JP6711146B2 - Image forming set, image forming apparatus, and image forming method - Google Patents

Description

The present invention relates to an image forming set, an image forming apparatus, and an image forming method.

Inkjet printers have been remarkably popular due to their advantages of low noise and low running cost, and color printers capable of printing on plain paper have also been actively introduced to the market. However, image color reproducibility, scratch resistance, durability, light resistance, image dryness, character bleeding (feathering), color boundary bleeding (color bleed), beading, double-sided printability, ejection stability, etc. It is very difficult to satisfy all the required characteristics, and the ink to be used is selected according to the priority characteristics according to the application.

In order to solve such a problem, a recording medium pre-coated with a material for fixing the coloring material in the ink when an image is formed on the surface of the recording medium, or a white pigment or a water-soluble polymer on the surface A recording medium coated with is proposed. However, these proposals are expensive because they need to be subjected to the above-described special processing, and are therefore limited to special applications such as photographic image output and have not been widely spread.
Therefore, in order to correspond to a general recording medium as well, by spraying or applying a treatment liquid having a cohesive property of a coloring material on the recording medium in advance, and jetting the ink to the portion to print, a plain paper or Ink jet recording methods have been proposed that can increase image density and saturation even in coated printing paper.

It is necessary to select the type, amount, and physical property value of the aggregating agent contained in the treatment liquid depending on the polarity of the coloring material in the ink and the dispersion method. For example, when the coloring material pigment is dispersed in an anionic water-soluble resin, the cationic polymer, the cationic fine particles, the organic acid and the polyvalent metal salt exhibit cohesiveness. However, if the agglutination reaction is too fast, the ink droplets may not spread because they agglomerate before they permeate the surface of the recording medium and spread. ) Can be effectively suppressed, but the image density and saturation may be rather low. On the other hand, if the agglutination reaction is too slow, in the case of a recording medium without a surface coating layer such as plain paper, the ink may penetrate into the interior, resulting in poor color development or beading.
Further, if the reactivity of the coagulant contained in the treatment liquid is too strong, the coating member such as the roller for coating the treatment liquid may be deteriorated or rusted. Or a method of extremely lowering the pH is not preferable.
For example, a two-component aqueous ink set for inkjet recording has been proposed in which a first pigment ink containing a resin having at least one of a hydroxy group and a carboxyl group is combined with a second ink containing a vinylamine-based polymer. (For example, see Patent Document 1).

An object of the present invention is to provide an image forming set which has both high image density and saturation, and excellent image quality without occurrence of beading and prevention of corrosion of a coating member by a treatment liquid. ..

An image forming set of the present invention as a means for solving the above problems is an image forming set having a treatment liquid applied to a recording medium and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anionic group and a group containing an aromatic ring, a colorant, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. It is 0 or less.

According to the present invention, it is possible to provide an image forming set which has both high image density and chroma, excellent image quality without beading, and prevention of corrosion of a coating member by a treatment liquid.

FIG. 1 is a diagram showing an example of a recording apparatus using the ink of the present invention. FIG. 2 is a perspective view of a main tank that stores the ink of the present invention. FIG. 3 is a schematic view showing an example of an image forming apparatus having the treatment liquid application mechanism of the present invention. FIG. 4 is a schematic view showing another example of the image forming apparatus having the treatment liquid coating mechanism of the present invention.

(Image forming set)
The image forming set of the present invention is an image forming set having a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a structural unit containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. It is 0 or less.

In the image forming set of the present invention, in the prior art, the acid value of the resin contained in the first ink containing the coloring material is regulated to 1 mgKOH/g or more and 200 mgKOH/g or less. There is no description about the amine value of the ink, and it is based on the finding that it is not possible to achieve both excellent image quality with high image density and saturation and no beading, and prevention of corrosion of coating members by the treatment liquid. It is a thing.

As the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative is higher, the ink can be fixed on the paper surface with a smaller amount of the treatment liquid, but the coating member such as the coating roller is easily corroded. In the corroded portion, uneven coating of the treatment liquid occurs. Therefore, thereafter, image unevenness occurs in the image formed by the ink. Also, if the amine value of the treatment liquid is higher than the acid value of the copolymer in the ink, the dots will be fixed when the ink has landed on the recording surface of the recording medium, and the entire paper surface can be covered with dots. Since it disappears, the image has low image density and saturation. On the other hand, if the treatment liquid has a low amine value, it will not be able to react sufficiently with the copolymer in the ink, and the dots will spread after landing on the recording medium, such as coated paper, that has low absorbency, and adjacent dots Randomly coalescing causes abnormal images such as beading and color bleeding, and for highly absorbent recording media such as plain paper, it penetrates inside the paper and causes color Since the material cannot be fastened, there is a problem that the image density and the saturation become low.
For such a problem, the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative in the treatment liquid and the acid value (mgKOH/g) of the copolymer in the ink are used. By setting the ratio (amine value/acid value) of 1.0 or more to 3.0 or less, the coating member that exhibits excellent performance even for various absorptive recording media and is in contact with the treatment liquid can be obtained. The present inventors have completed the present invention by finding that they do not corrode.

Therefore, in the image forming set of the present invention, the treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a structural unit containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. It is 0 or less, preferably 1.2 or more and 2.7 or less.
The acid value is defined by the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like present in 1 g of oil and fat, and the acid value is measured by a neutralization measuring method and a potentiometric measuring method. There is.
As the amine value, a total amine value indicating the total amount of primary, secondary, and tertiary amines is used, and is defined by mg of hydrochloric acid required to neutralize 1 g of the sample and equivalent potassium hydroxide, and It can be determined by the Japanese titration method.

The image forming set of the present invention has the treatment liquid applied to the recording medium and the ink applied to the recording medium to which the treatment liquid is applied.

<Ink>
The ink contains a copolymer having a structural unit containing an anion group and a structural unit containing a group containing an aromatic ring, a coloring material, an organic solvent, and water, and may further contain other components as necessary. Contains ingredients.

<<Copolymer>>
The copolymer is contained as a dispersant for the coloring material.
The copolymer has a structural unit containing an anion group and a structural unit containing a group containing an aromatic ring, and further contains other structural units as necessary.

Preferable examples of the aromatic ring in the structural unit containing the group containing an aromatic ring include a naphthyl group and a biphenyl group. Of these, a naphthyl group is preferable. When the naphthyl group-containing copolymer is used in the ink, it has an excellent pigment adsorbing power due to the π-π stacking with the pigment that is the coloring material in the ink, so that it is brought into contact with the pigment on the recording medium during printing. As a result, the pigment is quickly aggregated on the surface of the recording medium, and beading (spots) can be prevented.

-Structural unit containing anion group-
The structural unit containing the anionic group is preferably a structural unit represented by the following general formula (3).

However, in the general formula (3), R ₉ represents either a hydrogen atom or a methyl group, and M ⁺ represents either a hydrogen ion or a cation. In the case of the cation, oxygen adjacent to the cation exists as O ⁻ .

In the general formula (3), examples of the M ⁺ cation include sodium ion, potassium ion, lithium ion, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion. , Tetrahexylammonium ion, triethylmethylammonium ion, tributylmethylammonium ion, trioctylmethylammonium ion, 2-hydroxyethyltrimethylammonium ion, tris(2-hydroxyethyl)methylammonium ion, propyltrimethylammonium ion, hexyltrimethylammonium ion , Octyl trimethyl ammonium ion, nonyl trimethyl ammonium ion, decyl trimethyl ammonium ion, dodecyl trimethyl ammonium ion, tetradecyl trimethyl ammonium ion, hexadecyl trimethyl ammonium ion, octadecyl trimethyl ammonium ion, didodecyl dimethyl ammonium ion, ditetradecyl dimethyl ammonium ion , Dihexadecyldimethylammonium ion, dioctadecyldimethylammonium ion, ethylhexadecyldimethylammonium ion, ammonium ion, dimethylammonium ion, trimethylammonium ion, monoethylammonium ion, diethylammonium ion, triethylammonium ion, monoethanolammonium ion, Diethanolammonium ion, triethanolammonium ion, methylethanolammonium ion, methyldiethanolammonium ion, dimethylethanolammonium ion, monopropanolammonium ion, dipropanolammonium ion, tripropanolammonium ion, isopropanolammonium ion, morpholinium ion, N- Examples thereof include methylmorpholinium ion, N-methyl-2-pyrrolidonium ion and 2-pyrrolidonium ion.

Examples of the monomer having the structural unit represented by the general formula (3) include acrylic acid, methacrylic acid, and salts thereof.

Examples of the monomer having a structural unit containing an anion group include, in addition to the above monomers, vinyl sulfonic acid, a compound represented by the following structural formula (d), a compound represented by the following structural formula (e), and the like. Is mentioned.

-Structural unit containing a group containing an aromatic ring-
The structural unit containing a group containing an aromatic ring is preferably any one of the following general formulas (4) and (5).

However, in the general formula (4), R ₁₀ represents either a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms.

However, in the general formula (5), R ₁₁ represents either a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms.

Examples of the monomer composed of any of the structural units represented by the general formula (4) and the general formula (5) include compounds represented by the following structural formulas.

Examples of the monomer having a structural unit containing a group containing an aromatic ring include styrene and compounds represented by the following structural formula (b) in addition to the above monomers.

The copolymer may have a repeating unit derived from another polymerizable monomer in addition to the structural unit represented by the general formula (3) and the general formula (4) or (5).
The other polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polymerizable hydrophobic monomer, a polymerizable hydrophilic monomer, and a polymerizable surfactant. ..

Examples of the polymerizable hydrophobic monomer include unsaturated ethylene monomers having an aromatic ring such as styrene, α-methylstyrene, 4-t-butylstyrene, and 4-chloromethylstyrene; methyl (meth)acrylate; Ethyl (meth)acrylate, -n-butyl (meth)acrylate, dimethyl maleate, dimethyl itaconic acid, dimethyl fumarate, lauryl (meth)acrylate (C12), tridecyl (meth)acrylate (C13), ( Tetradecyl (meth)acrylate (C14), pentadecyl (meth)acrylate (C15), hexadecyl (meth)acrylate (C16), heptadecyl (meth)acrylate (C17), nonadecyl (meth)acrylate (C19), ( Alkyl (meth)acrylate such as eicosyl (meth)acrylate (C20), henicosyl (meth)acrylate (C21), and docosyl (meth)acrylate (C22); 1-heptene, 3,3-dimethyl-1-pentene , 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 1-octene, 3,3-dimethyl-1-hexene, 3 ,4-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 3,5,5-trimethyl-1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene Unsaturated ethylene monomers having an alkyl group such as 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and 1-dococene. These may be used alone or in combination of two or more.

Examples of the polymerizable hydrophilic monomer include maleic acid or a salt thereof, monomethyl maleate, itaconic acid, monomethyl itaconate, fumaric acid, 4-styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, or Anionic unsaturated ethylene monomers such as unsaturated ethylene monomers containing phosphoric acid, phosphonic acid, alendronic acid or etidronic acid; 2-hydroxyethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono (Meth)acrylate, tetraethylene glycol mono(meth)acrylate, (meth)acrylamide, N-methylol (meth)acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide , Nt-butyl acrylamide, N-octyl acrylamide, Nt-octyl acrylamide and the like nonionic unsaturated ethylene monomers. These may be used alone or in combination of two or more.
The content of the polymerizable hydrophobic monomer and the polymerizable hydrophilic monomer is the total of the monomers forming the structural unit represented by the general formula (3) and the general formula (4) or (5). The amount is preferably 5% by mass or more and 100% by mass or less.

The polymerizable surfactant is an anionic or nonionic surfactant having at least one radically polymerizable unsaturated double bond group in the molecule.
Examples of the anionic surfactant, ammonium sulfate base ^_(-SO 3 - _NH ^{4 +)} hydrocarbon compound having a sulfate group and an allyl group _{(-CH 2} -CH = CH 2), such as, ammonium sulfate base (-SO ₃ ^- NH ₄ ⁺⁾ sulfate group and methacrylic group _{[-CO-C (CH 3) =} CH 2 ], such as the hydrocarbon compound having, or ammonium sulfate base ^_(-SO 3 - _NH ^{4 +),} such as sulfate groups and one - an aromatic hydrocarbon compound having a propenyl group (-CH = _CH 2 _{CH 3)} and the like.
Examples of the anionic surfactant include Eleminol JS-20 and RS-300 manufactured by Sanyo Kasei Co., Ltd., Aqualon KH-10, Aqualon KH-1025, and Aqualon KH-05 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. , Aqualon HS-10, Aqualon HS-1025, Aqualon BC-0515, Aqualon BC-10, Aqualon BC-1025, Aqualon BC-20, and Aqualon BC-2020.

Examples of the nonionic surface active agent, e.g., a 1-propenyl group (-CH = _CH 2 _{CH 3)} polyoxyethylene group _{[- (C 2 H 4 O} ) n-H] a hydrocarbon compound having a or Examples thereof include aromatic hydrocarbon compounds. Examples of the nonionic surfactants include Aqualon RN-20, Aqualon RN-2025, Aqualon RN-30, and Aqualon RN-50 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Latemur PD-104, Latemur manufactured by Kao Corporation. PD-420, latemuru PD-430, latemuru PD-450, etc. are mentioned.

The polymerizable surfactants may be used alone or in combination of two or more.
The content of the polymerizable surfactant is 0.1 mass with respect to the total amount of the monomers forming the structural unit represented by the general formula (3) and the general formula (4) or (5). % Or more and 10 mass% or less is preferable.

<Method for producing copolymer>
The method for producing the copolymer used in the present invention is not particularly limited, and various polymerization methods such as bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, and other known polymerization methods are used. can do. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system or a continuous system. Although not limited to these polymerization methods, radical polymerization using a radical polymerization initiator shown below is preferable because the polymerization operation and adjustment of the molecular weight are easy, and a solution polymerization method in which polymerization is performed in a mixed solvent of an organic solvent and water is preferable. More preferable.

The copolymer having the general formula (3) and the structural unit represented by the general formula (4) or (5) is a solvent in a flask equipped with a stirrer, a thermometer, and a nitrogen introducing tube, It can be obtained by reacting a monomer component in the presence of a polymerization initiator and under reflux of nitrogen gas at a temperature of 50° C. or higher and 150° C. or lower. The viscosity of the aqueous solution or dispersion of the synthesized copolymer can be adjusted by changing the molecular weight, and the monomer concentration during polymerization, the amount of polymerization initiator, the polymerization temperature, and the polymerization time may be changed.
Regarding the polymerization temperature, if the polymerization is carried out at a high temperature for a short time, a low molecular weight copolymer tends to be obtained, and if the polymerization is carried out at a low temperature for a long time, a high molecular weight copolymer tends to be obtained. Regarding the content of the polymerization initiator, the larger the content, the easier it is to obtain a low molecular weight copolymer, and the smaller the content, the easier it is to obtain a high molecular weight copolymer. Regarding the monomer concentration during the reaction, a higher concentration tends to give a low molecular weight copolymer, and a lower concentration tends to give a higher molecular weight copolymer.

The weight average molecular weight of the copolymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3,000 or more and 60,000 or less, more preferably 5,000 or more and 40,000 or less, It is more preferably 10,000 or more and 30,000 or less. When the weight average molecular weight is within the preferable range, it is advantageous in that the dispersion stability and the ejection stability are good when used in an ink for inkjet recording.
The weight average molecular weight can be measured by, for example, gel permeation chromatography (GPC).

As shown in the following reaction formulas (1) to (3), the copolymer is prepared by first adding naphthalenecarbonyl chloride (A-1) and an excess amount of a diol compound in the presence of an acid acceptor such as amine or pyridine. To give a naphthalenecarboxylic acid hydroxyalkyl ester (A-2). Then, after reacting 2-methacryloyloxyethyl isocyanate (A-3) with the above (A-2) to obtain a monomer (A-4), a (meth)acrylic acid monomer in the presence of a radical polymerization initiator. By copolymerizing with (A-5), the copolymer (A-6) used in the present invention can be obtained.
Here, the weight average molecular weight of the monomer (A-4) is 357 to 596 because L in the general formula (c) is an alkylene group having 2 to 18 carbon atoms and R ₁₀ is a hydrogen atom or a methyl group. Is.

However, in said reaction formula (1)-(3), R<_9> , R< ₁₀ > and L represent the same meaning as said general formula (3) and said general formula (4).

The radical polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate and peroxy ester. , Cyano-based azobisisobutyronitrile, azobis(2-methylbutyronitrile), azobis(2,2'-isovaleronitrile), non-cyano-based dimethyl-2,2'-azobisisobutyrate, etc. Is mentioned. Among these, organic peroxides and azo compounds are preferable, and azo compounds are particularly preferable, because the molecular weight is easily controlled and the decomposition temperature is low.
The content of the radical polymerization initiator is appropriately selected depending on the intended purpose without any limitation, but it is preferably 1% by mass or more and 10% by mass or less based on the total amount of the polymerizable monomers.

An appropriate amount of a chain transfer agent may be added to adjust the molecular weight of the polymer.
Examples of the chain transfer agent include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecylmercaptan, 1-dodecanethiol, and thioglycerol.
The polymerization temperature is appropriately selected depending on the intended purpose without any limitation, but it is preferably 50°C or higher and 150°C or lower, more preferably 60°C or higher and 100°C or lower. The polymerization time is also not particularly limited and may be appropriately selected depending on the purpose, but is preferably 3 hours or more and 48 hours or less.

The copolymer used in the present invention is particularly preferably, as long as it has the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) or (5). There is no limitation, and it can be appropriately selected according to the purpose, and examples thereof include a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer. These may be used alone or in combination of two or more. Of these, random copolymers are preferable.

The copolymer is obtained by polymerizing a monomer composed of the structural unit represented by the general formula (3) and a monomer composed of the structural unit represented by the general formula (4) or (5), if necessary. And may be neutralized.
By neutralizing the ionic group of the copolymer with an alkali metal or an organic amine, the affinity for water is increased and the copolymer can be provided with water dispersibility.
Examples of the alkali metal include lithium, sodium, potassium and the like.
Examples of the organic amine include alkyl amines such as mono-, di- or trimethylamine, mono-, di- or triethylamine, tetraethylammonium hydroxide; ethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, Alcohol amines such as monopropanolamine, dipropanolamine, tripropanolamine, isopropanolamine, trishydroxymethylaminomethane, 2-amino-2-ethyl-1,3 propanediol (AEPD); choline, morpholine, N-methyl Examples include cyclic amines such as monoforlin, N-methyl-2-pyrrolidone, and 2-pyrrolidone.
Among these, tetraethylammonium hydroxide or dimethylethanolamine is preferable from the viewpoint of both image density and storage stability.

Molar ratio (M1/M2) of the number of moles of the structural unit containing the anionic group (M1) and the number of moles of the structural unit containing the group containing the aromatic ring (M2) that constitute the copolymer. Is preferably 0.1 or more and 10 or less, more preferably 0.5 or more and 5 or less, still more preferably 1 or more and 3 or less.
When the molar ratio (M1/M2) is in the above range, it becomes difficult for a structural unit containing a group containing an aromatic ring to be adsorbed and released on the surface of the pigment, and the pigment particles adsorbed by the copolymer are Since the ink has good hydrophilicity so that it can be stably dispersed in water, while the ink has good dispersion stability, it is hydrophilic when dropped on a recording medium coated with the treatment liquid containing the polyamine derivative and the polyamide derivative of the present invention. The pigment particles do not flow due to the aggregation of the anionic groups of the functional copolymer. Therefore, when the recording medium is plain paper with high absorbency, the pigment remains on the surface of the recording medium and the image density and saturation are high. Since no match occurs, a good image without beading can be obtained.

As a method for dispersing the pigment using the copolymer, a kneading disperser using balls such as a bead mill or a ball mill, a kneading disperser using a shearing force such as a roll mill, or an ultrasonic disperser is used. be able to.
The mass ratio (B/A) of the content A (mass %) of the copolymer and the content B (mass %) of the pigment in the ink is preferably 1.0 or more and 10.0 or less, and 2 It is more preferably 0.0 or more and 6.0 or less, still more preferably 3.0 or more and 5.0 or less.
If the mass ratio (B/A) is 1.0 or more, the amount of the copolymer that cannot be adsorbed on the surface of the pigment and can be dissolved in the medium composed of water and the organic solvent can be reduced, so that the viscosity can be kept low. Therefore, stable ejection is possible from the inkjet nozzle. Further, when the mass ratio (B/A) is 10.0 or less, the storage stability of the pigment dispersion can be improved.

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

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

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

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

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

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

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

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with the pigment. Further, it is also possible to manufacture an ink by mixing a pigment and other materials such as water and a dispersant to form a pigment dispersion, and mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. A disperser may be used for dispersion.
There is no particular limitation on the particle size of the pigment in the pigment dispersion, but since the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high, the maximum frequency in terms of maximum number is 20 nm or more. The thickness is preferably 500 nm or less, more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell KK).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the purpose, but from the viewpoint of obtaining good ejection stability and increasing the image density, it is 0.1 mass. % Or more and 50% by mass or less is preferable, and 0.1% by mass or more and 30% by mass or less is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

<Resin>
The type of resin contained in the ink is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, and butadiene resin. Examples thereof include resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, acrylic silicone resins and the like.
You may use the resin particle which consists of these resins. It is possible to obtain ink by mixing resin particles with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is used as a dispersion medium. As the resin particles, those synthesized appropriately may be used, or commercially available products may be used. Further, these may be used alone or in combination of two or more kinds of resin particles.

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

The content of the resin is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of fixability and storage stability of the ink, 1% by mass or more and 30% by mass or less based on the total amount of the ink. Is preferable and 5 mass% or more and 20 mass% or less is more preferable.

The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of enhancing the image quality such as ejection stability and image density, the maximum frequency in conversion to the maximum number is Is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell KK).

<Additive>
If necessary, a surfactant, a defoaming agent, an antiseptic/antifungal agent, an anticorrosive agent, a pH adjusting agent and the like may be added to the ink.

<Surfactant>
As the surfactant, any of silicone-based surfactants, fluorine-based surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used.
The silicone surfactant is not particularly limited and can be appropriately selected according to the purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain-modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and side-chain both-end modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound having a polyalkylene oxide structure introduced into the side chain of the Si moiety of dimethylsiloxane.
Examples of the fluorinated surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphoric acid ester compound, a perfluoroalkyl ethylene oxide adduct and a perfluoroalkyl ether group in the side chain. A polyoxyalkylene ether polymer compound is particularly preferable because it has a low foaming property. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salts. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in its side chain include a sulfuric acid ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in its side chain and a perfluoroalkyl ether group in its side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counterions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ and NH(CH ₂ CH ₂ OH). ₃ etc. are mentioned.
Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of nonionic surfactants include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan. Examples thereof include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl acid salt, and salt of polyoxyethylene alkyl ether sulfate.
These may be used alone or in combination of two or more.

The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and side-modified. Examples thereof include polydimethyl siloxane modified at both chain ends, and a polyether modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant. preferable.
As such a surfactant, those synthesized appropriately may be used, or commercially available products may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Kagaku, etc.
The polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the general formula (S-1) is represented by dimethylpolyethylene. Examples thereof include those introduced into the side chain of the Si portion of siloxane.
[General formula (S-1)]
(However, in the general formula (S-1), m, n, a, and b represent an integer. R and R′ represent an alkyl group or an alkylene group.)
As the above polyether-modified silicone-based surfactant, commercially available products can be used, for example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-. 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc. are mentioned.

The fluorine-based surfactant is preferably a fluorine-substituted compound having 2 to 16 carbon atoms, and more preferably a fluorine-substituted compound having 4 to 16 carbon atoms.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in its side chain.
Among these, polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain are preferable because they have a low foaming property, and are particularly fluorine-based represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.
[General Formula (F-1)]
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
[General Formula (F-2)]
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or CnF _2n+1 and n is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ -CnF _2n+1 and n is 4 to 6. An integer, or CpH _2p+1 and p is an integer of 1 to 19. a is an integer of 4-14.
A commercially available product may be used as the above-mentioned fluorine-based surfactant.
Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by DIC Corporation); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont) ); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omnova Co., Ltd.), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. Among these, good printing quality, especially color developability, penetrability to paper, wettability, From the point that the level dyeing property is remarkably improved, FS-300 manufactured by DuPont, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., OMNOVA Polyfox PF-151N and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable.

The content of the surfactant in the ink is appropriately selected depending on the intended purpose without any limitation, but it is 0.001 mass% from the viewpoint of excellent wettability and ejection stability and improving image quality. % Or more and 5 mass% or less is preferable, and 0.05 mass% or more and 5 mass% or less is more preferable.

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

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

<Rust preventive>
The rust preventive agent is not particularly limited, and examples thereof include acid sulfite and sodium thiosulfate.

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

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

<Treatment liquid>
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water, and further contains other components as necessary.
As the other components, a surfactant, an antifoaming agent, a pH adjusting agent, an antiseptic/antifungal agent, an antirust agent, etc. may be contained.
As the organic solvent, surfactant, defoaming agent, pH adjusting agent, antiseptic/antifungal agent, rust preventive agent, the same materials as those used in the ink can be used, and other materials used in known treatment liquids can be used. it can.

-Polyamine derivative, polyamide derivative-
As the polyamine derivative or the polyamide derivative, for example, at least one water-soluble selected from polyamine-epihalohydrin copolymer, polyamide-epihalohydrin copolymer, polyamide polyamine-epihalohydrin copolymer, and amine-epihalohydrin copolymer. A cationic polymer can be preferably used, and a quaternary ammonium salt type cationic polymer other than these compounds, or a water-dispersible cationic polymer may be used as the water-soluble cationic polymer in some cases. Among these, at least one of the compound represented by the following general formula (1) and the compound represented by the following general formula (2) is preferable.

However, in the general formula (1), R _{1 to} R ₈ are any of an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkenyl group, and a benzyl group, X represents a halogen atom, and n represents 1 or 2.

However, in the general formula (2), X represents a halogen atom, n represents an integer of 1 or more, and preferably 1 or more and 5 or less.

In the general formulas (1) and (2), X represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The content of at least one of the polyamine derivative and the polyamide derivative in the treatment liquid is preferably 5 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 40 mass% or less, and 15 mass% or more and 30 mass% or less. The following are more preferable. When the content is 5% by mass or more, the pigment in the ink dropped after applying the treatment liquid is sufficiently aggregated, so that the penetration of the pigment into a recording medium such as plain paper having high absorptivity does not occur. The effect of being suppressed and improving the image density and saturation can be obtained, and in a recording medium such as coated paper having low absorptivity, the ink droplets do not coalesce, so that the occurrence of beading can be suppressed. Further, when the content is 50% by mass or less, the ink droplets dropped after the application of the treatment liquid spreads and the dots of the image can fill the recording surface, so that the effect of improving the image density and the saturation can be obtained. Further, it is possible to suppress the occurrence of corrosion of the coating roller and the like due to the acid in the treatment liquid.

-Recording medium-
The recording medium is appropriately selected depending on the intended purpose without any limitation, and examples thereof include plain paper, coated paper for printing, glossy paper, special paper, cloth, film, and OHP sheet. These may be used alone or in combination of two or more. Among these, plain paper and coated paper for printing are preferable. The plain paper is advantageous in that it is inexpensive. Further, the coated paper for printing is relatively inexpensive as compared with glossy paper and is advantageous in that it gives a smooth and glossy image.

The printing coated paper preferably has a support and a coating layer on the support.
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include papers mainly composed of wood fibers, sheet-like materials such as nonwoven fabrics composed mainly of wood fibers and synthetic fibers. ..
The coating layer contains a pigment and a binder (binder), and further contains a surfactant and other components as necessary.
As the pigment, an inorganic pigment or a combination of an inorganic pigment and an organic pigment can be used.
Examples of the inorganic pigment include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, Examples thereof include zinc hydroxide and chlorite. These may be used alone or in combination of two or more. Among them, kaolin is particularly preferable because it has excellent glossiness and can have a texture close to that of offset printing paper.

Examples of the organic pigment include water-soluble dispersions such as styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. These may be used alone or in combination of two or more.

Other components may be added to the coating layer, if necessary, within a range that does not impair the objects and effects of the present invention. Examples of the other components include additives such as alumina powder, pH adjusters, preservatives and antioxidants.

In the recording medium, a back layer may be further formed on the back surface of the support, another layer may be formed between the support and the coating layer, or another layer may be formed between the support and the back layer, and a protective layer may be formed on the coating layer. It can be provided. Each of these layers may be a single layer or a plurality of layers.

Examples of the coated paper for printing include OK top coat + (plus), OK top coat S, OK Casablanca, OK Casablanca V, OK Trinity, OK Trinity NaVi, New Age, New Age W, OK Top Coat Matt N. , OK Royal Coat, OK Top Coat Dull, Z Coat, OK Kyuhime, OK Kyuo, OK Kyuo Satin, OK Top Coat+, OK Non Wrinkle, OK Coat V, OK Coat N Green 100, OK Matt Coat Green 100 , New Age Green 100, Z Coat Green 100 (all manufactured by Oji Paper Co., Ltd.); Aurora Coat, Shiraioi Mat, Imperial Mat, Silver Diamond, Recycle Coat 100, Cycle Mat 100 (all manufactured by Nippon Paper Industries Co., Ltd. ); Mucoat, Muwhite, Mumat, Whitemumat (all manufactured by Hokuetsu Paper Mills Co., Ltd.); Thunderbird Court N, Regina Thunderbird Court 100, Thunderbird Mat Court N, Regina Thunderbird Mat 100 (all are Chuetsu Pulp & Paper Co., Ltd. Made by Mitsubishi Paper Co., Ltd.; Pearl Coat, White Pearl Coat N, New V Matt, White New V Mat, Pearl Coat REW, White Pearl Coat NREW, New V Mat REW, White New V Mat REW (all manufactured by Mitsubishi Paper Mills Co., Ltd. ); OK coat L, royal coat L, OK coat LR, OK white L, OK royal coat LR, OK coat L green 100, OK matte coat L green 100 (both manufactured by Oji Paper Co., Ltd.); Easter DX, recycled Coat L100, Aurora L, Recycle Mat L100, <SSS> Energy White (both manufactured by Nippon Paper Industries Co., Ltd.); Utrilo Coat L, Matisse Coat (both manufactured by Daio Paper Co., Ltd.); High Alpha, Alpha Matte, (N) Kinmari L, Kinmari HiL (all manufactured by Hokuetsu Paper Mills Ltd.); N Pearl Coat L, N Pearl Court LREW, Swing Mat REW (all manufactured by Mitsubishi Paper Mills Ltd.); Super Emine, Emine, Chaton ( All are made by Chuetsu Pulp Industry Co., Ltd.; OK Medium quality coat, (F)MCOP, OK Astrogross, OK Astrodal, OK Astromat (all made by Oji Paper Co., Ltd.); King O (Nippon Paper Co., Ltd.) Made); OK Royal Light S Green 100, OK Everlight Coat, OK Everlight R, OK Evergreen, Clean Hit MG, OK micro coating super eco G, eco green dull, OK micro coating mat eco G100, OK starlight coat, OK soft royal, OK bright, clean hit G, Yamayuri bright, Yamayuri bright G, OK aqualite coat, OK Royal Light S Green 100, OK Bright (Rough Tsuya), Snow Mat, Snow Mat DX, OK Kyuhime, OK Yuri (all manufactured by Oji Paper Co., Ltd.); Pyrene DX, Pegasus Hyper 8, Aurora S, Andean DX, Super Andean DX, Space DX, Seine DX, Special Gravure DX, Pegasus, Silver Pegasus, Pegasus Harmony, Greenland DX100, Super Greenland DX100, <SSS> Energy Light, <SSS> Energy Light, EE Henry (any Also manufactured by Nippon Paper Industries Co., Ltd.; Kant Excel, Excel Super B, Excel Super C, Kant Excel Val, Utrilo Excel, Heine Excel, Dante Excel (all manufactured by Daio Paper Co., Ltd.); Cosmo Ace (Daishowa Paperboard Co., Ltd.) Company made); Semi L, High Beta, High Gamma, Shiromari L, Humming, White Humming, Semi HiL, Shiromari HiL (Hokuetsu Paper Mills); Ruby Light HREW, Pearl Soft, Ruby Light H (any , Mitsubishi Paper Mills Co., Ltd.; Shaton, Ariso, Smash (all manufactured by Chuetsu Pulp Industries Co., Ltd.); Star Cherry, Cherry Super (all manufactured by Marusumi Paper Co., Ltd.) and the like.

<Post-treatment liquid>
The post-treatment liquid is not particularly limited as long as it can form a transparent layer. The post-treatment liquid is obtained by selecting and mixing an organic solvent, water, a resin, a surfactant, an antifoaming agent, a pH adjusting agent, an antiseptic/antifungal agent, an antirust agent, etc., if necessary. Further, the post-treatment liquid may be applied to the entire recording area formed on the recording medium, or may be applied only to the area where the ink image is formed.

-Image forming apparatus having treatment liquid application mechanism-
Here, regarding the method for applying the treatment liquid to the recording medium and recording the image with the ink containing the coloring material before the treatment liquid is dried and solidified, the image forming apparatus having the treatment liquid application mechanism of FIG. A specific example will be described. The image forming apparatus having the treatment liquid application mechanism of FIG. 3 is an image forming apparatus of a type that scans an inkjet recording head to form an image.
In the image forming apparatus having the processing liquid application mechanism of FIG. 3, the recording medium 6 is sent out by the paper feed roller 7 and the processing liquid 1 filled in the processing liquid container 42 by the applying roller 4 and the counter roller 5 is evenly distributed on the recording medium. Thinly applied to. The treatment liquid is drawn up by the drawing-up roller 3 and uniformly applied to the application roller 4 by the film thickness control roller 2. The recording medium is fed to the recording scanning unit having the inkjet recording head 20 while being applied with the treatment liquid. Since the length of the paper path from the end portion (A portion in FIG. 3) of the treatment liquid application operation to the recording scan start portion (B portion in FIG. 3) is set longer than the length in the feeding direction of the recording medium, The application of the treatment liquid can be completely completed at the point when the recording liquid reaches the recording scan start portion. In this case, the treatment liquid can be applied before the inkjet recording head 20 starts scanning for printing and before the recording medium 6 is intermittently conveyed, so that the recording medium is continuously conveyed at a constant speed. And can be applied uniformly and evenly. In the image forming apparatus of FIG. 3, the recording medium that requires pre-processing is supplied from the lower cassette, and the recording medium that is unnecessary or is not processed is supplied from the upper cassette. It is convenient to provide a long route.

FIG. 4 shows another specific example of an image forming apparatus having a treatment liquid coating mechanism. The image forming apparatus having the treatment liquid application mechanism of FIG. 4 is an image forming apparatus of the type that scans the inkjet recording head to form an image. This is an example of a compact device configuration as compared with the device of FIG.
The recording medium 17 is sent out by the paper feed roller 7, and the application liquid 4 and the counter roller 5 apply the processing liquid 1 filled in the processing liquid container 42 uniformly and thinly to the recording medium. The processing liquid is drawn up by the drawing-up roller 3, and is uniformly applied to the application roller 4 by the film thickness control roller 2. The recording medium passes through the recording scanning unit having the inkjet recording head 20 while being applied with the treatment liquid, and is sent until the recording medium completes the application of the treatment liquid. The head is returned to the print scan start position. The completion of application can be detected, for example, by providing a known recording medium detection unit (not shown) near the outlet of the treatment liquid application device. This detection means is not always necessary. By inputting information on the length of the recording medium to the controller in advance and controlling the number of rotations of the motor, the feed amount of the outer circumference of the conveying roller of the recording medium is set to the length of the recording medium. A corresponding system configuration may be adopted.

The recording medium to which the treatment liquid is applied is conveyed to the recording scanning position again before the treatment liquid is dried and solidified. At this time, the recording medium is intermittently adjusted in timing with the scanning of the ink jet recording head 20. Be transported to. When returning the same path as when the recording medium is returned, the trailing edge of the paper will re-enter the treatment liquid application device, causing problems such as uneven coating, stains, and paper jams. At this time, the recording medium guide 31 switches the direction. That is, when the recording medium is fed back after the treatment liquid is applied to the recording medium, the recording medium guide 31 is moved to the position indicated by the dotted line in the drawing by a known means such as a solenoid or a motor. As a result, the recording medium is conveyed to the position of the recording medium guide 34, so that it is possible to prevent the recording medium from becoming dirty or jammed.

<Recorded matter>
The recorded matter used in the invention has an image formed by using the ink set of the invention on a recording medium.
A recorded matter can be obtained by recording with the image forming apparatus and the image forming method of the present invention.

<Recording device, recording method>
The ink set of the present invention can be suitably used for various recording apparatuses using an inkjet recording method, such as a printer, a facsimile apparatus, a copying apparatus, a printer/fax/copier complex machine, and a three-dimensional modeling apparatus.
In the present invention, the recording device and the recording method are a device capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of recording using the device. The recording medium means a medium to which ink or various treatment liquids can be attached even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices such as a pre-processing device and a post-processing device. ..
The recording device and the recording method may have a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printing surface or the back surface of the recording medium. The heating means and the drying means are not particularly limited, but, for example, a warm air heater or an infrared heater can be used. The heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording device and the recording method are not limited to those in which a significant image such as a character or a figure is visualized by ink. For example, the thing which forms patterns, such as a geometric pattern, and the thing which models a three-dimensional image are also included.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head unless otherwise limited.
Further, this recording device is not limited to a desktop type, and can be used as a wide recording device capable of printing on an A0 size recording medium, or for example, continuous paper wound in a roll shape as a recording medium. It also includes a continuous form printer.
An example of the recording device will be described with reference to FIGS. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism section 420 is provided inside the exterior 401 of the image forming apparatus 400. Each ink containing portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminate film. It is formed of a member. The ink container 411 is housed in a container case 414 made of plastics, for example. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus main body is opened. The main tank 410 is detachably attached to the cartridge holder 404. As a result, the ink discharge ports 413 of the main tank 410 and the ejection heads 434 for the respective colors communicate with each other via the supply tubes 436 for the respective colors, and ink can be ejected from the ejection heads 434 to the recording medium.

This recording device can include not only a part for ejecting ink, but also a device called a pre-processing device, a post-processing device, or the like.
As one mode of the pretreatment device and the posttreatment device, as in the case of the inks of black (K), cyan (C), magenta (M), yellow (Y), etc., a pretreatment liquid and a posttreatment liquid are included. There is a mode in which a liquid storage section and a liquid ejection head are added and a pretreatment liquid and a posttreatment liquid are ejected by an inkjet recording method.
As another aspect of the pretreatment apparatus and the posttreatment apparatus, there is an aspect in which a pretreatment apparatus and a posttreatment apparatus other than the ink jet recording method are provided by, for example, a blade coating method, a roll coating method, a spray coating method.

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

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

Hereinafter, a method for measuring the weight average molecular weight of the copolymer, the acid value, and the amine value of the polyamine derivative or the polyamide derivative used in Examples and Comparative Examples will be described.

<Measurement of weight average molecular weight>
The weight average molecular weight was measured as follows.
Column constant temperature bath CTO-20A (manufactured by Shimadzu Corporation), detector RID-10A (manufactured by Shimadzu Corporation), eluent flow path pump LC-20AD (manufactured by Shimadzu Corporation), degasser DGU-20A (stock company). The weight average molecular weight was measured by GPC method using Shimadzu Corporation) and auto sampler SIL-20A (Shimadzu Corporation).
As the column, an aqueous SEC column TSKgelG3000PWXL having an exclusion limit molecular weight of 2×10 ^5, a TSKgelG5000PWXL having an exclusion limit molecular weight of 2.5×10 ⁶ , and a TSKgelG6000PWXL having an exclusion limit molecular weight of 5×10 ⁷ (manufactured by Tosoh Corporation). The connected one was used. As the sample, a sample prepared with an eluent to 2 g/100 mL was used. As the eluent, an aqueous solution in which the contents of acetic acid and sodium acetate were adjusted to 0.5 mol/L was used. The column temperature was 40° C. and the flow rate was 1.0 mL/min. Calibration curves are standard samples of 9 polyethylene glycols with molecular weights of 1,065, 5,050, 24,000, 50,000, 107,000, 140,000, 250,000, 540,000 and 920,000. Was manufactured using.

<Measurement of acid value>
The acid value is defined as the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like present in 1 g of oil and fat, and was measured by the following neutralization titration method.
0.5 g to 2.0 g of a dried sample (copolymer) is precisely weighed and placed in an Erlenmeyer flask, sufficiently dissolved in 100 mL of tetrahydrofuran (THF), and 10 drops of a phenolphthalein solution is added dropwise. A 0.1 mol/L potassium hydroxide/methanol solution (titer f ₁ ) was dropped from a buret and slightly colored (pink), where the end point was read and the titration amount (mL) was read. The acid value was calculated.
Acid value (mgKOH/g)={titration amount (mL)×56.11 (mg/mL)×0.1×f ₁ }/sample (g)

<Measurement of amine value>
Using the total amine number indicating the total amount of primary, secondary, and tertiary amines as the amine number, it is defined by the hydrochloric acid required to neutralize 1 g of the sample and the equivalent number of mg of potassium hydroxide. The amine value was determined by the titration method.
0.5 g to 2.0 g of a dried sample (polyamine derivative or polyamide derivative) is precisely weighed and placed in an Erlenmeyer flask and sufficiently dissolved in 30 mL of ethanol. A 0.2 mol/L ethanolic hydrochloric acid solution (titer f ₂ ) was dropped from a buret, and when the color changed from green to yellow, the end point was read, the titration amount (mL) was read, and the amine value was calculated by the following formula. It was
Amine value (mgKOH/g)={titration amount (mL)×56.11 (mg/mL)×0.2×f ₂ }/sample (g)

(Synthesis example 1 of polyamine derivative)
-Synthesis of polyamine derivative A-
In a 1 L separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 237.58 g (1.4 mol) of an N,N-dimethylallylamine hydrochloride aqueous solution having a concentration of 71.66% by mass and a concentration of 60 were added. 0.17% by mass of N-methyldiallylamine hydrochloride aqueous solution 147.23 g (0.6 mol) was added to obtain an aqueous solution having a monomer concentration of 67.27% by mass. This aqueous solution was heated to 60° C., and after the temperature became constant, 4.56 g (1.0 mol% with respect to the monomer) of ammonium persulfate was added as a radical polymerization initiator to initiate polymerization.
After 2 hours and 4 hours from the start of the polymerization, 4.56 g (1.0 mol% based on the monomer) of ammonium persulfate was added, respectively. Further, after each of 23 hours, 24 hours, 25 hours, 26 hours, 27 hours and 28 hours, 9.13 g (2.0 mol% based on the monomer) of ammonium persulfate was added. Then, the polymerization reaction was continued for another 3 hours to obtain a brown solution (polyamine derivative A) of a copolymer of N,N-dimethylallylamine hydrochloride and N-methyldiallylamine hydrochloride (charged molar ratio 0.7:0.3). Got Distilled water was added to this solution to prepare an aqueous solution having a solid content concentration of 50% by mass.
Regarding the obtained polyamine derivative A, the weight average molecular weight determined by GPC was 1,800, and the amine value determined by titration was 390 mgKOH/g.

(Synthesis example 2 of polyamine derivative)
-Synthesis of Polyamine Derivative B-
A 500 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 134.7 g (0.5 mol) of a diallyldimethylammonium chloride aqueous solution having a concentration of 60% by mass and 176 g of distilled water, and the pH was adjusted to 3 to 3 with hydrochloric acid. Adjusted to 4. Next, 18.3 g (0.25 mol) of acrylamide and 3.9 g of sodium hypophosphite were added and dissolved by stirring at 50°C. Next, the internal temperature was raised to 60° C., and 1.7 g of an ammonium persulfate aqueous solution having a concentration of 28.5% by mass was added. While keeping the internal temperature at 60°C to 65°C, 3.5 g was further added after 4 hours. Then, the mixture was reacted at 60° C. for 20 hours to obtain a diallyldimethylammonium chloride-acrylamide copolymer (polyamine derivative B) having a solid content concentration of 30% by mass.
Regarding the obtained polyamine derivative B, the weight average molecular weight determined by GPC was 3,000, and the amine value determined by titration was 420 mgKOH/g.

(Synthesis example 3 of polyamine derivative)
-Synthesis of polyamine derivative C-
In a 300 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 100 mL of diallyldimethylamine hydrochloride/dimethyl sulfoxide having a concentration of 1 mol/L and 100 mL of sulfur dioxide/dimethyl sulfoxide solution having a concentration of 1 mol/L were mixed. Then, 0.82 g of azobisisobutyronitrile was added as a polymerization initiator, and polymerization was carried out at 40° C. for 24 hours. The reaction solution was dropped into methanol to precipitate the copolymer, which was filtered with a glass filter and dried under reduced pressure to obtain 18 g of a copolymer (polyamine derivative C). Distilled water was added to this solution to prepare an aqueous solution having a solid content concentration of 50% by mass.
Regarding the obtained polyamine derivative C, the weight average molecular weight determined by GPC was 3,000, and the amine value determined by titration was 250 mgKOH/g.

(Synthesis example 4 of polyamide derivative)
-Synthesis of polyamide derivative D-
A 3 liter four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube was charged with 495 g (4.8 mol) of diethylenetriamine, and 877 g (6.0 mol) of adipic acid was added with stirring. In addition, the temperature was raised while removing generated water out of the system, the reaction was carried out at 150° C. for 5 hours, and then 1,000 g of water was gradually added to obtain a polyamide polyamine-containing liquid. This polyamidepolyamine-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 polyamide polyamine-containing liquid (0.214 mol as an amino group) obtained above, 3.8 g (30 equivalent %) of acetic acid and 4.3 g (15 equivalent%) of 30 mass% sodium hydroxide aqueous solution were charged, and water 6 0.7 g was added to make the solid content 50 mass %.
Then, 19.8 g (100 equivalent %) of epichlorohydrin was added dropwise at 30° C. over 1 hour, and then maintained at the same temperature for 1 hour, and 0.8 g (2 equivalent%) of sodium metabisulfite was added, After the start of dropping of epichlorohydrin, the temperature was maintained for 5 hours. Subsequently, 1.1 g (10 equivalent %) of 98% sulfuric acid and 127.0 g of water were added to make the solid content 30% by mass, and then heated to 75°C. Furthermore, after maintaining at this temperature until the viscosity of the reaction liquid at 25° C. reaches 300 mPa·s, 40.5 g of water is added to make the solid content 26 mass %, and after cooling to 25° C. or lower, 30 mass % Sulfuric acid to pH 3.5, then 88% by mass formic acid to pH 3.0, and solid content concentration 25.0% by mass, viscosity at 15% by mass 51.6 mPa·s of the general formula In (2), a polyamide derivative D having a structure of n=9 was obtained.
Regarding the obtained polyamide derivative D, the weight average molecular weight determined by GPC was 2,750, and the amine value determined by titration was 185 mgKOH/g.

(Synthesis example 5 of polyamine derivative)
-Synthesis of Polyamine Derivative E-
In a 300 mL three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 64.87 g (0.50 mol) of a monoallylamine hydrochloride aqueous solution having a concentration of 72.11 mass% and N having a concentration of 60.21 mass% were added. 100.99 g (0.50 mol) of N-dimethylallylamine hydrochloride aqueous solution was added, and 13.45 g of water was added to obtain an aqueous solution having a monomer concentration of 60% by mass. This aqueous solution was heated to 60° C., and after the temperature became constant, as a radical polymerization initiator, 2.2′-azobis(2-amidinopropane) dihydrochloride 8.68 g (3.2 with respect to the monomer) (Mol %) was added to initiate the polymerization. In addition, 8.68 g of 2,2′-azobis(2-amidinopropane) dihydrochloride was added after 24 hours, 48 hours and 72 hours from the start of the polymerization. Then, the polymerization reaction was continued for another 24 hours.
Then, the obtained pale yellow reaction solution was put into 3 liters of an acetone-isopropanol mixed solvent (mass ratio 1:1) to reprecipitate the copolymer, which was filtered with a glass filter and thoroughly washed. Then, it was vacuum dried at 60° C. for 48 hours to obtain a brown solution of a copolymer of monoallylamine hydrochloride and N,N-dimethylallylamine hydrochloride (charged molar ratio 0.5:0.5) (polyamine derivative E). ) Got. Distilled water was added to this solution to prepare an aqueous solution having a solid content concentration of 50% by mass.
Regarding the obtained polyamine derivative E, the weight average molecular weight determined by GPC was 800, and the amine value determined by titration was 525 mgKOH/g.

(Synthesis Example 1 of Copolymer)
-Synthesis of Copolymer a-
62.0 g (525 mmol) of ethylene glycol (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added. To this solution, a solution prepared by dissolving 50.0 parts by mass (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of methylene chloride was added dropwise with stirring over 2 hours, and then at room temperature, 6 Stir for hours. The obtained reaction solution was washed with water, the organic phase was isolated, dried over magnesium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride/methanol (volume ratio 98/2) as an eluent to obtain 52.5 parts by mass of 2-naphthoic acid-2-hydroxyethyl ester. It was
Next, 42.1 parts by mass (155 mmol) of 2-naphthoic acid-2-hydroxyethyl ester was dissolved in 80 mL of dry methyl ethyl ketone and heated to 60°C. After 24.0 parts by mass (155 mmol) of 2-methacryloyloxyethyl isocyanate (Showa Denko KK, Karens MOI) dissolved in 20 mL of dry methyl ethyl ketone was added dropwise to this solution while stirring over 1 hour. The mixture was stirred at 70°C for 12 hours. After cooling to room temperature, the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride/methanol (volume ratio 99/1) as an eluent, and in the general formula (4), R ₁₀ was hydrogen atom and L was carbon number 2 57.0 parts by mass of a monomer represented by the following structural formula (4-1), which is an alkylene group of

Next, in the general formula (3), R ₉ is represented by the structural formula (4-1), and 1.30 parts by mass (22.0 mmol) of acrylic acid (manufactured by Aldrich Co.) represented by a hydrogen atom. 7.18 parts by mass (20.0 mmol) of the monomer was dissolved in 40 mL of dry methyl ethyl ketone to prepare a monomer solution. After heating 10% by mass of the monomer solution to 75° C. under an argon stream, 0.273 parts by mass (1.67 mmol) of 2,2′-azoiso(butyronitrile) (manufactured by Tokyo Kasei Co., Ltd.) was added to the remaining monomer solution. Was added dropwise over 1.5 hours, and the mixture was stirred at 65° C. for 7 hours. After cooling to room temperature, the obtained reaction solution was dropped into hexane. The precipitated copolymer was filtered off and dried under reduced pressure to obtain 8.13 parts by mass of the copolymer.
While the obtained copolymer is dissolved in an aqueous potassium hydroxide solution so as to be 100% acid-neutralized, the concentration of the copolymer is adjusted with ion-exchanged water so that the concentration of the copolymer is 10% by mass. Got
The copolymer a thus obtained has a molar ratio (M1/M2) between the molar number (M1) of the structural unit containing an anion group and the molar number (M2) of the structural unit containing a group containing an aromatic ring. Was 1.1, and the weight average molecular weight measured by GPC was 9,800, and the acid value measured by acid value titration was 145 mgKOH/g.

(Synthesis Example 2 of Copolymer)
-Synthesis of Copolymer b-
In Synthesis Example 1 of copolymer, acrylic acid (manufactured by Aldrich Co.) was changed to 3.00 parts by mass (50.8 mmol), and the monomer represented by the structural formula (4-1) was replaced with the following structural formula (b). A copolymer was obtained in the same manner as in Synthesis Example 1 of copolymer, except that the amount of the monomer represented by 3.57 parts by mass (20.3 mmol) was changed and the reaction was carried out at 60° C. for 12 hours.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. b was obtained.
The copolymer b thus obtained had a molar ratio (M1/M2) of 2.5 and had a weight average molecular weight of 22,000 as measured by GPC, and an acid value measured by acid value titration. , 410 mg KOH/g.

(Synthesis Example 3 of Copolymer)
-Synthesis of Copolymer c-
In the synthesis example 1 of the copolymer, acrylic acid (manufactured by Aldrich Co.) was changed to 5.50 parts by mass (50.9 mmol) of vinyl sulfonic acid (manufactured by Asahi Kasei Finechem Co., Ltd.), and the structural formula (4-1) was used. The same procedure as in Synthesis Example 1 of copolymer except that the monomer represented by the structural formula (b) was changed to 2.99 parts by mass (17.0 mmol) and the reaction was performed at 60° C. for 10 hours. To obtain a copolymer.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. I got c.
The copolymer c thus obtained had a molar ratio (M1/M2) of 3.0, and was measured using GPC. The weight average molecular weight was 19,000. The acid value was measured by acid value titration. It was 325 mgKOH/g.

(Synthesis Example 4 of Copolymer)
-Synthesis of Copolymer d-
In Synthesis Example 1 of Copolymer, acrylic acid (manufactured by Aldrich) was changed to 5.00 parts by mass (23.8 mmol) of a monomer (phosmer M, manufactured by Unichemical Co., Ltd.) represented by the following structural formula (d). Except that the monomer represented by the structural formula (4-1) was changed to 2.10 parts by mass (11.9 mmol) of the monomer represented by the structural formula (b) and the reaction was performed at 60° C. for 17 hours. A copolymer was obtained in the same manner as in Synthesis Example 1 of Copolymer.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. d was obtained.
The copolymer d thus obtained had a molar ratio (M1/M2) of 2.0 and had a weight average molecular weight of 36,000 as measured by GPC, and an acid value measured by acid value titration. It was 275 mgKOH/g.

(Synthesis Example 5 of Copolymer)
-Synthesis of copolymer e-
In Synthesis Example 1 of copolymer, acrylic acid (manufactured by Aldrich Co.) was used as a monomer (4-methacrylamido-1-hydroxybutane-1,1-diphosphonic acid) represented by the following structural formula (e) 6.50. The monomer represented by the structural formula (4-1) was changed to 1.03 parts by mass (5.9 mmol) of the monomer represented by the structural formula (b) at 60°C. A copolymer was obtained in the same manner as in Synthesis Example 1 of Copolymer except that the reaction was carried out for 22 hours.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. e was obtained.
The copolymer e thus obtained had a molar ratio (M1/M2) of 3.5 and was measured using GPC. The weight average molecular weight was 50,000. The acid value was measured by acid value titration. 280 mg KOH/g

(Synthesis Example 6 of Copolymer)
-Synthesis of copolymer f-
In Synthesis Example 1 of the copolymer, 2.00 parts by mass of acrylic acid (manufactured by Aldrich) and methacrylic acid (manufactured by Aldrich) in which R ₉ is a methyl group in the general formula (3) (26.7 mmol). )), the monomer represented by the structural formula (4-1) was changed to 5.21 parts by mass (29.6 mmol) of the monomer represented by the structural formula (b), and the mixture was reacted at 60° C. for 13 hours. A copolymer was obtained in the same manner as in Synthesis Example 1 of copolymer except for the above.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. got f.
The copolymer f thus obtained had a molar ratio (M1/M2) of 0.9 and was measured using GPC. The weight average molecular weight was 24,000, and the acid value was measured by acid value titration. , 200 mg KOH/g.

(Synthesis Example 7 of Copolymer)
-Synthesis of copolymer g-
In Synthesis Example 1 of copolymer, acrylic acid (manufactured by Aldrich Co.) was used in an amount of 2.50 parts by mass (33.3 mmol) of methacrylic acid (manufactured by Aldrich Co.) in which R ₉ represents a methyl group in the general formula (3). ), the monomer represented by the structural formula (4-1) was changed to 5.78 parts by mass (55.6 mmol) of a styrene monomer, and the reaction was performed at 60° C. for 13 hours. A copolymer was obtained in the same manner as in 1.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. g was obtained.
The copolymer g thus obtained had a molar number ratio (M1/M2) of 0.6 and was measured using GPC. The weight average molecular weight was 24,000, and the acid value was measured by acid value titration. It was 215 mgKOH/g.

(Synthesis Example 8 of Copolymer)
-Synthesis of copolymer h-
In Synthesis Example 1 of copolymer, 1.00 parts by mass of acrylic acid (manufactured by Aldrich Co.) and methacrylic acid (manufactured by Aldrich Co.) in which R ₉ is a methyl group in the general formula (3) (13. 3 mmol), the monomer represented by the structural formula (4-1) was changed to 7.57 parts by mass (14.8 mmol) of the monomer represented by the following structural formula (4-2), and the temperature was changed to 60° C. for 13 hours. A copolymer was obtained in the same manner as in Synthesis Example 1 of copolymer except that the reaction was performed.

Next, while the obtained copolymer is dissolved in a tetraethylammonium hydroxide aqueous solution so as to be 100% acid-neutralized, the concentration of the copolymer is adjusted to 10% by mass by ion-exchanged water. A copolymer was obtained.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. got h.
The copolymer h thus obtained had a molar ratio (M1/M2) of 0.9 and was measured using GPC. The weight average molecular weight was 24,000, and the acid value was measured by acid titration. , 100 mg KOH/g.

(Synthesis Example 9 of Copolymer)
-Synthesis of Copolymer i-
In Synthesis Example 1 of copolymer, acrylic acid (manufactured by Aldrich Co.) was used in an amount of 1.30 parts by mass (17.3 mmol) of methacrylic acid (manufactured by Aldrich Co.) in which R ₉ is a methyl group in the general formula (3). ), the monomer represented by the structural formula (4-1) is changed to 7.09 parts by mass (17.3 mmol) of the monomer represented by the following structural formula (5-1), and reacted at 60° C. for 13 hours. A copolymer was obtained in the same manner as in Synthesis Example 1 of Copolymer except that the above was carried out.
The copolymer obtained by dissolving the obtained copolymer in an aqueous solution of tetraethylammonium hydroxide so as to neutralize the acid with 100% and adjusting the concentration with ion-exchanged water so that the concentration of the copolymer becomes 10% by mass. got i.
The copolymer i thus obtained had a molar ratio (M1/M2) of 1.0 and was measured using GPC. The weight average molecular weight was 24,000, and the acid value was measured by acid value titration. , 120 mg KOH/g.

(Synthesis Example 10 of Copolymer)
-Synthesis of Copolymer j-
In Synthesis Example 1 of copolymer, acrylic acid (manufactured by Aldrich Co.) was changed to 1.30 parts by mass (22.0 mmol), and the monomer represented by the structural formula (4-1) was replaced by the following structural formula (4- A copolymer was obtained in the same manner as in Synthesis Example 1 of copolymer, except that the monomer represented by 3) was changed to 6.29 parts by mass (14.7 mmol) and reacted at 60° C. for 11 hours.
The obtained copolymer was dissolved in an aqueous dimethylethanolamine solution so as to be 100% acid-neutralized, and the concentration of the copolymer was adjusted with ion-exchanged water so that the concentration of the copolymer was 10% by mass. Got
The copolymer j thus obtained had a molar ratio (M1/M2) of 1.5 and was measured using GPC. The weight average molecular weight was 20,000, and the acid value was measured by acid value titration. , 160 mg KOH/g.

(Synthesis Example 11 of Copolymer)
-Synthesis of Copolymer k-
In Synthesis Example 1 of copolymer, acrylic acid (manufactured by Aldrich Co.) was changed to 2.00 parts by mass (33.9 mmol), and the monomer represented by the structural formula (4-1) was replaced with the structural formula (5-1). A copolymer was obtained in the same manner as in Synthesis Example 1 of copolymer, except that the amount of the monomer represented by 6.) was changed to 6.93 parts by mass (16.9 mmol) and the reaction was performed at 60° C. for 15 hours.
While the obtained copolymer is dissolved in a dimethylethanolamine aqueous solution so as to be 100% acid-neutralized, the concentration of the copolymer is adjusted to 10% by mass with ion-exchanged water to obtain a copolymer k. Got
The copolymer k thus obtained had a molar ratio (M1/M2) of 2.0 and a weight average molecular weight of 30,000 as measured by GPC, and an acid value measured by acid value titration. , 200 mg KOH/g.

(Example 1)
<Preparation of treatment liquid>
Polyamine derivative A solution: 60.0 parts by mass 3-Ethyl-3-hydroxymethyloxetane: 10.0 parts by mass 1,3-butanediol: 5.0 parts by mass 2-Ethyl-1,3-hexane Diol: 0.5 parts by mass Emulgen LS-106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by Kao Corporation): 0.1 parts by mass 2-amino-2-ethyl-1,3-propanediol: 0 0.2 parts by mass Proxel LV (antiseptic/antifungal agent, manufactured by Arch Chemicals Japan Co., Ltd.): 0.1 parts by mass Deionized water: 24.1 parts by mass Dissolve and mix the ingredients of the above formulation in ion exchanged water. Then, it was filtered through a filter having an average pore size of 0.5 μm to obtain a treatment liquid 1.

<Preparation of pigment dispersion>
-NIPEX160IQ (carbon black, manufactured by Orion Engineered Carbons Co., Ltd.): 15.0 parts by mass-Copolymer a (copolymer concentration 10% by mass): 37.5 parts by mass-Ion-exchanged water: 47.5 parts by mass When the copolymer a was added to the ion-exchanged water and dissolved, and the carbon black NIPEX160IQ was mixed and sufficiently moistened by stirring, a 0.2 mm diameter was obtained in a Dynomill KDL A type (manufactured by WAB) as a kneading device. The zirconia beads in Example 1 were filled and kneading was performed at 2,000 rpm for 20 minutes. The mill base was taken out and filtered with a filter having an average pore size of 1 μm to obtain a pigment dispersion 1.

<Preparation of ink>
Pigment dispersion 1: 30.0 parts by mass 2-Pyrrolidone: 5.0 parts by mass 1,3-Butanediol: 15.0 parts by mass Glycerin: 15.0 parts by mass 2-Ethyl-1,3 -Hexanediol: 2.0 parts by mass TEGO wet-270 (polyether-modified polysiloxane surfactant, manufactured by Evonik): 0.5 parts by mass 2-amino-2-ethyl-1,3-propanediol: 0.5 parts by mass ・Proxel LV (antiseptic and fungicide, manufactured by Arch Chemicals Japan): 0.1 parts by mass ・Ion-exchanged water: 31.9 parts by mass After dissolving in ion-exchanged water to prepare a vehicle, it was mixed with the pigment dispersion 1 and filtered through a filter having an average pore size of 1 μm to obtain an ink 1.
The amine value/acid value in Example 1 was calculated to be 2.7.

(Example 2)
<Preparation of treatment liquid>
Treatment liquid 2 was obtained in the same manner as treatment liquid 1, except that isopropylideneglycerol was used instead of 3-ethyl-3-hydroxymethyloxetane in treatment liquid 1.

<Preparation of ink>
Ink 1 used in Example 1 was used.
The value of amine value/acid value in Example 2 was calculated to be 2.7.

(Example 3)
<Preparation of treatment liquid>
Treatment liquid 3 was obtained in the same manner as treatment liquid 1 except that N,N-dimethyl-β-butoxypropionamide was used instead of 3-ethyl-3-hydroxymethyloxetane of treatment liquid 1.

<Preparation of ink>
Ink 1 used in Example 1 was used.
The amine value/acid value in Example 3 was calculated to be 2.7.

(Example 4)
<Preparation of treatment liquid>
-Polyamine derivative B solution: 60.0 parts by mass-Glycerin: 15.0 parts by mass-2-Ethyl-1,3-hexanediol: 0.5 parts by mass-Emulgen LS-106 (polyoxyethylene polyoxypropylene alkyl ether) , Kao Co., Ltd.): 0.1 parts by mass 2-Amino-2-ethyl-1,3 propanediol: 0.2 parts by mass Proxel LV (antiseptic and fungicide, manufactured by Arch Chemicals Japan Co.): 0.1 parts by mass Ion-exchanged water: 24.1 parts by mass The materials of the above formulation were dissolved in ion-exchanged water, mixed and filtered through a filter having an average pore size of 0.5 μm to obtain a treatment liquid 4.

<Preparation of pigment dispersion>
Ink Jet Yellow 4GC (CI Pigment Yellow 155, manufactured by Clariant Japan Co., Ltd.): 15.0 parts by mass Copolymer a (copolymer concentration 10% by mass): 37.5 parts by mass Ion exchange Water: 47.5 parts by mass The copolymer a is added to and dissolved in the ion-exchanged water, the Ink Jet Yellow 4GC is mixed, and the mixture is sufficiently moistened by stirring. (Manufactured by the company) was filled with zirconia beads having a diameter of 0.2 mm, and kneading was performed at 2,000 rpm for 60 minutes. The mill base was taken out and filtered with a filter having an average pore size of 1 μm to obtain a pigment dispersion 4.

<Preparation of ink>
Pigment Dispersion 4: 30.0 parts by mass 3-Ethyl-3-hydroxymethyloxetane: 20.0 parts by mass Glycerin: 15.0 parts by mass 2-Ethyl-1,3-hexanediol: 2.0 Parts by mass ・TEGO wet-270 (polyether-modified polysiloxane surfactant, manufactured by Evonik): 0.5 parts by mass 2-amino-2-ethyl-1,3 propanediol: 0.5 parts by mass ・Proxel LV (Antiseptic and antifungal agent, manufactured by Arch Chemicals Japan Co., Ltd.): 0.1 parts by mass Ion-exchanged water: 31.9 parts by mass Dissolve the ingredients of the above formulation other than the pigment dispersion 4 in the ion-exchanged water. After the vehicle was prepared, it was mixed with the pigment dispersion 4 and filtered through a filter having an average pore size of 1 μm to obtain ink 4.
The amine value/acid value in Example 4 was calculated to be 2.9.

(Example 5)
<Preparation of treatment liquid>
The treatment liquid 4 of Example 4 was used.

<Preparation of ink>
Ink 5 was obtained in the same manner as Ink 4, except that isopropylideneglycerol was used instead of 3-ethyl-3-hydroxymethyloxetane in Ink 4 of Example 4.
The amine value/acid value in Example 5 was calculated to be 2.9.

(Example 6)
<Preparation of treatment liquid>
The treatment liquid 4 of Example 4 was used.

<Preparation of ink>
Ink 6 was obtained in the same manner as Ink 4 except that N,N-dimethyl-β-butoxypropionamide was used instead of 3-ethyl-3-hydroxymethyloxetane in Ink 4 of Example 4.
The amine value/acid value in Example 6 was calculated to be 2.9.

(Example 7)
<Preparation of treatment liquid>
The treatment liquid 4 of Example 4 was used.

<Preparation of ink>
An ink except that 20.0 parts by mass of 3-ethyl-3-hydroxymethyloxetane in Ink 4 of Example 4 was replaced with 5.0 parts by mass of 2-pyrrolidone and 15.0 parts by mass of 1,3-butanediol. Ink 7 was obtained in the same manner as in 4.
The amine value/acid value in Example 7 was calculated to be 2.9.

(Example 8)
<Preparation of treatment liquid>
DK6852 (modified polyamine resin aqueous solution represented by the general formula (1), solid content 50% by mass, manufactured by Hoshiko PMC Co., Ltd.): 60.0 parts by mass 3-ethyl-3-hydroxymethyloxetane: 10.0 Parts by mass 1,3-butanediol: 5.0 parts by mass 2-ethyl-1,3-hexanediol: 0.5 parts by mass Emulgen LS-106 (polyoxyethylene polyoxypropylene alkyl ether, Kao Corporation) Made): 0.1 parts by mass 2-amino-2-ethyl-1,3 propanediol: 0.2 parts by mass Proxel LV (antiseptic/antifungal agent, manufactured by Arch Chemicals Japan): 0.1 parts by mass Parts-Ion-exchanged water: 24.1 parts by mass The materials of the above formulation were dissolved in ion-exchanged water, mixed, and filtered through a filter having an average pore size of 0.5 µm to obtain a treatment liquid 8.

<Preparation of pigment dispersion>
FASTOGEN Super Magenta JM2120 (CI Pigment Red 202/CI Pigment Violet 19 mixed crystal, manufactured by DIC Corporation): 15.0 parts by mass Copolymer b (copolymer concentration 10% by mass): 37.5 parts by mass Ion-exchanged water: 47.5 parts by mass The copolymer b is added to and dissolved in the ion-exchanged water, the FASTOGEN Super Magenta JM2120 is mixed, and the mixture is kneaded when sufficiently wet by stirring. As a device, a Dyno-mill KDL A type (manufactured by WAB) was filled with zirconia beads having a diameter of 0.2 mm, and kneading was performed at 2000 rpm for 10 minutes. The mill base was taken out and filtered with a filter having an average pore size of 1 μm to obtain a pigment dispersion 8.

<Preparation of ink>
Ink 8 was obtained in the same manner as Ink 1 except that Pigment Dispersion 1 in Ink 1 of Example 1 was replaced with Pigment Dispersion 8.
The amine value/acid value in Example 8 was calculated to be 1.0.

(Example 9)
<Preparation of treatment liquid>
The treatment liquid 8 of Example 8 was used.

<Preparation of pigment dispersion>
Pigment Dispersion 9 was obtained in the same manner as Pigment Dispersion 8 except that Copolymer c was used instead of Copolymer b in Pigment Dispersion 8 of Example 8.

<Preparation of ink>
Ink 9 was obtained in the same manner as Ink 8, except that the pigment dispersion 8 in Ink 8 of Example 8 was replaced with the pigment dispersion 9.
The amine value/acid value of Example 9 was calculated to be 1.3.

(Example 10)
<Preparation of treatment liquid>
The treatment liquid 8 of Example 8 was used.

<Preparation of pigment dispersion>
A pigment dispersion 10 was obtained in the same manner as in the pigment dispersion 8 except that the copolymer b in the pigment dispersion 8 of Example 8 was replaced with the copolymer d.

<Preparation of ink>
Ink 10 was obtained in the same manner as Ink 8, except that the pigment dispersion 8 in Ink 8 of Example 8 was replaced with the pigment dispersion 10.
The amine value/acid value in Example 10 was calculated to be 1.5.

(Example 11)
<Preparation of treatment liquid>
The treatment liquid 8 of Example 8 was used.

<Preparation of pigment dispersion>
Pigment Dispersion 11 was obtained in the same manner as Pigment Dispersion 8 except that Copolymer e was used instead of Copolymer b in Pigment Dispersion 8 of Example 8.

<Preparation of ink>
Ink 11 was obtained in the same manner as Ink 8, except that the pigment dispersion 8 in Ink 8 of Example 8 was replaced with the pigment dispersion 11.
The amine value/acid value in Example 11 was calculated to be 1.5.

(Example 12)
<Preparation of treatment liquid>
The treatment liquid 8 of Example 8 was used.

<Preparation of pigment dispersion>
A pigment dispersion 12 was obtained in the same manner as in the pigment dispersion 8 except that the copolymer b in the pigment dispersion 8 of Example 8 was replaced with the copolymer f.

<Preparation of ink>
Ink 12 was obtained in the same manner as Ink 8, except that pigment dispersion 8 in Ink 8 of Example 8 was replaced with pigment dispersion 12.
The amine value/acid value in Example 12 was calculated to be 2.1.

(Example 13)
<Preparation of treatment liquid>
A treatment liquid 13 was obtained in the same manner as in Example 4 except that the polyamine derivative B in the treatment liquid 4 of Example 4 was replaced with the polyamine derivative C.

<Preparation of pigment dispersion>
Cyanine blue A220JC (CI Pigment Blue 15:3, manufactured by Dainichiseika Co., Ltd.): 15.0 parts by mass Copolymer f (copolymer concentration 10% by mass): 37.5 parts by mass Exchanged water: 47.5 parts by mass The copolymer f was added to and dissolved in the ion-exchanged water, the cyanine blue A220JC was mixed, and when sufficiently agitated, a Dynomill KDL A type (WAB) was used as a kneading device. (Manufactured by the company) was filled with zirconia beads having a diameter of 0.2 mm, and kneading was performed at 2,000 rpm for 20 minutes. The pigment dispersion 13 was obtained by taking out the mill base and filtering it with a filter having an average pore diameter of 1 μm.

<Preparation of ink>
Pigment Dispersion 13: 30.0 parts by mass 3-Ethyl-3-hydroxymethyloxetane: 15.0 parts by mass N,N-Dimethyl-β-butoxypropionamide: 5.0 parts by mass Butanediol: 15.0 parts by mass 2-Ethyl-1,3-hexanediol: 2.0 parts by mass ・TEGO wet-270 (polyether-modified polysiloxane surfactant, manufactured by Evonik): 0.5 parts by mass 2-amino-2-ethyl-1,3 propanediol: 0.5 parts by mass Proxel LV (antiseptic and fungicide, manufactured by Arch Chemicals Japan): 0.1 parts by mass Deionized water: 31. 9 parts by mass Materials of the above formulation other than the pigment dispersion 13 are dissolved in the ion-exchanged water to prepare a vehicle, which is then mixed with the pigment dispersion 13 and filtered through a filter having an average pore size of 1 μm to prepare the ink 13. Obtained.
The amine value/acid value in Example 13 was calculated to be 1.3.

(Example 14)
<Preparation of treatment liquid>
The treatment liquid 13 of Example 13 was used.

<Preparation of pigment dispersion>
Pigment Dispersion 14 was obtained in the same manner as Pigment Dispersion 13 except that Copolymer g was used instead of Copolymer f in Pigment Dispersion 13 of Example 13.

<Preparation of ink>
Ink 14 was obtained in the same manner as Ink 13, except that the pigment dispersion 13 in Ink 13 of Example 13 was replaced with the pigment dispersion 14.
The amine value/acid value in Example 14 was calculated to be 1.2.

(Example 15)
<Preparation of treatment liquid>
The treatment liquid 13 of Example 13 was used.

<Preparation of pigment dispersion>
A pigment dispersion 15 was obtained in the same manner as the pigment dispersion 13 except that the copolymer f in the pigment dispersion 13 of Example 13 was replaced with the copolymer h.

<Preparation of ink>
Ink 15 was obtained in the same manner as Ink 13, except that the pigment dispersion 13 in Ink 13 of Example 13 was replaced with the pigment dispersion 15.
The amine value/acid value in Example 15 was calculated to be 2.5.

(Example 16)
<Preparation of treatment liquid>
The treatment liquid 13 of Example 13 was used.

<Preparation of pigment dispersion>
Pigment Dispersion 16 was obtained in the same manner as Pigment Dispersion 13 except that Copolymer i was used instead of Copolymer f in Pigment Dispersion 13 of Example 13.

<Preparation of ink>
Ink 16 was obtained in the same manner as Ink 13 except that the pigment dispersion 13 in Ink 13 of Example 13 was changed to pigment dispersion 16.
The amine value/acid value in Example 16 was calculated to be 2.1.

(Example 17)
<Preparation of treatment liquid>
Polyamide derivative D solution (the above general formula (2)): 60.0 parts by mass N,N-dimethyl-β-butoxypropionamide: 10.0 parts by mass 2-pyrrolidone: 5.0 parts by mass Ethyl-1,3-hexanediol: 0.5 parts by mass Emulgen LS-106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by Kao Corporation): 0.1 parts by mass 2-amino-2-ethyl-1 , 3-Propanediol: 0.2 parts by mass Proxel LV (antiseptic and fungicide, manufactured by Arch Chemicals Japan Co., Ltd.): 0.1 parts by mass Ion-exchanged water: 24.1 parts by mass It was dissolved in exchanged water, mixed, and filtered with a filter having an average pore size of 0.5 μm to obtain a treatment liquid 17.

<Preparation of pigment dispersion>
A pigment dispersion 17 was obtained in the same manner as in the pigment dispersion 16 except that the copolymer j in the pigment dispersion 13 of Example 16 was replaced with the copolymer j.

<Preparation of ink>
Ink 17 was obtained in the same manner as Ink 13, except that pigment dispersion 13 in Ink 13 of Example 13 was replaced with pigment dispersion 17.
The amine value/acid value in Example 17 was calculated to be 1.2.

(Example 18)
<Preparation of treatment liquid>
The treatment liquid 17 of Example 17 was used.

<Preparation of pigment dispersion>
Inkjet Magenta E5B 02 (CI Pigment Violet 19, Clariant Japan KK): 15.0 parts by mass Copolymer f (copolymer concentration 10% by mass): 37.5 parts by mass Ion exchange Water: 47.5 parts by mass The copolymer f is added to and dissolved in the ion-exchanged water, the Inkjet Magenta E5B 02 is mixed, and the mixture is sufficiently moistened by stirring. (Manufactured by the company) was filled with zirconia beads having a diameter of 0.2 mm and kneaded at 2,000 rpm for 20 minutes. The pigment dispersion 18 was obtained by taking out the mill base and filtering it with a filter having an average pore size of 1 μm.

<Preparation of ink>
An ink 18 was obtained in the same manner as the ink 17, except that the pigment dispersion 17 in the ink 17 of Example 17 was replaced with the pigment dispersion 18.
The amine value/acid value in Example 18 was calculated to be 1.2.

(Example 19)
<Preparation of treatment liquid>
The treatment liquid 17 of Example 17 was used.

<Preparation of pigment dispersion>
-Yellow No. 55 (CI Pigment Yellow 74, manufactured by Dainichiseika Co., Ltd.): 15.0 parts by mass-Copolymer j (copolymer concentration 10% by mass): 37.5 parts by mass-Ion-exchanged water: 47. 5 parts by mass The copolymer j was added to the ion-exchanged water to dissolve it, and the yellow No. When 55 was mixed, stirred and sufficiently moistened, dyno mill KDL A type (manufactured by WAB) as a kneading device was filled with zirconia beads having a diameter of 0.2 mm, and kneading was performed at 2,000 rpm for 60 minutes. The pigment dispersion 19 was obtained by taking out the mill base and filtering it with a filter having an average pore size of 1 μm.

<Preparation of ink>
Ink 19 was obtained in the same manner as Ink 17, except that the pigment dispersion 17 in Ink 17 of Example 17 was replaced with the pigment dispersion 19.
The amine value/acid value in Example 19 was calculated to be 1.2.

(Example 20)
<Preparation of treatment liquid>
The treatment liquid 17 of Example 17 was used.

<Preparation of pigment dispersion>
・NIPEX160IQ (carbon black, manufactured by Orion Engineered Carbons Co., Ltd.): 15.0 parts by mass ・Copolymer j (copolymer concentration 10% by mass): 37.5 parts by mass ・Ion exchange water: 47.5 parts by mass Part When the copolymer j was added to the ion-exchanged water to dissolve it, the NIPEX160IQ was mixed, and when sufficiently agitated, a Dynomill KDL A type (manufactured by WAB) with a diameter of 0.2 mm was used as a kneading device. It was filled with zirconia beads and kneaded at 2,000 rpm for 20 minutes. The mill base was taken out and filtered with a filter having an average pore size of 1 μm to obtain a pigment dispersion 20.

<Preparation of ink>
Ink 20 was obtained in the same manner as Ink 17, except that the pigment dispersion 17 in Ink 17 of Example 17 was replaced with pigment dispersion 20.
The amine value/acid value in Example 20 was calculated to be 1.2.

(Example 21)
<Preparation of treatment liquid>
The same formulation as in the treatment liquid 17, except that the polyamide derivative D in the treatment liquid 17 of Example 17 was replaced with Charol DC-902P (polyamine derivative aqueous solution, active ingredient 52% by mass, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). The process liquid 21 was obtained using the method.

<Preparation of ink>
Ink 20 of Example 20 was used.
The amine value/acid value in Example 21 was calculated to be 2.2.

(Example 22)
<Preparation of treatment liquid>
The same formulation as in the treatment liquid 17, except that the polyamide derivative D in the treatment liquid 17 in Example 17 was replaced with Charol DM-283P (polyamine derivative aqueous solution, active ingredient 50% by mass, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The processing liquid 22 was obtained using the method.

<Preparation of pigment dispersion>
XPB506 (carbon black, manufactured by Orion Engineered Carbons Co., Ltd.): 15.0 parts by mass Copolymer k (copolymer concentration 10% by mass): 37.5 parts by mass Ion-exchanged water: 47.5 parts by mass Parts When the copolymer k was added to the ion-exchanged water to dissolve it, the XPB506 was mixed, and the mixture was stirred and sufficiently moistened, a 0.2 mm diameter zirconia was added to a Dyno-mill KDL A type (manufactured by WAB) as a kneading device. The beads were filled and kneading was performed at 2,000 rpm for 20 minutes. The mill base was taken out and filtered with a filter having an average pore size of 1 μm to obtain a pigment dispersion 22.

<Preparation of ink>
Ink 22 was obtained in the same manner as Ink 17, except that pigment dispersion 17 in Ink 17 of Example 17 was replaced with pigment dispersion 22.
The amine value/acid value in Example 22 was calculated to be 1.4.

(Comparative Example 1)
<Preparation of treatment liquid>
The treatment liquid 4 of Example 4 was used.

<Preparation of ink>
Ink 15 of Example 15 was used.
The amine value/acid value in Comparative Example 1 was calculated to be 4.2.

(Comparative example 2)
<Preparation of treatment liquid>
The treatment liquid 17 of Example 17 was used.

<Preparation of ink>
Ink 10 of Example 10 was used.
The amine value/acid value in Comparative Example 2 was calculated to be 0.7.

(Comparative example 3)
<Preparation of treatment liquid>
A treatment liquid 23 was obtained by using the same formulation and method as the treatment liquid 2, except that the polyamine derivative A in the treatment liquid 2 of Example 2 was replaced with the polyamine derivative E.

<Preparation of ink>
Ink 2 of Example 2 was used.
The amine value/acid value in Comparative Example 3 was calculated to be 3.6.

(Comparative example 4)
<Preparation of treatment liquid>
The treatment liquid 17 of Example 19 was used.

<Preparation of pigment dispersion>
Pigment dispersion was carried out in the same manner as in Pigment dispersion 19 except that the copolymer j in the pigment dispersion 19 of Example 19 was replaced with a nonionic dispersion resin (BYK2012, acid value 7 mgKOH/g, manufactured by BYK Chemie). I got body 23.

<Preparation of ink>
Ink 23 was obtained in the same manner as Ink 19 except that pigment dispersion 19 in Ink 19 of Example 19 was replaced with pigment dispersion 23.
The amine value/acid value in Comparative Example 4 was calculated to be 26.4.

Next, Table 1 shows the amine value/acid value of Examples 1 to 22 and Comparative Examples 1 to 4. Further, Table 2 shows the treatment liquid formulations of Examples 1 to 22 and Comparative Examples 1 to 4. In addition, Table 3 shows the ink formulations of Examples 1 to 22 and Comparative Examples 1 to 4.

*DK6852: modified polyamine resin aqueous solution represented by the general formula (1), solid content 50 mass%, manufactured by Hoshikou PMC Co., Ltd. * Charol DC-902P: polyamine derivative aqueous solution, active ingredient 52 mass%, Daiichi Kogyo Seiyaku Co., Ltd. Company * Charol DM-283P: polyamine derivative aqueous solution, active ingredient 50% by mass, Daiichi Kogyo Seiyaku Co., Ltd. * nonionic dispersion resin (byk2012, acid value 7 mgKOH/g, manufactured by BYK Chemie)

The contents of the abbreviations in Table 2 are as follows.
*EHO: 3-ethyl-3-hydroxymethyloxetane *IPG: isopropylidene glycerol *DBPA: N,N-dimethyl-β-butoxypropionamide *2P: 2-pyrrolidone *13BD: 1,3-butanediol *GLY: Glycerin *2E13HD: 2-ethyl-1,3-hexanediol *LS106: Emulgen LS-106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by Kao Corporation)
*AEPD: 2-amino-2-ethyl-1,3-propanediol *LV: Proxel LV (antiseptic/antifungal agent, manufactured by Arch Chemicals Japan)

The contents of the abbreviations in Table 3 are as follows.
*EHO: 3-ethyl-3-hydroxymethyl oxetane *IPG: isopropylidene glycerol *DBPA: N,N-dimethyl-β-butoxypropionamide *2P:2-pyrrolidone *13BD: 1,3-butanediol *GLY: Glycerin*2E13HD: 2-ethyl-1,3-hexanediol*wet270: TEGO wet-270 (polyether-modified polysiloxane surfactant, manufactured by Evonik)
*AEPD: 2-amino-2-ethyl-1,3-propanediol *LV: Proxel LV (antiseptic/antifungal agent, manufactured by Arch Chemicals Japan)

Next, various characteristics of the image forming sets having the prepared Examples 1 to 22 and Comparative Examples 1 to 4 and the treatment liquid were evaluated as follows. The results are shown in Tables 4 and 5.

<Image density (black ink/plain paper)>
Using an image forming apparatus having a treatment liquid application mechanism shown in FIG. 3 at 23° C. and 50% RH, each treatment liquid prepared in Examples and Comparative Examples was uniformly applied to one side of 500 mg/m on the following evaluation paper. ^{2 to} 600 mg/m ^{2 was} applied.
Next, the black inks produced in the examples and comparative examples were printed using the image forming apparatus having the treatment liquid application mechanism shown in FIG. As the printed image, a chart with 64 point characters "■" prepared by Microsoft Word (manufactured by Microsoft) was punched out at a recording density of 600 dpi x 600 dpi, and after naturally drying, the "■" part of the printed surface was reflected. Color spectrophotometric densitometer (X-Rite 938, manufactured by X-Rite Co., Ltd.) was used for the color measurement, and the evaluation was made according to the following evaluation criteria. The allowable range is B or more.
[Evaluation paper]
My paper (plain paper, made by Ricoh Co., Ltd.)
[Evaluation criteria]
A: 1.4 or more B: 1.3 or more and less than 1.4 C: 1.2 or more and less than 1.3 D: less than 1.2

<Image density (black ink/coated paper)>
Using the image forming apparatus having the treatment liquid application mechanism shown in FIG. 3 used for the above-mentioned image density measurement (black ink/plain paper), the recording paper was changed to the following coated paper, and the recording density was 1,200 dpi×1,200 dpi. Printing was performed in the same manner except that the above was changed to, and the 64 point character "■" on the printing surface was measured with a reflective color spectrophotometric densitometer (X-Rite 938, manufactured by X-Rite), and the following evaluation criteria were used. It was judged by. The allowable range is B or more.
[Evaluation paper]
OK Top Coat + (Coated paper, made by Oji Paper Co., Ltd.)
[Evaluation criteria]
A: 1.9 or more B: 1.7 or more and less than 1.9 C: 1.5 or more and less than 1.7 D: less than 1.5

<Saturation measurement (color ink/plain paper)>
A similar method was used except that the image forming apparatus having the treatment liquid application mechanism shown in FIG. 3 used for the above-mentioned image darkness measurement (black ink/plain paper) was used and color inks (yellow, magenta, cyan) were used. Printing was performed using the above, and the value of L ^* a ^* b ^* was measured using a reflective color spectral colorimetric densitometer (X-Rite 938, manufactured by X-Rite). From this data, the saturation C ^* =[(a ^* ) ² +(b ^* ) ² ] ^1/2 was calculated and the saturation value of the standard color (Japan color ver. 2) (yellow: 91.34, The ratio of the measured saturation to magenta: 74.55, cyan: 62.82) was calculated and evaluated based on the following criteria. The allowable range is B or more.
[Evaluation paper]
My paper (plain paper, made by Ricoh Co., Ltd.)
[Evaluation criteria]
A: 1.00 or more B: 0.90 or more and less than 1.00 C: 0.80 or more and less than 0.90 D: less than 0.80

<Saturation measurement (color ink/coated paper)>
Using the image forming apparatus having the treatment liquid application mechanism shown in FIG. 3 used for the above-described saturation measurement (color ink/plain paper), the recording paper was changed to the following coated paper, and the recording density was 1,200 dpi×1,200 dpi. Using the same method, except that the value was changed to, the ratio of saturation to the reference value was calculated and evaluated according to the following criteria. The allowable range is B or more.
[Evaluation paper]
OK Top Coat + (Coated paper, made by Oji Paper Co., Ltd.)
[Evaluation criteria]
A: 1.10 or more B: 1.00 or more and less than 1.10 C: 0.90 or more and less than 1.00 D: less than 0.90

<Strikethrough density>
In the case of plain paper, which has a high ink absorption property, the ink may penetrate into the inside of the medium, and the image may be seen through from the back of the printed surface, which is called the show-through density.
Using the above-mentioned 64 point character “■” part where the image density and saturation of the image surface were measured, an image was recorded from the back side of the recording paper using a reflective color spectrophotometric densitometer (X-Rite 938, manufactured by X-Rite). The value obtained by measuring the density was set as r _1, and the image-free portion of the back surface (non-image portion) was set as r ₀ by measuring the image density using the same reflection type color spectral colorimeter. A value (r ₁ −r ₀ ) obtained by subtracting r ₀ from r _{1 of} each solid image was calculated, and strikethrough density was evaluated according to the following evaluation criteria. The allowable range is B or more.
[Evaluation paper]
My paper (plain paper, made by Ricoh Co., Ltd.)
[Evaluation criteria]
A: r ₁ −r ₀ <0.05
B: 0.05≦r ₁ −r ₀ <0.10
C: 0.10≦r ₁ −r ₀ <0.20
D: 0.20≦r ₁ −r ₀

<Beading>
Coated paper with a coating layer such as printing paper, which has a poor ink absorption property, has a phenomenon in which adjacent dots are attracted to a solid image and the image appears to be jarring. This is called beading. ..
The beading was visually evaluated based on the following criteria by using the above-mentioned 64 point character "■" part where the image density and the saturation of the image surface were measured. The allowable range is B or more.
[Evaluation paper]
OK Top Coat + (Coated paper, made by Oji Paper Co., Ltd.)
[Evaluation criteria]
A: No beading can be seen B: Beading can be identified by staring C: Beading can be identified without staring D: Violent beading

<Corrosion resistance (treatment liquid application roller)>
The film thickness control roller 2, the application roller 4 and the counter roller 5 in the image forming apparatus having the treatment liquid application mechanism shown in FIG. 3 are immersed in the treatment liquid used in the examples and the comparative examples, respectively, and the temperature is kept at 70° C. for 2 weeks. After standing, the surface condition of the roller was observed and the corrosion resistance was evaluated according to the following criteria. The allowable range is B or more.
[Evaluation criteria]
A: No change was observed on all roller surfaces B: Some roller surfaces were changed, but recovered by cleaning C: Some roller surfaces were observed not recovered (cleaned) ing)
D: Changes were seen on all roller surfaces, and did not recover by cleaning (corrosion)

Aspects of the present invention are as follows, for example.
<1> An image forming set comprising a treatment liquid applied to a recording medium and an ink applied to the recording medium to which the treatment liquid has been applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a structural unit containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. The image forming set is characterized by being 0 or less.
<2> In the image forming set according to <1>, at least one of the polyamine derivative and the polyamide derivative is a compound represented by any one of the following general formula (1) and the following general formula (2). is there.
However, in the general formula (1), R _{1 to} R ₈ are any of an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkenyl group, and a benzyl group, X represents a halogen atom, and n represents 1 or 2.
However, in the general formula (2), X represents a halogen atom, and n represents an integer of 1 or more.
<3> The image forming set according to any one of <1> to <2>, wherein the group containing an aromatic ring is either a naphthyl group or a biphenyl group.
<4> The image forming set according to any one of <1> to <3>, wherein the structural unit containing the anion group is represented by the following general formula (3).
However, in the general formula (3), R ₉ represents either a hydrogen atom or a methyl group, and M ⁺ represents either a hydrogen ion or a cation.
<5> The structural unit containing a group containing an aromatic ring is any one of <1> to <4>, which is any one of the following general formulas (4) and (5). Is an image forming set.
However, in the general formula (4), R ₁₀ represents either a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms.
However, in the general formula (5), R ₁₁ represents either a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms.
<6> In the copolymer, the molar ratio (M1/) between the number of moles of the structural unit containing the anionic group (M1) and the number of moles of the structural unit containing a group containing the aromatic ring (M2). M2) is the image forming set according to any one of <1> to <5>, which is 1 or more and 3 or less.
<7> The organic solvent contained in the treatment liquid is at least one selected from 3-ethyl-3-hydroxymethyloxetane, isopropylideneglycerol, and 3-butoxy-N,N-dimethylpropionamide. The image forming set according to any one of <1> to <6>.
<8> The organic solvent contained in the ink is at least one selected from 3-ethyl-3-hydroxymethyloxetane, isopropylidene glycerol, and 3-butoxy-N,N-dimethylpropionamide. The image forming set according to any one of 1> to <7>.
<9> The image forming set according to any one of <1> to <8>, wherein the weight average molecular weight of the copolymer is 3,000 or more and 60,000 or less.
<10> The molar ratio (M1) of the molar number (M1) of the structural unit containing the anionic group constituting the copolymer to the molar number (M2) of the structural unit containing the group containing an aromatic ring. /M2) is 0.1 or more and 10 or less, and the image forming set according to any one of <1> to <9>.
<11> The content of at least one of the polyamine derivative and the polyamide derivative is 5% by mass or more and 50% by mass or less with respect to the total amount of the treatment liquid, according to any one of <1> to <10>. It is an image forming set.
<12> An image forming apparatus comprising: a treatment liquid applying unit that applies a treatment liquid to a recording medium; and an ink applying unit that applies ink to the recording medium to which the treatment liquid is applied.
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a structural unit containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. The image forming apparatus is 0 or less.
<13> The image forming apparatus according to <12>, wherein the recording medium is at least one of plain paper and coated paper for printing.
<14> An image forming method comprising: a treatment liquid applying step of applying a treatment liquid to a recording medium; and an ink applying step of applying ink to the recording medium to which the treatment liquid is applied.
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a structural unit containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. The image forming method is characterized by being 0 or less.
<15> The image forming method according to <14>, wherein the recording medium is at least one of plain paper and coated printing paper.

The image forming set according to any one of <1> to <11>, the image forming apparatus according to any of <12> to <13>, and any one of <14> to <15>. According to the image forming method, it is possible to solve the above-mentioned problems in the related art and achieve the object of the present invention.

JP, 2014-005448, A

400 image forming apparatus 401 exterior of image forming apparatus 401c cover of apparatus body 404 cartridge holder 410 main tanks 410k, 410c, 410m, 410y for each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 Ink storage section 413 Ink discharge port 414 Storage container case 420 Mechanism section 434 Discharge head 436 Supply tube

Claims (15)

An image forming set comprising a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a structural unit containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. 0 Ri der below,
The organic solvent contained in the ink is at least one selected from 3-ethyl-3-hydroxymethyloxetane, isopropylidene glycerol, and 3-butoxy-N,N-dimethylpropionamide. Image forming set. The image forming set according to claim 1, wherein at least one of the polyamine derivative and the polyamide derivative is a compound represented by any one of the following general formula (1) and the following general formula (2).
However, in the general formula (1), R _{1 to} R ₈ are any of an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkenyl group, and a benzyl group, X represents a halogen atom, and n represents 1 or 2.
However, in the general formula (2), X represents a halogen atom, and n represents an integer of 1 or more. The image forming set according to claim 1, wherein the group containing an aromatic ring is either a naphthyl group or a biphenyl group. The image forming set according to claim 1, wherein the structural unit containing an anion group is represented by the following general formula (3).
However, in the general formula (3), R ₉ represents either a hydrogen atom or a methyl group, and M ⁺ represents either a hydrogen ion or a cation. The image forming set according to claim 1, wherein the structural unit containing a group containing an aromatic ring is one of the following general formulas (4) and (5).
However, in the general formula (4), R ₁₀ represents either a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms.
However, in the general formula (5), R ₁₁ represents either a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms. In the copolymer, the number of moles of the structural unit containing an anionic group and (M1), the molar ratio of the moles (M2) of the structural unit containing a group containing the aromatic ring (M1 / M2) is The image forming set according to claim 1, which is 1 or more and 3 or less. The organic solvent contained in the treatment liquid is at least one selected from 3-ethyl-3-hydroxymethyloxetane, isopropylideneglycerol, and 3-butoxy-N,N-dimethylpropionamide. The image forming set according to any one of 6 above. An image forming set comprising a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. 0 or less,
At least one of the polyamine derivative and the polyamide derivative is a compound represented by any one of the following general formulas (1) and (2).
However, in the general formula (1), R ₁ ~ R ₈ Is an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkenyl group, or a benzyl group, X represents a halogen atom, and n represents 1 or 2.
However, in the general formula (2), X represents a halogen atom, and n represents an integer of 1 or more. An image forming set comprising a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
The group containing an aromatic ring is any of a naphthyl group and a biphenyl group,
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. An image forming set, which is 0 or less. An image forming set comprising a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
The structural unit containing the anion group is represented by the following general formula (3),
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. An image forming set characterized by being 0 or less.
However, in the general formula (3), R ₉ Represents either a hydrogen atom or a methyl group, and M ⁺ Represents either a hydrogen ion or a cation. An image forming set comprising a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
The structural unit containing a group containing an aromatic ring is one of the following general formulas (4) and (5),
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. An image forming set characterized by being 0 or less.
However, in the general formula (4), R ₁₀ Represents a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms.
However, in the general formula (5), R ₁₁ Represents a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 2 to 18 carbon atoms. An image forming set comprising a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
In the copolymer, the molar ratio (M1/M2) between the molar number (M1) of the structural unit containing the anionic group and the molar number (M2) of the structural unit containing the group containing an aromatic ring is 1 or more and 3 or less,
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. An image forming set characterized by being 0 or less. An image forming set comprising a treatment liquid applied to a recording medium, and an ink applied to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. 0 or less,
The organic solvent contained in the treatment liquid is at least one selected from 3-ethyl-3-hydroxymethyloxetane, isopropylidene glycerol, and 3-butoxy-N,N-dimethylpropionamide. Image forming set. An image forming apparatus comprising: a treatment liquid applying unit that applies a treatment liquid to a recording medium; and an ink applying unit that applies ink to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. 0 or less,
The organic solvent contained in the ink is at least one selected from 3-ethyl-3-hydroxymethyloxetane, isopropylidene glycerol, and 3-butoxy-N,N-dimethylpropionamide. Image forming apparatus. An image forming method comprising: a treatment liquid applying step of applying a treatment liquid to a recording medium; and an ink applying step of applying ink to the recording medium to which the treatment liquid is applied,
The treatment liquid contains at least one of a polyamine derivative and a polyamide derivative, an organic solvent, and water,
The ink contains a copolymer having a structural unit containing a group containing an anion group and a group containing an aromatic ring, a coloring material, an organic solvent, and water.
2. The ratio (amine value/acid value) of the amine value (mgKOH/g) of at least one of the polyamine derivative and the polyamide derivative to the acid value (mgKOH/g) of the copolymer is 1.0 or more. 0 or less,
The organic solvent contained in the ink is at least one selected from 3-ethyl-3-hydroxymethyloxetane, isopropylidene glycerol, and 3-butoxy-N,N-dimethylpropionamide. Image forming method.