JP5966612B2 - Treatment liquid, method for producing the same, and image forming method - Google Patents

Description

  The present invention relates to a processing liquid and an image forming method.

In the recording ink used in the ink jet recording system, glycerin is mainly used as an organic solvent because it is environmentally friendly and the discharge head is not clogged due to storage. However, since the glycerin is highly hydrophilic due to its structure, when discharged onto a recording medium, it breaks hydrogen bonds of cellulose fibers of the recording medium together with water, resulting in curling and cockling (recording medium undulations). Problem).
In addition, when 3-methyl-1,3-butanediol, which is an organic solvent having a strong hydrophobicity compared to the glycerin, is used, the curl resistance is improved, but the storage stability is greatly inferior to that of glycerin. There's a problem.
Further, an ink composition using sodium hyaluronate having excellent moisture retention has been proposed (see Patent Document 1). However, the sodium hyaluronate has many hydrophilic groups because of its structure, and there is a problem of curling after printing on a recording medium. Furthermore, the sodium hyaluronate has a higher surface tension than the glycerin and has a problem with respect to scratch resistance after printing on a recording medium.

  In addition, as a treatment liquid capable of suppressing the occurrence of curling of a recording medium when an aqueous ink is used, a liquid containing a vegetable oil having a hydroxyl group or a vegetable oil-based oil having a hydroxyl group has been proposed (see Patent Document 2). ). However, since this proposal is an oil-based processing liquid using vegetable oil, the penetrating power to the recording medium is large, and the penetration of the processing liquid to the back surface of the recording medium and the decrease in image density occur. There is a problem.

  Therefore, it is desired to provide a processing liquid and an image forming method that are suitably used for image formation having both storage stability, curl resistance, and scratch resistance.

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a processing liquid used for image formation having storage stability, curling resistance, and scratch resistance.

  The treatment liquid of the present invention as a means for solving the above-described problems contains a hyaluronic acid compound, an organic acid compound, a cationic polymer, an organic solvent, a fluorosurfactant, and water.

  According to the present invention, it is possible to solve the problems in the prior art, achieve the object, and provide a processing solution used for image formation having storage stability, curl resistance, and scratch resistance. it can.

FIG. 1 is a schematic diagram (side explanatory view) showing an example of an image forming apparatus used in the present invention. FIG. 2 is a schematic block diagram of the control unit in FIG. FIG. 3 is a schematic diagram showing an example of a head arrangement in the head unit of the image forming apparatus used in the present invention. FIG. 4 is a schematic diagram showing the heads arranged in the head unit of FIG. FIG. 5 is a diagram illustrating an example of an ink cartridge used in the image forming apparatus used in the present invention. FIG. 6 is a diagram including a case (exterior) of the ink cartridge of FIG. FIG. 7 is a schematic diagram showing an example of a discharge method from a discharge head in the image forming apparatus used in the present invention. FIG. 8 is a schematic diagram showing an example of a coating method using three rollers. FIG. 9 is a schematic diagram illustrating an example of a coating method using two rollers.

(Processing liquid)
The treatment liquid of the present invention contains a hyaluronic acid compound, an organic acid compound, a cationic polymer, an organic solvent, a fluorosurfactant, and water, and contains a foam suppressant and, if necessary, other components. Become.
The treatment liquid is used in an image forming method and an image forming apparatus described later and does not contain a colorant.

-Hyaluronic acid compound-
By containing the hyaluronic acid compound in the treatment liquid, storage stability, curl resistance, and scratch resistance can be improved.
Examples of the hyaluronic acid compound include hyaluronic acid, derivatives of hyaluronic acid, and salts thereof. Examples of the salt include alkali metals such as lithium, sodium and potassium, ammonium, alkanolamine, and basic amino acids.
Among these, sodium hyaluronate and acetylated sodium hyaluronate represented by the following general formula (1) are preferable, and sodium acetylated hyaluronate represented by the following general formula (1) is particularly preferable.
<General formula (1)>
However, In the general formula (1), n represents an integer of 1 or more, R represents represents any of a hydrogen atom, and _CH 3 CO. Moreover, 2.6-3.8 are preferable for the acetyl group substitution degree which shows the ratio by which the hydroxyl group is substituted by the acetyl group.

Since the acetylated sodium hyaluronate has a hydrophilic group and a hydrophobic group in its structure, the probability of cleaving hydrogen bonds in cellulose is lower than that of general organic solvents, resulting in improved curl resistance. To do. Further, the acetylated sodium hyaluronate can hold about twice as much water as sodium hyaluronate and can also reduce the surface tension.
The weight average molecular weight of the acetylated sodium hyaluronate is preferably 10,000 to 1,000,000, and more preferably 50,000 to 500,000.
The content of the sodium hyaluronate in the treatment liquid is preferably 1.0% by mass to 5.0% by mass, more preferably 1.5% by mass to 5.0% by mass, and 2.0% by mass to 4.% by mass. 0% by mass is more preferable. When the content is less than 1.0% by mass, the storage stability, curl resistance, and scratch resistance may not be improved. When the content exceeds 5.0% by mass, it is relatively hydrophobic. Causes problems such as the penetration of the processing liquid penetrating to the back side of the recording medium due to its strength and the decrease in image density due to the recording ink colorant used in combination with the processing liquid entering the recording medium. Sometimes.

-Organic acid compounds-
The organic acid compound preferably has a carboxyl group in its structure. The organic acid compound is produced in the body, contained in foods, etc., has little human residue, and many are odorless, which is preferable in terms of use at home and office.
Examples of the organic acid compound include succinic acid, citric acid, malic acid, tartaric acid, lactic acid, and salts thereof. Examples of the salt include alkali metals, ammonium, alkanolamine, and basic amino acids. Among these, lactic acid and ammonium lactate are particularly preferable.
The organic acid compound in the treatment liquid reacts with the carboxyl group-containing resin in the recording ink to cause aggregation of a pigment as a colorant on the recording medium, thereby improving the image quality.

  The content of the organic acid compound in the treatment liquid is preferably 30% by mass or less, and more preferably 20% by mass or less. When the content of the organic acid compound exceeds 30% by mass, the aggregating action of the pigment due to the reaction between the carboxyl group-containing resin in the recording ink and the organic acid compound is increased, resulting in a recording medium. The dot diameter on the top will be smaller. This indicates that the spread of the dots is reduced. In particular, when the solid image is not sufficiently filled, the influence of the background color of the recording medium may appear in the image.

-Cationic polymer-
The cationic polymer is preferably water-soluble, and a polymer obtained by polymerizing a monomer containing an amine and epihalohydrin is used. The cationic polymer obtained by polymerizing these monomers contains a hydroxyl group, an ammonium cation, etc. in the main chain, and when the treatment liquid comes into contact with the recording ink by releasing a halogen anion in an aqueous solution. It is considered that it has a function of enhancing the buffering action and the action of aggregating the pigment.
Examples of the cationic polymer include a polyamine-epihalohydrin copolymer, a polyamide-epihalohydrin copolymer, a polyamide polyamine-epihalohydrin copolymer, and an amine-epihalohydrin copolymer. Among these, a copolymer represented by the following general formula (A), a copolymer containing a repeating unit represented by the following general formula (B), and an amine monomer, and represented by the following structural formula (C) And at least one selected from a copolymer obtained by polymerizing a monomer represented by the following general formula (D).
<General formula (A)>
In the general formula (A), R ₁ ~R ₈ is an alkyl group, hydroxyalkyl group, any of the alkenyl and benzyl groups,, X represents a halogen atom. n represents an integer of 1 or 2.

Examples of the alkyl group in R ₁ to R _8, preferably those having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, and the like.
Examples of the hydroxyalkyl group in R _{1 to} R ₈ include those obtained by substituting some of the hydrogen atoms of the alkyl group with hydroxyl groups.
Examples of the alkenyl group in R _{1 to} R ₈ include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and a decenyl group.
X represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

<General formula (B)>
However, in said general formula (B), X shows a halogen atom and m shows an integer greater than or equal to 1.
X in the general formula (B) represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

<Structural formula (C)>

<General formula (D)>
However, in said general formula (D), X shows a halogen atom.
X in the general formula (D) represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the amine monomer include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, iminobispropylamine, and the like. Among these, an amine monomer represented by the following structural formula (E) is particularly preferable because it is industrially produced and easily available.
<Structural formula (E)>

  The weight average molecular weight of the cationic polymer varies depending on the type of copolymer and can be appropriately selected. However, in the case of an amide-epihalohydrin copolymer, 500 to 100,000 are preferable, and the polyamide-epihalohydrin copolymer or In the case of a polyamide polyamine-epihalohydrin copolymer, 10,000 to 5 million is preferable, and in the case of an amine-epihalohydrin copolymer, 700 to 50,000 is preferable. When the weight average molecular weight exceeds each of the above upper limits, the aqueous solution may not be formed. When the weight average molecular weight does not satisfy the lower limits, the effect of the treatment liquid may be reduced.

  There is no restriction | limiting in particular in the said cationic polymer, What was synthesize | combined suitably may be used and a commercial item may be used. Examples of the synthesis method include a method of polymerizing a monomer containing an amine and an epihalohydrin, a method of graft polymerization of a monomer containing an epihalohydrin on a polyamide obtained by polymerizing a monomer containing an amine and a carboxylic acid, and the like. .

  As content in the said processing liquid of the said cationic polymer, 1 mass%-40 mass% are preferable, and 3 mass%-30 mass% are more preferable. When the content exceeds 40% by mass, the effect of improving the image quality is not changed even if the content is increased, and the viscosity of the processing solution may be excessively increased. On the other hand, when the content is less than 1% by mass, the effect of improving the image quality may be reduced.

-Fluorosurfactant-
The fluorosurfactant is added to lower the surface tension of the treatment liquid.
One of the characteristics required for the treatment liquid is that it can be appropriately wetted with various recording media and can be discharged without unevenness. By making it easy to wet moderately, the penetration speed into various recording media can be increased, and problems such as scratch resistance and bleeding can be improved. When the permeability of the treatment liquid is low, a large amount of the treatment liquid stays near the surface of the recording medium, and when the recording ink containing the colorant comes into contact with the recording ink, the recording ink is caused by an organic acid or the like in the treatment liquid. When the carboxyl group-containing resin containing the colorant is excessively agglomerated, the solid image is insufficiently filled due to the decrease in the dot diameter. Further, when the colorant stays excessively on the surface of the recording medium, problems such as fixing properties also occur. For these reasons, in order to improve wettability, it is common to lower the surface tension by adding a fluorosurfactant. In particular, fluorosurfactants having a fluoroalkyl group are made water-soluble. In this case, it is preferable because it has the ability to greatly reduce the surface tension.
As the fluorosurfactant, a compound represented by the following structural formula is particularly preferable.

  The fluorine-based surfactant represented by the structural formula does not contain PFOS (perfluorooctane sulfonic acid) and PFOA (perfluorooctanoic acid), and is excellent from the viewpoint of global environmental pollution.

-Foam suppressant-
The surface active ability of the fluorine-based surfactant represented by the above structural formula is very high, and even if a commonly used silicone antifoaming agent is added, once the bubbles are generated, the bubbles disappear. Will remain. As a result, ejection failure may occur when ejection is performed by the ejection head. Therefore, N-octyl-2-pyrrolidone, 2,4,7,9-tetramethyldecane-4,7-diol, and 2,5,8,11-tetra are used to suppress the generation of bubbles in the treatment liquid. It is preferable to add at least one selected from methyldodecane-5,8-diol. By using the antifoaming agent and the fluorosurfactant in combination, the generation of bubbles can be suppressed, and problems caused by bubbles can be eliminated.
The surface tension of the treatment liquid is determined by the ratio of the fluorosurfactant and the foam suppressor. If it is necessary to reduce the surface tension of the treatment liquid depending on the type of the recording medium, the surface tension of the fluorosurfactant It is necessary to increase the content. However, since there is a problem of foaming when the content of the fluorosurfactant is increased, the content of the fluorosurfactant is based on the total content of the fluorosurfactant and the foam suppressor. 40 mass% or less is preferable, and 30 mass% or less is more preferable.

-Organic solvent-
Examples of the organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, Etc. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyhydric alcohols include glycerin, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, Ethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, hexylene glycol, trimethylolethane, trimethylolpropane, 1,2,3-butanetriol, 1,2,4 -Butanetriol, 1,2,6-hexanetriol, petriol, and the like.
Examples of the polyhydric alcohol alkyl ethers include 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 ether, and the like. Can be mentioned.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, and the like.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, and the like.
Among these, glycerin and 1,3-butanediol are particularly preferable. These have excellent effects on solubility and prevention of jetting property defects due to water evaporation. In addition, a treatment liquid having excellent storage stability and discharge stability can be produced.
1 mass%-40 mass% are preferable with respect to the said process liquid, and, as for content of the said organic solvent, 5 mass%-30 mass% are more preferable.

-Water-
Examples of the water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, or ultrapure water.
There is no restriction | limiting in particular as content in the said process liquid of the said water, Although it can select suitably according to the objective, 60 mass parts or less are preferable with respect to 100 mass parts of said process liquid, 30 mass parts- 50 parts by mass is more preferable. When the water content exceeds 60 parts by mass, the viscosity of the treatment liquid increases due to the evaporation of water during application of the treatment liquid to a recording medium or during the standing period of the treatment liquid application means. Or gelation may occur, or insoluble matter may precipitate.

<< Other ingredients >>
There is no restriction | limiting in particular as said other component, It can select suitably as needed, For example, a pH adjuster, an antibacterial agent, a chelating reagent, a rust inhibitor, antioxidant, a ultraviolet absorber, an oxygen absorber , Light stabilizers, and the like.

-PH adjuster-
The treatment solution containing an organic acid compound has an acidic pH of around 4. If it is used as it is, corrosion of the metal member proceeds, and various problems may occur if it is used for a long time. Therefore, you may add a pH adjuster according to a condition.
Examples of the pH adjuster include 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and the like. Although the addition amount of the pH adjuster depends on the pH of the organic acid compound to be added, it is preferable to adjust appropriately so that the pH of the entire treatment liquid becomes 4-8.

  Examples of the antibacterial agent include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol, and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

  The treatment liquid is prepared by dispersing or dissolving a hyaluronic acid compound, a cationic polymer, an organic solvent, a fluorosurfactant, a foam inhibitor, and other components in water as necessary, and stirring and mixing as necessary. To manufacture. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, and the like. It can be carried out.

  There is no restriction | limiting in particular as a physical property of the said processing liquid, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, pH, etc. are the following ranges.

The viscosity of the treatment liquid at 25 ° C. is preferably 0.5 mPa · s to 20 mPa · s.
Here, the said viscosity can be measured at 25 degreeC, for example using a viscometer (RE-550L, Toki Sangyo Co., Ltd. make).
The surface tension of the treatment liquid is preferably 40 mN / m or less, more preferably 35 mN / m or less at 25 ° C.
As pH of the said processing liquid, 4-10 are preferable, for example.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes a treatment liquid application step and a recording ink application step, and further includes other steps as necessary.
The image forming apparatus used in the present invention includes a treatment liquid application unit and a recording ink application unit, and further includes other units as necessary.
In the present invention, the treatment liquid can be applied by the treatment liquid application means either before or after the image formation by the recording ink application means, but storage stability, curl resistance, and It is preferable to apply the treatment liquid before the image formation by the recording ink applying means from the viewpoint that it can have scratch resistance.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus used in the present invention, the treatment liquid application step can be performed by the treatment liquid application means, and the recording ink application step is performed by the method described above. It can be performed by a recording ink applying means, and the other steps can be performed by the other means.

<Processing liquid application process and processing liquid application means>
The treatment liquid application step is a step of applying the treatment liquid of the present invention onto a recording medium, and is performed by the treatment liquid application unit.

As a method for applying the treatment liquid to the recording medium, for example, either a liquid discharge method or a coating method is preferable.
The liquid discharge method is not particularly limited and can be appropriately selected according to the purpose. The drive method of the discharge head is a piezoelectric element actuator using PZT or the like, a method of applying thermal energy, an electrostatic force. An on-demand type head using an actuator or the like that is used can be used, or a continuous ejection type charge control type head can be used.

  Examples of the coating method include blade coating, gravure coating, gravure offset coating, wire bar coating, bar coating, roller coating, knife coating, air knife coating, comma coating, and U comma coating. , AKKU coating method, smoothing coating method, micro gravure coating method, reverse roller coating method, 4 to 5 roller coating method, dip coating method, curtain coating method, slide coating method, die coating method and the like. Among these, a wire bar coating method and a roller coating method are particularly preferable.

The pretreatment step is effective even when performed on a recording medium whose surface is sufficiently dried or on a recording medium which has been image-formed and is being dried. In addition, a drying process can be provided as needed with respect to the recording medium which performed the pre-processing process. In this case, the recording medium can be dried with a roll heater, a drum heater, or hot air.
Adhesion amount of the recording medium of the processing solution in the pretreatment step is ^{preferably 0.1g / m 2 ~30.0g / m 2} , 0.2g / m 2 ~10.0g / m 2 is more preferable. When the adhesion amount is less than 0.1 g / m ² , the improvement in image quality may be hardly observed. When the adhesion amount exceeds 30.0 g / m ² , the drying property of the processing solution is deteriorated, and the curling is further reduced. May occur.

<Recording ink application step and recording ink application means>
The recording ink applying step is a step of applying a recording ink containing a colorant, an organic solvent, a fluorosurfactant, a foam suppressor, and water onto a recording medium, and the recording ink applying unit Is done.

<< Recording ink >>
The recording ink contains a colorant, an organic solvent, a fluorosurfactant, and water, and contains a carboxyl group-containing resin, a foam inhibitor, and other components as necessary.

-Colorant-
The colorant is used to color the recording ink and improve the image density, and is not particularly limited, and can be appropriately selected from known pigments and dyes according to the purpose. Pigments are preferred.

  The pigment may be either an inorganic pigment or an organic pigment, and may be used alone or in combination of two or more. In addition, although you may contain dye simultaneously for the purpose of color tone adjustment, it is possible to use within the range which does not degrade a weather resistance.

  Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Among these, carbon black is particularly preferable. In addition, as said carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, and a thermal method, is mentioned, for example.

  Examples of the organic pigment include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable. Examples of the azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments. Examples of the polycyclic pigment include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinofullerone pigments. Examples of the dye chelates include basic dye chelates and acidic dye chelates.

There is no restriction | limiting in particular as a color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black color include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), oxidation, and the like. Examples thereof include metals such as titanium, organic pigments such as aniline black (CI pigment black 1), and the like.

  Examples of the color are 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 , 408, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant 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; I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like.

As the colorant, it is preferable to use a polymer emulsion in which a pigment is contained in polymer fine particles.
The polymer emulsion in which a pigment is contained in the polymer fine particle is one in which a pigment is enclosed in the polymer fine particle, or a pigment adsorbed on the surface of the polymer fine particle. In this case, it is not necessary for all the pigments to be encapsulated or adsorbed, and the pigments may be dispersed in the emulsion as long as the effects of the present invention are not impaired.
Examples of the polymer that forms the polymer emulsion (polymer in the polymer fine particles) include vinyl polymers, polyester polymers, polyurethane polymers, and the like. Among these, vinyl polymers and polyester polymers are preferable, and polymers disclosed in JP 2000-53897 A and JP 2001-139849 A can be used.

Colorant particles obtained by coating inorganic particles with an organic pigment or carbon black may also be used.
Examples of the method for coating the inorganic particles with carbon black include a submerged drying method by coagulation and precipitation, and a dry mixing method in which mechanical force is applied while mixing. Examples of the method of coating the inorganic particles with an organic pigment include a method of depositing the organic pigment in the presence of the inorganic particles and a method of mechanically mixing and grinding the inorganic particles and the organic pigment. In this case, for example, when coating with an organic pigment having excellent thermal stability, a chemical vapor deposition technique can be used. Further, if necessary, if an organosilane compound layer formed from polysiloxane and alkylsilane is provided between the inorganic particles and the organic pigment, the adhesion between them can be improved.

Examples of the inorganic particles include titanium dioxide, silica, alumina, iron oxide, iron hydroxide, and tin oxide. The inorganic particles preferably have a small aspect ratio, and are particularly preferably spherical. Moreover, when adsorbing a color colorant on the surface of the inorganic particles, the inorganic particles are preferably colorless and transparent or white, but when adsorbing a black colorant, black inorganic particles are used. It doesn't matter.
The primary particle diameter of the inorganic particles is preferably 100 nm or less, and more preferably 5 nm to 50 nm.

Examples of the organic pigment covering the inorganic particles include black pigments such as carbon black and aniline black. Examples of color pigments include anthraquinone, phthalocyanine blue, phthalocyanine green, diazo, monoazo, pyranthrone, perylene, heterocyclic yellow, quinacridone, and (thio) indigoid.
Among these, phthalocyanine pigments, quinacridone pigments, monoazo yellow pigments, diazo yellow pigments, and heterocyclic yellow pigments are particularly preferable from the viewpoint of color developability.
Examples of the phthalocyanine pigment include copper phthalocyanine blue or a derivative thereof (CI pigment blue 15: 3, CI pigment blue 15: 4), aluminum phthalocyanine, and the like.
Examples of the quinacridone pigment include C.I. I. Pigment orange 48, C.I. I. Pigment orange 49, C.I. I. Pigment red 122, C.I. I. Pigment red 192, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment violet 19, C.I. I. Pigment violet 42, and the like.
Examples of the monoazo yellow pigment include C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 151, and the like.
Examples of the diazo yellow pigment include C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, and the like.
Examples of the heterocyclic yellow pigment include C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 138, and the like.

The mass ratio between the inorganic particles and the organic pigment or carbon black (inorganic particles: colorant) as the colorant is preferably 3: 1 to 1: 3, and more preferably 3: 2 to 1: 2. If the ratio of the colorant is too small, color developability and coloring power may be lowered. If the ratio of the colorant is too large, transparency and color tone may be deteriorated.
As the colorant particles obtained by coating the inorganic particles with an organic pigment or carbon black, commercially available products can be used. Examples of the commercially available products include silica / carbon black composite materials manufactured by Toda Kogyo Co., Ltd., silica / phthalocyanine. C. I. Pigment Blue 15: 3 composite material, silica / diazo yellow composite material, silica / quinacridone C.I. I. Pigment red 122 composite material, and the like.
For example, when inorganic particles having a primary particle size of 20 nm are coated with an equal amount of organic pigment, the primary particle size is about 25 nm. Therefore, if it can be dispersed in the form of primary particles using an appropriate dispersant, a very fine pigment-dispersed ink having a dispersed particle diameter of 25 nm can be produced.
The primary particle diameter of the colorant particles is preferably 5 nm to 100 nm, and more preferably 30 nm to 80 nm in the recording ink. When the primary particle size is less than 5 nm, the recording ink may be thickened or the colorant particles may be aggregated during long-term storage. When the primary particle size exceeds 100 nm, the recording ink may be used for recording paper, film, or the like. When printing on a medium, there may be a printed matter in which the saturation and lightness of the printing portion are reduced. The primary particle size of the colorant particles means the smallest unit of colorant particles that cannot be finely pulverized by mechanical shearing.

  The content of the colorant in the recording ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 20% by mass, and more preferably 2% by mass to 15% by mass. .

-Organic solvent-
The recording ink uses water as a solvent, but an organic solvent is used for the purpose of preventing the recording ink from drying and improving dispersion stability.
Examples of the organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, Etc. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyhydric alcohols include glycerin, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, Ethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, hexylene glycol, trimethylolethane, trimethylolpropane, 1,2,3-butanetriol, 1,2,4 -Butanetriol, 1,2,6-hexanetriol, petriol, and the like.
Examples of the polyhydric alcohol alkyl ethers include 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 ether, and the like. Can be mentioned.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactam, Etc.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, and the like.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, and the like.
Among these, glycerin and 1,3-butanediol are particularly preferable. These have excellent effects on solubility and prevention of jetting property defects due to water evaporation. In addition, a recording ink excellent in storage stability and ejection stability can be produced.

In addition to the organic solvent, the recording ink may be used in combination with a saccharide or a derivative thereof as necessary.
The saccharide is mainly used for improving the drying resistance, and examples thereof include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides and derivatives thereof. Specific examples include glucose, mannose, fructose, ribose, xylose, trehalose, and manntotriose. Here, the polysaccharide means a saccharide in a broad sense and includes substances widely present in nature such as α-cyclodextrin and cellulose.
Examples of the saccharide derivatives include reducing saccharides and oxidized saccharides of the saccharides. Among these, a sugar alcohol is preferable, and examples of the sugar alcohol include maltitol and sorbit.
The content of the organic solvent is preferably 1% by mass to 40% by mass and more preferably 5% by mass to 30% by mass with respect to the recording ink.

-Fluorosurfactant-
The fluorine-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate compounds, and perfluoroalkyl surfactant compounds. Examples thereof include a fluoroalkylethylene oxide adduct and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain. These may be used individually by 1 type and may use 2 or more types together.

Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like.
Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acid and perfluoroalkyl carboxylate.
Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate esters, perfluoroalkyl phosphate salts, and the like.
Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include, for example, 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. And salts of polyoxyalkylene ether polymers possessed by
Examples of the counter ion of the salt in the fluorosurfactant include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ and the like.

There is no restriction | limiting in particular as said fluorine-type surfactant, You may use what was synthesize | combined suitably or may use a commercial item. As said commercial item, Asahi Glass Co., Ltd. Surflon series (S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145), Full Lard Series (FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431) manufactured by Sumitomo 3M Limited, MegaFac manufactured by DIC Corporation Series (F-470, F-1405, F-474), Dupont Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Neos FT- 110, FT-250, FT-252, FT-400S, FT-150, FT-400SW, OM-nova PF-151N, etc. The
Among these, the fluorine-type surfactant represented by the following general formula is preferable.
However, in said general formula, n shows the integer of 2-6 and a shows the integer of 15-50. Y is —C _b H _{2b + 1} (where b represents an integer of 11 to 19), or CH ₂ CH (OH) CH ₂ —C _m F _{2m + 1} (where m represents an integer of 2 to 6). Represents.

Examples of the fluorine-based surfactant include compounds represented by the following structural formulas.

Among these, the fluorine-type surfactant represented by the following structural formula is especially preferable.

  The fluorosurfactant represented by the structural formula does not contain PFOS (perfluorooctane sulfonic acid) and PFOA (perfluorooctanoic acid), and is excellent from the viewpoint of global environmental pollution. ing.

  The content of the fluorosurfactant in the recording ink is preferably 0.01% by mass to 4% by mass, and more preferably 0.1% by mass to 1% by mass. When the content is less than 0.01% by mass, the effect of adding the fluorosurfactant may be lost. When the content exceeds 4% by mass, the permeability to the recording medium becomes higher than necessary. There may be a case where image density is lowered and show-through occurs.

  In addition to the fluorine-based surfactant, the recording ink may contain other surfactant. Examples of the other surfactants include silicone surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants.

There is no restriction | limiting in particular as said silicone type surfactant, According to the objective, it can select suitably. Among these, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, and side chain both terminal modified polydimethylsiloxane. Those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a group are particularly preferred because they exhibit good properties as an aqueous surfactant.
As said silicone type surfactant, what was synthesize | combined suitably may be used, or a commercial item may be used. As said commercial item, things, such as Big Chemie, Shin-Etsu Silicone Co., Ltd., Toray Dow Corning Silicone Co., Ltd., can be obtained easily.
As the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
As said polyether modified silicone compound, what was synthesize | combined suitably may be used, or a commercial item may be used. As a commercial item, Shin-Etsu Chemical Co., Ltd. KF-618, KF-642, KF-643, etc. are mentioned, for example.

Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, succinate sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.
Examples of the nonionic surfactant include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and the like.
Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, , 5-dimethyl-1-hexyn-3-ol, and the like. Examples of commercially available acetylene glycol surfactants include Surfynol series (104, 82, 465, 485, TG) manufactured by Air Products.

Examples of amphoteric surfactants include lauryl amino pyropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, stearyl dimethyl amine oxide, dihydroethyl lauryl amine oxide, Polyoxyethylene coconut oil alkyldimethylamine oxide, dimethylalkyl (coconut) betaine, dimethyl lauryl betaine and the like can be mentioned. Examples of commercially available amphoteric surfactants include Nikko Chemicals Co., Ltd., Nippon Emulsion Co., Ltd., Nippon Shokubai Co., Ltd., Toho Chemical Co., Ltd., Kao Co., Ltd., Adeka Co., Ltd., Lion Co., Ltd., Aoki Oil & Fat Co., Ltd. Products such as Sanyo Chemical Co., Ltd. can be easily obtained.
The various surfactants may be used alone or in combination. Even if it is not easily dissolved in the recording ink alone, it may be solubilized by mixing a plurality of the inks and can exist stably.

-Foam suppressant-
The surface active ability of the fluorosurfactant is very high, and even if a commonly used silicone antifoaming agent is added, the generated bubbles remain without disappearing. As a result, ejection failure may occur when ejecting ink. Accordingly, N-octyl-2-pyrrolidone, 2,4,7,9-tetramethyldecane-4,7-diol, and 2,5,8,11- are used to suppress the generation of bubbles in the recording ink. At least one selected from tetramethyldodecane-5,8-diol is added. By using the antifoaming agent and the fluorosurfactant in combination, the generation of bubbles can be suppressed, and problems caused by bubbles can be eliminated.
The surface tension of the recording ink is determined by the ratio of the fluorosurfactant and the antifoaming agent. When the surface tension of the recording ink needs to be lowered depending on the type of the recording medium, the fluorosurfactant is used. It is necessary to increase the ratio of the agent. However, since the problem of foaming occurs when the ratio of the fluorosurfactant is increased, the content of the fluorosurfactant is relative to the total content of the fluorosurfactant and the foam suppressor. 40 mass% or less is preferable, and 30 mass% or less is more preferable.

-Carboxyl group-containing resin-
The recording ink preferably contains a carboxyl group-containing resin. As a result, the organic acid compound in the treatment liquid and the carboxyl group-containing resin in the recording ink react to cause aggregation of the pigment as a colorant on the recording medium, so that high image quality is achieved. Can do. In addition, by including the carboxyl group-containing resin, an effect such as improvement of scratch resistance can be expected.
The carboxyl group-containing resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include maleic acid resin, styrene-maleic acid resin, rosin-modified maleic acid resin, alkyd resin, and modified alkyd resin. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

As the carboxyl group-containing resin, commercially available products can be used. Examples of the commercially available products include Marquide series manufactured by Arakawa Chemical Co., Ltd., Harimac series manufactured by Harima Chemical Co., Ltd. Is mentioned.
The addition form of the carboxyl group-containing resin may be added in a form in which the pigment as the colorant is included (microencapsulated) with the carboxyl group-containing resin, or the colorant is dispersed with the carboxyl group-containing resin. Form may be sufficient.
The content of the carboxyl group-containing resin in the recording ink is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass.

-Water-
Examples of the water include ion exchange water, ultrafiltration water, reverse osmosis water, pure water such as distilled water, or ultrapure water.
There is no restriction | limiting in particular as content in the said recording ink of the said water, Although it can select suitably according to the objective, 60 mass parts or less are preferable with respect to 100 mass parts of said recording inks, 30 masses Part-50 mass parts is more preferable. When the water content exceeds 60 parts by mass, the viscosity of the recording ink is increased by the evaporation of moisture during application of the recording ink to the recording medium or during the standing period of the recording ink application unit. May increase, gelation may occur, or insoluble matter may precipitate.

<< Other ingredients >>
In addition to the above-described components, the recording ink further includes a penetrant, polymer particles, a pH adjuster, an antibacterial agent, a chelating reagent, a rust inhibitor, an antioxidant, an ultraviolet absorber, oxygen, if necessary. An absorber, a light stabilizer, etc. are mentioned.

-Penetration agent-
As the penetrant, a polyol compound or glycol ether compound having 8 to 11 carbon atoms is preferably used. These are partially water-soluble compounds that have the effect of increasing the penetration rate into the recording medium and preventing bleeding, and having a solubility of 0.1% to 4.5% by weight in water at 25 ° C. is there.
Examples of the polyol compound having 8 to 11 carbon atoms include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and 1,2-octanediol. It is done.
Examples of the glycol ether compound include polyhydric alcohol alkyl ether compounds and polyhydric alcohol aryl ether compounds.
Examples of the polyhydric alcohol alkyl ether compound include 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 ether, and the like. Can be mentioned.
Examples of the polyhydric alcohol aryl ether compound include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
The penetrant is a component having a higher boiling point than water and a liquid at 25 ° C., and the content in the recording ink is preferably 0% by mass to 10% by mass, and 0.5% by mass to 5% by mass. % Is more preferable.

-Polymer particles-
As the polymer particles, those having film-forming properties are preferably used. Here, the film-forming property means the property that when the polymer particles are dispersed in water to form an emulsion, a resin film is formed when the water in the aqueous emulsion is evaporated.

When the polymer particles are contained, the polymer particles form a film when the volatile components in the recording ink evaporate, and serve to firmly fix the colorant in the recording ink to the recording medium. impose. Thereby, it is possible to realize an image excellent in scratch resistance and water resistance.
In order to form a film at room temperature, the polymer particles preferably have a minimum film-forming temperature of 30 ° C. or lower, more preferably 10 ° C. or lower. Here, the minimum film-forming temperature is a value obtained when a polymer emulsion obtained by dispersing the polymer particles in water is thinly cast on a metal plate such as aluminum and the temperature is increased. It means the lowest temperature at which a continuous film is formed. Examples of the polymer particles include Randy PL series manufactured by Miyoshi Oil & Fat Co., Ltd.
The volume average particle diameter of the polymer particles is preferably 5 nm to 200 nm, and more preferably 10 nm to 100 nm.
As the polymer particles, those having a single particle structure can be used. For example, when an alkoxysilyl group is contained in the emulsion particles, it comes into contact with water remaining due to fusion of the emulsions due to water evaporation during the coating film formation process, and hydrolyzes to form silanol groups. Moreover, when silanol groups remain, alkoxysilyl groups or silanols react with each other to form a strong cross-linked structure with siloxane bonds. When reactive functional groups coexist in the polymer fine particles in this way, a network structure can be formed by reacting these functional groups during film formation without adding a curing agent.
It is also possible to use polymer particles having a core-shell structure comprising a core part and a shell part surrounding the core part. The core-shell structure here means a form in which two or more kinds of polymers having different compositions are present in phase separation in the particles. Therefore, not only the form in which the shell part completely covers the core part, but also a part of the core part may be covered. Further, a part of the polymer of the shell part may form a domain or the like in the core particle. Further, it may have a multilayer structure of three or more layers including one or more layers having different compositions between the core portion and the shell portion.

The polymer particles can be obtained by a known method such as emulsion polymerization of an unsaturated vinyl monomer (unsaturated vinyl polymer) in water containing a polymerization catalyst and an emulsifier.
The content of the polymer particles in the recording ink is preferably 0.5% by mass to 20% by mass, and more preferably 1% by mass to 5% by mass. When the content is less than 0.5% by mass, the scratch resistance and water resistance improvement function may not be sufficiently exhibited. When the content exceeds 20% by mass, the viscosity increases due to drying, and the polymer particles are fixed. Problems such as ejection failure may occur.

-PH adjuster-
Colorant particles (composite pigment particles) obtained by coating the inorganic particles with an organic pigment or carbon black have a strong tendency to show acidity when kneaded and dispersed in water together with an anionic dispersant. The surface of the composite pigment dispersed in a medium such as water is negatively charged because it is encapsulated in an anionic dispersant, but since the entire recording ink is acidic, the inside has a positive charge. It is in a state in which the negative charge on the particle surface is easily neutralized. In this state, the dispersed particles agglomerate and cause discharge failure. Therefore, it is preferable to stabilize the dispersion state by adding the pH adjusting agent to keep it alkaline and to stabilize discharge.
The pH of the recording ink is preferably 9-11. When the pH exceeds 11, the amount of the material for dissolving the ink supply unit or the like becomes large, and problems such as deterioration or leakage of the recording ink, defective discharge, etc. occur.
The pH adjusting agent is preferably added to the kneaded dispersion together with additives such as a wetting agent and a penetrating agent, rather than being added when the pigment is kneaded and dispersed in water together with the dispersant. This is because depending on the pH adjusting agent, dispersion may be destroyed by addition.
Examples of the pH adjuster include alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like.
Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

  Examples of the antibacterial agent include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol, and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

  The recording ink is produced by dispersing or dissolving an organic solvent, a colorant, a surfactant, and water, preferably a carboxy group-containing resin, and other components in water, and further stirring and mixing as necessary. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, and the like. Can be done.

  The physical properties of the recording 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 recording ink at 25 ° C. is preferably 5 mPa · s to 25 mPa · s. By setting the ink viscosity to 5 mPa · s or more, the effect of improving the printing density and the character quality can be obtained. On the other hand, by suppressing the ink viscosity to 25 mPa · s or less, it is possible to ensure dischargeability.
Here, the said viscosity can be measured at 25 degreeC, for example using a viscometer (RE-550L, Toki Sangyo Co., Ltd. make).
The surface tension of the recording ink is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25 ° C. When the surface tension exceeds 35 mN / m, leveling of the recording ink on the recording medium is difficult to occur, and the drying time may be prolonged.
The pH of the recording ink is preferably 7 to 12, for example, and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the recording ink.

  There is no restriction | limiting in particular as coloring of the said recording ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black, etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

<< Recording medium >>
The recording medium is not particularly limited and can be appropriately selected according to the purpose. For example, plain paper, glossy paper, special paper, cloth, film, OHP sheet, general-purpose printing paper, etc. can be suitably used. It is.

<Ink cartridge>
Each of the cartridges filled with the processing liquid or the recording ink is accommodated in a container, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, an ink bag formed of a plastic container, an aluminum laminate film, or the like can be used. And the like.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 5 is a diagram showing an example of the ink cartridge used in the present invention, and FIG. 6 is a diagram including a case (exterior) of the ink cartridge of FIG.
As shown in FIG. 5, the recording ink is filled into the ink bag 241 from the ink inlet 242 and exhausted, and then the ink inlet 242 is closed by fusion. In use, the recording ink is supplied to the apparatus by inserting a needle of the apparatus main body into the ink discharge port 243 made of a rubber member. The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 6, the ink bag 241 is usually accommodated in a cartridge case 244 made of plastic, and is used as an ink cartridge 240 that is detachably attached to various image forming apparatuses.
Further, if the processing liquid is put in the ink cartridge 240 instead of the recording ink and used as a cartridge for the processing liquid, it can be detachably mounted on various image forming apparatuses in the same manner as the ink cartridge. it can.

Here, FIG. 1 shows a schematic diagram (side view) of an example of an image forming apparatus used in the present invention.
The image forming apparatus 101 includes head units 110K, 110C, 110M, and 110Y that have integrated recording ink ejection heads, and maintenance units 111K, 111C, and 111M that perform head maintenance corresponding to the head units. 111Y, ink cartridges 107K, 107C, 107M, 107Y for supplying ink, and sub ink tanks 108K, 108C, 108M, 108Y for storing a part of the recording ink from the cartridge and supplying ink to the head with an appropriate pressure ing.

  Further, a conveyance belt 113 that sucks and conveys the recording medium 114 by the suction fan 120, conveyance rollers 119 and 121 that support the conveyance belt 113, a tension roller 115 that controls the conveyance belt 113 to maintain an appropriate tension, and a conveyance belt 113 are provided. A platen 124 and a platen roller 118 for maintaining appropriate flatness, a charging roller 116 for applying electrostatic charge for attracting the recording medium 114, a discharge roller 117 for pressing the recording medium 114, and a discharged recording medium 114 are stocked. A paper discharge mechanism comprising a paper discharge tray 104, a paper feed tray 103 for stocking the recording medium 114 to be printed, separation pads 112 and 122 for feeding the recording medium 114 one by one from the paper feed tray, and the recording sent A counter row that securely adsorbs the medium 114 to the charging belt. 123, and a paper feeding mechanism including a manual feed tray 105 to be used when the paper feed by manual feed.

Further, a waste liquid tank 109 for collecting waste liquid discharged after maintenance and an operation panel 106 capable of operating the apparatus and displaying the apparatus state are also provided.
The nozzle rows of each head unit are arranged so as to be orthogonal to the conveyance direction of the recording medium 114, and form a nozzle row that is longer than the recording area. The recording medium 114 is separated from the sheet feeding tray into one sheet by a separation roller, and is fixed on the conveyance belt by being in close contact with the conveyance belt by a pressure roller, and liquid is applied to the recording medium when passing under the head unit. By ejecting the droplets, patterning can be performed on the recording medium with the droplets at high speed, separated from the conveying belt by the separation claw, and supported by the ejection rollers and the ejection rollers, the recorded matter is placed on the ejection tray. Discharged.
In this image forming apparatus, a coating mechanism is provided as a mechanism for processing the surface of a recording medium with a processing liquid, and a coating method using three rollers is employed. The processing liquid 135 is supplied from the processing liquid storage tank 140 through a path (not shown), is pumped up to the roller surface by the pumping roller 137, and is transferred to the film pressure control roller 138. Subsequently, the processing liquid transferred to the application roller 136 is transferred and applied to the recording medium 114 passing between the application liquid and the counter roller 139 for application.

  The application amount of the processing liquid transferred to the application roller 136 is performed by controlling the nip thickness with the application roller 136. When it is not desired to apply the treatment liquid, the movable blade 134 can be pressed against the application roller 136 so that the treatment liquid does not remain on the application roller 136, and the treatment liquid on the surface of the application roller can be scraped off. Thereby, it is possible to prevent functional troubles such as thickening due to drying caused by the treatment liquid remaining on the application roller 136, adhesion of the application counter roller 139, and application unevenness. In addition, as shown in FIG. 1, one sheet feeding unit is provided at the top and bottom, and the lower sheet feeding unit is used when processing liquid is applied, and the upper sheet feeding unit is used when processing liquid is not applied. You may make it the method of doing.

In addition to the roller application, it is also possible to spray the treatment liquid by a discharge method. For example, a treatment liquid can be filled in a head similar to 110K and ejected onto the recording medium 114 in the same manner as ink, and the ejection amount and ejection position can be controlled with high accuracy and ease. Further, a roller coating method and a spray coating method may be used in combination.
Regardless of which method is used, the treatment liquid can be applied in an arbitrary amount at an arbitrary position.
In addition, the hot air blowing fan 150 heats the recording medium to which the processing liquid and ink are attached, so that the fixing property can be improved by promoting drying. In this example, the heating process is performed on the recording medium after printing with a hot air fan. However, the heating process may be performed on the recording medium before printing or before and after printing. It may be performed not only by a means such as a heating roller.

FIG. 3 is a schematic diagram illustrating an example of a head arrangement in the head unit of the image forming apparatus.
The head unit fixes the heads 154A to 154L to the head outer peripheral member 160, and the heads are fixed in a staggered arrangement so that a part of the nozzles overlap.
FIG. 4 is a schematic diagram showing the heads arranged in the head unit of FIG. 3. Each head is provided with nozzles 200 that are opened in a zigzag arrangement in two rows in the nozzle plate 201. The head outer peripheral member is sealed with a filler 202 to eliminate a gap from the nozzle surface side.

Next, an overview of the control unit of the image forming apparatus shown in FIG. 1 will be described with reference to FIG. FIG. 2 is a schematic block diagram of the control unit.
The control unit 300 includes a CPU 301 that controls the entire apparatus, a program executed by the CPU 301, a nozzle surface contamination degree value for predetermined ink ejection used in the present invention, a nozzle surface contamination allowable threshold, drive waveform data, ROM 302 for storing other fixed data, RAM 303 for temporarily storing image data, a non-volatile memory (NVRAM) 304 for holding data even while the apparatus is powered off, and image data An ASIC 305 for processing various signal processing, image processing for rearrangement, and other input / output signals for controlling the entire apparatus is provided.

  The control unit 300 includes a host I / F 306 for transmitting and receiving data and signals to and from the host side, and a head drive control unit 307 that generates a drive waveform for driving and controlling the pressure generating means of the recording head 154. A recording medium conveyance motor drive control unit 308 for driving the recording medium conveyance motor 309, a maintenance unit movement motor drive control unit 312 for driving the head unit (carriage) movement motor 311, and an electromagnetic valve 315 for the ink path. An ink path valve control unit 314 for controlling the opening / closing of the ink, a cap suction motor 317, a liquid feed suction motor drive control unit 316 for controlling the drive of the ink supply motor 318, and detection according to the moving amount and moving speed of the transport belt 319. An encoder that outputs a signal, a sensor that detects environmental temperature and environmental humidity (whichever is acceptable) Detection signal from 23, the ink amount detection signal of the sub ink tank, and a like I / O 322 for inputting detection signals from various sensors (not shown). An operation panel 106 for inputting and displaying information necessary for the apparatus is connected to the control unit 300.

The control unit 300 receives print data and the like from the host side of an information processing device such as a personal computer, an image reading device such as an image scanner, an imaging device such as a digital camera, and the like via a cable or a network at the host I / F 306. To do.
The CPU 301 reads and analyzes the print data in the reception buffer included in the host I / F 306, performs necessary image processing and data rearrangement in the ASIC 305, and sets the head width of the recording head 154 to 1 Image data (dot pattern data) corresponding to the page is sent to the head drive control unit 307 in synchronization with the clock signal.

Then, the CPU 301 reads and analyzes the print data in the reception buffer included in the host I / F 306, performs necessary image processing, data rearrangement processing, and the like in the ASIC 305, and sends it to the head drive control unit 307. Transfer image data. The generation of dot pattern data for image output may be performed, for example, by storing font data in the ROM 302, or image data is developed into bitmap data by a printer driver on the host side and stored in this apparatus. You may make it forward.
The head drive control unit 307 selectively applies to the pressure generating means of the recording head 154 based on image data (dot pattern data) corresponding to one page of the recording head 154 input in page units. Drive.

Although not shown, when the processing liquid is applied with a roller, it is necessary to control the driving of a coating roller group such as a coating roller, so that a coating motor control unit, a motor to be controlled, and a control sensor are provided. And provide.
Furthermore, when the treatment liquid is ejected, there is a risk of nozzle clogging due to color mixing unless the maintenance operation is different from that for other recording inks. For this reason, it is preferable to provide a maintenance unit moving motor for the treatment liquid in addition to the recording ink.

Here, as a form in which the processing liquid is applied to the recording medium, methods such as FIGS.
FIG. 7 describes an ejection method from the ejection head. A recording head for ejecting the treatment liquid 135 is provided on the upstream side in the transport direction of the recording medium 114, and a recording ink 130 is provided on the downstream side in the transport direction. The processing liquid 135 and the recording ink 130 ejected in advance based on predetermined image data can be mixed on the recording medium 114.
FIG. 8 shows a coating method using three rollers, but since details are shown in FIG. 1, description thereof is omitted here.
FIG. 9 describes an application method using two rollers. The treatment liquid 135 discharged from the discharge head is controlled to a predetermined film thickness by the application roller 401 and the film thickness control roller 402 and applied to the recording medium 114. To do. Further, the excess processing liquid remaining on the application roller 401 is collected by the movable blade 134. Although not shown here, a recording ink ejection head is provided in the lower part of the transport direction in FIG.

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

(Synthesis Example 1)
Methyl ethyl ketone in the reaction vessel of an automatic polymerization reaction device (manufactured by Sakai Sangyo Co., Ltd., polymerization tester DSL-2AS type) having a reaction vessel equipped with a stirring device, a dropping device, a temperature sensor, and a reflux device having a nitrogen introduction device on the top Of the reaction vessel was purged with nitrogen while stirring. The reaction vessel was heated at 80 ° C. while maintaining a nitrogen atmosphere, and then 75.0 g of methacrylic acid-2-hydroxyethyl, 77.0 g of methacrylic acid, 80.0 g of styrene and 150 butyl methacrylate were added by a dropping device. A mixed solution of 0.0 g, 98.0 g of butyl acrylate, 20.0 g of methyl methacrylate, and 40.0 g of “Perbutyl (registered trademark) 0” (manufactured by NOF Corporation) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was further continued at the same temperature for 15 hours, and an anionic group-containing styrene-acrylic copolymer having an acid value of 100 mgKOH / g, a weight average molecular weight of 21,000, and a glass transition temperature Tg (calculated value) of 31 ° C. A methyl ethyl ketone solution of union A was obtained. After completion of the reaction, a part of methyl ethyl ketone was distilled off under reduced pressure to obtain an anionic group-containing styrene-acrylic copolymer A solution having a nonvolatile content adjusted to 50% by mass.

(Preparation Example 1)
In a mixing tank equipped with a jacket for cooling, 1,000 g of carbon black (manufactured by Colombian Carbon Co., Raven 1080), 800 g of the anionic group-containing styrene-acrylic copolymer A solution of Synthesis Example 1 above, water 143 g of an aqueous sodium oxide solution, 100 g of methyl ethyl ketone, and 1,957 g of water were charged and mixed with stirring. The mixed solution is passed through a dispersion device (SC Mill SC100, manufactured by Mitsui Mining Co., Ltd.) filled with zirconia beads having a diameter of 0.3 mm, and dispersed for 6 hours by a circulation method (a method of returning a dispersion station from the dispersion device to the mixing tank). did. The number of revolutions of the dispersing device was 2,700 rpm, and the temperature of the dispersion liquid was kept at 40 ° C. or less through the cooling jacket through cold water. After completion of the dispersion, the dispersion stock solution was extracted from the mixing tank, and then the mixing tank and the dispersion device flow path were washed with 10,000 g of water, and the diluted dispersion liquid was obtained together with the dispersion stock solution. The diluted dispersion was put into a glass distillation apparatus, and the whole amount of methyl ethyl ketone and a part of water were distilled off. After cooling to room temperature, 10 mass% hydrochloric acid was added dropwise with stirring to adjust the pH to 4.5, and the solid content was filtered with a Nutsche filter device (manufactured by Nippon Chemical Machinery Co., Ltd., pressure filter) and washed with water. did. After taking the cake into a container and adding 200 g of a 20% by mass aqueous potassium hydroxide solution, the dispersion is carried out with a disperser (manufactured by Tokushu Kika Kogyo Co., Ltd., TK homodisper), and water is further added to adjust the nonvolatile content. An aqueous pigment dispersion in which composite particles coated with an anionic group-containing styrene-acrylic copolymer obtained by neutralizing carbon black having a nonvolatile content of 20% by mass in potassium hydroxide was dispersed in an aqueous medium was obtained.

(Preparation Example 2)
In Preparation Example 1, except that carbon black was replaced with copper phthalocyanine (SEIKALIGHT BLUE A612, manufactured by Dainichi Seika Co., Ltd.), copper phthalocyanine having a nonvolatile content of 20% by mass in potassium hydroxide was the same as Preparation Example 1. An aqueous pigment dispersion was obtained in which the composite particles coated with the anionic group-containing styrene-acrylic copolymer neutralized with 1 were dispersed in an aqueous medium.

(Synthesis Example 2)
-Synthesis of cationic polymer-
In a 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 657.2 g of water, 58.4 g of triethylenetetramine, and 108 g of 50% by mass dimethylamine were charged. Under the introduction of gas, 192.4 g of epichlorohydrin was appropriately reduced over 1.5 hours so as not to exceed 40 ° C., and then heated to 70 ° C. and kept warm for 1.5 hours. Next, the pH is adjusted to 7.5 with a 30% by mass aqueous sodium hydroxide solution, and the temperature is further maintained at 70 ° C. for 1.5 hours, the pH is adjusted to 3.5 with a 30% by mass sulfuric acid aqueous solution, and the reaction is cooled. Was completed. The obtained reaction product was a cationic polymer having a solid content concentration of 29.9% by mass and a pH of 3.5. The viscosity of the obtained cationic polymer at a solid content concentration of 10% by mass was 20 cps. The obtained cationic polymer of Synthesis Example 2 is a cationic polymer represented by the general formula (A).

(Synthesis Example 3)
-Synthesis of cationic polymer-
In a 500 mL four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 36.8 g of water, 157.6 g (0.8 mol) of 30% by mass trimethylamine aqueous solution, 50% by mass dimethylamine 36.1 g (0.4 mol) of an aqueous solution and 7.3 g (0.1 mol) of diethylamine were charged, and 92.5 g (1.0 mol) of epichlorohydrin was cooled while cooling so as not to exceed 40 ° C. under introduction of nitrogen gas. Mol) was added dropwise over 4 hours. After completion of the dropwise addition, the temperature was raised to 80 ° C. and the reaction was carried out at that temperature for 2 hours. Then, it cooled to 30 degreeC and adjusted the reaction liquid with a sulfuric acid and water, and obtained the cationic polymer of pH3.9 and solid content concentration 50 mass%. The obtained cationic polymer of Synthesis Example 3 is a cationic polymer represented by the general formula (B).

(Synthesis Example 4)
-Synthesis of cationic polymer-
495 g (4.8 mol) of diethylenetriamine was charged into a 3 liter four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen introduction tube, and 877 g (6.0 mol) of adipic acid was added with stirring. Then, the temperature was raised while removing generated water out of the system, and the mixture was reacted at 150 ° C. for 5 hours, and then 1,000 g of water was gradually added to obtain a polyamide polyamine-containing liquid. The polyamide polyamine-containing liquid had a solid content of 52.1% by mass, and the viscosity at 25 ° C. when the solid content was 50% by mass was 380 mPa · s. 100 g of the polyamidopolyamine-containing liquid obtained above (0.214 mol as an amino group), 3.8 g (30 equivalent%) of acetic acid and 4.3 g (15 equivalent%) of a 30% by mass aqueous sodium hydroxide solution were charged with water 6 0.7 g was added to adjust the solid content to 50% by mass. Next, 19.8 g (100 equivalent%) of epichlorohydrin was added dropwise at 30 ° C. over 1 hour, and held at the same temperature for 1 hour, and 0.8 g (2 equivalent%) of sodium metabisulfite was added, It was held at the same temperature for 5 hours after the start of epichlorohydrin addition. Next, 1.1 g (10 equivalent%) of 98% sulfuric acid and 127.0 g of water were added to adjust the solid content to 30% by mass, and then heated to 75 ° C. Furthermore, after maintaining at this temperature until the viscosity at 25 ° C. of the reaction solution reached 300 mPa · s, 40.5 g of water was added to make the solid content 26 mass%, and after cooling to 25 ° C. or lower, 30% The pH was adjusted to 3.5 with sulfuric acid, and then adjusted to pH 3.0 with 88% by mass formic acid to obtain a cationic polymer having a solid content concentration of 25.0% by mass. The viscosity of the obtained cationic polymer at a solid content concentration of 15% by mass was 51.6 mPa · s.
The obtained cationic polymer of Synthesis Example 4 is composed of an amine monomer (diethylenetriamine), a monomer represented by the structural formula (C) (adipic acid), and a monomer represented by the general formula (D) (epichloromethane). Hydrin).

(Examples 1-23 and Comparative Examples 1-8)
<Manufacture of recording ink>
First, the carboxyl group-containing resin, organic solvent, fluorosurfactant, penetrant, pH adjuster, antibacterial agent, and water shown in Table 1 below were stirred for 1 hour and mixed uniformly.
Next, the foam suppressor shown in the following Table 1 was added, and the mixture was further stirred for 1 hour and mixed uniformly. Thereafter, the aqueous pigment dispersions of Preparation Examples 1 and 2 shown in Table 1 below were added, and the mixture was further stirred for 1 hour and mixed uniformly. This mixture was subjected to pressure filtration through a polyvinylidene fluoride membrane filter having an average pore size of 0.8 μm to remove coarse particles and dust, and recording inks of Examples 1 to 23 and Comparative Examples 1 to 8 were produced.
In each recording ink, the colorant is added in such a ratio that the solid content of the aqueous pigment dispersions of Preparation Examples 1 and 2 is 8% by mass.

<Manufacture of treatment liquid>
Materials such as the cationic polymers and hyaluronic acid compounds of Synthesis Examples 2 to 4 shown in Table 1 below were stirred for 1 hour and mixed uniformly. This mixture was subjected to pressure filtration through a polyvinylidene fluoride membrane filter having an average pore diameter of 0.8 μm to remove coarse particles and dust, and treatment liquids of Examples 1 to 23 and Comparative Examples 1 to 8 were obtained.

<Application of treatment liquid>
Next, about 100 mg of the prepared treatment liquid of each of the above Examples and Comparative Examples was recorded on a recording medium (Ricoh Co., Ltd., My Co., Ltd.) using a wire bar (coil diameter: 0.02 mm) manufactured by Kobayashi Manufacturing Co., Ltd. (Paper, A4 size) was uniformly applied and dried.

<Applying recording ink>
Next, by using an image forming apparatus (Ricoh Co., Ltd., IPSIO GX5000), each recording ink was ejected at a printing speed of 30 rpm onto a recording medium to which the treatment liquid was applied to obtain a printing sample.
Next, various characteristics of the print sample, the recording ink, and the treatment liquid were evaluated as follows. The results are shown in Table 1.

<Image density>
For the print sample, the image density of a solid portion of a 3 cm square solid image formed with a dot pattern was measured with a spectrocolorimetric densitometer (type 939) manufactured by X-Rite. The larger the image density value, the better.

<Transfer density (fixability, scratch resistance)>
Using a friction tester (trade name: Clock Meter CM-1, manufactured by Toyo Seiki Seisakusho Co., Ltd.), a white cotton cloth with a load of 900 g is used for the solid portion of a solid image of 3 cm square formed with a dot pattern. Five reciprocating rubs were performed, and the transfer density of the recording ink onto the white cotton cloth after the five reciprocating rubs was measured with a spectrocolorimetric densitometer (939 type) manufactured by X-Rite. The smaller the transfer density, the better the image fixability (abrasion resistance).

<Curl evaluation>
For the print sample, a solid image of 10 cm × 15 cm was printed at the leading end of the image, and the curl amount after 10 seconds from the print was placed gently on a flat desk with the curled surface up, and 4 of the A4 size recording medium. The height of the corner was measured on a JIS class 1 scale, and the four-point measurement values were averaged to determine the curl amount. Note that the allowable range is a curl amount of 50 mm or less.

<Bubbling property>
10 mL each of the recording ink and the treatment liquid was put into a 100 mL measuring cylinder and allowed to stand overnight. Thereafter, the graduated cylinder was placed in a 10 ° C. constant temperature water bath for 30 minutes or more to adjust the liquid temperature. When the liquid temperature was sufficiently accustomed, air was blown into a predetermined syringe and bubbled to a height of 100 mL. Thereafter, the foam height after 30 seconds was measured. In addition, the bubble height of 50 mL or less is an allowable range.

<Storage stability>
20 mL each of the recording ink and the treatment liquid are placed in a glass bottle, left in a thermostat at 70 ° C. for 2 weeks, and the difference between the initial viscosity and the viscosity after storage for 2 weeks (viscosity increase level) is measured, The evaluation was divided into the following three stages. In addition, the measurement of the viscosity was performed at 25 degreeC using the viscometer (A & D company make, SV-10).
〔Evaluation criteria〕
◯: No increase in viscosity is observed in both the recording ink and the treatment liquid (viscosity change rate from initial viscosity is less than 1%)
Δ: Slight increase in viscosity is observed in both the recording ink and the treatment liquid (viscosity change rate from initial viscosity is 1% or more and less than 5%)
X: A marked increase in viscosity is observed in both the recording ink and the treatment liquid (viscosity change rate from initial viscosity is 5% or more)

In Table 1, abbreviations and the like represent the following contents.
* Carboxyl group-containing resin: rosin-modified maleic resin (Harima Chemical Co., Ltd., Harimac 145P)
* Fluorosurfactant: Fluorosurfactant (active ingredient: 40% by mass, manufactured by Dupont, Zonyl FS-300)
* Fluorosurfactant: Fluorosurfactant of the following structural formula (i) <Structural formula (i)>
* Antifoaming agent: KM-72F (Self-emulsifying type silicone antifoaming agent, manufactured by Shin-Etsu Silicone Co., Ltd., 100% by mass)
* Antibacterial agent: LV (S) (Proxel LV, antiseptic and antifungal agent, manufactured by Avecia)
* Hyaluronic acid compound: Sodium hyaluronate (manufactured by Shiseido Co., Ltd., 1% by weight aqueous solution of sodium biohyaluronate, (MP-PE) N, weight average molecular weight: about several millions)
* Hyaluronic acid compound: sodium acetylated hyaluronate (manufactured by Shiseido Co., Ltd., 1% by weight aqueous solution of sodium acetylated hyaluronate, weight average molecular weight: about several million)

The aspect of the present invention is as follows.
<1> A treatment liquid comprising a hyaluronic acid compound, an organic acid compound, a cationic polymer, an organic solvent, a fluorosurfactant, and water.
<2> The treatment liquid according to <1>, wherein the hyaluronic acid compound is acetylated sodium hyaluronate.
<3> The treatment liquid according to any one of <1> to <2>, wherein a content of the hyaluronic acid compound in the treatment liquid is 1.0% by mass to 5.0% by mass.
<4> The treatment liquid according to any one of <1> to <3>, wherein the organic acid compound is lactic acid or ammonium lactate.
<5> The cationic polymer is a copolymer represented by the following general formula (A), a copolymer containing a repeating unit represented by the following general formula (B), an amine monomer, and the following structural formula (C ) And at least one selected from a copolymer obtained by polymerizing a monomer represented by the following general formula (D): <1> to <4> It is a processing liquid.
<General formula (A)>
However, in said general formula (A), R < ₁ > -R < ₈ > shows either an alkyl group, a hydroxyalkyl group, an alkenyl group, and a benzyl group, X shows a halogen atom. n represents an integer of 1 or 2.
<General formula (B)>
However, in said general formula (B), X shows a halogen atom and m shows an integer greater than or equal to 1.
<Structural formula (C)>
<General formula (D)>
However, in said general formula (D), X shows a halogen atom.
<6> The treatment liquid according to any one of <1> to <5>, wherein the fluorosurfactant is a compound represented by the following structural formula.
<7> A treatment liquid application step of applying the treatment liquid according to any one of <1> to <6> on a recording medium;
A recording ink applying step for applying a recording ink containing a colorant, an organic solvent, a fluorosurfactant, and water on a recording medium;
An image forming method comprising:
<8> The recording ink contains a carboxyl group-containing resin,
The image forming method according to <7>, wherein the fluorosurfactant in the recording ink is a compound represented by the following structural formula.
<9> The treatment liquid and the recording ink contain an antifoaming agent, and the antifoaming agent is N-octyl-2-pyrrolidone, 2,4,7,9-tetramethyldecane-4,7-diol, and The image forming method according to any one of <7> to <8>, wherein the image forming method is at least one selected from 2,5,8,11-tetramethyldodecane-5,8-diol.
<10> The application of the recording ink onto the recording medium is a liquid ejection method,
The image forming method according to any one of <7> to <9>, wherein the treatment liquid is applied to the recording medium by either a liquid ejection method or a coating method.
<11> A treatment liquid application unit that applies the treatment liquid according to any one of <1> to <6> on a recording medium;
A recording ink applying means for applying a recording ink containing a colorant, an organic solvent, a fluorosurfactant, and water on a recording medium;
An image forming apparatus comprising:

DESCRIPTION OF SYMBOLS 101 Image forming apparatus 107K Ink cartridge 107C Ink cartridge 107M Ink cartridge 107Y Ink cartridge 110K Head unit 110C Head unit 110M Head unit 110Y Head unit 114 Recording medium 130 Ink for recording 135 Processing liquid 136 Application roller 240 Ink cartridge

JP 2001-240779 A JP 2010-125816 A

Claims (11)

  A treatment liquid comprising a hyaluronic acid compound, an organic acid compound, a cationic polymer, an organic solvent, a fluorosurfactant, and water.   The treatment liquid according to claim 1, wherein the hyaluronic acid compound is acetylated sodium hyaluronate.   The treatment liquid according to any one of claims 1 to 2, wherein a content of the hyaluronic acid compound in the treatment liquid is 1.0% by mass to 5.0% by mass.   The treatment liquid according to claim 1, wherein the organic acid compound is lactic acid or ammonium lactate. Cationic polymer, according to claim 1 is at least one copolymer represented by the following general formula (A), and which is a copolymer or we choose including a repeating unit represented by the following general formula (B) To 4. The treatment liquid according to any one of 4 to 4.
<General formula (A)>
However, in said general formula (A), R < ₁ > -R < ₈ > shows either an alkyl group, a hydroxyalkyl group, an alkenyl group, and a benzyl group, X shows a halogen atom. n represents an integer of 1 or 2.
<General formula (B)>
However, in said general formula (B), X shows a halogen atom and m shows an integer greater than or equal to 1. The treatment liquid according to claim 1, wherein the fluorosurfactant is a compound represented by the following structural formula.
A treatment liquid application step of applying the treatment liquid according to claim 1 onto a recording medium;
A recording ink applying step for applying a recording ink containing a colorant, an organic solvent, a fluorosurfactant, and water on a recording medium;
An image forming method comprising: The recording ink contains a carboxyl group-containing resin,
The image forming method according to claim 7, wherein the fluorosurfactant in the recording ink is a compound represented by the following structural formula.
  The processing liquid and the recording ink contain an antifoaming agent, and the antifoaming agent includes N-octyl-2-pyrrolidone, 2,4,7,9-tetramethyldecane-4,7-diol, and 2,5. The image forming method according to claim 7, which is at least one selected from 1,8,11-tetramethyldodecane-5,8-diol. Application of the recording ink onto the recording medium is a liquid ejection method,
The image forming method according to claim 7, wherein the treatment liquid is applied to the recording medium by either a liquid discharge method or a coating method. A method for producing a treatment liquid containing a hyaluronic acid compound, an organic acid compound, a cationic polymer, an organic solvent, a fluorosurfactant, and water,
The cationic polymer is a copolymer represented by the following general formula (A), a copolymer containing a repeating unit represented by the following general formula (B), an amine monomer, and the following structural formula (C). A method for producing a treatment liquid, which is at least one selected from a copolymer obtained by polymerizing a monomer represented by the following general formula (D).
<General formula (A)>
However, in the general formula (A), R ₁ ~ R ₈ Represents one of an alkyl group, a hydroxyalkyl group, an alkenyl group, and a benzyl group, and X represents a halogen atom. n represents an integer of 1 or 2.
<General formula (B)>
However, in said general formula (B), X shows a halogen atom and m shows an integer greater than or equal to 1.
<Structural formula (C)>
<General formula (D)>
However, in said general formula (D), X shows a halogen atom.