base material. Can be done.
The total amount of the flocculant is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, based on the entire first pretreatment liquid. Since the flocculant is ionic, it is possible to prevent the surface quality of the substrate from being altered by an excessive amount of the flocculant. In addition, it is possible to prevent the storage stability of the first pretreatment solution from being lowered by an excessive amount of the flocculant.
For example, the aggregating agent is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 15% by mass, based on the entire first pretreatment liquid.

The first pretreatment solution may further contain a penetrant in addition to the flocculant. Thereby, the permeability of the first pretreatment liquid to the base material can be further enhanced, and the permeation of the flocculant into the base material can be further promoted. Further, in the method of first applying the first pretreatment liquid and then applying the second pretreatment liquid, the base material and the first pretreatment liquid are difficult to be compatible with each other, so that the first pretreatment liquid is permeated. It is advisable to add an agent.
As the penetrant, a surfactant, a water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less, or a combination thereof can be used. Specifically, the same penetrant that can be blended in the second pretreatment liquid described later can be used.
The surfactant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the first pretreatment liquid.
The water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, and 10 to 30% by mass, based on the total amount of the first pretreatment liquid. Mass% is more preferred.
The total amount of the penetrant is preferably 0.1% by mass or more, and more preferably 1% by mass or more, based on the entire first pretreatment liquid. Thereby, the permeation of the first pretreatment liquid into the substrate can be further promoted.
The penetrant is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, based on the entire first pretreatment liquid. If the amount of the penetrant exceeds 60% by mass, the components of the first pretreatment liquid may permeate too much depending on the base material, and it may be difficult to obtain the cohesive effect of the coloring material.
For example, the penetrant is preferably 0.1 to 60% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 40% by mass, based on the entire first pretreatment liquid.

The first pretreatment liquid can further contain water. For example, the first pretreatment liquid preferably contains water as a main solvent. The water is not particularly limited, and examples thereof include ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is a highly volatile solvent and easily evaporates from the base material after being applied to the base material, which can accelerate the drying of the printed matter. In addition, water is harmless, highly safe, and does not have problems such as VOC, so that the surface-treated base material can be made environmentally friendly.
The amount of water is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and may be 50 to 80% by mass with respect to the total amount of the first pretreatment liquid.

The first pretreatment liquid may contain a water-soluble organic solvent together with or in place of water.
As the water-soluble organic solvent, a water-soluble organic solvent may be selected and used from the penetrants that can be blended in the second pretreatment liquid described later. Further, a water-soluble organic solvent that can be blended with the water-based ink described later may be used. The water-soluble organic solvent may be used alone or in combination of two or more, and it is preferable to form a single phase in a mixed solvent with water.
The water-soluble organic solvent is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, based on the total amount of the first pretreatment liquid.

The total amount of water and the water-soluble organic solvent (if only one of them is contained, the same applies hereinafter) is preferably 30 to 99% by mass, preferably 40 to 95% by mass, based on the total amount of the first pretreatment liquid. % Is more preferable, and may be 50 to 90% by mass.

The first pretreatment liquid may further contain a binder resin. By including the binder resin, the fixability of the first pretreatment liquid to the substrate can be further enhanced. In addition, the fixing of the water-based ink to the substrate can be further improved.
As the binder resin, a non-ionic resin can be preferably used so as not to affect the ionicity of the flocculant. The non-ionic resin may be either water-soluble or water-dispersible. Further, as the non-ionic resin, a non-ionic resin can be selected and used from the resin components that can be blended in the water-based ink described later. When the first pretreatment liquid contains a cationic resin as a coagulant, the cationic resin can also have a function as a binder resin.
In addition, the first pretreatment liquid may further contain a cross-linking component in order to cross-link the binder resin. Examples of the cross-linking component include blocked isocyanate, oxazoline group-containing compound, (poly) carbodiimide, aziridine, chelating agent, silane coupling agent and the like.
When the binder resin is blended, the binder resin is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the first pretreatment liquid. When the first pretreatment liquid contains a cationic resin, the total amount of the cationic resin and the binder resin is preferably in this range.
When a cross-linking component is blended, the cross-linking component is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, based on the total amount of the first pretreatment liquid.

Similar to the water-based ink described later, the first pretreatment liquid is, for example, a moisturizer, an antifoaming agent, a pH adjuster, an antioxidant, a preservative, and a surface tension lowering agent within a range that does not impair the effects of the present invention. , An optional component such as an ultraviolet absorber may be further contained.

The method for producing the first pretreatment liquid is not particularly limited, and the first pretreatment liquid can be appropriately produced by a usual method. For example, the first pretreatment liquid can be prepared by putting all the components into a stirrer such as a three-one motor in a batch or divided manner, mixing or dispersing them, and optionally passing through a filter such as a membrane filter. ..

"Second pretreatment liquid"
The second pretreatment liquid preferably does not contain a flocculant and contains a penetrant. Thereby, the second pretreatment liquid can have an action of modifying the surface of the base material and promoting the penetration of the water-based ink into the base material. Then, the second pretreatment liquid can enhance the fixability of the water-based ink on the base material. In addition, it is possible to promote the penetration of the water-based ink into the back surface side of the printed matter and further enhance the visibility from the back surface side of the printed matter.
The second pretreatment liquid preferably contains a penetrant and water, and the main solvent is preferably water. Further, a water-soluble organic solvent may be used in addition to or in place of water.

The second pretreatment liquid preferably has a small action of aggregating the coloring material on the base material. Further, it is more preferable that the second pretreatment liquid has a smaller action of aggregating the coloring material on the substrate than the first pretreatment liquid.
The second pretreatment liquid preferably does not contain a coagulant in order to reduce the action of coagulating the coloring material. For example, the coagulant is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and substantially 0% by mass, based on the total amount of the second pretreatment liquid. It may be there. Further, the second pretreatment liquid preferably does not contain a flocculant to be blended in the first pretreatment liquid.
The details of the flocculant are as described in the first pretreatment solution.

As the penetrant, for example, a surfactant, a water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less, or a combination thereof can be preferably used.

Here, the SP value is an SP value obtained by the Fedors formula, and specifically, is a value calculated by the following formula proposed by Fedors. In the following equation, Δei is the evaporation energy of the atom or atomic group of the i component, and Δvi is the molar volume of the atom or atomic group of the i component (Hansen Solution Parameters: A User's Handbook, Second Edition, Charles). See M. Hansen, CRC Press, 2007).
δ = [(sumΔei) / (sumΔvi)] ^1/2

As the surfactant, there are an ionic surfactant and a nonionic surfactant, and the nonionic surfactant can be preferably used. Since the nonionic surfactant does not affect the charge balance of the water-based ink and does not have an action of aggregating the coloring material of the water-based ink, it can be preferably used as a penetrant.
Ionic surfactants such as cationic surfactants, anionic surfactants, and amphoteric surfactants may affect the charge balance of the aqueous ink and cause the colorants to aggregate. Therefore, when an ionic surfactant is used, it is preferable to use one that does not affect the charge balance of the water-based ink. For example, an ionic surfactant that can be blended with a water-based ink can be used. Specifically, when the color material of the water-based ink is carbon black, an anionic dispersant is often used. In this case, an anionic surfactant can be used as the penetrant for the second pretreatment liquid. The ionic surfactant that can be blended with such a water-based ink is as described in the section on the water-based ink described later.

Further, the surfactant may be either a low molecular weight surfactant or a high molecular weight surfactant (generally, a surfactant having a molecular weight of about 2000 or more), but a high molecular weight surfactant may be used. It can be preferably used.
The HLB value of the surfactant is preferably 5 to 20.

Examples of nonionic surfactants include silicone-based surfactants, acetylene glycol-based surfactants, polyoxyethylene alkyl ether-based surfactants, polyoxypropylene alkyl ether-based surfactants, and polyoxyethylene alkyl phenyl ethers. Surfactants, polyoxypropylene alkylphenyl ether surfactants, polyoxyethylene fatty acid ester surfactants, polyoxypropylene fatty acid ester surfactants, sorbitan fatty acid ester surfactants, polyoxyethylene sorbitan fatty acid ester Examples thereof include based surfactants, polyoxyethylene sorbitol fatty acid ester-based surfactants, and glycerin fatty acid ester-based surfactants. These may be used alone or in combination of two or more.

Among these, silicone-based surfactants, acetylene glycol-based surfactants, or combinations thereof can be preferably used, and among them, silicone-based surfactants are more preferable.
Since the silicone-based surfactant has a very high surface tension lowering ability and contact angle lowering ability, the second pretreatment liquid can be rapidly diffused on the base material surface even if the base material surface is not hydrophilic. Can be done. As a result, since the second pretreatment liquid can be uniformly fixed on the surface of the base material, the water-based ink is uniformly fixed on the treated portion at the time of printing, and a high-colored and high-quality printed image can be obtained. it can.
Among the silicone-based surfactants, a polyether-modified silicone-based surfactant, an alkyl-aralkyl co-modified silicone-based surfactant, an acrylic silicone-based surfactant and the like can be preferably used. Examples of commercially available silicone-based surfactants include "Silface SAG series (trade name)" manufactured by Nissin Chemical Industry Co., Ltd.

Commercially available products of acetylene glycol-based surfactants include, for example, "surfinol 104E and 104H" which are acetylene glycols and "surfinol 420, 440, 465 and 485" which have a structure in which ethylene oxide is added to acetylene glycol (all of the above). Product name, manufactured by Air Products and Chemicals), acetylene glycol "Orfin E-1004, E-1010, E-1020, PD-002W, PD-004, EXP.4001, EXP.4200, EXP.4123, EXP. 4300 ”(trade name, manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylene glycol“ acetylenol E00, E00P ”, and“ acetylenol E40, E100 ”with a structure in which ethylene oxide of acetylene glycol is added (all above are trade names). , Kawaken Fine Chemical Co., Ltd.), etc.

Examples of other nonionic surfactants include Kao Corporation's Emargen series "Emargen 102KG, Emargen 103, Emargen 104P, Emargen 105, Emargen 106, Emargen 108, Emargen 120, Emargen 147, Emargen 150, Emargen 220, Examples thereof include polyoxyethylene alkyl ether-based surfactants such as "Emargen 350, Emargen 404, Emargen 420, Emargen 705, Emargen 707, Emargen 709, Emargen 1108, Emargen 4085, Emargen 2025G".

The above-mentioned surfactants may be used alone or in combination of two or more.
The surfactant is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, based on the total amount of the second pretreatment liquid.
From the viewpoint of water resistance, the surfactant is preferably 10% by mass or less, more preferably 8% by mass or less, based on the total amount of the second pretreatment liquid.

As a water-soluble organic solvent as a penetrant, when the SP value is 14 (cal / cm ³ ) ^1/2 or less, the permeability of the second pretreatment liquid to the substrate can be promoted. In addition, the action of permeating the water-based ink into the base material can be more effectively obtained on the base material.
Examples of the water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less include 1,2-butanediol (SP value 12.8) and 1,6-hexanediol (SP value 13.5). ), 1,2-propanediol (SP value 13.5), glycerin (SP value 16.4), dipropylene glycol (SP value 13.6), diethylene glycol monoethyl ether (SP value 10.9), diethylene glycol mono Butyl ether (SP value 10.5), diethylene glycol monophenyl ether (SP value 11.7), diethylene glycol benzyl ether (SP value 11.5), ethylene glycol propyl ether (SP value 11.1), diethylene glycol monoethyl acetate (SP) Values include 9.3), tripropylene glycol dimethyl ether (SP value 8.4), N-methyl-2-pyrrolidone (SP value 11.2) and the like.
The unit of SP value in parentheses is (cal / cm ³ ) ^1/2 .

The lower limit of the SP value of the water-soluble organic solvent is not particularly limited, but is preferably 9 (cal / cm ³ ) ^1/2 or more. When the SP value is less than 9 (cal / cm ³ ) ^1/2 , the dispersibility or solubility of the coloring material in the water-based ink is lowered, and aggregation may occur. In the case of water-soluble coloring materials, a decrease in solubility may occur. Further, when the coloring material is dispersed by the dispersant, depending on the type of resin, the solubility of the resin in the solvent becomes too high, and the resin adsorbed on the coloring material is peeled off, so that the coloring materials are separated from each other. It may agglomerate. By using a water-soluble organic solvent having an SP value of 9 (cal / cm ³ ) ^1/2 or more, the action of agglomerating the color material of the water-based ink on the substrate can be reduced.

The above-mentioned water-soluble organic solvent may be used alone or in combination of two or more.
The water-soluble organic solvent as the penetrant is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, based on the total amount of the second pretreatment liquid.
The water-soluble organic solvent as the penetrant is preferably 100% by mass or less, more preferably 80% by mass or less, still more preferably 60% by mass or less, based on the total amount of the second pretreatment liquid. Since the water-soluble organic solvent as a penetrant has both functions of a penetrant and a solvent, a second pretreatment liquid containing the water-soluble organic solvent as a penetrant as a single component may be formed.

The above-mentioned penetrants may be used alone or in combination of two or more. When two or more kinds of penetrants are used, it is preferable to select two or more kinds of penetrants so as not to impair each other's action, and to adjust the blending ratio thereof. Further, by including a surfactant as the penetrant, the permeability of the second pretreatment liquid can be further enhanced. Further, it is preferable to use a surfactant as a penetrant in combination with a water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less.
The penetrant is preferably 0.5% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, based on the entire second pretreatment liquid. When a surfactant is used as the penetrant, the permeability of the second pretreatment liquid can be improved more effectively even in a small amount.
The penetrant is not limited to this, but is preferably 100% by mass or less, more preferably 80% by mass or less, still more preferably 60% by mass or less, based on the entire second pretreatment liquid.
For example, the penetrant is preferably 0.5 to 100% by mass, more preferably 10 to 80% by mass, and even more preferably 30 to 60% by mass, based on the entire second pretreatment liquid.

The second pretreatment liquid can further contain water. For example, the second pretreatment liquid preferably contains water as a main solvent. The water is not particularly limited, and examples thereof include ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is a highly volatile solvent and easily evaporates from the base material after being applied to the base material, which can accelerate the drying of the printed matter. In addition, water is harmless, highly safe, and does not have problems such as VOC, so that the surface-treated base material can be made environmentally friendly.
The amount of water is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and may be 10 to 80% by mass with respect to the total amount of the second pretreatment liquid.

The second pretreatment liquid may contain a water-soluble organic solvent together with water or in place of water.
As the water-soluble organic solvent, a water-soluble organic solvent may be selected and used from the above-mentioned penetrants. Further, a water-soluble organic solvent that can be blended with the water-based ink described later may be used. The water-soluble organic solvent may be used alone or in combination of two or more, and it is preferable to form a single phase in a mixed solvent with water.
The water-soluble organic solvent is preferably 10 to 100% by mass, more preferably 30 to 90% by mass, and may be 50 to 80% by mass with respect to the total amount of the second pretreatment liquid.

The total amount of water and the water-soluble organic solvent is preferably 50 to 100% by mass, more preferably 70 to 99% by mass, and may be 80 to 98% by mass with respect to the total amount of the second pretreatment liquid.

The second pretreatment liquid may further contain a binder resin. By including the binder resin, the fixability of the second pretreatment liquid to the substrate can be further enhanced. In addition, the fixing of the water-based ink to the substrate can be further improved.
As the binder resin, it is preferable that the binder resin does not have an action of aggregating the coloring material of the water-based ink, and a non-ionic resin can be preferably used. The non-ionic resin may be either water-soluble or water-dispersible. Further, as the non-ionic resin, a non-ionic resin can be selected and used from the resin components that can be blended in the water-based ink described later. When the second pretreatment liquid contains a polymer-based nonionic surfactant as a penetrant, the nonionic surfactant can also have a function as a binder resin.
In addition, the second pretreatment liquid may further contain a cross-linking component in order to cross-link the binder resin. As the cross-linking component, the one described in the first pretreatment liquid can be used.
When the binder resin is blended, the binder resin is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the second pretreatment liquid from the viewpoint of fixability and on-machine stability. .. When the second pretreatment liquid contains a polymer-based nonionic surfactant, the total amount of the nonionic surfactant and the binder resin is preferably in this range.
When a cross-linking component is blended, the cross-linking component is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, based on the total amount of the second pretreatment liquid.
From the viewpoint of backside concentration, it is preferable that the second pretreatment liquid does not contain a fixing resin. Since the fixable resin may reduce the permeability, the back surface concentration may decrease.

The second pretreatment liquid, like the water-based ink described later, is, for example, a moisturizer, an antifoaming agent, a pH adjuster, an antioxidant, a preservative, and a surface tension lowering agent within a range that does not impair the effects of the present invention. , An optional component such as an ultraviolet absorber may be further contained.
The method for producing the second pretreatment liquid is not particularly limited, and the second pretreatment liquid can be produced by the same method as the above-mentioned first pretreatment liquid.

"Water-based ink"
The water-based ink preferably contains a coloring material and water.

The coloring material may be either a pigment or a dye, may be used alone, or both may be used in combination. From the viewpoint of weather resistance and water resistance of the printed matter, a pigment can be preferably used as the coloring material.

As the pigment, a non-white pigment, a white pigment, or a combination thereof can be used.
For example, when a base material having a color or surface shape such as cloth is used as the base material, a base layer is formed by using white ink using a white pigment to hide the color of the base material. , There is a way to record an image from above.
Examples of non-white pigments include azo-based, phthalocyanine-based, dye-based, condensed polycyclic, nitro-based, and nitroso-based organic pigments (Brilliant Carmine 6B, Lake Red C, Watching Red, Disazo Yellow, Hansa Yellow, etc. Phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, metal oxides and sulfides, and ocher, ultramarine blue, Inorganic pigments such as navy blue; carbon blacks such as furnace carbon black, lamp black, acetylene black, and channel black can be used.

As the white pigment, for example, inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide can be used. In addition to the inorganic pigment, hollow resin fine particles and solid resin fine particles can also be used. Of these, titanium oxide can be preferably used from the viewpoint of hiding power. As the titanium oxide, it is preferable to use a titanium oxide surface-treated with alumina or silica in order to suppress the photocatalytic action.
The volume-based average particle size of the pigment is preferably 50 nm or more from the viewpoint of color development, preferably 500 nm or less from the viewpoint of discharge stability, and more preferably 200 nm or less. For example, the average particle size of the pigment is preferably 50 to 500 nm, more preferably 50 to 200 nm.

A self-dispersing pigment whose surface is modified with a hydrophilic functional group may be used. Examples of commercially available self-dispersing pigments include CAB-O-JET series "CAB-O-JET200, CAB-O-JET300, CAB-O-JET250C, CAB-O-JET260M, CAB-O-JET270" manufactured by CABot. , "BONJET BLACK CW-1S, CW-2, CW-3" manufactured by Orient Chemical Co., Ltd. (all are trade names).
A microencapsulated pigment in which the pigment is coated with a resin may be used.
A pigment dispersion in which the pigment is dispersed in advance using a pigment dispersant may be used. Examples of commercially available pigment dispersions include "HOSTAJET series" manufactured by Clariant AG and "FUJI SP series" manufactured by Fuji Dye Co., Ltd. (both are trade names). Further, a pigment dispersion in which the pigment is dispersed by a pigment dispersant described later may be used.

The above-mentioned pigments may be used alone or in combination of two or more.
The pigment varies depending on the type, but from the viewpoint of color development and the like, the solid content is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and 1 to 10% by mass with respect to the total amount of the water-based ink. % Is more preferable.

The water-based ink may further contain a pigment dispersant in order to stably disperse the pigment in water.
As pigment dispersants, for example, as commercial products, TEGO Disperse series "TEGO Disperse 740W, TEGO Disperse 750W, TEGO Disperse 755W, TEGO Disperse 757W, TEGO Disperse 760W" manufactured by EVONIK, Japan Lubrizol Solsparse series "Solsparse 20000, Solsparse 27000, Solsparse 41000, Solsparse 41090, Solsparse 43000, Solsparse 44000, Solsparse 46000", John Krill series "John Krill 57, John Krill 60, John Krill 62" made by Johnson Polymer Co., Ltd. , John Krill 63, John Krill 71, John Krill 501 ", BYK's" DISPERBYK-102, DISPERBYK-185, DISPERBYK-190, DISPERBYK-193, DISPERBYK-199 "and the like (all are trade names).
Examples of the surfactant-type dispersant include anionic interfaces such as Kao Corporation's Demor series "Demor EP, Demor N, Demor RN, Demor NL, Demor RNL, and Demor T-45" (all trade names). Nonionic surfactants such as Kao Corporation's Emargen series "Emargen A-60, Emargen A-90, Emargen A-500, Emargen B-40, Emargen L-40, Emargen 420" (all trade names) Activators can be mentioned.

As the pigment dispersant, one type may be used alone, or two or more types may be used in combination.
The pigment dispersant varies depending on the type and is not particularly limited, but is generally blended in the range of 0.005 to 0.5 with respect to the pigment 1 in terms of the mass ratio of the solid content to the total amount of the water-based ink. Is preferable.

As the dye, a dye generally used in the technical field of printing can be used, and the dye is not particularly limited. Specific examples thereof include basic dyes, acidic dyes, direct dyes, soluble bat dyes, acidic mordant dyes, mordant dyes, reactive dyes, bat dyes, sulfide dyes, etc. Among these, water-soluble dyes, reduction dyes, etc. Those that become more water-soluble can be used. More specifically, azo dyes, rhodamine dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, triphenylmethane dyes, diphenylmethane dyes, methylene blue and the like can be mentioned.

The above-mentioned dyes may be used alone or in combination of two or more.
The dye varies depending on the type, but from the viewpoint of color development and the like, the solid content is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and 1 to 10% by mass with respect to the total amount of the water-based ink. % Is more preferable.

The water-based inkjet ink preferably contains water. The water is not particularly limited as long as it functions as a solvent for the ink, and distilled water, ion-exchanged water, deionized water and the like can be used.
The amount of water is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, based on the total amount of ink.
Depending on the amount of the coloring material added, the amount of water may be 95% by mass or less, or 90% by mass or less, based on the total amount of the ink.

The ink may contain a water-soluble organic solvent in addition to or in place of water. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and can be dissolved or miscible in water can be used, and a water-soluble organic solvent that uniformly mixes with the same volume of water at 20 ° C. at 1 atm is used. Is preferable.

Examples of the water-soluble organic solvent include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1,3-propanediol, 1,3-butanediol, and 1,2-butanediol. , 1,2-Pentanediol, 1,2-hexanediol, 2-methyl-2-propanol and other lower alcohols; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene Glycols such as glycols and tripropylene glycols; glycerin; acetylines (monoacetylene, diacetin, triacetin); diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , Triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, triethylene glycol monohexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether , Derivatives of glycols such as tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane and the like can be used.
Further, as the water-soluble organic solvent, for example, polyethylene glycol having an average molecular weight of 200, 300, 400, 600 or the like in the range of 190 to 630, and an average molecular weight of 400 or the like having an average molecular weight of 200 to 600 are in the range. Low molecular weight polyalkylene glycols such as diol type polypropylene glycol and triol type polypropylene glycol having an average molecular weight in the range of 250 to 800 such as average molecular weights of 300 and 700 can also be used.

As the water-soluble organic solvent, one type may be used alone, or two or more types may be used in combination. Further, among the above-mentioned water-soluble organic solvents, by using a water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less, the permeability of the water-based ink to the substrate can be further enhanced. it can. The water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less is as described in the section of the second pretreatment liquid described above.
The water-soluble organic solvent is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, preferably 10 to 50% by mass, and may be 20 to 40% by mass with respect to the total amount of the ink. When two or more kinds of water-soluble organic solvents are blended, the total amount thereof is preferably in this range.

The water-based ink may further contain a surfactant.
Surfactants are roughly classified into ionic surfactants such as cationic surfactants, anionic surfactants and amphoteric surfactants, and nonionic surfactants. Further, either a low molecular weight surfactant or a high molecular weight surfactant (generally, a surfactant having a molecular weight of about 2000 or more) may be used, but a low molecular weight surfactant can be preferably used. .. The HLB value of the surfactant is preferably 5 to 20.
By blending this surfactant, it becomes easier to stably eject the ink using an inkjet recording device, and it becomes easier to more appropriately control the penetration of the water-based ink into the substrate, which is preferable.

As the surfactant, a nonionic surfactant can be preferably used. In addition, the nonionic surfactant has little effect on the charge balance of the water-based ink, and can maintain good dispersibility and solubility of the coloring material.
As the nonionic surfactant, a nonionic surfactant as a penetrant that can be blended in each of the above-mentioned pretreatment liquids can be used.

Further, by using an anionic surfactant as the surfactant, it is possible to act as a pigment dispersant while obtaining the action of the surfactant. Examples of such anionic surfactants include Kao Corporation's Emar series "Emar 0, Emar 10, Emar 2F, Emar 40, Emar 20C", Neoperex series "Neoperex GS, Neoperex G-15," etc. Neo Perex G-25, Neo Perex G-65 ", Perex Series" Perex OT-P, Perex TR, Perex CS, Perex TA, Perex SS-L, Perex SS-H ", Demor Series" Demor N, Demor NL " , Demor RN, Demor MS ", etc. (all are product names).

Further, depending on the type of coloring material or the like, an amphoteric surfactant may be used as the surfactant.
Examples of the amphoteric surfactant include Kao Corporation's Anchor series "Anchor 20BS, Anchor 24B, Anchor 86B, Anchor 20YB, Anchor 20N" (all trade names).

The amount of the active ingredient of the surfactant is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, based on the total amount of the water-based ink. On the other hand, the amount of the surfactant is preferably 5% by weight or less, more preferably 4% by weight or less, still more preferably 3% by weight or less, based on the total amount of the water-based ink.

The water-based ink can further include a water-dispersible resin, a water-soluble resin, or a combination thereof. By containing at least one of the water-dispersible resin and the water-soluble resin in the ink, the coloring material can be sufficiently fixed to the base material, and thus high coloring property can be obtained with a small amount of the coloring material.
Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, neutralized polyacrylic acid, acrylic acid / maleic acid copolymer, acrylic acid / sulfonic acid copolymer, styrene / maleic acid copolymer and the like. Be done. These may be used alone or in combination of two or more.

In the case of a water-dispersible resin, it is preferable to use anionic resin particles having a negatively charged particle surface and a negative charge. This is capable of forming an oil-in-water (O / W) emulsion by dispersing in particles without being dissolved in water. Like the self-emulsifying resin, the anionic functional group of the resin may be present on the particle surface, or the surface of the resin particle may be surface-treated such as attaching an anionic dispersant. The anionic functional group is typically a carboxy group, a sulfo group or the like, and the anionic dispersant is an anionic surfactant or the like. When the surface of the resin particles is anionic, a chemical interaction with the flocculant in the first pretreatment liquid is obtained, and as a result, the fixing of the coloring material is further strengthened and the durability of the image is improved. Can be enhanced.
The surface charge amount of the anionic water-dispersible resin particles is preferably -20 to −500 μeq / g, more preferably -20 to -100 μeq / g.

As the type of water-dispersible resin, it is preferable to use a resin that forms a transparent coating film. Further, the water-dispersible resin can be blended as a resin emulsion in the production of ink.
Typically, urethane resin, (meth) acrylic resin, styrene / (meth) acrylic resin, polyester resin, olefin resin, vinyl chloride resin, vinyl acetate resin, melamine resin, amide resin, ethylene-vinyl chloride copolymer resin, Styrene- (meth) acrylic resin, styrene-maleic anhydride copolymer resin, vinyl acetate- (meth) acrylic copolymer resin, vinyl acetate-ethylene copolymer resin, silicone resin, etc., and composite resins thereof, etc. Can be mentioned.
As described above, an anionic functional group can be introduced into these resins, or a surface treatment with an anionic dispersant or the like can be applied to give a negative surface charge.

Among these water-dispersible resins, it is preferable to use a urethane resin having a glass transition temperature (Tg) of 35 to 40 ° C. from the viewpoint of stable discharge performance from the recording head and fixability to the substrate. ..
Examples of commercially available water-dispersible urethane resins include "Superflex 460, 420, 470, 460S (carbonate-based urethane resin emulsions, all trade names)" and 150HS (ester ether-based urethanes) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Resin emulsions (trade names), 740 (aromatic isocyanate-based ester-based urethane resin emulsions, trade names) ”, DSM's“ NeoRez R-9660, R-2170 (aliphatic polyester-based urethane resin emulsions, all products Name), NeoRez R-966, R-967, R-650 (aliphatic polyether urethane resin emulsion, all trade names), R-986, R-9603 (aliphatic polycarbonate, all trade names), etc. Can be mentioned.

Further, from the viewpoint of stability in ink, it is also preferable to use a (meth) acrylic resin or a (meth) acrylic resin copolymer.
Examples of these commercially available products include "Movinyl 966A, 6963, 6960 (acrylic resin emulsion, all trade names), 669D (styrene / acrylic resin emulsion, all trade names)" and BASF of Nippon Synthetic Chemical Industry Co., Ltd. "John Krill 7100, PDX-7370, PDX-7341 (styrene / acrylic resin emulsion, all trade names)", DIC Co., Ltd. "Boncoat EC-905EF, 5400EF, CG-8400 (acrylic / styrene emulsion)" , Etc. can be mentioned.
The water-dispersible resin may be composed of one type of resin such as urethane resin and acrylic resin, or may be composed of a combination of a plurality of types of resins as a composite resin, and further, these resin emulsions. May be a mixture of.

Further, as the water-dispersible resin, a non-ionic or amphoteric water-dispersible resin may be used because it has little influence on the charge balance of the water-based ink. Examples of these commercially available products include "Mobile 7720" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Boncoat 40-418EF" manufactured by DIC Corporation, "HUX-895, HUX-830" manufactured by ADEKA Corporation, and No. Examples include "Superflex 500M, Superflex E-4800" manufactured by Ichiko Pharmaceutical Co., Ltd. (both are trade names).

In the water-dispersible resin emulsion, the water-dispersible resin particles forming the emulsion may have a particle size suitable for the inkjet recording method, and generally have an average particle size (measured on a volume basis by a dynamic light scattering method). The average particle size) is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. The lower limit of the average particle size of the water-dispersible resin particles is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more from the viewpoint of ink storage stability.

The total amount of the water-soluble resin and the water-dispersible resin is preferably 0.1 to 15 with respect to 1 of the coloring material, more preferably 1 to 10 and 3 to 7 in terms of the mass ratio of the solid content to the total amount of the water-based ink. Is even more preferable. By setting the resin content in this range, the fixability and image quality of the image printed on the surface of the base material can be sufficiently ensured. When the ratio of the resin to the coloring material 1 is 0.1 or more, the fixability of the image can be further improved. When the ratio of the resin to the color material 1 is 15 or less, the on-machine stability of the water-based ink can be further improved.

The total amount of the water-soluble resin and the water-dispersible resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass, based on the total amount of the water-based ink.
The total amount of the water-soluble resin and the water-dispersible resin is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the water-based ink.
For example, the total amount of the water-soluble resin and the water-dispersible resin is preferably 0.1 to 20% by mass, more preferably 1 to 20% by mass, and may be 5 to 10% by mass with respect to the total amount of the water-based ink. ..

The water-based ink may further contain a cross-linking component in order to cross-link the resin component to strengthen the coating film and further enhance the fixability. Examples of the cross-linking component include blocked isocyanate, oxazoline group-containing compound, (poly) carbodiimide, aziridine, chelating agent, silane coupling agent and the like.
The cross-linking agent is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, based on the total amount of the water-based ink.

In addition to the above components, the ink contains, for example, a moisturizer, an antifoaming agent, a pH adjuster, an antioxidant, a preservative, a surface tension lowering agent, an ultraviolet absorber, etc., as long as the effects of the present invention are not impaired. Any additional component may be added.

The method for producing the ink is not particularly limited, and the ink can be appropriately produced by a known method. For example, all the components can be collectively or divided and dispersed in a known disperser such as a bead mill, and if desired, can be prepared by passing through a known filter such as a membrane filter. For example, a mixed solution in which the entire amount of water and the coloring material is uniformly mixed is prepared in advance, dispersed by a disperser, and then the remaining components are added to the dispersant and passed through a filter. Can be done.

The viscosity of the water-based ink can be adjusted as appropriate, but from the viewpoint of ejectability, for example, the viscosity at 23 ° C. is preferably 1 to 30 mPa · s.
The pH of the water-based ink is preferably 7.0 to 10.0, more preferably 7.5 to 9.0, from the viewpoint of ink storage stability.

The water-based inkjet ink set according to the embodiment is a water-based ink containing a first pretreatment liquid containing a coagulant, a second pretreatment liquid containing no coagulant and containing a penetrant, and a coloring material and water. And include. Details of the first pretreatment liquid, the second pretreatment liquid, and the water-based ink are as described above.
The pretreatment liquid set for an aqueous inkjet ink according to one embodiment includes a first pretreatment liquid containing a coagulant and a second pretreatment liquid containing no coagulant and containing a penetrant. The details of the first pretreatment liquid and the second pretreatment liquid are as described above.

"Recording method"
In the method for producing a printed matter according to one embodiment, one of the first pretreatment liquid and the second pretreatment liquid, the other of the first pretreatment liquid and the second pretreatment liquid, and the water-based ink are used in this order. It is preferable that the first pretreatment liquid and the second pretreatment liquid are applied to the recording area of the material and discharged so as to land on the base material in a certain order.
Either one of the first pretreatment liquid and the second pretreatment liquid may be first applied to the recording area of the base material, and then the other may be applied. As a result, the coagulant of the first pretreatment liquid and the penetrant of the second pretreatment liquid are superposed on the substrate, and the image quality and fixability of the printed matter can be improved. The stacking order of the first pretreatment liquid and the second pretreatment liquid is the same over the entire recording area of the base material, so that the water-based ink does not spread from the landing site on the base material. It is possible to suppress the occurrence of image unevenness and increase the image density. Further, the components of the first pretreatment liquid and the second pretreatment liquid are uniformly applied onto the base material, and the compatibility between the treated surface of each pretreatment liquid and the water-based ink is improved. Therefore, the fixing property can be further improved.

Further, when one kind of pretreatment liquid containing both a coagulant and a penetrant is used, there is a problem that the pretreatment liquid does not sufficiently permeate into the inside of the base material. By separately applying the first pretreatment liquid and the second pretreatment liquid to the base material, the penetration of the pretreatment liquid into the base material is promoted, and then to the base material of the water-based ink to be applied. It is possible to improve the fixability of the ink. Further, by separately applying the first pretreatment liquid and the second pretreatment liquid to the base material, the coagulant of the first pretreatment liquid forms a concentration gradient in the thickness direction of the base material. As a result, the image quality and fixability of the printed matter can be improved in a more balanced manner.
Further, by appropriately controlling the ratio of the two pretreatment liquids depending on the base material, the balance between image quality and fixability can be further improved. When one type of pretreatment liquid is used, there is a problem that the concentration is insufficient due to over-permeation of the pretreatment liquid and the fixing is insufficient due to insufficient permeation.

When the first pretreatment liquid and the second pretreatment liquid are applied to the base material in this order, the coagulant of the first pretreatment liquid first applied to the base material is then applied. It will be pushed into the inside of the base material by the penetrant and solvent of the pretreatment liquid of 2. As a result, excessive ink agglomeration due to the coagulant is suppressed, and the ink is prevented from remaining excessively on the outermost surface of the base material which is easily affected by an external force, so that the fixability of the printed matter can be further improved.
When the second pretreatment liquid and the first pretreatment liquid are applied to the base material in this order, the penetrant of the second pretreatment liquid is first applied to the base material and then applied. A part of the coagulant remains on the surface of the base material while the coagulant of the first pretreatment liquid permeates the inside of the base material. As a result, the color material of the water-based ink is aggregated and stays relatively near the surface of the base material, and the image density of the printed matter can be further increased. Further, by first applying the penetrant of the second pretreatment liquid to the base material, the penetrant permeates from the inside of the base material to the back surface side, and the coagulant and the ink also permeate into the base material due to the priming effect. Can be done. Thereby, image unevenness can be further reduced. Further, the density on the back surface of the printed matter can be further increased for use in applications where the visibility of the image from the back surface side of the base material is required.

Hereinafter, a method of applying the first pretreatment liquid, the second pretreatment liquid, and the water-based ink to the recording area of the base material in this order will be described. The method of applying the second pretreatment liquid, the first pretreatment liquid, and the water-based ink to the recording area of the base material in this order has the following configurations of the first pretreatment liquid and the second pretreatment. Since this can be done by reversing the composition of the liquid, detailed description thereof will be omitted.

The first pretreatment liquid and the second pretreatment liquid can be independently applied to the recording area of the base material by using an inkjet recording device.
It is preferable that the first pretreatment liquid and the second pretreatment liquid are independently applied to the region corresponding to the recording region with the water-based ink. By not applying the first pretreatment liquid and the second pretreatment liquid to areas other than the recording area, it is possible to prevent the water-based ink from spreading to areas other than the recording area and further prevent image bleeding. .. Further, since the first pretreatment liquid and the second pretreatment liquid are not applied to the area other than the recording area, it is possible to prevent the color and texture of the base material surface of the portion other than the recording area from being impaired. The first pretreatment liquid and the second pretreatment liquid may be applied to a region other than the recording area with the water-based ink, or may be applied to a part or the entire surface of the base material.

Next, the base material treated with the first pretreatment liquid and the second pretreatment liquid can be coated with the water-based ink in the recording area of the base material by using an inkjet recording device.
By applying in such an order, it is possible to record an image in which the first pretreatment liquid, the second pretreatment liquid, and the water-based ink are laminated in this order on the substrate.

The applied amounts of the first pretreatment liquid and the second pretreatment liquid cannot be uniformly specified because they differ depending on the type and material of the base material, respectively, but in order to improve the image quality and fixability. the per imparting ^area, preferably ^{1g / m 2 ~100g / m 2} , more preferably ^{3g / m 2 ~50g / m 2} , 5g / m 2 ~30g / m 2 it is more preferred.
The amount of the water-based ink applied cannot be uniformly specified because it differs depending on the type and material of the base material, but in order to increase the image density, 1 g / m ^{2 to} 500 g / m ² is preferable per applied area. more preferably ^{3g / m 2 ~100g / m 2} , 5g / m 2 ~50g / m 2 it is more preferred.
By separately applying the first pretreatment liquid and the second pretreatment liquid to the base material, the amount of volatile components such as water and solvent given to the base material increases, so that the ability to retain water and the like is large. A cloth or the like can be preferably used as a base material.

After the water-based ink is applied to the base material, the base material may be dried to remove volatile components such as water and a solvent, and the image may be fixed on the base material. The image to be recorded is not particularly limited, and may be any pattern, characters, a combination of patterns and characters, a solid image, a photographic image, or the like.
In order to obtain a high-quality image, (i) reduce the ink droplets, (ii) slow down the printing speed, (iii) perform one-way printing, (iv) increase the printing resolution, or (i) v) It is effective to use printing conditions such as printing by combining these methods.

The first pretreatment liquid, the second pretreatment liquid, and the water-based ink can be applied to the substrate by using a general inkjet recording device, and the application is not limited to the recording method, the recording device, or the like.
The inkjet recording device may be, for example, any of a piezo method, an electrostatic method, a thermal method, etc., and a droplet such as ink is ejected from the recording head based on a digital signal, and the ejected droplet is used as a base. It is preferable that the material is landed and an image is recorded. The piezo method is preferable from the viewpoint that even high-viscosity ink can be ejected.
For example, using an inkjet recording device including at least three recording heads, a first pretreatment liquid, a second pretreatment liquid, and a water-based ink are ejected from each recording head and applied to a substrate to give an image. Can be recorded. Further, while the base material is conveyed once, the first pretreatment liquid, the second pretreatment liquid, and the water-based ink may be ejected from the respective recording heads and applied to the base material to record an image. preferable.

The application of the first pretreatment liquid, the second pretreatment liquid, and the water-based ink to the substrate can be performed using a general recording head. For example, a serial type inkjet recording device including a serial type recording head or a linehead type inkjet recording device including a linehead type recording head can be used.

When the first pretreatment liquid containing a coagulant is used, when the nozzle portion for discharging the first pretreatment liquid and the nozzle portion for discharging the water-based ink are arranged in the vicinity, the nozzle for discharging the water-based ink Although this is not a problem in a configuration in which only the portions are arranged, mist containing a coagulant may be generated from the nozzle portion that ejects the first pretreatment liquid and adheres to the nozzle portion that ejects the water-based ink. As a result, the water-based ink aggregates at the nozzle portion to cause nozzle clogging, which may cause ejection failure. In a line-head type inkjet recording device, even if one of the nozzles in the line-shaped nozzle row does not eject, the effect on the image becomes large. Therefore, when using the first pretreatment liquid containing a flocculant, it is preferable to use a serial type inkjet recording device.

Further, in the line head type inkjet recording device, it is difficult to switch the arrangement of the recording heads for applying the first pretreatment liquid and the second pretreatment liquid depending on the base material and the required performance. The serial type inkjet recording device can be preferably used because the order of applying the first pretreatment liquid and the second pretreatment liquid can be controlled.

When two or more kinds of pretreatment liquids are applied to the base material, it is preferable to adjust the total amount of the two or more kinds of pretreatment liquids and the water-based ink applied to the base material per unit time. If the total amount of these applied amounts increases in a short period of time, the penetration of the pretreatment liquid and the water-based ink applied later into the substrate may be delayed. For example, when the timing of applying the first pretreatment liquid and the timing of applying the second pretreatment liquid are almost the same, the permeation into the base materials of the first pretreatment liquid and the second pretreatment liquid is delayed. , The flocculant and penetrant may remain on the surface of the substrate in a mixed state. Further, depending on the combination of the first pretreatment liquid and the second pretreatment liquid, the penetration into the substrate may be further delayed. If the water-based ink is applied before the two pretreatment liquids have sufficiently penetrated into the base material, the water-based ink starts to aggregate on the surface of the base material, and there is a problem that the fixability of the image is lowered. Therefore, when two or more types of pretreatment liquids are used, a serial type inkjet recording device can be preferably used rather than a line head type inkjet recording device in order to more easily adjust the application interval of each pretreatment liquid.

For example, the application interval from the application of the first pretreatment liquid to the application of the second pretreatment liquid varies depending on the type or amount of the volatile component contained in each pretreatment liquid, but is 1 ms (m seconds) or more. Is preferable, and 10 ms or more is more preferable. As a result, the second pretreatment liquid can be applied after the first pretreatment liquid begins to permeate into the base material, so that it is possible to prevent the two pretreatment liquids from remaining on the surface of the base material. ..
On the other hand, the application interval from the application of the first pretreatment liquid to the application of the second pretreatment liquid is preferably within 10 s (seconds), more preferably within 1 s. As a result, the second pretreatment liquid can be applied before the first pretreatment liquid dries on the base material, and the coagulant of the first pretreatment liquid can be more permeated into the base material. ..

The application interval from the application of the second pretreatment liquid to the application of the water-based ink varies depending on the type or amount of the volatile components contained in each pretreatment liquid and the water-based ink, but is preferably 10 ms or more, preferably 100 ms or more. Is more preferable, and 1 s or more is more preferable. As a result, the water-based ink can be applied after the second pretreatment liquid has sufficiently penetrated into the base material, so that the water-based ink can be more permeated into the inside of the base material.
On the other hand, the application interval from the application of the second pretreatment liquid to the application of the water-based ink is preferably 100 s or less, and more preferably 10 s or less. Thereby, before the first pretreatment liquid and the second pretreatment liquid are dried on the base material, the water-based ink can be applied and the water-based ink can be more permeated into the base material.

When a serial type inkjet recording device is used, by controlling the moving speed of the recording head in the main scanning direction, the application interval between the first pretreatment liquid and the second pretreatment liquid and the second pretreatment liquid are applied. The application interval between the ink and the water-based ink can be adjusted more easily. The same applies when the order of applying the first pretreatment liquid and the second pretreatment liquid is different.
Further, by using the recording head unit shown in FIG. 2, which will be described later, the application interval between the second pretreatment liquid and the water-based ink can be adjusted to be longer. Further, by using the recording head unit shown in FIG. 3, which will be described later, the application interval between the second pretreatment liquid and the water-based ink and the application interval between the first pretreatment liquid and the second pretreatment liquid can be further increased. It can be adjusted longer.

In one embodiment, of the first pretreatment liquid and the second pretreatment liquid, between the two dots of the pretreatment liquid that first lands on the substrate, the distance between the dots is the shortest in the main scanning direction. landing time difference [Delta] T _X, and it is preferable that at least one of the landing time difference [Delta] T _Y between two dots distance is the shortest among the dots in a direction intersecting the main scanning direction is equal to or greater than 10 ms. Hereinafter also referred to as a landing time difference [Delta] T are collectively the landing time difference [Delta] T _X and landing time difference [Delta] T _Y.
As a result, the permeability of the two pretreatment liquids can be enhanced, the anchor effect of the ink film can be easily obtained, and the fixability of the image can be improved.
Here, the "main scanning direction (hereinafter, also referred to as the main scanning direction X)" is the direction in which dots are continuously ejected, which is the main scanning direction of the recording head in the serial type and the recording head in the line head type. It becomes the longitudinal direction of. The "direction intersecting the main scanning direction (hereinafter, also referred to as direction Y)" is a direction intersecting the main scanning direction at right angles to the main scanning direction as long as it intersects the main scanning direction in which dots are continuously ejected. It may be a direction that intersects the main scanning direction at an angle other than perpendicular to the main scanning direction. In a typical inkjet recording device, the base material is conveyed in a direction orthogonal to the main scanning direction X, and two dots having the shortest distance between the dots are landed in the direction orthogonal to the main scanning direction X.

When the pretreatment liquid contains a resin component, the resin tends to have poor permeability. For example, the water-dispersible resin tends to be particulate and difficult to penetrate, and the water-soluble resin thickens due to volatilization of water. It tends to be difficult to penetrate. When the pretreatment liquid that lands on the substrate first of the two pretreatment liquids contains a resin, the landing time difference ΔT is set to 10 ms or more so that even if the pretreatment liquid containing the resin is used, two of them are used. The permeability of the pretreatment liquid can be further enhanced.

The landing time difference ΔT is preferably 10 ms or more, more preferably 20 ms or more, and even more preferably 100 ms or more.
On the other hand, the landing time difference ΔT is preferably within 30 s, more preferably within 5 s, and even more preferably within 3 s. If it exceeds 30 s, the pretreatment liquid that first lands on the substrate starts to dry and / or forms a film, and the permeability may be inferior.
For example, the landing time difference ΔT is preferably 10 ms to 5 s, more preferably 20 ms to 3 s.
Note that the landing time difference [Delta] T _x and [Delta] T _Y may be at least one or more 10 ms, both may be more than 10 ms. Each of the preferred range of the landing time difference [Delta] T _x and [Delta] T _Y is the same as [Delta] T as described above.

The method of setting the landing time difference ΔT to 10 ms or more is not particularly limited, but for example, it can be performed using a serial type inkjet recording device.
When ejection is performed using a serial type recording head, for example, the landing time difference ΔT _x between two dots having the shortest distance between dots in the main scanning direction X may be 10 ms or more. In this case, for example, you can control the moving speed of the main scanning direction X of serial type recording head, to adjust the [Delta] T _X above 10 ms. Alternatively, it is possible to adjust the landing positions of the main scanning direction X of serial type recording head is controlled so as to have a predetermined distance or more, the landing time difference [Delta] T _X above 10 ms. Furthermore, these may be combined.

Also, when performing discharging using a serial type recording head, for example, the distance between the dots in the direction Y crossing the main scanning direction is the landing time difference [Delta] T _Y between the two dots of the shortest may be more 10 ms. In this case, for example, by using a serial inkjet recording apparatus that conveys the base material in a direction orthogonal to the main scanning direction, the pretreatment liquid is first scanned while scanning the serial recording head in the main scanning direction X. When the pretreatment liquid is discharged to the line, the base material is moved by one line in the transport direction, and then the pretreatment liquid is discharged to the next second line on the base material in the same manner, the transport speed of the base material and the recording head by controlling the moving speed, etc., the landing time difference [Delta] T _Y can be adjusted to more than 10 ms.
The landing time difference [Delta] T _X and landing time difference [Delta] T _Y have, respectively alone or may be controlled in combination.

Hereinafter, a specific method for producing a printed matter using a serial type inkjet recording device will be described.
The serial type inkjet recording device is movably attached in the main scanning direction (hereinafter, also referred to as the main scanning direction X), and conveys a base material to a serial type recording head provided with a nozzle portion and a position facing the recording head. It is equipped with a transport device to be used. While moving the serial recording head in the main scanning direction X, an operation of ejecting ink from the nozzle portion and an operation of moving the base material in a transport direction intersecting the main scanning direction (hereinafter, also referred to as a transport direction Y). The image can be recorded on the base material by repeating the above steps.

An example of a serial inkjet recording device includes a recording head unit that can move in the main scanning direction X and a transport device that transports the base material in the transport direction Y, and the recording head unit includes a first recording head and a second recording head. A recording head and a third recording head are provided at least. The recording head unit can be reciprocated in the main scanning direction X by the drive belt. One of the first pretreatment liquid and the second pretreatment liquid is supplied to the first recording head, and the other of the first pretreatment liquid and the second pretreatment liquid is supplied to the second recording head. The water-based ink is supplied to the third recording head, and the first pretreatment liquid, the second treatment liquid, and the water-based ink are ejected from the respective recording heads, so that these are laminated on the base material to obtain an image. Can be recorded.

The transfer device for the base material may be one in which the recording head unit is fixed to the inkjet recording device and the base material is moved in the transfer direction Y by using a transfer roller or the like to pass through a position facing the recording head. .. Further, the base material transfer device may be a device in which the base material is fixedly placed on the mounting portion and the recording head unit is moved to relatively transport the base material in the transport direction Y. Good. Preferably, the substrate is conveyed in a direction orthogonal to the main scanning direction of the recording head unit.
Further, the recording device may be provided with a heating device that heats the base material at any stage during printing or before and after printing. By heating the base material with the heating device, it is possible to accelerate the drying of each pretreatment liquid and the water-based ink. Further, when each pretreatment liquid and the water-based ink contain a resin component, the formation of a resin film can be promoted.
Further, the recording device may include an input device for inputting image data to be printed. The input device may include an external input unit that receives image data captured from a scanner or a personal computer. Based on this image data, it is possible to control the ejection of the water-based ink from each recording head, and to eject each pretreatment liquid in advance to the recording area where the water-based ink is ejected.

The serial inkjet recording apparatus according to one embodiment includes, for example, a first recording head to which one of a first pretreatment liquid and a second pretreatment liquid is supplied, and a first pretreatment liquid and a second pretreatment liquid. It has a serial recording head unit including a second recording head to which the other of the treatment liquids is supplied and a third recording head to which water-based ink is supplied, and the first pretreatment liquid is supplied from the first recording head. And the step of applying one of the second pretreatment liquids to the recording area of the base material, and applying the other of the first pretreatment liquid and the second pretreatment liquid to the recording area of the base material from the second recording head. The step and the step of applying the water-based ink from the third recording head to the recording area of the base material can be performed in this order. According to this, one of the first pretreatment liquid and the second pretreatment liquid, the other of the first pretreatment liquid and the second pretreatment liquid, and the water-based ink are laminated on the substrate in this order. Then, the first pretreatment liquid and the second pretreatment liquid are landed on the base material in a certain order, and a printed matter in which an image is recorded can be obtained.

As a specific method, the first recording head, the second recording head, and the third recording head are arranged in this order in the main scanning direction of the recording head, and the recording head unit is placed in one of the main scanning directions. One of the first pretreatment liquid and the second pretreatment liquid from the first recording head, and the other of the first pretreatment liquid and the second pretreatment liquid from the second recording head while moving in the direction. And water-based ink can be applied to the recording area of the substrate in this order from the third recording head.

FIG. 1 shows a top view schematically showing an example of a serial type recording head unit according to an embodiment.
In the recording head unit 100 shown in FIG. 1, the first recording head 11, the second recording head 12, and the second recording head 12 from the downstream side of the outward path (from left to right in the figure, the same applies hereinafter) along the main scanning direction X. The recording heads 13 of 3 are arranged in a row in this order. The third recording head 13 has four recording heads 13K, 13C, 13M, and 13Y for each of the four color water-based inks of black (K), cyan (C), magenta (M), and yellow (Y). Be prepared. The same applies to FIGS. 2 and 3 described later.
Then, the first pretreatment liquid is supplied to the first recording head 11, the second pretreatment liquid is supplied to the second recording head 12, and the water-based ink is supplied to the third recording head 13. While moving the recording head unit 100 in the outward path direction of the main scanning direction X, the first pretreatment liquid is discharged from the first recording head 11, and the second pretreatment liquid is discharged from the second recording head 12. By ejecting the water-based ink from the third recording head 13, the first pretreatment liquid, the second pretreatment liquid, and the water-based ink can be applied to the base material in this order.
In the configuration of the recording head unit 100, the granting order is only the outward path in the main scanning direction X, and the granting order is reversed in the return path. Therefore, in order to obtain this order of granting, it is advisable to print only on the outward trip and not on the return trip.

As a specific other method, the first recording head and the second recording head are arranged in a row in the main scanning direction of the recording head unit, and the third recording head is arranged in the first recording head and the second recording head. A step of arranging the recording head on the downstream side in the transport direction of the base material and applying one of the first pretreatment liquid and the second pretreatment liquid to the recording area of the base material from the first recording head, and The steps of applying the other of the first pretreatment liquid and the second pretreatment liquid from the second recording head to the recording area of the base material are performed in this order, and then the base material is conveyed to the recording head unit in the transport direction. A step of applying the water-based ink from the third recording head to the recording area of the base material treated by the first pretreatment liquid and the second pretreatment liquid can be performed by moving.

FIG. 2 shows a top view schematically showing another example of the serial recording head unit according to one embodiment.
In FIG. 2, in the recording head unit 100, a first recording head 11 to which a first pretreatment liquid is supplied and a second recording head 12 to which a second pretreatment liquid is supplied are recorded head units. A first head row arranged in the main scanning direction X of 100, and a third recording head 13 to which water-based ink is supplied downstream of the first head row in the transport direction Y of the base material are included. It includes a second head row.
Then, while moving the recording head unit 100 in the main scanning direction X, the operation of discharging the first pretreatment liquid from the first recording head 11 and discharging the second pretreatment liquid from the second recording head 12 The operation of moving the base material in the transport direction Y and ejecting the water-based ink from the third recording head 13 to the recording area on the base material to which the first pretreatment liquid and the second pretreatment liquid are applied. By repeating the above steps, the first pretreatment liquid, the second pretreatment liquid, and the water-based ink can be applied to the substrate in this order.
In the configuration of the recording head unit 100, the granting order is only the outward path (from left to right in the figure) in the main scanning direction X, and the granting order is reversed in the return path. Therefore, in order to obtain this order of granting, it is advisable to print only on the outward trip and not on the return trip.

FIG. 3 shows a top view schematically showing still another example of the serial recording head according to the embodiment.
FIG. 3 shows an example in which the arrangement of the first recording head 11 and the second recording head 12 is different in FIG. 2 described above. In FIG. 3, the first recording head 11 and the second recording head are arranged apart from each other. More specifically, the first recording head 11 is located on one side of the recording head unit 100 with respect to the main scanning direction X, and the second recording head 12 is located on the other side of the recording head unit with respect to the main scanning direction X. Located on the side. More preferably, the first recording head 11 and the second recording head 12 are arranged so as not to overlap with the third recording head 13 from which the water-based ink is discharged in the transport direction Y. With such an arrangement, the mist derived from the coagulant of the first pretreatment liquid can be prevented from adhering to the nozzle for ejecting the second pretreatment liquid and the nozzle for ejecting the water-based ink. .. Thereby, the nozzle clogging of the second recording head 12 and the third recording head 13 can be further prevented.
In the recording head unit shown in FIGS. 1 to 3 described above, in order to reverse the order of applying the first pretreatment liquid and the second pretreatment liquid, the second pretreatment liquid is applied to the first recording head 11. May be supplied and the first pretreatment liquid may be supplied to the second recording head 12.

When ejection is performed on the outward path and the return path of the serial recording head, the ejection order of the two types of pretreatment liquid and the water-based ink is switched between the outward path and the return path of the recording head according to the conventional recording method. Then, the stacking order of the two types of pretreatment liquids is changed for each line adjacent to the transfer direction Y of the base material. An explanatory diagram illustrating this conventional recording method is shown in FIG.
In FIG. 4, (a) shows the arrangement of the recording head unit 100 from the upper surface, and the case where the first pretreatment liquid is discharged from the first recording head 11 in each pass is represented by a hatch circle. The case where the second pretreatment liquid is discharged from the second recording head 12 is represented by a white circle. Further, (b) shows the surface of the base material P from the upper surface, and the first pretreatment liquid and the second pretreatment liquid are in this order in each line along the main scanning direction of the recording head unit 100. The case of stacking is shown in the order of hatch circles and white circles from the left in the figure, and the case of stacking in the reverse order is shown in the order of white circles and hatch circles from the left in the figure.

In FIG. 4, as shown in FIG. 4A, in the first pass of the outward route, the first recording head 11 moves ahead of the second recording head 12, so that the first pretreatment is performed on the base material. The second pretreatment liquid is discharged next to the liquid. Then, as shown in (b) in the figure, the first pretreatment liquid and the second pretreatment liquid are laminated in this order on the base material.
In the second pass of the return route, since the second recording head 12 moves ahead of the first recording head 11, the first pretreatment liquid is discharged onto the base material after the second pretreatment liquid. The second pretreatment liquid and the first pretreatment liquid are laminated on the substrate in this order.
In the third pass on the outward route, the first pretreatment liquid and the second pretreatment liquid are laminated in this order on the substrate as in the first pass.
In the obtained printed matter, the stacking order of the two types of pretreatment liquids is switched in the lines adjacent to each other in the transport direction of the base material. In the base material treated with the two types of pretreatment liquids in this way, the aggregation of the color material of the water-based ink becomes non-uniform on the base material, and the permeation of the water-based ink into the base material becomes non-uniform. There is a problem that the image quality and fixability of the printed matter are deteriorated.

In the recording method according to one embodiment, a first recording head is provided on the downstream side of the outward path along the main scanning direction X of the recording head unit, a second recording head is provided on the upstream side, and the recording head unit is moved on the outward path. When the first pretreatment liquid is first discharged from the first recording head, then the second pretreatment liquid is discharged from the second recording head, and the recording head unit is moved on the return path. It is preferable that neither the first pretreatment liquid nor the second pretreatment liquid is discharged. As a result, the first pretreatment liquid and the second pretreatment liquid are laminated on the base material in this order over the entire surface of the recording area of the base material. That is, in FIG. 4, it is preferable to repeat only the discharge in the first pass of the outward route and not to discharge in the second pass of the return route. Further, in FIG. 4, the second pretreatment liquid and the first front on the base material are formed by repeating only the second pass of the return route without discharging the first and third passes of the outward route. The treatment liquids are laminated in this order.
In the case of using the recording head unit 100 shown in FIGS. 2 and 3, after the first pretreatment liquid and the second pretreatment liquid are discharged so as to be laminated on the base material, the third recording head 13 is moved to each front. An image can be recorded by transporting the base material so as to face the application region of the treatment liquid and ejecting the water-based ink from the third recording head 13.

Further, the first pretreatment liquid and the second pretreatment liquid may be applied in both directions of the outward trip and the return trip using a serial type inkjet recording device. In this method, the productivity can be further improved as compared with the case where the first pretreatment liquid and the second pretreatment liquid are discharged on one of the outward and return paths in the main scanning direction and not on the other. In the following description, the movement order of the outward path and the return path in the main scanning direction is not particularly limited, and the outward path and the return path may be in the reverse order. Further, in the following description, the order of applying the first pretreatment agent and the second pretreatment agent may be reversed.

As an example of the bidirectional recording method, a recording head unit in which the first recording head and the second recording head are arranged in the main scanning direction X is used, and the first recording head to the second recording head are used in the outward path in the main scanning direction. The pretreatment liquid of 1 is applied onto the base material, and the second pretreatment liquid is applied from the second recording head so as to overlap the first pretreatment liquid applied in the outward route on the return route in the main scanning direction. There is a method of applying it on the material.
In the example shown in FIG. 1, the water-based ink can be applied onto the substrate from the third recording head so as to overlap the second pretreatment liquid while further moving the recording head unit in the outward path in the main scanning direction. it can. In the example shown in FIG. 2 or 3, after the second treatment liquid is applied, the base material is moved in the transport direction Y, and the recording head unit is moved in the main scanning direction while the second pretreatment liquid is applied. The water-based ink can be applied onto the substrate from the third recording head so as to overlap with the substrate.

As another example of the bidirectional recording method, a recording head unit in which the first recording head is arranged on the upstream side with respect to the transport direction Y of the base material and the second recording head is arranged on the downstream side thereof. By using, the first pretreatment liquid is applied onto the base material from the first recording head in the outward path in the main scanning direction X, the base material is moved in the transport direction, and the first pretreatment liquid is applied in the return path in the main scanning direction. The second pretreatment liquid can be applied onto the substrate from the second recording head so as to overlap the pretreatment liquid.
In order to apply the two pretreatment liquids more efficiently, in the return path in the main scanning direction, the second pretreatment liquid is applied from the second recording head to the substrate, and the first recording head to the first The pretreatment liquid of the above may be applied onto the substrate. Similarly, in the outward path in the main scanning direction, the first pretreatment liquid is applied onto the base material from the first recording head, and the second pretreatment liquid is applied to the base material from the second recording head. You may.
In the configuration in which the first recording head and the second recording head are arranged in the transport direction, a recording head unit in which the third recording head is arranged further downstream of the second recording head in the transport direction is used. After applying the second treatment liquid, the substrate is moved in the transport direction, and the recording head unit is moved in the main scanning direction so as to overlap the second pretreatment liquid for the third recording. Water-based ink can be applied onto the substrate from the head.

As yet another example of the bidirectional recording method, a first recording head and a second recording head are arranged in the main scanning direction X, and the base material is conveyed to the first recording head and the second recording head, respectively. A recording head unit in which a plurality of nozzles are formed in a row along the direction Y can be used. While reciprocating the recording head unit in the main scanning direction, the base material is moved in the transport direction to apply the first pretreatment liquid onto the base material from the nozzle on the upstream side in the transport direction of the first recording head. To form a plurality of lines and continuously move the base material in the transport direction, from the nozzle on the downstream side in the transport direction of the second recording head, and from the nozzle on the upstream side of the first recording head. The second pretreatment liquid was applied onto the base material so as to overlap the applied first pretreatment liquid, and the first pretreatment liquid and the second pretreatment liquid were laminated in this order. Multiple lines can be formed.
In the example shown in FIG. 1, the third recording head in which a plurality of nozzles are formed in a row along the transport direction is used, and the third recording head is further downstream of the nozzles of the second recording head in the transport direction. The water-based ink can be applied onto the base material from the nozzle of the recording head of No. 1 so as to overlap the second pretreatment liquid applied from the nozzle on the upstream side in the transport direction.
In the example shown in FIG. 2 or 3, after the second treatment liquid is applied, the base material is moved in the transport direction Y, and the recording head unit is moved in the main scanning direction while the second pretreatment liquid is applied. The water-based ink can be applied onto the substrate from the third recording head so as to overlap with the substrate.

Specifically, in the recording head units shown in FIGS. 1 to 3, a plurality of nozzles are formed in a row on the first recording head 11 and the second recording head 12 along the transport direction Y of the base material, respectively. Bidirectional granting can be performed using the configuration described above. In each recording head, the plurality of nozzles are arranged apart from each other in the transport direction Y.
First, the recording head unit 100 is ejecting droplets of the first pretreatment liquid so as to correspond to one dot from one nozzle on the upstream side in the transport direction Y of the base material of the first recording head 11. Is moved in the outward path direction of the main scanning direction X, and dots are continuously landed in the main scanning direction X to apply the first pretreatment liquid in a line shape having a width of 1 dot. Next, the base material is moved in the transport direction Y, and the droplets ejected from one nozzle adjacent to the downstream side of the transport direction Y with respect to the one nozzle at the tip of the first recording head 11 are Similar to the previous line-shaped first pretreatment liquid, the first line-shaped pretreatment liquid on the base material is landed adjacent to the upstream side in the transport direction Y of the base material. Is provided with a line-shaped first pretreatment liquid. At this time, on the base material, the two dots adjacent to each other in the transport direction Y of the base material land on the base material by controlling the time for the recording head unit to move in the transport direction Y, the moving speed of the recording head unit, and the like. the time difference [Delta] T _Y may be equal to or larger than 10 ms.
Further, among the plurality of nozzles of the first recording head, two or more nozzles that are continuously arranged in the transport direction Y are used, and the nozzles are separated in the transport direction Y in one pass according to the nozzle spacing. Two or more rows of line-shaped first pretreatment liquids are applied, and then, in the same manner as described above, upstream of the transfer direction Y of the base material of each of the line-shaped first pretreatment liquids. A line-shaped first pretreatment liquid can be applied to the side. In this method, the amount of image recording per pass of the recording head unit can be increased, and the productivity can be further increased.

Next, the second pretreatment liquid is ejected from the nozzle of the second recording head 12 so as to overlap the dots of the first pretreatment liquid landed on the base material, and the dots are formed by landing on the base material. be able to.
For example, for one line-shaped recording region, the first pretreatment liquid is discharged from a nozzle on the upstream side of the base material of the first recording head 11 in the transport direction Y, and then applied to the base. While moving the material in the transport direction Y, the second pretreatment liquid is transferred from the second recording head 12 on the downstream side of the base material transport direction Y with respect to the position of the nozzle of the first recording head 11. It may be given by being discharged from a nozzle.

Next, in the example shown in FIG. 1, a third recording head in which a plurality of nozzles are formed in a row along the transport direction is used to transport the base material in the transport direction Y while transporting the second recording head. A water-based ink is used as a base material so as to overlap the dots formed by overlapping the first pretreatment liquid and the second pretreatment liquid from the nozzle of the third recording head, which is further downstream of the nozzle in the transport direction. Dots can be formed by ejecting upwards and landing on the substrate.
In the example shown in FIG. 2 or 3, the third recording is performed so that the first pretreatment liquid and the second pretreatment liquid overlap the dots formed while transporting the base material in the transport direction Y. A water-based ink is ejected from the head 13 and landed on the base material to form dots.
By repeating the above operation, the first pretreatment liquid, the second pretreatment liquid, and the water-based ink are applied to the substrate in this order, and the first treatment liquid and the second pretreatment liquid are kept constant. It can land on the base material in the order of.

In the above-mentioned bidirectional printing, when recording an image having a resolution N times the resolution of the recording head, N lines are formed in a region corresponding to the distance between adjacent nozzles in the transport direction Y of the base material. Can be done by Here, N is a positive integer.
Specifically, in the case of recording an image of 1200 dpi using a recording head of 300 dpi, it is preferable to form four dots in a region corresponding to the distance between nozzles adjacent to each other in the transport direction Y of the recording head. Therefore, it is preferable that four lines are formed in the region corresponding to the distance between the nozzles adjacent to each other in the transport direction Y of the base material.

The line head type inkjet recording method uses a line head type recording head which is arranged in the width direction of the base material which intersects and preferably is orthogonal to the transport direction of the base material and has nozzle rows in a row in the width direction of the base material. It can be carried out.
As an example of the line head type inkjet recording device, a transport device for transporting the base material in the transport direction Y and at least three recording heads arranged in a line in a direction X intersecting the transport direction Y of the base material are provided. Be prepared. The at least three recording heads are a first recording head to which the first pretreatment liquid is supplied from the upstream side along the transport direction Y of the base material, and a second recording head to which the second pretreatment liquid is supplied. A third recording head in which the water-based ink is shared is provided in this order. Then, by ejecting the first pretreatment liquid, the second treatment liquid, and the water-based ink from each nozzle row, these can be laminated on the base material in this order to record an image. ..
In the line head type inkjet recording device, the base material of the two types of pretreatment liquid and the water-based ink is determined by determining the arrangement order of the recording heads to which the two types of pretreatment liquid and the water-based ink are supplied. The order of granting to can be determined.
Further, in order to reverse the order of applying the first pretreatment liquid and the second pretreatment liquid, the second pretreatment liquid is supplied to the first recording head, and the first recording head is supplied with the first pretreatment liquid. The pretreatment liquid may be supplied.

The base material to which the water-based ink is applied can be provided as a printed matter as it is.
The base material may be heat-treated after the application of the water-based ink. As a result, volatile components such as water contained in the water-based ink, the first pretreatment liquid and the second pretreatment liquid can be removed from the base material, and the fixability of the image can be further improved. Further, by removing the volatile component before the color material of the water-based ink gets wet and spreads, bleeding of the color material can be prevented and the image quality can be further improved. Further, when the water-based ink contains a resin component, the resin component of the water-based ink forms a more uniform resin film on the base material by heating, so that the fixability can be further improved.
The heating temperature is preferably 50 to 250 ° C, more preferably 100 to 200 ° C.

Before the coagulant of the first pretreatment liquid dries and adheres to the surface of the base material, before the application of the second pretreatment liquid, in order to allow the coagulant to penetrate into the base material by the second pretreatment liquid. It is preferable to apply the second pretreatment liquid in a state where the base material is wet with the first pretreatment liquid without heat treatment. The base material may be heat-treated after the application of the first pretreatment liquid and before the application of the second pretreatment liquid.
Further, in order to further exert the action of permeating the color material of the water-based ink by the second pretreatment liquid into the base material, the base material is subjected to the first pretreatment without heat treatment before applying the water-based ink. It is preferable to apply the water-based ink in a wet state by applying the liquid and the second pretreatment liquid. The base material may be heat-treated after the application of the first pretreatment liquid and the second pretreatment liquid and before the application of the water-based ink.
For example, it is preferable to apply the first pretreatment liquid, the second pretreatment liquid, and the water-based ink by a wet-on-wet method. By applying two types of pretreatment liquids in a wet-on-wet method, the other pretreatment liquid is discharged while the pretreatment liquid that has landed on the substrate first does not dry and maintains fluidity. Can be done. As a result, the pretreatment liquid that has landed on the base material first is easily permeated into the base material so as to be pushed. As a result, the density on the back surface can be further increased, and the fixability due to the anchor effect can be further improved.
The same applies to the case where the second pretreatment liquid and the first pretreatment liquid are applied to the base material in this order.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

"Preparation of coagulant and penetrant"
Tables 1 and 2 show the formulations of the agglomerate as the first pretreatment solution and the penetrant as the second pretreatment solution. Each component was premixed according to the blending ratio shown in the table, and then stirred at 100 rpm for 30 minutes with a mix rotor. Then, it was filtered through a nylon syringe filter having a pore size of 5 μm to obtain a coagulated liquid and a penetrant.

"Manufacturing of water-based ink"
Table 3 shows the formulations of water-based inks. Each component was premixed according to the blending ratio shown in the table, and then stirred at 100 rpm for 30 minutes with a mix rotor. Then, it was filtered through a nylon syringe filter having a pore size of 5 μm to obtain an aqueous ink.

The components used are as follows.
(Coagulant)
Lactic acid: Organic acid.
PRINT RITE DP-375: Cationic water-dispersible resin particles, manufactured by Lubrizol, 32% by mass of active ingredient.
Calcium chloride: Multivalent metal salt.
Charol DC-303P: Cationic water-soluble resin, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., active ingredient amount 41%.

(Penetrating agent)
Dipropylene glycol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., boiling point 231 ° C.
1,2-Butanediol: manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 194 ° C.
Diethylene glycol monoethyl ether: manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 194 ° C.
Orphine E1010: Acetylene glycol-based surfactant manufactured by Nissin Chemical Industry Co., Ltd.
Silface SAG503A: Silicone-based surfactant manufactured by Nissin Chemical Industry Co., Ltd.
Silface SAG002: Silicone-based surfactant manufactured by Nissin Chemical Industry Co., Ltd.
(solvent)
Diethylene glycol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., boiling point 245 ° C.

(Aqueous ink component)
CAB-O-JET300: Self-dispersing pigment, manufactured by Cabot Japan Co., Ltd., active ingredient 15% by mass.
Superflex 740: Anionic urethane resin emulsion, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., active ingredient 40% by mass.
Movinyl 966A: Acrylic resin emulsion, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., active ingredient 45% by mass.
Takenate WB3936: Isocyanate-based cross-linking agent, manufactured by Mitsui Chemicals, Inc., 36% by mass of active ingredient.
Glycerin: manufactured by Wako Pure Chemical Industries, Ltd., boiling point 290 ° C.
Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd., boiling point 197.3 ° C.

"Making printed matter"
Printing was performed according to the following procedure using the combination of the penetrant, the coagulant, and the water-based ink shown in Table 4, and a printed matter was obtained.
A 100% polyester woven fabric was used as the base material.
A serial type inkjet printer using a recording head having a resolution of 300 dpi was used as the printer. The arrangement position of the serial type recording head unit is shown in FIG. In FIG. 2, the coagulating liquid was supplied to the first recording head 11, the penetrating liquid was supplied to the second recording head 12, and the water-based ink was supplied to the black recording head 13K of the third recording head.

In Examples 1 to 11, a penetrant, a coagulant, and a water-based ink were applied to the substrate in this order to prepare a printed matter.
Specifically, using a 300 dpi recording head, the penetrant, the coagulant, and the water-based ink were each ejected by bidirectional printing of 1200 dpi × 1200 dpi, and a single color solid image of 200 mm × 200 mm was printed. The movement of the base material by one line in the transport direction Y corresponds to a quarter of the distance between the nozzles in the transport direction Y. Also, the landing time difference [Delta] T _Y between adjacent lines in the conveying direction Y of the base material of the permeate on the substrate was not less than 10 ms.

Further, a plurality of nozzles are formed in each of the first recording head 11, the second recording head 12, and the third recording head 13 along the transport direction Y of the base material. The second recording head 12 discharges the penetrant from three consecutive nozzles on the upstream side in the transport direction Y, and transports the base material while reciprocating the recording head unit in the main scanning direction X to transport the base material. The penetrant was discharged onto the substrate so that four rows of lines were formed at the distance between the nozzles adjacent to each other in the transport direction Y.
At this time, when the nozzles a, b, and c are set from the upstream side in the transport direction Y, the first line of the penetrant is formed from each of the three nozzles on the outward path in the main scanning direction X. Next, the base material is transported, and the penetrant is based from the nozzle b on the return path of the main scanning direction X so as to be adjacent to the upstream side of the transport direction Y of the first line of the penetrant discharged from the nozzle a. A second line was formed by discharging onto the material. In the formation of the second line, the penetrant was discharged from the nozzle a and the nozzle c at similar intervals. By repeating this operation, four lines of the penetrant were formed at the distance between the nozzles adjacent to each other in the transport direction Y of the base material.

The base material is continuously transported in the transport direction Y, and the region where the four lines of the permeate is formed is downstream of the three nozzles ahead of the second recording head 12 in the transport direction Y. At a position facing the nozzle of the first recording head 11 on the side, the substrate is moved while reciprocating the recording head unit in the main scanning direction so as to overlap the four lines of the permeate. The coagulating liquid was discharged onto the base material from the recording head 11 of No. 1 to form four lines in which the permeating liquid and the coagulating liquid were laminated in this order. The method for discharging the coagulated liquid is the same as that for the penetrant described above.
Further, the base material is continuously transported in the transport direction Y, and the region of four lines formed by laminating the penetrant and the coagulant is a position facing the third recording head 13 on the downstream side in the transport direction Y. Then, while moving the recording head unit in the main scanning direction, the water-based ink was ejected from the third recording head 13, and the penetrant, the coagulant, and the water-based ink were laminated in this order to form an image.

In Examples 12 and 13, a coagulant, a penetrant, and a water-based ink were applied to the substrate in this order to prepare a printed matter. Specifically, in Examples 1 to 11, a solid image having a resolution of 1200 dpi was formed by the same procedure except that the order of applying the penetrant and the coagulant was reversed. Landing time difference [Delta] T _Y between lines conveying adjacent in the direction Y of the substrate aggregation solution on the substrate was not less than 10 ms.

In Comparative Example 1, only the water-based ink 1 was applied to the base material.
In Comparative Example 2, only the coagulant 1 was applied to apply the water-based ink 1.
In Comparative Example 3, the coagulant 2, the coagulant 3, and the water-based ink 1 were applied to the substrate in this order to prepare a printed matter.
In Comparative Example 4, only the penetrant 1 was applied to apply the water-based ink 1.
In Comparative Examples 1, 2 and 4, a solid image having a resolution of 1200 dpi was formed by not applying both or one of the penetrant and the coagulant in Examples 1 to 11.
In Comparative Example 3, a solid image having a resolution of 1200 dpi was formed by the same procedure except that two kinds of coagulants were used instead of the penetrant and the coagulant in Examples 1 to 11.

In Comparative Example 5, the coagulant, the penetrant, and the water-based ink are applied in this order on the outward route, and the penetrant, the coagulant, and the water-based ink are applied in this order on the return route according to the conventional ejection method shown in FIG. Then, a printed matter was produced.
In the printed matter of Comparative Example 5, the coagulating liquid and the penetrating liquid are laminated in a different order between the outward route and the return route, and the water-based ink is applied from above.

After printing each printed matter, the printed matter was heat-pressed at 180 ° C. for 1 minute.
In the above-mentioned printed matter, both the coagulating liquid and the penetrating liquid were applied to the region corresponding to the recording region of the water-based ink.
The amount of the penetrant applied per applied area is 20 g / m ² , the amount of the coagulant applied per applied area is 20 g / m ^2, and the amount of the water-based ink applied per applied area is 20 g / m. ^{It was set to 2} .

"Evaluation"
The obtained printed matter was evaluated as follows. The results are shown in Table 4.

(image quality)
The surface of the obtained printed matter was visually observed, the surface OD value of the printed matter was measured, and the image quality was evaluated according to the following criteria. The OD value was measured using "X-Rite eXact" manufactured by X-Rite.
AA: No unevenness is observed on the surface of the printed matter, and the surface OD value is 1.30 or more.
A: No unevenness is observed on the surface of the printed matter, and the surface OD value is 1.25 or more.
B: There is little unevenness on the surface of the printed matter, and the surface OD value is higher than 1.20.
C: There is a lot of unevenness on the surface of the printed matter. Alternatively, the surface OD value is 1.20 or less.

(Fixability)
The test was carried out using a type II tester according to the method specified in JIS L0849. Dry friction was tested according to the drying test specified in JIS L0849, and evaluated according to the following criteria using a contaminated gray scale.
AA: Dry friction pollution grade 3 or higher.
A: Dry friction pollution class 2-3.
B: Dry friction pollution second grade.
C: Dry friction pollution less than grade 2.

(Backside density)
The backside OD value of the obtained printed matter was measured, and the backside density was evaluated according to the following criteria. The OD value was measured using the same device as the image quality evaluation described above.
A printed matter having a high back surface OD value is excellent in visibility of an image from the back surface, and is therefore in a preferable state for printing on cloth.
AA: The back surface OD value is 0.40 or more.
A: The back surface OD value is 0.35 or more.
B: The back surface OD value is 0.30 or more.
C: The back surface OD value is less than 0.30.

As shown in the table, according to the recording method of each example, it was possible to produce a printed matter having good image quality and fixability and having a sufficient backside density.
In Examples 1 to 3, the coagulant contained an organic acid and the penetrant contained a silicone-based surfactant, and better results were obtained in terms of fixability and backside concentration.
From Examples 1 to 8, it can be seen that the inclusion of lactic acid in the agglomerate gives better results in terms of fixability and backside concentration.
From Examples 1 to 8, it can be seen that the fixability is further improved by containing the lactic acid or cationic resin particles in the agglomerate.
From Examples 1 to 8, it can be seen that a printed matter having a higher back surface concentration can be obtained when the agglomerated liquid does not contain the cationic resin particles.

In Example 9, the penetrant contains an acetylene glycol-based surfactant. In Example 10, the penetrant is composed of a single component of diethylene glycol monoethyl ether. In Example 11, the penetrant is the same as in Example 9, and the coagulant is the same as in Examples 5 and 8. Good results were obtained in both cases.

In Example 12, the order of applying the penetrant and the coagulant was reversed in Example 1. In Example 13, the order of applying the penetrant and the coagulant was reversed in Example 11. Good results were obtained in both cases. By applying the penetrant and then the coagulant as in Examples 1 and 11, better results were obtained in terms of image quality and backside concentration.

In Comparative Example 1, the water-based ink was applied without pretreatment, and the results of image quality and backside density could not be sufficiently obtained.
Comparative Example 2 is provided with only one type of coagulant. Comparative Example 3 is provided with only two types of coagulant. Comparative Example 4 is provided with only one type of penetrant. Since neither of them was applied in combination with the penetrant and the coagulant, sufficient results could not be obtained.
In Comparative Example 5, the order of applying the penetrant and the coagulant is reversed between the outward path and the return path of the recording head. On printed matter, the stacking order of the penetrant and the coagulant is reversed for each line corresponding to the path, so that the coagulant component and the penetrant component do not form a uniform layer, and the image quality and fixability are considered to deteriorate. Be done.

11 1st recording head 12 2nd recording head 13 3rd recording head 100 Recording head unit

Claims (7)

Using an inkjet recording device, one of the first pretreatment liquid and the second pretreatment liquid, the other of the first pretreatment liquid and the second pretreatment liquid, and the water-based ink are recorded on the substrate in this order. The first pretreatment liquid and the second pretreatment liquid are discharged so as to land on the base material in a certain order, and the first pretreatment liquid is a coagulant. The method for producing a printed matter, wherein the second pretreatment liquid does not contain a coagulant and contains a penetrant. The method for producing a printed matter according to claim 1, wherein the second pretreatment liquid, the first pretreatment liquid, and the water-based ink are applied to a substrate in this order. The method for producing a printed matter according to claim 1 or 2, wherein the flocculant contains an organic acid. Any of claims 1 to 3, wherein the penetrant comprises at least one selected from the group consisting of a surfactant and a water-soluble organic solvent having an SP value of 14 (cal / cm ³ ) ^1/2 or less. The method for producing a printed matter according to item 1. The method for producing a printed matter according to claim 4, wherein the surfactant contains a silicone-based surfactant. Of the first pretreatment liquid and the second pretreatment liquid, the landing time difference ΔT between the two dots having the shortest distance between the dots in the main scanning direction of the pretreatment liquid that first lands on the substrate. _X, and at least one of the landing time difference [Delta] T _Y between the main distance between the scanning direction in the dot in the direction crossing is two having the shortest dots is equal to or greater than 10 ms, according to any one of claims 1 5 How to manufacture printed matter. The method for manufacturing a printed matter according to any one of claims 1 to 6, wherein the inkjet recording device is a serial type inkjet recording device.

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