JP2021020394A - Liquid composition, ink set, printing method, and printer - Google Patents

Abstract

To provide a liquid composition having storage stability for a long time, wherein the liquid composition is applied to the surface of a printing object, resulting in a printed matter with high laminate strength.SOLUTION: A liquid composition contains a water-soluble cationic polymer obtained by the reaction of a monomer including amine and epihalohydrin, a resin excluding the water-soluble cationic polymer, an organic solvent, and water.SELECTED DRAWING: Figure 1C

Description

The present invention relates to a liquid composition, an ink set, a printing method, and a printing apparatus that can be used for surface treatment of a printed matter.

Inkjet printers have advantages such as low noise, low running cost, and easy color printing, so they are widely used in general households as digital signal output devices.
In recent years, a technique for forming images by inkjet not only for household use but also for packaging materials such as foods, beverages and daily necessities has been developed.
In Japan, non-absorbent printed matter such as plastic film is used as the printed matter to which the inkjet is applied, and inks for that purpose have been developed.

An example of the need for direct inkjet printing on such plastic films is, for example, packaging printing for food and daily necessities, which is very high because there are many opportunities to see printed matter at close range. Image quality is required.
However, when inkjet printing is performed on a non-absorbent printed matter, penetration drying does not occur, so ink droplets may spread excessively and outline characters (also called negative characters) may be crushed and become unreadable. .. The state in which outline characters are crushed is called "negative character crushing".

In order to deal with such problems, a technique is known in which a reaction liquid containing a coagulant (liquid composition for surface treatment) and an ink containing a coloring material are applied to a non-absorbable recording medium in this order (patented). Reference 1).

The charge-repulsive resin emulsion, which is generally used as a liquid composition for surface treatment, cannot secure sufficient dispersion stability in the coexistence with a polyvalent metal salt, and therefore has excellent storage stability for a long period of time. There is no liquid composition for surface treatment.
In addition, most of such packaging applications are generally packaging materials obtained by printing on the back surface of a plastic film, applying an adhesive on the printing layer, and laminating a film that can be heat-sealed. There was no primer capable of producing sufficient lamination strength in the non-printed portion where the primer was exposed and in the printed portion where the primer was covered with ink.

An object of the present invention is to provide a liquid composition which has storage stability for a long period of time and which can obtain a printed matter having high lamination strength by coating on the surface of a printed matter. To do.

The present invention relates to a liquid composition as described in (1) below.
(1) A liquid composition comprising a water-soluble cationic polymer obtained by reacting a monomer containing an amine and epihalohydrin, a resin other than the water-soluble cationic polymer, an organic solvent, and water.

The liquid composition of the present invention has long-term storage stability, and by applying it to the surface of the printed matter, a printed matter having high lamination strength can be obtained.

FIG. 1A is a schematic cross-sectional view for explaining the state of the recording unit of the recorded object of the present embodiment (No. 1). FIG. 1B is a schematic cross-sectional view for explaining the state of the recording unit of the recorded object of the present embodiment (No. 2). FIG. 1C is a schematic cross-sectional view for explaining the state of the recording unit of the recorded object of the present embodiment (No. 3). FIG. 2 is a diagram showing an example of the recording device of the present invention. FIG. 3 is a perspective view of a main tank containing the ink according to the present invention. FIG. 4 is an external perspective explanatory view of the liquid discharge head according to the embodiment of the present invention. FIG. 5 is a cross-sectional explanatory view in a direction orthogonal to the nozzle arrangement direction of the head. FIG. 6 is a partial cross-sectional explanatory view in a direction parallel to the nozzle arrangement direction of the head. FIG. 7 is a plan explanatory view of the nozzle plate of the head. FIG. 8A is a plan explanatory view of each member constituting the flow path member of the head (No. 1). FIG. 8B is a plan explanatory view of each member constituting the flow path member of the head (No. 2). FIG. 8C is a plan explanatory view of each member constituting the flow path member of the head (No. 3). FIG. 8D is a plan explanatory view of each member constituting the flow path member of the head (No. 4). FIG. 8E is a plan explanatory view of each member constituting the flow path member of the head (No. 5). FIG. 8F is a plan explanatory view of each member constituting the flow path member of the head (No. 6). FIG. 9A is a plan explanatory view of each member constituting the common liquid chamber member of the head (No. 1). FIG. 9B is a plan explanatory view of each member constituting the common liquid chamber member of the head (No. 2). FIG. 10 is a block diagram showing an example of the liquid circulation system according to the present invention. FIG. 11 is a cross-sectional explanatory view showing an example of the recording device of the present invention. FIG. 12 is a schematic view showing another example of the apparatus for applying the liquid composition of the present invention.

When a dispersion liquid in which negatively charged particles are dispersed is applied to a printed matter (for example, a recording medium) to which the liquid composition of the present invention is attached, the dispersion liquid is acted on by the water-soluble cationic polymer contained in the liquid composition. At the same time as the dispersion medium contained in is diffused, the particles are aggregated. Further, since the particles are fixed at a shallow position inside the printed matter (for example, a recording medium) due to the diffusion of the dispersion medium and the aggregation of the particles, the polyvalent metal salt that may be contained in the liquid composition No crystals are formed, and a recorded material having high scratch resistance can be obtained.

In addition, the liquid composition of the present invention has an excellent effect of suppressing the liquid composition from adhering to the member even when the member comes into contact with the region to which the liquid composition is applied.

<< Liquid Composition >>
The liquid composition of the present embodiment will be described in more detail below with reference to preferred embodiments. First, it is expected that the liquid composition of the present embodiment will be used to fix a dispersion liquid (here, an ink in which negatively charged particles containing a colorant are dispersed) using FIGS. 1A to 1C. The mechanism is explained. 1A to 1C are schematic cross-sectional views for explaining a state of a recording unit of a recorded object of the present embodiment. When the liquid composition of the present embodiment is applied to a recording medium 101 made of a paper body, an adhering portion 102 of the liquid composition is formed on the recording medium (see FIG. 1A). An ink in which negatively charged particles 103 containing a colorant are dispersed in a dispersion medium 104 (hereinafter referred to as "vehicle") is applied to the adhesion portion 102. Examples of the negatively charged particles 103 containing the colorant include particles of the negatively charged colorant, particles containing the negatively charged compound and the colorant, and the like. When the ink is applied to the adhesion portion 102, the liquid composition contained in the adhesion portion 102 comes into contact with the ink (see FIG. 1B). In this case, the action of the water-soluble cationic polymer contained in the liquid composition acts so as not to significantly change the hydrogen ion concentration (pH) and the metal ion concentration (buffering action). Therefore, it is possible to prevent the colorants contained in the ink from rapidly aggregating due to the acid-base reaction and depositing many colorants on the recording medium. As a result, the ink is diffused in the surface direction of the recording medium (direction of arrow A in FIG. 1B), and the area of the recorded dots is increased, so that the density of the image (characters, symbols, etc. are also included) is improved. To do. Next, when the ink permeates the adhesion portion 102 (direction of arrow B in FIG. 1B) of the liquid composition of the recording medium 101, the pigment 104 contained in the ink aggregates and is fixed by the action of the water-soluble cationic polymer (FIG. See 1C). It is considered that the pigment 104 is fixed at a shallow position inside the recording medium in this way to improve the scratch resistance and reduce the occurrence of feathering and color bleeding.

It is desirable that the liquid composition of the present embodiment is in a state of being quickly absorbed by the recording medium after being applied to the printed matter (for example, a recording medium). In the present embodiment, the absorption of the liquid composition into the recording medium is referred to as "drying". In order to dry the liquid composition quickly, the surface tension of the liquid composition is preferably 30 mN / m or less. The liquid composition may be dried after being applied to the recording medium, and the ink may be fixed even if the water or the like contained in the vehicle is not vaporized to maintain the liquid state. The quality of the recorded image can be improved. In the present embodiment, the state in which water or the like contained in the vehicle vaporizes and cannot maintain the liquid state is referred to as "solidification". Hereinafter, each component such as a water-soluble cationic polymer contained in the liquid composition of the present embodiment will be described in order.

<Water-soluble cationic polymer>
As the water-soluble cationic polymer used in the liquid composition of the present embodiment, a water-soluble cationic polymer obtained by reacting a monomer containing an amine and epihalohydrin, which functions as a flocculant, is used. The water-soluble cationic polymer obtained by reacting these monomers contains a hydroxyl group, an ammonium cation, etc. in the main chain, and by liberating the halogen anion in the aqueous solution, it has a buffering action and a pigment when it comes into contact with the ink. It is considered to have a function of enhancing the action of aggregating. Specific examples of the water-soluble cationic polymer include at least one of a water-soluble cationic polymer selected from a polyamine-epihalohydrin polymer, a polyamide-epihalohydrin polymer, a polyamide polyamine-epihalohydrin polymer, and an amine-epihalohydrin polymer. It is preferably used. More preferably, the water-soluble cationic polymer is represented by a polymer represented by the following formula (1), a polymer having a repeating unit represented by the following formula (2), and an amine monomer and the following formula (4). At least one selected from a polymer obtained by reacting a monomer with a monomer represented by the following formula (5) is used. Examples of this amine monomer include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, iminobispropylamine, etc., which are represented by the following formula (3) because they are industrially manufactured and easily available. Monomers are preferred.

However, in the above formula (1), in the formula, R1 to R8 may be the same or different, and each has an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, and a carbon number of carbon atoms. It represents an alkenyl group or a benzyl group of 1 to 8, where X represents a halogen atom (eg, F, Cl, Br, I) and n represents 1 or 2.
However, in the above formula (2), X represents a halogen atom (for example, F, Cl, Br, I), and m represents an integer of 1 or more. Further, both ends of the polymer represented by the formula (2) may be a monomer constituting a repeating unit, a known initiator or the like.
However, in the above formula (5), X represents a halogen atom (for example, F, Cl, Br, I).

The above-mentioned water-soluble cationic polymer is obtained by (i) a method of polymerizing a monomer containing an amine and epihalohydrin, and (ii) a monomer containing epihalohydrin in a polyamide obtained by polymerizing a monomer containing an amine and a carboxylic acid. It is obtained by a known method such as a method of graft polymerization. The weight average molecular weight of the water-soluble cationic polymer varies depending on the type of polymer, and is preferably in the range of 5 to 100,000 in the case of a polyamine-epihalohydrin polymer, and 5 in the case of a polyamide-epihalohydrin polymer or a polyamide polyamine-epihalohydrin polymer. The range is preferably one million or less, and in the case of an amine-epihalohydrin polymer, the range is preferably 700 to 50,000. If the weight average molecular weight exceeds each of the above upper limits, it may not be an aqueous solution, and if it does not reach each of the lower limits, the effect of the treatment with the liquid composition may be reduced.

The content of the water-soluble cationic polymer in the liquid composition is preferably 1% by mass or more and 40% by mass or less, and more preferably 3% by mass or more and 30% by mass or less of the entire liquid composition of the present embodiment. is there. When the content is 40% by mass or less, it is possible to prevent the viscosity of the liquid composition from increasing too much while obtaining the effect of improving the image quality by increasing the content. When the content is 1% by mass or more, the effect of improving the quality of the image can be sufficiently obtained.

<Resin>
The liquid composition of the present invention contains a resin (other resin, other resin particles) other than the water-soluble cationic polymer. As the resin other than the water-soluble cationic polymer, a nonionic resin is preferable. As the nonionic resin, it is preferable to have at least one selected from a polyolefin resin, a polyvinyl acetate resin, a polyvinyl chloride resin, a urethane resin, a styrene butadiene resin and a copolymer thereof.
These resins are preferably used as resin particles. By containing the other resin particles, the liquid composition can further improve the adhesion to a non-permeable recording medium such as a plastic film. This includes a similar structure when the liquid composition dries on a printed material (eg, a recording medium) and the water-soluble cationic polymer and the resin particles are physically close together to form a film together. This is because they interact with each other to promote uniform film formation.

[Dispersion method of resin particles]
A dispersant such as a surfactant may be contained in the resin particles as needed, but from the viewpoint that an ink having better coating film performance can be easily obtained, a so-called self-emulsifying resin emulsion is used. preferable.

Hereinafter, nonionic resin particles, which are examples of the constituent components of the liquid composition of the present invention, will be described.

<Nonionic resin particles>
The nonionic resin particles in the present invention are resin particles that can be dispersed without using electric charges.
The nonionic resin particles in the present invention are acidic such as carboxyl group and sulfo group by thermal decomposition GC-MS (for example, GC-17A manufactured by Shimadzu Corporation) after isolation of solid content from the liquid composition by centrifugation. Refers to resin fine particles in which a monomer containing a functional group or a basic functional group such as an amino group is not detected.
The chemical structure of the resin particles is not particularly limited, and any resin particles that can disperse nonions can be used, but polyolefin resin, polyvinyl acetate resin, polyvinyl chloride resin, urethane resin, and styrene butadiene can be used. When it is at least one selected from the resin and a copolymer thereof, it is preferable because strong adhesion to various substrates can be obtained, and further, an ethylene-vinyl acetate copolymer resin and an ethylene-vinyl acetate-vinyl chloride copolymer are used. More preferably, it is a resin or an olefin-modified urethane resin.

The glass transition temperature Tg of the nonionic resin particles is preferably -30 to 30 ° C, more preferably 25 to 25 ° C.
When Tg is -30 ° C or higher, the resin film becomes sufficiently tough and the precoat layer becomes more robust, and when Tg is 30 ° C or lower, the resin film forming property is improved and sufficient flexibility is ensured. Therefore, the adhesion to the base material is strong, which is preferable.
In the present invention, the glass transition temperature is determined by using, for example, a differential scanning calorimetry (DSC) device (device name: DSC120U, manufactured by Seiko Instruments Co., Ltd.) at a measurement temperature of 30 ° C. to 300 ° C. per minute. It can be measured at a heating rate of 5 ° C.

The content of the resin in the liquid composition is preferably 0.1% by mass or more and 30.0% by mass or less, and more preferably 0.5% by mass or more and 20.0% by mass or less.
If it is 0.5% by mass or more, the resin can sufficiently coat the base material, so that the adhesion to the base material is improved. There is no risk of deterioration of adhesion to the plastic.

The mass ratio of the water-soluble cationic polymer to the resin (water-soluble cationic polymer: resin) in the liquid composition is not particularly limited and may be appropriately selected depending on the intended purpose, but 50: 1 to 1 : 5 is preferable, and 3: 1 to 1: 3 is more preferable.

Further, if necessary, a basic substance can be added to the liquid composition for the purpose of neutralizing the acidic component in the resin particles and dispersing it in water.
The basic substance is not particularly limited and may be appropriately selected depending on the intended purpose, but sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine and propanolamine. , Diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholin, etc. Can be mentioned. Among these, ammonia, triethylamine, 2-amino-2-methyl-1-propanol and morpholine are preferable.
The content of the basic substance can be arbitrarily adjusted according to the amount of the acidic component of the resin particles.

Further, the resin particles are preferably used as a resin emulsion, and the resin emulsion may be obtained by any method.
As the resin emulsion, a water-soluble organic solvent, a preservative, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet absorber and the like can be further added, if necessary.

<Ammonium organic acid salt>
The liquid composition of the present embodiment may contain an ammonium organic acid salt for the purpose of improving the quality of the formed image. From the viewpoint of solubility in water, this ammonium organic acid includes ammonium lactate, ammonium acetate, ammonium propionate, ammonium lactate, ammonium oxalate, ammonium tartrate, ammonium aquarium (diammonium amber), diammonium malonate, Diammonium hydrogen citrate, triammonium citrate and ammonium L-glutamate are preferably used, and more preferably ammonium lactate.

The content of the ammonium organic acid salt in the liquid composition is preferably 1% by mass or more and 40% by mass or less, and more preferably 3% by mass or more and 30% by mass or less of the whole liquid composition. It is particularly preferable that it is by mass% or more and 15% by mass or less. When the content is 40% by mass or less, it is possible to prevent the viscosity of the liquid composition from increasing too much while obtaining the effect of improving the image quality by increasing the content. When the content is 1% by mass or more, the effect of improving the quality of the image can be sufficiently obtained.

The mass ratio of the water-soluble cationic polymer to the organic acid ammonium salt (water-soluble cationic polymer: organic acid ammonium salt) in the liquid composition is not particularly limited and may be appropriately selected depending on the intended purpose. 10: 1 to 1: 5 is preferable, and 5: 1 to 1: 1 is more preferable.

An ink set composed of the liquid composition and an ink containing a coloring material is suitable because a printed matter having excellent scratch resistance and image density can be obtained.

When the glass transition temperature Tg1 of the nonionic resin particles contained in the liquid composition is lower than the glass transition temperature Tg2 of the resin particles contained in the ink, the lamination strength of the printed portion becomes excellent. Suitable. The glass transition temperature Tg1 of the nonionic resin particles contained in the liquid composition is more preferably 20 ° C. or more lower than the glass transition temperature Tg2 of the resin particles contained in the ink.

The printing method includes a surface modification step of surface-modifying the printed matter (hereinafter, also referred to as “recording medium”), a liquid composition applying step of applying the liquid composition to the printed matter, and discharging the ink. It is preferable to have a printing step because the lamination strength of the printed portion and the non-printed portion is improved, and further improved when the surface modification step is a corona discharge treatment or a streamer discharge treatment.

When the printing method further includes a heat treatment step after printing, heat promotes film formation of the thermoplastic resin in the ink, which is desirable because scratch resistance is improved.

In the liquid composition applying step, when the adhesion amount of the liquid composition is 0.4 to ² g / m ^2, it is preferable because it is easy to achieve both negative character crushing and lamination strength.

In the printing step, when the amount of ink adhered is 4 to 14 g / m ^2, it is preferable because it is easy to achieve both image density and quick-drying.

When the printing method includes a printing step of applying the non-white ink to the printed matter and a printing step of applying the white ink to the printed matter as the printing step of ejecting the ink, a wide color gamut and a high density image can be obtained. It is suitable because it can be obtained.

The medium of the liquid composition of the present invention is an aqueous medium, but if necessary, a medium other than water may be added, such as a water-soluble organic solvent, a surfactant, and other trace additives. And so on.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-Pentanediol, 1,5-Pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone. , 1,3-Dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N- Amidos such as dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. And so on.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because it not only functions as a wetting agent but also has good drying properties.

The content of the organic solvent in the liquid composition is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of drying property and discharge reliability of the liquid composition, 5% by mass or more and 60% by mass or more. The following is preferable, 10% by mass or more and 30% by mass or less is more preferable, and 10% by mass or more and 25% by mass or less is further preferable.

When the liquid composition contains any one of 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol as the organic solvent, the film-forming property of the resin is improved, and the abrasion resistance is further improved. It is preferable because the property is improved.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, and side chain double-ended modified polydimethylsiloxane. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the Si side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkylcarboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkylethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. A polyoxyalkylene ether polymer compound is particularly preferable because it has a low foaming property. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counterions of the salts in these fluorine-based surfactants are Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH). _3rd grade can be mentioned.
Examples of the amphoteric tenside agent include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.
Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include ethylene oxide adducts of fatty acid esters and acetylene alcohols.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
These may be used alone or in combination of two or more.

As other trace additives, an antifoaming agent, an antiseptic antifungal agent, an anticorrosive agent and the like may be contained.

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

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

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

<< Ink >>
Next, the ink of the present invention will be described.
The ink includes, for example, a coloring material. The ink preferably contains a resin.

<Resin>
The resin preferably has, for example, resin particles.
The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good scratch resistance and high image hardness, 10 nm or more and 1,000 nm or less are preferable. It is more preferably 10 nm or more and 200 nm or less, and particularly preferably 10 nm or more and 100 nm or less.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of scratch resistance and storage stability of the ink, 1% by mass or more and 30% by mass with respect to the total amount of the ink. The following is preferable, and 5% by mass or more and 20% by mass or less is more preferable.

The resin particles are preferably thermoplastic resin particles.
For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, acrylic silicone resin and the like can be mentioned.

As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used.
Examples of the commercially available resin particles include Microgel E-1002, E-5002 (styrene-acrylic resin particles, manufactured by Nippon Paint Co., Ltd.) and Boncoat 4001 (acrylic resin particles, manufactured by Dainippon Ink and Chemicals Co., Ltd.). ), Boncoat 5454 (styrene-acrylic resin particles, manufactured by Dainippon Ink and Chemicals Co., Ltd.), SAE-1014 (styrene-acrylic resin particles, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin particles, Saiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin particles, manufactured by Roam & Haas), Nanokrill SBCX-2821, 3689 (acrylic silicone resin particles, manufactured by Toyo Ink Mfg. Co., Ltd.), Examples thereof include # 3070 (methyl methacrylate polymer resin particles, manufactured by Gokoku Dye Co., Ltd.).
Among these, acrylic resin, urethane resin, and polyester resin are more preferable from the viewpoint of obtaining adhesion to the primer and excellent scratch resistance.

The glass transition temperature Tg2 of the resin particles is preferably higher than room temperature, and more preferably 30 ° C. or higher and 90 ° C. or higher.
Further, it is preferable that the glass transition temperature Tg2 of the resin particles is higher than the glass transition temperature Tg1 of the nonionic resin particles contained in the liquid composition because the lamination strength of the printed portion is excellent. The glass transition temperature Tg2 of the resin particles is more preferably 20 ° C. or more higher than the glass transition temperature Tg1 of the nonionic resin particles contained in the liquid composition.

<Color material>
The color of the ink of the present invention is not particularly limited, and examples thereof include white ink and non-white ink.
ISO-2469 (JIS-8148) is a standard for the whiteness of white ink, and generally, when the value is 70 or more, it is used as a white color material.
The coloring material used for the white ink is preferably a metal oxide, and examples thereof include titanium oxide, iron oxide, tin oxide, zirconium oxide, and iron titanate (composite oxide of iron and titanium).
White particles having a hollow structure are also preferable.
Examples of white particles having a hollow structure used for white ink include hollow resin particles and inorganic hollow particles.
Examples of the resin composition of the hollow resin particles include acrylic resins such as acrylic resin, styrene-acrylic resin, and crosslinked styrene-acrylic resin, urethane-based resins, and malein-based resins.
Examples of the material of the inorganic hollow particles include oxides of metals such as silicon, aluminum, titanium, strontium, and zirconium that exhibit white color, nitrides, and nitrides oxide, and various inorganic compounds such as glass and silica. ..
When a metal oxide is used as the coloring material for the white ink, it is excellent in that the whiteness is increased, and when white particles having a hollow structure are used, it is difficult to settle and is excellent in the settling property.

Examples of the non-white ink include color ink, black ink, gray ink, clear ink, metallic ink and the like.
Examples of the color ink include cyan ink, magenta ink, yellow ink, light cyan ink, light magenta ink, red ink, green ink, blue ink, orange ink, violet ink and the like.
The color material used for the non-white ink is not particularly limited as long as it exhibits non-white color, and can be appropriately selected depending on the intended purpose, and examples thereof include dyes and pigments. These may be used alone or in combination of two or more. Of these, pigments are preferred.
Examples of the pigment include inorganic pigments and organic pigments.

Examples of the inorganic pigment include calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black produced by known methods such as contact method, furnace method, and thermal method. Be done. These may be used alone or in combination of two or more.

Examples of the organic pigment include azo pigments (including, for example, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments). , Kinacridone pigment, dioxazine pigment, indigo pigment, thioindigo pigment, isoindolinone pigment, quinophthalone pigment, etc.), dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black, etc. Can be mentioned. These may be used alone or in combination of two or more.
In addition, hollow resin particles and inorganic hollow particles can also be used.
Among these pigments, those having a good affinity with a solvent are preferably used.

Examples of the pigments for black include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, and iron (CI pigment black 11). , Organic pigments such as aniline black (CI pigment black 1) and the like.
These may be used alone or in combination of two or more.

For color, for example, C.I. I. Pigment Yellow 1,3,12,13,14,17,24,34,35,37,42 (yellow iron oxide), 53,55,74,81,83,95,97,98,100,101,104 , 108, 109, 110, 117, 120, 138, 150, 153, 155; C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51; C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219; C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63; C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36 and the like. These may be used alone or in combination of two or more.

As the dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 52, 80, 82, 249, 254, 289; C.I. I. Acid Blue 9, 45, 249; C.I. I. Acid Black 1, 2, 24, 94; C.I. I. Hood Black 1, 2; C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173; C.I. I. Direct Red 1, 4, 9, 80, 81, 225, 227; C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202; C.I. I. Dilekdo Black 19, 38, 51, 71, 154, 168, 171, 195; C.I. I. Reactive Red 14, 32, 55, 79, 249; C.I. I. Reactive Black 3, 4, 35 and the like can be mentioned. These may be used alone or in combination of two or more.
The coloring material used for the metallic ink is a metal unit, an alloy, or a fine powder obtained by finely pulverizing a metal compound, and more specifically, aluminum, silver, gold, nickel, chromium, tin, zinc, indium, and the like. It may consist of any one or more of a group of metals consisting of titanium, silicon, copper, or platinum, or an alloy obtained by combining these groups of metals, or a group of these. It is obtained by finely pulverizing any one or more of oxides, nitrides, sulfides, and carbides of a single metal or an alloy.

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

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

<Pigment dispersion>
It is possible to obtain ink by mixing a material such as water or an organic solvent with a coloring material. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. It is preferable to use a disperser for dispersion.
The particle size of the pigment in the pigment dispersion is not particularly limited, but for non-white pigments, the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is also improved. The diameter is preferably 30 to 110 nm. The volume average particle size of the metal oxide is preferably 150 to 400 nm, more preferably 200 to 300 nm, from the viewpoint that a high whiteness can be obtained for the white pigment. For the hollow resin particles, the average volume particle size is preferably 200 to 1000 nm. The average volume particle size of the inorganic hollow particles is preferably 10 to 200 nm from the viewpoint of obtaining high dispersion stability and high whiteness. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1 mass is used. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable. It is preferable that the pigment dispersion is degassed by filtering coarse particles with a filter, a centrifuge, or the like, if necessary.

Similar to the liquid composition, the ink of the present invention may be added with a water-soluble organic solvent, a surfactant, other trace additives and the like, if necessary, and specific examples are as described above.

The ink of the present invention is produced, for example, by dispersing or dissolving the constituent components in an aqueous medium, and further stirring and mixing them as necessary.
Stirring and mixing can be performed with a stirrer using ordinary stirring blades, a magnetic stirrer, a high-speed disperser, or the like.

The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

<Ink set>
It can be an ink set composed of the liquid composition and the ink. As the ink of the ink set, non-white ink and / or white ink can be used.
In the ink set, when the glass transition temperature Tg1 of the nonionic resin particles contained in the liquid composition is lower than the glass transition temperature Tg2 of the thermoplastic resin particles contained in the ink, the lamination strength of the printed portion is excellent. Therefore, it is suitable. The glass transition temperature Tg1 of the nonionic resin particles contained in the liquid composition is more preferably 20 ° C. or more lower than the glass transition temperature Tg2 of the thermoplastic resin particles contained in the ink.

<Printed matter>
The printed matter used in the present invention can be used without particular limitation, and plain paper, glossy paper, special paper, cloth and the like can be used, but it can be particularly preferably used for a non-permeable base material. ..
The non-permeable base material in the present invention refers to a base material having a surface having low water permeability, absorbency and / or adsorptivity, and is a material that does not open to the outside even if there are many cavities inside. Is also included.
More quantitatively, it refers to a base material having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.

Among the non-permeable base materials, a resin film is preferable, and particularly good adhesion to a polypropylene film film, a polyethylene terephthalate film, and a nylon film can be obtained.
Examples of the polypropylene film include Toyobo P-2002, P-2102, P-2161, P-4166, SUNTOX PA-20, PA-30, PA-20W, Futamura Chemical FOA, FOS, FOR and the like. Can be mentioned.
Examples of the polyethylene terephthalate film include Toyobo E-5100, E-5102, Toray P60, P375, Teijin DuPont Film G2, G2P2, K, SL and the like.
Examples of the nylon film include Toyobo Harden films N-1100, N-1102, N-1200, Unitika ON, NX, MS, NK and the like.
The ink of the present invention is desirable because when a heating step is provided after printing, the residual solvent in the ink coating film is reduced and the adhesion to the base material is further improved.

<Printing method, printing equipment>
The printing method of the present invention is a printing method in which a liquid composition and ink are adhered to a printed matter, and the ink set of the present invention is used as an ink set having the liquid composition and ink.
The printing method of the present invention preferably includes a surface modification step of surface-modifying the printed matter, a liquid composition applying step of imparting the liquid composition to the printed matter, and a printing step of ejecting the ink. ..
The printing method of the present invention is a method for producing a printed matter.

<Surface modification process>
In the surface modification step, any treatment method capable of eliminating unevenness at the time of coating the liquid composition and improving the adhesion may be used, for example, corona treatment, atmospheric pressure plasma treatment, frame treatment, ultraviolet rays. Irradiation treatment, etc. can be mentioned.
These treatment methods can be carried out using a known device.
The surface modification step can be said to be a step of modifying the surface state of the printed matter itself to a preferable state for applying the liquid composition, and the surface modification step is another step on the surface of the printed matter. It is different from the step of applying the material (for example, the process of applying the liquid composition).

Among the above treatment methods, the surface modification of the printed surface is preferably a corona treatment step of performing a corona discharge treatment on the printed surface or a streamer treatment (plasma treatment) of performing a streamer discharge treatment. These are preferably used because they are superior in output stability of corona discharge and can uniformly surface-modify the printed surface as compared with atmospheric pressure plasma treatment, frame treatment and ultraviolet irradiation treatment. Be done.

<Liquid composition application process>
The liquid composition applying step is not particularly limited as long as it is a step of applying the liquid composition to the printed matter, and can be appropriately selected depending on the intended purpose. For example, a blade coating method or a gravure coating method can be used. Method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, Examples thereof include a 4- to 5-roll roll coating method, a dip coating method, a curtain coating method, a slide coating method, and a die coating method.

In the wet adhesion amount to the substrate of the liquid composition imparted the liquid composition in step (adhesion amount of the liquid composition prior to drying of the printing substrate) ^{is, 0.1g / m 2 ~10.0g / m} 2 preferably ^there, and more preferably ^{1.0g / m 2 ~3.0g / m 2} . When the wet adhesion amount is 0.1 g / m ² or more, the image quality (density, saturation, color bleeding, feathering) of the recorded material is improved, and when it is 10.0 g / m ² or less, 10. The same agglomeration effect as when it exceeds 0 g / m ² is exhibited, the texture of the recorded material is not impaired, the drying process does not take time, and there is no problem in terms of cost.

The liquid composition adhering to the printed matter is preferably dried. In this case, the liquid composition adhering to the printed matter is transferred to the transport member that comes into contact from the liquid composition applying step to printing by ejecting ink, and the image quality is improved due to the occurrence of obstacles in the transport member and the accumulation of stains. A method of artificially drying may be used so as not to cause a decrease, and the drying temperature is preferably 40 ° C. to 130 ° C., more preferably 80 ° C. to 100 ° C. Examples of the drying method include a heat drum method, an oven method, a hot air blowing method, a preheater method, and a heating roller method. Moreover, you may use the method which combined these methods. The term "drying" here does not mean that the liquid composition is absorbed by the printed matter and becomes apparently dry, but the liquid in the liquid composition such as water evaporates and becomes a liquid state. It means that it cannot be maintained and solidifies.

<Printing process>
The printing step is a step of ejecting ink onto a printed matter to which the liquid composition is applied.
An inkjet method is preferably used for the printing process.
In the printing step, a nozzle for ejecting ink, a plurality of individual liquid chambers communicating with the nozzle, an inflow flow path for flowing ink into the individual liquid chamber, and an ink flowing out from the individual liquid chamber. It is preferable that the printing process uses an ink ejection head having an outflow flow path to eject ink for printing.
The printing method preferably includes a circulation step of circulating the ink from the outflow channel to the inflow channel.
Ink containing a resin component may be prone to ejection turbulence due to fluctuations over time, but by having a circulation process, high-quality images with few image defects such as ejection turbulence can be produced with high productivity. Obtainable.

It is preferable to have a heat treatment step after the printing step.
When non-white ink and white ink are used as the ink, the ink is applied in the order of non-white ink and white ink, and in the order of white ink and non-white ink. Further, it is preferable to have a heat treatment step after the non-white printing step and after the white printing step.
As the heat treatment, it is preferable to perform the heat treatment at 30 ° C. or higher and 100 ° C. or higher and 60 ° C. or higher and 80 ° C. or lower from the viewpoint that a sufficient drying effect can be obtained and the printed matter is not damaged.
The heating time is preferably 10 seconds or more and 10 minutes or less and 1 minute or more and 2 minutes or less from the viewpoint that a sufficient drying effect can be obtained and the printed matter is not damaged.
Further, in the printing step of applying the non-white ink to the printed matter and the printing step of applying the white ink to the printed matter, the adhesion amount of the non-white ink and the white ink is preferably ⁴ to 14 g / m ² .
The white ink may be applied to the entire surface of the printed matter to form a background and a base, or may be applied to a part of the printed matter to form a base. Further, when white ink is applied to a part of the printed matter, for example, it may be applied to the same place as the place where printing is performed using non-white ink, or partly common to the place where printing is performed. It may be given to a place. When printing with a non-white ink on a layer made of white ink, when a transparent base material is used as a printed matter, compared with a case where the non-white ink is directly applied onto the transparent base material, The visibility of the image is improved. When white ink is applied to a portion where an image is not formed, it is possible to form various images such as a background can be formed.
The base referred to here means a base when viewed from an image surface to which non-white ink is applied. Even when the non-white ink and the white ink are applied to the object to be printed in this order, the white ink serves as a base when viewed from the image surface to which the non-white ink is applied.

The printing apparatus of the present invention includes an ink set of the present invention and an ejection head for ejecting ink from the ink set.
The ink ejection head discharges ink from the nozzle, a plurality of individual liquid chambers communicating with the nozzle, an inflow flow path for inflowing ink into the individual liquid chamber, and ink out of the individual liquid chamber. It is preferable that the printing apparatus is provided with a circulation means for circulating the ink from the outflow flow path toward the inflow flow path.

The ink used in the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present application, the printing device and the printing method are devices capable of adhering ink and the liquid composition of the present invention to a printed matter (for example, a recording medium), and a method for recording using the device. ..
The printed matter means a material to which ink and various treatment liquids can adhere even temporarily.
This printing device is referred to as a device for adhering a liquid composition and a head portion for ejecting ink, as well as means for feeding, transporting, and discharging printed matter, other pretreatment devices, and post-treatment devices. It can include devices to be printed and the like.
The printing apparatus and printing method may include a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printed surface and the back surface of the printed matter. The heating means and the drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the printing apparatus and printing method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form a three-dimensional image are also included.
Further, the printing apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise specified.

Further, as this printing device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous line printer is also included.
An example of the recording device which is the printing device of the present invention will be described with reference to FIGS. 2 to 3.
FIG. 2 is a perspective explanatory view of the device. FIG. 3 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanical unit 420 is provided in the exterior 401 of the image forming apparatus 400. Although not shown in FIG. 2, it has a pretreatment apparatus for applying the liquid composition of the present invention. Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packaged with, for example, an aluminum laminate film. It is formed of members. The ink container 411 is housed in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
Here, the case where yellow (Y), cyan (C), magenta (M), and black (K) are used has been described, but yellow (Y), cyan (C), magenta (M), and black (K) have been described. At least one of the above can be replaced with white ink, or white ink can be added to these.

On the other hand, a cartridge holder 404 is provided behind the opening when the cover 401c of the main body of the apparatus is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink discharge port 413 of the main tank 410 and the discharge head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be discharged from the discharge head 434 to the recording medium.

An apparatus for forming an image with ink after applying the liquid composition of the present invention to a printed matter as a pretreatment liquid will be described with reference to FIG.
FIG. 11 is a diagram showing an example of a recording device of a type that scans an inkjet recording head to form an image.
In the apparatus of FIG. 11, the printed matter 306 is sent out by the paper feed roller 307, and the liquid composition 301 is uniformly and thinly applied to the printed matter 306 by the applying roller 304 and the counter roller 305. The liquid composition 301 is pumped up by the pumping roller 303, and is uniformly applied to the applying roller 304 by the film thickness control roller 302. The printed matter 306 to which the liquid composition 301 is applied is sent to a recording scanning unit having an inkjet recording head 320.
Another example of the pretreatment liquid device is shown in FIG. In the pretreatment apparatus shown in FIG. 12, the pretreatment liquid 205 is stored inside the pretreatment liquid storage container 204. Here, a thin film of the pretreatment liquid 205 is formed on the surface of the coating roller 209 by the stirring / supplying roller 206, the transfer roller 207, and the thinning roller 208. Then, the coating roller 209 rotates while being pressed against the rotating opposing roller 201, and the recording medium 203 passes between them, so that the pretreatment liquid 205 is applied to the surface of the recording medium 203. At this time, the pressure adjusting device 202 can adjust the nip pressure between the opposing roller 201 and the coating roller 209, and can control the coating amount of the pretreatment liquid 205. Further, the coating amount of the pretreatment liquid 205 can be controlled by adjusting the rotation speeds of the coating roller 209 and the opposing roller 201. The coating roller 209 and the opposing roller 201 are driven by a power source such as a drive motor, and the rotation speed of the coating roller 209 and the opposing roller 201 can be controlled by adjusting the energy of the power source.

In this way, when the pretreatment liquid 205 is applied to the recording area of the recording medium 203 using the coating roller 209, the pretreatment liquid 205 having a relatively high viscosity can be thinly applied onto the recording medium 203, resulting in uneven color. Can be further suppressed.
The method for applying the pretreatment liquid in the pretreatment section is not limited to the roll coating method, and examples thereof include a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, and a roll coating method.
The pretreatment liquid 205 may be applied to the entire recording area of the recording medium 203, or may be applied only to the area where the image is formed.

In the dried recording medium 203, an image is formed by the inkjet recording unit according to the image data.

An example of the liquid discharge head according to the embodiment of the present invention will be described with reference to FIGS. 4 to 9A and 9B. FIG. 4 is an external perspective explanatory view of the liquid discharge head, FIG. 5 is a cross-sectional explanatory view in a direction orthogonal to the nozzle arrangement direction of the head, and FIG. 6 is a cross-sectional explanatory view in a direction parallel to the nozzle arrangement direction of the head. 7 is a plan explanatory view of the nozzle plate of the head, FIGS. 8A to 8F are plan explanatory views of each member constituting the flow path member of the head, and FIGS. 9A and 9B constitute a common liquid chamber member of the head. It is a plane explanatory view of each member.

In this liquid discharge head, a nozzle plate 1, a flow path plate 2, and a diaphragm member 3 as a wall surface member are laminated and joined. A piezoelectric actuator 11 that displaces the diaphragm member 3, a common liquid chamber member 20, and a cover 29 are provided.
The nozzle plate 1 has a plurality of nozzles 4 for discharging a liquid.
The flow path plate 2 forms an individual liquid chamber 6 leading to the nozzle 4, a fluid resistance portion 7 communicating with the individual liquid chamber 6, and a liquid introduction portion 8 communicating with the fluid resistance portion 7. Further, the flow path plate 2 is formed by laminating and joining a plurality of plate-shaped members 41 to 45 from the nozzle plate 1 side, and laminating and joining these plate-shaped members 41 to 45 and the diaphragm member 3 to form a flow path. The member 40 is configured.
The diaphragm member 3 has a filter portion 9 as an opening through the liquid introduction portion 8 and the common liquid chamber 10 formed by the common liquid chamber member 20.
The inflow flow path may be a flow path connected to the individual liquid chamber 6 and may be a flow path "in front" of the individual liquid chamber inflow, and the liquid introduction unit 8 and the common liquid chamber 10 correspond to the inflow flow path. To do.
The diaphragm member 3 is a wall surface member that forms the wall surface of the individual liquid chamber 6 of the flow path plate 2. The diaphragm member 3 has a two-layer structure (not limited), and is formed of a first layer for forming a thin-walled portion from the flow path plate 2 side and a second layer for forming a thick-walled portion, and the first layer is an individual liquid. A deformable vibration region 30 is formed in a portion corresponding to the chamber 6.

Here, as shown in FIG. 7, a plurality of nozzles 4 are arranged in a staggered pattern on the nozzle plate 1.
As shown in FIG. 8A, the plate-shaped member 41 constituting the flow path plate 2 includes a through groove portion (meaning a groove-shaped through hole) 6a constituting the individual liquid chamber 6, a fluid resistance portion 51, and a circulation flow path. Through-groove portions 51a and 52a constituting the 52 are formed.
Similarly, as shown in FIG. 8B, the plate-shaped member 42 is formed with a through groove portion 6b constituting the individual liquid chamber 6 and a through groove portion 52b forming the circulation flow path 52.
Similarly, as shown in FIG. 8C, the plate-shaped member 43 is formed with a through groove portion 6c constituting the individual liquid chamber 6 and a through groove portion 53a having the nozzle arrangement direction forming the circulation flow path 53 as the longitudinal direction. ..
Similarly, as shown in FIG. 8D, the plate-shaped member 44 includes a through groove portion 6d forming the individual liquid chamber 6, a through groove portion 7a forming the fluid resistance portion 7, and a through groove portion 8a forming the liquid introduction portion 8. , A through groove portion 53b having a longitudinal direction of the nozzle arrangement forming the circulation flow path 53 is formed.
Similarly, as shown in FIG. 8E, the plate-shaped member 45 has a through groove portion 6e constituting the individual liquid chamber 6 and a through groove portion 8b (filter downstream side liquid) having the nozzle arrangement direction forming the liquid introduction portion 8 as the longitudinal direction. A through groove portion 53c having a longitudinal direction of the nozzle arrangement forming the circulation flow path 53 is formed.
As shown in FIG. 8F, the diaphragm member 3 is formed with a vibration region 30, a filter portion 9, and a through groove portion 53d whose longitudinal direction is the nozzle arrangement direction forming the circulation flow path 53. In this way, by forming the flow path member by laminating and joining a plurality of plate-shaped members, it is possible to form a complicated flow path with a simple structure.
With the above configuration, the flow path member 40 composed of the flow path plate 2 and the diaphragm member 3 has a fluid resistance portion 51, a circulation flow path 52, and circulation along the surface direction of the flow path plate 2 leading to each individual liquid chamber 6. A circulation flow path 53 in the thickness direction of the flow path member 40 leading to the flow path 52 is formed. The circulation flow path 53 is connected to the circulation common liquid chamber 50, which will be described later.
The outflow flow path may be a flow path connected to the individual liquid chamber 6 and may be a flow path "after" the inflow of the individual liquid chambers, and the circulation flow paths 52 and 53 and the common circulation liquid chamber 50 flow out. Corresponds to the road.

On the other hand, the common liquid chamber member 20 is formed with a common liquid chamber 10 to which liquid is supplied from the supply / circulation mechanism and a circulation common liquid chamber 50.
As shown in FIG. 9A, the first common liquid chamber member 21 constituting the common liquid chamber member 20 includes a through hole 25a for a piezoelectric actuator, a through groove portion 10a serving as a downstream common liquid chamber 10A, and a circulation common liquid chamber. A groove portion 50a having a bottom to be 50 is formed.
Similarly, as shown in FIG. 9B, the second common liquid chamber member 22 is formed with a through hole 25b for the piezoelectric actuator and a groove portion 10b serving as the upstream common liquid chamber 10B.
Further, with reference to FIG. 4, the second common liquid chamber member 22 is formed with a through hole 71a which is an end portion of the common liquid chamber 10 in the nozzle arrangement direction and a supply port portion through which the supply port 71 is passed.
Similarly, the first common liquid chamber member 21 and the second common liquid chamber member 22 are provided with the other end (the end opposite to the through hole 71a) of the circulation common liquid chamber 50 in the nozzle arrangement direction and the circulation port 81. Through holes 81a and 81b are formed.
In addition, in FIGS. 9A to 9B, the groove portion having a bottom is shown by applying a surface coating (the same applies to the following figures).

As described above, the common liquid chamber member 20 is composed of the first common liquid chamber member 21 and the second common liquid chamber member 22, and the first common liquid chamber member 21 is joined to the diaphragm member 3 side of the flow path member 40. Then, the second common liquid chamber member 22 is laminated and joined to the first common liquid chamber member 21.
Here, the first common liquid chamber member 21 forms a downstream common liquid chamber 10A which is a part of the common liquid chamber 10 leading to the liquid introduction portion 8 and a circulation common liquid chamber 50 leading to the circulation flow path 53. ing. Further, the second common liquid chamber member 22 forms the upstream common liquid chamber 10B which is the rest of the common liquid chamber 10.
At this time, the downstream common liquid chamber 10A and the circulation common liquid chamber 50, which are a part of the common liquid chamber 10, are arranged side by side in the direction orthogonal to the nozzle arrangement direction, and the circulation common liquid chamber 50 is the common liquid chamber 10. It is placed at the position projected inside.
As a result, the dimensions of the circulation common liquid chamber 50 are not restricted by the dimensions required for the flow path including the individual liquid chamber 6, the fluid resistance portion 7, and the liquid introduction portion 8 formed by the flow path member 40.
Then, the circulation common liquid chamber 50 and a part of the common liquid chamber 10 are arranged side by side, and the circulation common liquid chamber 50 is arranged at a position projected in the common liquid chamber 10 so as to be orthogonal to the nozzle arrangement direction. The width of the head in the direction can be suppressed, and the increase in size of the head can be suppressed. The common liquid chamber member 20 forms a circulation common liquid chamber 50 with a common liquid chamber 10 to which liquid is supplied from a head tank or a liquid cartridge.

On the other hand, on the side of the diaphragm member 3 opposite to the individual liquid chamber 6, a piezoelectric actuator 11 including an electromechanical conversion element as a driving means for deforming the vibration region 30 of the diaphragm member 3 is arranged. As shown in FIG. 6, the piezoelectric actuator 11 has a piezoelectric member 12 joined on a base member 13, and the piezoelectric member 12 is grooved by half-cut dicing to obtain a required number for one piezoelectric member 12. The columnar piezoelectric elements 12A and 12B are formed in a comb-teeth shape at predetermined intervals.
Here, the piezoelectric element 12A of the piezoelectric member 12 is a piezoelectric element that is driven by giving a drive waveform, and the piezoelectric element 12B is used as a mere column without giving a drive waveform, but all the piezoelectric elements 12A and 12B are driven. It can also be used as a piezoelectric element.
Then, the piezoelectric element 12A is joined to the convex portion 30a which is an island-shaped thick portion formed in the vibration region 30 of the diaphragm member 3. Further, the piezoelectric element 12B is joined to the convex portion 30b which is a thick portion of the diaphragm member 3.
The piezoelectric member 12 is formed by alternately stacking piezoelectric layers and internal electrodes. The internal electrodes are drawn out to their end faces to provide external electrodes, and the flexible wiring member 15 is connected to the external electrodes.

In the liquid discharge head configured in this way, for example, by lowering the voltage applied to the piezoelectric element 12A from the reference potential, the piezoelectric element 12A contracts, the vibration region 30 of the vibrating plate member 3 descends, and the volume of the individual liquid chamber 6 As the liquid expands, the liquid flows into the individual liquid chamber 6. After that, the voltage applied to the piezoelectric element 12A is increased to extend the piezoelectric element 12A in the stacking direction, and the vibration region 30 of the vibrating plate member 3 is deformed in the direction toward the nozzle 4 to contract the volume of the individual liquid chamber 6. As a result, the liquid in the individual liquid chamber 6 is pressurized, and the liquid is discharged from the nozzle 4.
Then, by returning the voltage applied to the piezoelectric element 12A to the reference potential, the vibration region 30 of the diaphragm member 3 is restored to the initial position, the individual liquid chamber 6 expands, and a negative pressure is generated. Therefore, at this time, the common liquid is generated. The liquid is filled from the chamber 10 into the individual liquid chamber 6. Therefore, after the vibration of the meniscus surface of the nozzle 4 is attenuated and stabilized, the operation for the next ejection is started.
The driving method of this head is not limited to the above example (pull-pushing), and pulling or pushing may be performed depending on the driving waveform. Further, in the above-described embodiment, the laminated piezoelectric element has been described as the pressure generating means for giving the pressure fluctuation to the individual liquid chamber 6, but the present invention is not limited to this, and a thin-film piezoelectric element can also be used. .. Further, it is possible to use a heat-generating resistor arranged in the individual liquid chamber 6 to generate air bubbles by the heat generated by the heat-generating resistor to cause pressure fluctuation, or to generate pressure fluctuation by using electrostatic force. ..

Next, an example of a liquid circulation system using the liquid discharge head according to the present embodiment will be described with reference to FIG.
FIG. 10 is a block diagram showing a liquid circulation system according to the present embodiment.
As shown in FIG. 10, the liquid circulation system includes a main tank, a liquid discharge head, a supply tank, a circulation tank, a compressor, a vacuum pump, a first liquid feed pump, a second liquid feed pump, a regulator (R), and a supply side pressure. It consists of a sensor and a pressure sensor on the circulation side. The supply-side pressure sensor is connected between the supply tank and the liquid discharge head to the supply flow path side connected to the supply port 71 (see FIG. 4) of the liquid discharge head. The circulation side pressure sensor is connected between the liquid discharge head and the circulation tank and is connected to the circulation flow path side connected to the circulation port 81 (see FIG. 4) of the liquid discharge head.
One of the circulation tanks is connected to the supply tank via the first liquid feed pump, and the other of the circulation tanks is connected to the main tank via the second liquid feed pump. As a result, the liquid flows from the supply tank through the supply port 71 into the liquid discharge head, is discharged from the circulation port and is discharged to the circulation tank, and further, the liquid is sent from the circulation tank to the supply tank by the first liquid feed pump. The liquid circulates by being pumped.
Further, a compressor is connected to the supply tank, and the pressure sensor on the supply side is controlled so that a predetermined positive pressure is detected. On the other hand, a vacuum pump is connected to the circulation tank, and the circulation side pressure sensor is controlled to detect a predetermined negative pressure. As a result, the negative pressure of the meniscus can be kept constant while the liquid is circulated through the liquid discharge head.
Further, when droplets are discharged from the nozzle of the liquid discharge head, the amount of liquid in the supply tank and the circulation tank decreases. Therefore, the liquid from the main tank to the circulation tank is appropriately used from the main tank to the circulation tank. It is desirable to replenish. The timing of liquid refilling from the main tank to the circulation tank depends on the detection result of the liquid level sensor installed in the circulation tank, such as refilling the liquid when the liquid level height of the ink in the circulation tank falls below the specified height. Can be controlled.

Next, the circulation of the liquid in the liquid discharge head will be described. As shown in FIG. 4, a supply port 71 communicating with the common liquid chamber and a circulation port 81 communicating with the circulation common liquid chamber 50 are formed at the end of the common liquid chamber member 20. The supply port 71 and the circulation port 81 are each connected to a supply tank / circulation tank (see FIG. 10) for storing liquid via a tube. Then, the liquid stored in the supply tank is supplied to the individual liquid chamber 6 via the supply port 71, the common liquid chamber 10, the liquid introduction section 8, and the fluid resistance section 7.
Further, while the liquid in the individual liquid chamber 6 is discharged from the nozzle 4 by driving the piezoelectric member 12, part or all of the liquid that remains in the individual liquid chamber 6 without being discharged is circulated in the fluid resistance portion 51. It is circulated to the circulation tank through the flow paths 52 and 53, the circulation common liquid chamber 50, and the circulation port 81. It should be noted that the circulation of the liquid can be carried out not only when the liquid discharge head is operated but also when the operation is stopped. By circulating during the suspension of operation, the liquid in the individual liquid chamber is constantly refreshed, and the aggregation and sedimentation of the components contained in the liquid can be suppressed, which is preferable.

Further, a recovery device for recovering the discharge defect of the head may be arranged. The recovery device has a cap means, a suction means, and a cleaning means. The head is moved to the recovery device side during printing standby, and the head is capped by the capping means, and the ejection port portion is kept in a wet state to prevent ejection defects due to ink drying. In addition, by ejecting ink that is not related to recording during recording, the ink viscosities of all ejection ports are kept constant, and stable ejection performance is maintained.
When ejection failure occurs, the ejection port (nozzle hole) of the head is sealed by the capping means, air bubbles, etc. are sucked out from the ejection port by the suction means through the tube, and ink, dust, etc. adhering to the ejection port surface. Is removed by cleaning means and the ejection failure is recovered. Further, the sucked ink is discharged to a waste ink reservoir installed in the lower part of the main body, and is absorbed and held by an ink absorber inside the waste ink reservoir.

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

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

<Cartridge>
The liquid composition of the present invention may be contained in a container, and further, if necessary, other members and the like appropriately selected may be provided as a cartridge.
The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. For example, at least an accommodating portion made of an aluminum laminate film, a resin film, or the like can be selected. Those having, etc. are preferably mentioned.

<Printed matter>
The printed matter according to the present invention is an image formed by using the printing method of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the example, "part" is "part by mass", and "%" is "% by mass" except for those in the evaluation criteria.

<< Preparation of liquid composition >>
<Preparation of Polyamine-Epihalohydrin Polymer, Polyamide-Epihalohydrin Polymer or Polyamide Polyamine-Epihalohydrin Polymer>

Production Example A-1: Amine-epichlorohydrin polymer A 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 95.1 g of water, and a 58% trimethylamine hydrochloride aqueous solution 131. 8.8 g (0.8 mol) was charged, and 74.0 g (0.8 mol) of epichlorohydrin was added dropwise over 3 hours while cooling so as not to exceed 40 ° C. under the introduction of nitrogen gas. After completion of the dropping, the temperature was raised to 80 ° C. and the reaction was carried out over 1 hour. Then, the mixture was cooled to 30 ° C., 36.1 g (0.4 mol) of a 50% aqueous dimethylamine solution and 14.8 g (0.2 mol) of calcium hydroxide were added, the temperature was raised to 80 ° C., and the reaction was carried out over 1 hour. I let you. Then, the reaction solution was adjusted to pH 4.0 and solid content concentration of 50% with hydrochloric acid and water to obtain Production Example A-1 (water-soluble cationic polymer A-1).

Preparation Example A-2: Amine-Epichlorohydrin Polymer Stirrer, thermometer, reflux condenser and nitrogen gas introduction tube in a 500 ml four-necked flask containing 36.8 g of water and 157.6 g of a 30% trimethylamine aqueous solution (157.6 g). 0.8 mol), 36.1 g (0.4 mol) of 50% dimethylamine aqueous solution, and 7.3 g (0.1 mol) of diethylamine were charged and cooled so as not to exceed 40 ° C. under the introduction of nitrogen gas. 92.5 g (1.0 mol) of epichlorohydrin was added dropwise over 4 hours. After completion of the dropping, the temperature was raised to 80 ° C. and the reaction was carried out at that temperature for 2 hours. Then, the mixture was cooled to 30 ° C., and the reaction solution was adjusted to pH 3.9 and a solid content concentration of 50% with sulfuric acid and water to obtain Production Example A-2 (water-soluble cationic polymer A-2). ..

Preparation Example A-3: Polyamide polyamine-epichlorohydrin polymer 495 g (4.8 mol) of diethylenetriamine in a 3 liter four-necked round bottom flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen introduction tube. Add 877 g (6.0 mol) of adipic acid while charging and stirring, raise the temperature while removing the generated water from the system, react at 150 ° C. for 5 hours, and then gradually add 1000 g of water to polyamide polyamine. The containing liquid was obtained. This polyamide polyamine-containing liquid had a solid content of 52.1%, and when the solid content was 50%, the viscosity at 25 ° C. was 380 mPa · s. 100 g (0.214 mol as an amino group) of the polyamide polyamine-containing solution obtained above, 3.8 g (30 equivalent%) of acetic acid and 4.3 g (15 equivalent%) of a 30% aqueous sodium hydroxide solution were charged, and water was added. 7 g was added to make the solid content 50%. Then, 19.8 g (100 eq%) of epichlorohydrin was added dropwise at 30 ° C. over 1 hour, the mixture was held at the same temperature for 1 hour, and 0.8 g (2 eq%) of sodium metabisulfite was added. It was kept at the same temperature for 5 hours after the start of dropping epichlorohydrin. Then, 1.1 g (10 equivalent%) of 98% sulfuric acid and 127.0 g of water were added to make the solid content 30%, and then the mixture was heated to 75 ° C. Further, after maintaining the reaction solution at this temperature until the viscosity of the reaction solution at 25 ° C. reaches 300 mPa · s, 40.5 g of water is added to make the solid content 26%, and after cooling to 25 ° C. or lower, 30% sulfuric acid is used. To pH 3.5, then to pH 3.0 with 88% formic acid, and production example A-3 (water-soluble) with a viscosity of 51.6 mPa · s at a solid content concentration of 25.0% and 15%. Cationic polymer A-3) was obtained.

Production Example A-4: Polyamine-Epichlorohydrin Polymer A 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 443.85 parts of water, and 41.27 diethylenetriamine. After charging the parts and dropping 111.04 parts of epichlorohydrin under the introduction of nitrogen gas over 1.5 hours so as not to exceed 40 ° C., octahydro-4,7-methanoindene-1 (2), 5 ( 6) -Add 19.4 parts of dimethaneamine and stir for 30 minutes. Then, add 18.51 parts of epichlorohydrin over 0.5 hours so as not to exceed 40 ° C. I kept it warm. Then, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 7.5, and the mixture was subsequently kept warm for 1.5 hours. The pH was adjusted to 3.5 with a 30% aqueous sulfuric acid solution and cooled to complete the reaction. The obtained reaction product had a solid content of 30.2%, a viscosity of 7.6 cps (solid content concentration of 10%), and Preparation Example A-4 (water-soluble cationic polymer A-4) having a pH of 3.9.

Production Example A-5: Polyamine-epichlorohydrin polymer A 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 657.2 parts of water, triethylenetetramine 58. 4 parts and 108 parts of 50% dimethylamine were charged, and 192.4 parts of epichlorohydrin was added dropwise over 1.5 hours so as not to exceed 40 ° C. under the introduction of nitrogen gas, and then the temperature was raised to 70 ° C. It was kept warm for 1.5 hours. Then, the pH was adjusted to 7.5 with a 30% aqueous sodium hydroxide solution, and the pH was further adjusted to 3.5 with a 30% aqueous sulfuric acid solution by keeping the temperature at 70 ° C. for 1.5 hours, and cooled to complete the reaction. The obtained reaction product had a solid content concentration of 29.9%, a viscosity of 20 cps (solid content concentration of 10%), and Preparation Example A-5 (water-soluble cationic polymer A-5) having a pH of 3.5.

(Preparation of emulsion of nonionic resin particles)
<Preparation of ethylene vinyl acetate resin emulsion A>
1061 g of PVA {polymerization degree 1700, saponification degree 88 mol%, PVA-217 manufactured by Kuraray Co., Ltd.}, ion-exchanged water 19440 g, L (+) in a pressure-resistant 50-liter autoclave equipped with a nitrogen inlet, a thermometer, and a stirrer. 12.7 g of sodium tartrate, 10.6 g of sodium acetate, and 0.4 g of ferrous chloride were charged and completely dissolved at 95 ° C., then cooled to 60 ° C. and subjected to nitrogen substitution.
Next, after charging 22360 g of vinyl acetate, ethylene was pressurized to 45 kg / cm ² and introduced, 1000 g of a 0.4% hydrogen peroxide aqueous solution was press-fitted over 5 hours, and emulsion polymerization was carried out at 60 ° C.
When the pH at the initial stage of polymerization was confirmed, it was pH = 5.2.

When the amount of residual vinyl acetate reached 10%, ethylene was released, the ethylene pressure was adjusted to 20 kg / cm ^2, and 50 g of a 3% hydrogen peroxide aqueous solution was press-fitted to continue the polymerization.
Ethylene was released and cooled when the amount of residual vinyl acetate monomer in the emulsion reached 1.5%.
After cooling, the pH was confirmed and found to be pH = 4.8. Then, 20 g of sodium bisulfite was added, and ethylene was removed for 1 hour at 30 ° C. under a reduced pressure of 100 mmHg.
After returning the reaction system to atmospheric pressure with nitrogen, 10 g of t-butyl hydroperoxide was added and the mixture was stirred for 2 hours.
When the pH at the end of the polymerization was confirmed, the pH was 4.7.

This emulsion was filtered to adjust the solid content to 50% to obtain an ethylene-vinyl acetate polymerization system resin emulsion A.
The Tg of the ethylene-vinyl acetate polymerization system resin emulsion A was measured by DSC (Thermo plus EVO2 / DSC manufactured by Rigaku) and found to be 0 ° C.

<Preparation of urethane resin emulsion A>
1/3 of polyethylene glycol monomethyl ether having a molecular weight of 1,000 is added to 1 mol of 1,6-hexanediol, 1.4 mol of dicyclohexylmethane diisocyanate, and 1 mol of isocyanurate trimer of 1,6-hexamethylene diisocyanate. 0.1 mol of the molarly reacted diisocyanate compound with respect to 1 mol of 1,6-hexanediol and 15% of the total mass of N-methyl-2-pyrrolidone were charged into a reaction flask, and 90 was charged under a nitrogen stream. The reaction was carried out at ° C. for 2 hours to obtain a prepolymer composition.

450 g of the prepolymer composition having a solid content of 85% obtained above was added dropwise to 600 g of water in which 0.2 g of a silicone-based defoamer SE-21 (manufactured by Wacker Silicon) was dissolved in 15 minutes, and 10 at 25 ° C. After minute stirring, the compound of the following formula (A), ethylenediamine, and adipic acid hydrazide were added dropwise to obtain a polyurethane resin emulsion A.
The Tg of the polyurethane resin emulsion A was measured by DSC (Thermo plus EVO2 / DSC manufactured by Rigaku) and found to be 20 ° C.

<Preparation of polyester resin emulsion A>
First, 3.0 parts of hydroxyethyl cellulose (Metroze 60SH-50, manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of nonionic emulsifier (Emulgen 1108, manufactured by Kao Corporation) are dissolved in 225 parts of water in advance in terms of solid content to dissolve the emulsifier. An aqueous solution was prepared.
Next, 150 parts of polylactic acid (Viroecol BE-450, manufactured by Toyobo) was dissolved in 300 parts of toluene in a reaction vessel equipped with a thermometer, a nitrogen introduction pipe, a stirrer and a cooling pipe, and the above emulsifier aqueous solution was added. Pre-emulsification was performed by stirring and mixing at 45 ° C. for 30 minutes to obtain a pre-emulsified product.
The preliminary emulsion was emulsified with a high-pressure emulsifier manufactured by Menton Gaulin at a pressure of 300 kg / m ² to obtain a fine emulsion.

After removing toluene by heating and vacuum distillation of this fine emulsion under the condition of 130 mmHg, a solid content was prepared to obtain a polyester emulsion having a solid content of 45%, a pH of 2.4 and a particle size of 0.32 μm, and then 25. The pH was adjusted to 7.0 with% aqueous ammonia.
0.6 part of a thickener (Primal ASE-60, manufactured by Rohm and Haas Japan) was added to this polyester emulsion to adjust the solid content to 40% to obtain a polyester resin emulsion A.
The Tg of the polyester resin emulsion A was measured by DSC (Thermo plus EVO2 / DSC manufactured by Rigaku) and found to be 0 ° C.

<Preparation of liquid composition>
The liquid composition was prepared by the following procedure. First, the materials shown in Table 1-1 and Table 1-2 below were mixed, stirred for 1 hour, and mixed uniformly. The obtained liquid was pressure-filtered with a polyvinylidene fluoride membrane filter having an average pore size of 5.0 μm to remove coarse particles and dust to prepare liquid compositions 1 to 12.

In Table 1-1 and Table 1-2, the blending amount of the water-soluble cationic polymer and the resin particles (emulsion) is the blending amount of the resin component.
In Tables 1-1 and 1-2, the amount of "pure water" includes the aqueous solution of the water-soluble cationic polymer and the amount of water in the emulsion.
In Table 1-1 and Table 1-2, the meanings of those not described in the preparation examples are as follows.
-Ammonium lactate: Kanto Chemical Co., Ltd., purity 73-77%
-Ammonium acetate: Kanto Chemical Co., Ltd., purity 97% or more-WS-4020: Polyamide-epichlorohydrin polymer (Seiko PMC Corporation, active ingredient 25% by mass)
-Sharoll DM-283P: A quaternary ammonium salt-type cationic polymer compound represented by the following formula (8) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., 50% by mass aqueous solution of active ingredient, molecular weight of about 28,000).

However, in the formula (8), X represents a halogen atom and n represents an integer.

-Emulsion of ethylene vinyl acetate resin emulsion B: Sumikaflex 951HQ (Tg: -25 ° C) manufactured by Sumika Chemtex, nonionic resin emulsion-Styrene-butadiene resin emulsion A: Nalstar SR-130 (Tg: -1 ° C) manufactured by Nippon A & L, Nonion Sex resin emulsion ・ Vinyl acetate acrylic resin emulsion A: Nissin Chemical's Vinibran 1225 (Tg: 9 ° C), nonionic resin emulsion ・ Anionic resin emulsion: Mitsui Chemical's Takelac W-5661 (urethane resin)
-Cationic resin emulsion: Unitika Arrow Base CB-1200 (polyolefin resin)
-FS-300: Fluorine-based surfactant (manufactured by DuPont)
-TEGO WET270: Silicone surfactant (manufactured by Evonik Industries)
-Proxel GXL: Antifungal agent containing 1,2-benzisothiazolin-3-one as the main component (manufactured by Abyssia, 20% by mass of component, containing dipropylene glycol)

<Evaluation of non-printed part laminate>
The prepared liquid composition was referred to as Bar Coater No. The OPP film and PET film were coated in 1 and dried at 80 ° C.
On top of that, an adhesive for dry lamination (main agent TM-320 / curing agent CAT-13B, manufactured by Toyo Morton Co., Ltd.) was applied to Bar Coater No. After coating with No. 4 and CPP (Pyrene P1128 manufactured by Toyobo Co., Ltd.) was attached, it was aged at 40 ° C. for 48 hours.
After cutting the laminate to a width of 15 mm, the T-type peel strength was measured and judged according to the following criteria, and up to B was set as an allowable range.
[Evaluation criteria]
A: A strength of 5N / 15mm or more can be obtained.
B: Strength of 3N / 15mm or more and less than 5N / 15mm can be obtained.
C: 1N / 15mm or more and less than 3N / 15mm can be obtained.
D: Only strength less than 1N / 15mm can be obtained.
The manufacturer names and grades of various films used in the substrate adhesion test are as follows.
-OPP (biaxially stretched polypropylene): Toyobo pipe wrench P2102
-PET (polyethylene terephthalate): Toyobo Espet E5100

<Preparation of pigment dispersion>
(Preparation of black pigment dispersion)
Carbon black manufactured by Tokai Carbon Co., Ltd .: 100 g of Seast SP (SRF-LS) is added to 3000 mL of a 2.5 N (specified) sodium hypochlorite solution, stirred at a temperature of 60 ° C. and a speed of 300 rpm, and reacted for 10 hours. Oxidation treatment was carried out to obtain a reaction solution containing a pigment having a carboxylic acid group added to the surface of carbon black.
This reaction solution was filtered, the filtered carbon black was neutralized with a sodium hydroxide solution, and ultrafiltration was performed to obtain a pigment dispersion.
Next, ultrafiltration with a dialysis membrane was performed using the pigment dispersion and ion-exchanged water, and further ultrasonic dispersion was performed to concentrate the pigment solid content to 20%. A black pigment dispersion having a volume average particle size of 100 nm. I got A.

(Preparation of cyan pigment dispersion)
In the preparation of the black dispersion A, a cyan pigment dispersion A having a volume average particle diameter of 62 nm was obtained in the same manner except that Hostaparm Blue B4G manufactured by Clariant was used as the coloring material.

(Preparation of magenta pigment dispersion)
In the preparation of the black dispersion A, a magenta pigment dispersion A having a volume average particle size of 87 nm was obtained in the same manner except that the color material used was Hostaparm Pink E02 manufactured by Clariant.

(Preparation of yellow pigment dispersion)
In the preparation of the black dispersion A, a yellow pigment dispersion A having a volume average particle diameter of 75 nm was obtained in the same manner except that Hansa Brilliant Yellow 5GX03 manufactured by Clariant was used as the coloring material.

(Preparation of white pigment dispersion)
Titanium oxide STR-100W (manufactured by Sakai Chemical Industry Co., Ltd.) 25 g, pigment dispersant TEGO Dispers 651 (manufactured by Ebonic) 5 g, and water 70 g are mixed and used in a bead mill (Research Lab, manufactured by Simmal Enterprises Co., Ltd.). Zirconia beads of 0.3 mmΦ were dispersed at a filling rate of 60% and 8 m / s for 5 minutes to obtain a white pigment dispersion A having a volume average particle size of 285 nm.

<Ink preparation method>
To prepare the ink, mix and stir with the formulations as shown in Table 2-1 and Table 2-2, and filter the non-white ink with a 0.2 μm polypropylene filter and the white ink with a 0.5 μm polypropylene filter. Made by
The following surfactants were used.
-FS-300 (DuPont fluorosurfactant)
In addition, the following preservatives were used.
-Proxel GXL: Antifungal agent containing 1,2-benzisothiazolin-3-one as the main component (manufactured by Abyssia, 20% by mass of component, containing dipropylene glycol)
The resins used are as follows.
-Urethane resin A: Superflex 210 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (Tg: 41 ° C)
-Urethane resin B: Superflex 420 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (Tg: -10 ° C)
-Acrylic resin A: DIC Boncoat CF-6140 (Tg: 12 ° C)
-Styrene acrylic resin A: Viniblanc 2685 (Tg: 50 ° C) manufactured by Nissin Chemical Co., Ltd.
-Polyester resin A: Unitika Elitel KA-5034 (Tg: 67 ° C)

In Tables 2-1 and 2-2, the blending amount of the pigment dispersion is the blending amount of the pigment component.
In Tables 2-1 and 2-2, the blending amount of the water-dispersible resin is the blending amount of the resin component.
In Tables 2-1 and 2-2, the amount of "pure water" includes the amount of water in the pigment dispersion and the emulsion of the water-dispersible resin.

<Example of ink set>
Depending on the combination of the liquid composition shown in Table 1-1 and Table 1-2 and the ink shown in Table 2-1 and Table 2-2, and the conditions, the ink set may apply the liquid composition and eject the ink. Then, the printing part lamination strength evaluation, the image density evaluation, the negative character crushing evaluation, the scratch resistance evaluation, and the dryness evaluation were carried out, and the ink set is shown in Table 3 and the evaluation result is shown in Table 4. The evaluation method is as described below.

<Evaluation of printed part laminate strength>
The produced ink is filled in an inkjet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), and the bar coater No. The liquid composition in step 1 was applied under the condition of 1.4 [g / m ² ] and then dried on the OPP film (Pyrene P2102 manufactured by Toyobo Co., Ltd.) under the condition of an ink adhesion amount of 10 [g / m ² ]. , A solid image was printed with ink and dried under the condition of 80 ° C. for 2 minutes. When black ink and color ink were used, a mixed solid image was printed.
A dry laminating adhesive (main agent TM-320 / curing agent CAT-13B, manufactured by Toyo Morton Co., Ltd.) is applied to the solid part with a bar coater, and CPP (Pyrene P1128 manufactured by Toyobo Co., Ltd.) is attached, and then at 40 ° C. Aged for 48 hours.
After cutting the laminate to a width of 15 mm, the peel strength was measured by T-type peeling (peeling speed: 300 mm / min).
Up to B is the allowable range.
[Evaluation criteria]
A: A strength of 5N / 15mm or more can be obtained.
B: Strength of 3N / 15mm or more and less than 5N / 15mm can be obtained.
C: 1N / 15mm or more and less than 3N / 15mm can be obtained.
D: Only strength less than 1N / 15mm can be obtained.

<Image density evaluation>
The produced ink is filled in an inkjet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), and the bar coater No. On the OPP film (Pyrene P2102 manufactured by Toyobo Co., Ltd.) after the liquid composition was applied in step 1, the ink (black ink) was printed at 1200 x 1200 dpi under the same conditions as the solid printing of "<Printed part laminate strength evaluation>". ) Was used to perform solid printing, the film was dried, and the concentration of the solid portion was measured with X-Rite 938 manufactured by SDG Co., Ltd., and judged according to the following criteria.
Up to B is the allowable range.
[Evaluation criteria]
A: Image density 2.0 or more B: Image density 1.5 or more and less than 2.0 C: Image density 1.0 or more and less than 1.5 D: Image density less than 1.0

<Negative character crush evaluation>
The produced ink is filled in an inkjet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), and the bar coater No. On the OPP film (Pyrene P2102 manufactured by Toyobo Co., Ltd.), which was dried after applying the liquid composition in step 1, using ink (black ink) under the same conditions as the solid printing of "<Printed part laminate strength evaluation>". , A Gothic white-out character chart was printed and dried.
The readability of the characters in the obtained image was judged with the naked eye, visually evaluated according to the following criteria, and up to B was set as the allowable range.
[Evaluation criteria]
S: 2pt Gothic font is readable.
A: 2pt is unreadable, but 3pt is readable.
B: 3pt is unreadable, but 4pt is readable.
C: 4pt is unreadable, but 5pt is readable.
D: 5pt is unreadable.

<Evaluation of dryness>
The produced ink is filled in an inkjet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), and the bar coater No. A solid image is printed using ink on an OPP film (Pyrene P2102 manufactured by Toyobo Co., Ltd.) that has been coated with the liquid composition in step 1 and then dried under the same conditions as the solid printing of "<Printed part laminate strength evaluation>". Then, it was dried at 25 ° C. for a predetermined time. When black ink and color ink were used, a mixed solid image was printed.
The filter paper was pressed against the solid portion after drying, and the determination was made according to the following criteria based on the degree of ink transfer to the filter paper.
[Evaluation criteria]
A: Transfer to filter paper disappears under drying conditions of 25 ° C for 15 minutes.
B: Transfer to filter paper is eliminated under drying conditions of 25 ° C. for 30 minutes.
C: Transfer to filter paper is eliminated under drying conditions of 25 ° C. for 60 minutes.
D: Transfer to filter paper does not disappear even under drying conditions of 25 ° C. for 60 minutes.

<Scratch resistance evaluation>
The produced ink is filled in an inkjet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), and the bar coater No. On the OPP film (Pyrene P2102 manufactured by Toyobo Co., Ltd.), which was dried after applying the liquid composition in No. 1, a solid image was printed using ink under the same conditions as the solid printing of "<Printed part laminate strength evaluation>". After printing, it was dried. When black ink and color ink were used, a mixed solid image was printed.
The solid part was rubbed with a dry cotton (Kanakin No. 3) under a load of 400 g, and the scratch resistance was judged according to the following criteria, and up to B was set as an allowable range.
[Evaluation criteria]
A: The image does not change even after rubbing 100 times or more.
B: Some scratches remain after rubbing 100 times, but it does not affect the image density.
C: The image density decreases during rubbing 100 times.
D: The image density is lowered by rubbing 50 times or less.

<Long-term storage stability>
The crystallization of the liquid compositions 1 to 12 was evaluated. 3.0 g of the liquid composition was placed in a petri dish having a diameter of 27 mm and allowed to stand in an environment of room temperature of 24 ° C. and humidity of 44% until crystals were formed. The crystallization of the liquid composition was evaluated based on the following evaluation criteria. The results are shown in Table 4. When the evaluation was B or higher, it was evaluated as practical.
[Evaluation criteria]
A: Time to crystallize 200 hours or more B: Time to crystallize 100 hours or more and less than 200 hours C: Time to crystallize 50 hours or more and less than 100 hours D: Crystal Less than 50 hours before

Aspects of the present invention are, for example, as follows.
<1> A liquid composition characterized by containing a water-soluble cationic polymer obtained by reacting a monomer containing an amine and epihalohydrin, a resin other than the water-soluble cationic polymer, an organic solvent, and water.
<2> The liquid composition according to <1>, wherein the resin contains a nonionic resin.
<3> The liquid according to <2>, wherein the nonionic resin has at least one selected from a polyolefin resin, a polyvinyl acetate resin, a polyvinyl chloride resin, a urethane resin, a styrene butadiene resin and a copolymer thereof. It is a composition.
<4> The liquid composition according to any one of <1> to <3>, wherein the resin is resin particles.
<5> The above-mentioned <2> to <4>, wherein the content of the nonionic resin is 0.5% by mass or more and 20.0% by mass or less with respect to the solid content of the liquid composition. It is a liquid composition.
<6> The liquid composition according to any one of <1> to <5>, which further contains an ammonium salt of an organic acid.
<7> The liquid composition according to <6>, wherein the organic acid ammonium salt is ammonium lactate.
<8> The water-soluble cationic polymer is a polymer represented by the following formula (1), a polymer having a repeating unit represented by the following formula (2), a monomer represented by the following formula (3), and the following formula. The liquid composition according to any one of <1> to <7>, which has at least one selected from a polymer obtained by reacting the monomer represented by (4) with the monomer represented by the following formula (5). It is a thing.
However, in the above formula (1), in the formula, R1 to R8 may be the same or different, and each has an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, and a carbon number of carbon atoms. It represents an alkenyl group or a benzyl group of 1 to 8, where X represents a halogen atom and n represents 1 or 2.
However, in the above formula (2), X represents a halogen atom and m represents an integer of 1 or more.
However, in the above formula (5), X represents a halogen atom.
<9> An ink set characterized by having the liquid composition according to any one of <1> to <8> and an ink containing a resin.
<10> The resin contained in the liquid composition has nonionic resin particles and has nonionic resin particles.
The resin contained in the ink has thermoplastic resin particles and has.
The ink set according to <9>, wherein the glass transition temperature Tg1 of the nonionic resin particles is lower than the glass transition temperature Tg2 of the thermoplastic resin particles.
<11> A printing method comprising a step of applying a liquid composition to a printed matter and a printing step of ejecting ink.
The printing method is characterized in that the ink set according to any one of <9> to <10> is used as the ink set having the liquid composition and the ink.
<12> The printing method according to <11>, which comprises a surface modification step of surface-modifying the printed matter.
<13> In the printing step, a nozzle for ejecting the ink, a plurality of individual liquid chambers communicating with the nozzle, an inflow flow path for flowing the ink into the individual liquid chamber, and the ink individually. This is a printing process in which the ink is ejected and printed using an ink ejection head having an outflow flow path for outflow from the liquid chamber.
The printing method according to any one of <11> to <12>, further comprising a circulation step of circulating the ink from the outflow channel to the inflow channel.
<14> A printing apparatus comprising the ink set according to any one of <9> to <10> and an ink ejection head for ejecting the ink of the ink set.
<15> The ink ejection head uses a nozzle for ejecting the ink, a plurality of individual liquid chambers communicating with the nozzle, an inflow flow path for inflowing the ink into the individual liquid chamber, and the ink. It has an outflow flow path for outflow from individual liquid chambers,
The printing apparatus according to <14>, further comprising a circulation means for circulating the ink from the outflow channel to the inflow channel.

The liquid compositions described in <1> to <8>, the ink sets described in <9> to <10>, the printing methods described in <11> to <13>, and the printing methods described in <14> to <14>. The printing apparatus according to 15> can solve the conventional problems and achieve the object of the present invention.

(About FIGS. 1A to 1C)
101 Recording medium 102 Adhesion 103 Particle 104 Dispersion medium (about FIGS. 2 and 3)
400 Image forming device 401 Image forming device exterior 401c Device body cover 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 Ink storage unit 413 Ink discharge port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube

(About FIGS. 4 to 9A and 9B)
1 Nozzle plate 2 Flow path plate 3 Vibrating plate member 4 Nozzle 6 Individual liquid chambers 6a, 6b, 6c, 6d, 6e Through groove portion 7 constituting the individual liquid chamber 7 Fluid resistance portion 7a Through groove portion 8 constituting the fluid resistance portion Liquid introduction Parts 8a, 8b Through groove part 9 that constitutes the liquid introduction part Filter part 10 Common liquid chamber 10A Downstream side common liquid chamber 10a Through groove part 10B Upstream side common liquid chamber 10b Groove part 11 Piezoelectric actuator 12 Piezoelectric member 12A, 12B Piezoelectric element 13 Base member 15 Flexible wiring member 20 Common liquid chamber member 21 First common liquid chamber member 22 Second common liquid chamber member 25a, 25b Through hole for piezoelectric actuator 30 Vibration region 30a, 30b Convex part 40 Flow path member 41 to 45 Plate-shaped member 50 Circulation common liquid chamber 50a Groove 51 Fluid resistance 51a Through groove 52, 53 that constitutes the fluid resistance part Through groove 53a, 53b, 53c, 53d that constitutes the circulation flow path Penetration that constitutes the circulation flow path Groove 71 Supply port 71a Through hole 81 Circulation port 81a, 81b Through hole

(About Fig. 11)
301 Liquid composition 302 Film thickness control roller 303 Pumping roller 304 Applying roller 305 Counter roller 306 Printed matter 307 Paper feed roller 320 Inkjet recording head

(About Fig. 12)
201 Opposing roller 202 Pressure regulator 203 Recording medium 204 Pretreatment liquid storage container 205 Pretreatment liquid 206 Stirring / supply roller 207 Transfer roller 208 Thinning roller 209 Coating roller 209

JP-A-2015-71738

Claims (15)

A liquid composition comprising a water-soluble cationic polymer obtained by reacting a monomer containing an amine and epihalohydrin, a resin other than the water-soluble cationic polymer, an organic solvent, and water. The liquid composition according to claim 1, wherein the resin contains a nonionic resin. The liquid composition according to claim 2, wherein the nonionic resin has at least one selected from a polyolefin resin, a polyvinyl acetate resin, a polyvinyl chloride resin, a urethane resin, a styrene butadiene resin and a copolymer thereof. The liquid composition according to any one of claims 1 to 3, wherein the resin is resin particles. The liquid composition according to any one of claims 2 to 4, wherein the content of the nonionic resin is 0.5% by mass or more and 20.0% by mass or less with respect to the solid content of the liquid composition. The liquid composition according to any one of claims 1 to 5, further comprising an ammonium organic acid salt. The liquid composition according to claim 6, wherein the organic acid ammonium salt is ammonium lactate. The water-soluble cationic polymer is a polymer represented by the following formula (1), a polymer having a repeating unit represented by the following formula (2), a monomer represented by the following formula (3), and the following formula (4). The liquid composition according to any one of claims 1 to 7, which has at least one selected from a polymer obtained by reacting the monomer represented by (5) with the monomer represented by the following formula (5).
However, in the above formula (1), in the formula, R1 to R8 may be the same or different, and each has an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, and a carbon number of carbon atoms. It represents an alkenyl group or a benzyl group of 1 to 8, where X represents a halogen atom and n represents 1 or 2.
However, in the above formula (2), X represents a halogen atom and m represents an integer of 1 or more.
However, in the above formula (5), X represents a halogen atom. An ink set comprising the liquid composition according to any one of claims 1 to 8 and an ink containing a resin. The resin contained in the liquid composition has nonionic resin particles and has nonionic resin particles.
The resin contained in the ink has thermoplastic resin particles and has.
The ink set according to claim 9, wherein the glass transition temperature Tg1 of the nonionic resin particles is lower than the glass transition temperature Tg2 of the thermoplastic resin particles. A printing method comprising a step of applying a liquid composition to a printed matter and a printing step of ejecting ink.
A printing method comprising using the ink set according to any one of claims 9 to 10 as the ink set having the liquid composition and the ink. The printing method according to claim 11, further comprising a surface modification step of surface modifying the printed matter. In the printing process, a nozzle for ejecting the ink, a plurality of individual liquid chambers communicating with the nozzle, an inflow flow path for flowing the ink into the individual liquid chamber, and the ink from the individual liquid chamber. This is a printing process in which the ink is ejected and printed by using an ink ejection head having an outflow flow path for outflow.
The printing method according to any one of claims 11 to 12, further comprising a circulation step of circulating the ink from the outflow channel to the inflow channel. A printing apparatus comprising the ink set according to any one of claims 9 to 10 and an ink ejection head for ejecting the ink of the ink set. The ink ejection head has a nozzle for ejecting the ink, a plurality of individual liquid chambers communicating with the nozzle, an inflow flow path for inflowing the ink into the individual liquid chamber, and the ink in the individual liquid chamber. Has an outflow channel for outflow from
The printing apparatus according to claim 14, further comprising a circulation means for circulating the ink from the outflow channel to the inflow channel.