# Patent

## Title
Ink jet recording method and liquid dispersant

## Abstract

An ink jet recording method including attaching a liquid dispersant in which an amphoteric polymer containing a core portion having a cation group and a shell portion having an anion group that covers the core portion is dispersed in a dispersing medium to a recording medium and discharging and attaching cationic ink containing a coloring material and water to the surface of the recording medium to which the liquid dispersant is attached.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application is based on and claims priority pursuant to 35 U.S.C. §119 to Japanese Patent Application No. 2010-265220 filed on Nov. 29, 2010 in the Japan Patent Office, the entire disclosure of which is hereby incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is related to an ink jet recording method and a liquid dispersant.
2. Description of the Background Art
In response to demand for inexpensive recording of color images in recent years, ink jet recording methods in which ink of multiple different colors is adhered to recording media have become widely used. However, in comparison with recorded materials produced by electrophotography, the recorded material produced by such ink jet recording methods tend to have fine lines that lack sharpness or are susceptible to bleeding at the boundaries between colors. These defects stem from such characteristics as agglomeration and penetration of the ink after the ink is adhered to the recording medium, and accordingly various methods have been researched and developed in an effort to improve these characteristics.
For example, Japanese patent no. 3323565 (JP-3323565-B) describes a method of forming images by adhering a processing liquid that contains a water-soluble resin having a carboxyl group or a sulfone group to a recording medium and then adhering ink that contains an alkali-soluble resin to the processing liquid. By this method, the alkali-soluble resin contained in the ink precipitates upon contact with an acidic first liquid. As a result, the dye in the ink is fixed close to the surface of the recording medium, thereby preventing bleeding at the color boundaries to obtain quality images. However, if an acidic water-soluble resin is used for the processing liquid, modification tends to occur to the recording medium with prolonged preservation, thereby degrading the preservability of the recorded material.
Unexamined Japanese patent application publication no. 2004-130792 (JP-2004-130792-A) describes a recording method using a reaction liquid containing a polyvalent metal and a nonionic polymer and an ink that contains a coloring material, without employing an acidic water-soluble resin. According to this method, since the reaction liquid has the function of destabilizing a dissolved or dispersed state of the coloring material in the ink so that the nonionic polymer increases the adhesion property of accumulations of coloring material matters, with the result that images having excellent abrasion resistance and without color bleeding can be obtained. However, to stabilize multivalent metal ions in the reaction liquid, the reaction liquid must be acidic. In such a case, modification tends to occur to the recording medium as in JP-3323565-B described above and the preservability of the recorded material deteriorates. In addition, since the nonionic water-soluble polymer as described in JP-2004-130792-A is re-dissolved even after forming a film, water-resistant and marker-resistant properties tend to be inferior.
In recent years, a recording method using a processing liquid that contains an amphoteric ionic polymer compound and a recording liquid that contains a coloring material have been proposed, as described in JP-2004-155868-A. Amphoteric ionic polymer compounds generally have minimum viscosity at the isoelectric point (the pH at which the average charge of the entire compound after ionization is zero). Therefore, by making the difference in pH between the pH of the recording liquid and the pH at the isoelectric point of the amphoteric ionic polymer compound larger than a predetermined value, the viscosity of the mixture of the processing liquid and the recording liquid formed when mixed on the recording medium suitably increases, thereby preventing occurrence of color bleeding.
However, in the method described above, fixing of the coloring material is not considered. As a result, abrasion resistance and marker resistance are not satisfactory. That is, if a processing liquid having an amphoteric polymer is used to prevent bleeding, the obtained adhesiveness is not satisfactory.
SUMMARY OF THE INVENTION
In view of the foregoing, the present invention provides an ink jet recording method including the steps of attaching a liquid dispersant in which an amphoteric polymer containing a core portion having a cation group and a shell portion having an anion group that covers the core portion is dispersed in a dispersion medium to the surface of a recording medium and discharging and attaching cationic ink containing a coloring material and water to the surface of the recording medium where the liquid dispersant is attached.
It is preferred that, in the ink jet recording method mentioned above, the coloring material of the cationic ink contains a cation group.
It is still further preferred that, in the ink jet recording method mentioned above, the an amount of the liquid dispersant attached to the recording medium as measured by a dynamic scanning absorptometer is from 10 ml/m2 to 25 ml/m2 for a contact time of 100 ms.
It is still further preferred that, in the ink jet recording method mentioned above, the liquid dispersant further contains an aqueous organic solvent and a surface active agent.
It is still further preferred that, in the ink jet recording method mentioned above, the surface active agent is a silicone-based surface active agent.
As another aspect of the present invention, a liquid dispersant for use in an ink jet recording method is provided which contains a dispersion medium and an amphoteric polymer containing a core portion having a cation group and a shell portion having an anion group that covers the core portion, the amphoteric polymer being dispersed in the dispersion medium.


DETAILED DESCRIPTION OF THE PRESENT DISCLOSURE
The ink jet recording method of the present disclosure includes a process of attaching a liquid dispersant (i.e., processing liquid) in which an amphoteric polymer having a core portion containing a cation group and a shell portion having an anion group which covers the core portion is dispersed in a dispersion medium to a recording medium and a process of discharging and attaching cationic ink containing a coloring material and water to the recording medium on which the liquid dispersant is attached.
Processing Liquid (Liquid Dispersion)
The processing liquid for use in the ink jet recording method of the present disclosure contains an amphoteric polymer (i.e., a polymer having both an anion group and a cation group) and a dispersing solvent.
An amphoteric polymer that has a core portion containing a cation group and a shell portion containing an anion group that covers the core portion is used as the amphoteric polymer to improve the fixing property.
Typical anionic polymers and amphoteric polymers are expected to agglomerate cationic ink attached to a recording medium, typically paper. However, the interaction between the polymers contained in a coloring material and a liquid dispersant is not strong enough to obtain a satisfying fixing property.
On the other hand, when the liquid dispersant for use in the ink jet recording method of the present disclosure contacts cationic ink on a recording medium, part of the anionic charges in the shell portion of the amphoteric polymer is consumed to neutralization of the coloring material, which causes agglomeration. The rest of the anionic group causes electrostatic mutual action with the cationic group present in the molecule and attracts the coloring material, resulting in formation of firm agglomerated body. That is, since such a firm agglomerated body of the coloring material is formed on the recording medium after the ink attachment, feathering (spread of a single color into a recording medium) and bleeding (spread and mixing at color boundaries) can be reduced, resulting in production of recorded materials having an excellent fixing property.
In this way, by using a liquid dispersant that contains a polymer having a shell portion containing a charge (anion) reverse to that of the cationic ink, agglomeration occurs first by the neutralization of charges and then the coloring material is attracted by the electrostatic mutual action between the rest of the charges (anion) and the charge (cation) of the core portion, resulting in increase of the agglomeration effect. Therefore, high definition images with less bleeding and excellent abrasion resistance, water resistance, and marker resistance can be obtained.
The amphoteric polymer of the liquid dispersant for use in the ink jet recording method of the present disclosure also serves as a charge preventing agent. While an amphoteric surface active agent having a small molecular weight moves to the inside of a recording medium, the above-mentioned amphoteric polymer forms a particle so that the polymer tends to stay on the surface of the recording medium, thereby reducing the surface resistance of the recording medium. Therefore, it is possible to prevent occurrence of mis-feed of the recording medium and production of images defected by charged ink mist.
Next, an example of the method of manufacturing the amphoteric polymer is specified.
There is no specific limitation to the selection of the manufacturing method. For example, methods using soap-free emulsification, emulsification polymerization, seed polymerization, or suspension polymerization can be suitably utilized.
To be specific, a polymerizable compound B having at least one kind of anionic group and a polymerizable compound C free from a cationic group and an anionic group are solution-polymerized to obtain a polymer B1. Any functional group that shows cationic property in an amphoteric polymer state can be used as the cation group. In addition, the functional group can be a non-neutralized functional group in the process of solution-polymerization. Furthermore, any functional group that shows anionic property in an amphoteric polymer state can be used as the anion group. In addition, the functional group can be a non-neutralized functional group in the process of solution-polymerization.
There is no specific limitation on the selection of the anionic group containing polymerizable compound B. α, β ethylene polymerizable compounds having an organic acid group are preferable. Specific examples thereof include, but are not limited to, acrylic acid, itaconic acid, maleic acid, t-butyl acrylic amide sulfonic acid, 2-acryloyloxy ethyl succinic acid, and 2-acryloyloxy ethyl phthalic acid. These can be used alone or in combination.
There is no specific limitation on the selection of the polymerizable compound C free from anionic group and cationic group. Preferred specific examples thereof include, but are not limited to, such as monomers of α, β ethylene polymerizable compounds having no organic acid or amino group, such as alkyl or cycloalkyl esters of acrylic acid or methacrylic acid, methyl acrylate, methyl methacylate, ethyl acrylate, ethylmethacrylate, n-butylacrylate, n-butylmethacrylate, i-butyl acrylate, i-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, and lauryl methacrylate; vinyl monomers such as styrene, vinyl toluene, α-methylstyrene, vinyl acetate, acrylonitrile, and methacrylonitrile; and hydroxyalkyl esters of acrylic acid or methacrylic acid such as 2-hydroxy ethylacrylate, 2-hydroxy ethyl methlacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. These can be used alone or in combination.
In this present disclosure, there is no specific limitation on the selection of a polymerization initiator to start the solution-polymerization. For example, azo-based initiators such as azobis isobutyl nitrile and peroxide compound-based polymerization initiators such as benzoyl peroxide can be suitably used.
After the polymer B1 is obtained, at least one kind of the cationic group containing polymerizable compound A is caused to react (neutralize) with the anion group in the polymer B1 with an equivalent ratio of the cation to the anion ranging from 0.1 to 1.5 to obtain an anionic polymerizable polymer B2. There is no specific limitation on the selection of the polymerizable compound A having a cationic group. Preferred specific examples thereof include, but are not limited to, α, β ethylene polymerizable compounds such as dimethyl amino methyl acrylate, diethyl amino methyl acrylate, dibutyl amino methyl acrylate, dihexyl amino methyl acrylate, dimethyl amino ethyl acrylate, diethyl amino ethyl acrylate, di(t-butyl)amino ethyl acrylate, diisohexyl amino ethyl acrylate, dihexyl amino propyl acrylate, and di(t-butyl)amino hexyl acrylate. These can be used alone or in combination.
Furthermore, an emulsion of the amphoteric polymer having a anionic shell portion (polymer B2) having an anion group and a cationic core portion (copolymer of polymerizable compounds A and C) having a cation group can be obtained by emulsion-polymerizing the polymer B2 and non-reacted polymerizable compounds A and C. The emulsion of the amphoteric polymer preferably has a volume average particle diameter of from 60 nm to 200 nm and more preferably from 80 nm to 150 nm. When the volume average particle diameter is too small, the viscosity of the emulsion tends to increase, thereby increasing the viscosity of the liquid dispersant using this emulsion, which makes it difficult to apply the liquid dispersant to a recording medium or discharge it from a head to a recording medium for attachment of the emulsion thereto. To the contrary, when the volume average particle diameter is too large, the gloss of a recording medium to which the liquid dispersant has been applied may decrease.
The liquid dispersant for use in the ink jet recording method of the present disclosure may contain a surface active agent. A surface active agent that can control penetrating (spreading) to a recording medium without affecting the charge of the emulsion of the amphoteric polymer is suitably used. Specific examples of such surface active agents include, but are not limited to, nonionic surface active agents such as polyoxyethylene alkyl ether, acetylene glycol-based surface active agents, fluorine-containing surface active agents, and silicone-based surface active agents.
The processing liquid (liquid dispersant) for use in the ink jet recording method of the present disclosure may contain a water-soluble organic solvent to control moisture evaporation and the penetrating characteristics. There is no specific limitation on the selection of the water-soluble organic solvents and any known water-soluble organic solvents can be suitably used. Specific examples thereof include, but are not limited to, polyols, polyol alkyl ethers, polyol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonates, and ethylene carbonate.
Specific examples of the polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-prpopane diol, 1,3-butane diol, 2,3-butane diol, 1,4-butane diol, 3-methyl-1,3-butane diol 1,5-pentane diol, tetraethylene glycol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, 2-methyl-2,4-pentane diol, polyethylene glycol, glycerol, 1,2,6-hexane triol, 1,2,4-butane triol, 1,2,3-butane triol, and petriol.
Specific examples of the polyol alkyl ethers include, but are not limited to, 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. Specific examples of the polyol aryl ethers include, but are not limited to, ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Specific examples of the nitrogen-containing heterocyclic compounds include, but are not limited to, 2-pyrolidone, N--methyl-2-pyrolidone, N-hydroxyethyle-2-pyrolidone, 1,3-dimethyl imidazoline, and ε-caprolactam.
Specific examples of the amides include, but are not limited to, formamide, N-methyl formamide, and N,N-dimethylformamide Specific examples of the amines include, but are not limited to, monoethanol amine, diethanol amine, triethanol amine, monoethyl amine, diethylamine, and triethyl amine Specific examples of the sulfur-containing compounds include, but are not limited to, dimethyl sulphoxide, sulfolane, and thiodiethanol.
These water-soluble organic solvents can be used alone or in combination.
The processing liquid for use in the ink jet recording method of the present disclosure for a recording medium preferably has a dynamic absorptivity of from 10 ml/m2 to 25 ml/m2 for a contact time of 100 ms at 25° C. and 50% RH and more preferably from 10 ml/2 to 20 ml/m2. When the dynamic absorptivity is too small, the absorption of the processing liquid tends to deteriorate, which leads to bleeding when a recording liquid containing a coloring material is overlapped. To the contrary, when the dynamic absorptivity is too large, the processing liquid easily spreads into a recording medium so that when a recording liquid containing a coloring material is overlapped, the contact between the recording liquid and the processing liquid tends to decrease, resulting in unsatisfactory agglomeration and fixing. The dynamic absorptivity can be measured by a dynamic scanning absorptometer (K350 Series D type, manufactured by KYOWA SEIKO INC.).
The liquid dispersant for use in the ink jet recording method of the present disclosure preferably has a viscosity of from 5 mPA·s to 1,000 mPa·s. When the viscosity is too small, the liquid easily penetrates plain paper, which leads to unsatisfactory image quality after ink jet recording and an increased strike-through. When the viscosity is too large, application or discharging of the liquid dispersant to a recording medium tends to be difficult. The viscosity of the liquid dispersant can be adjusted by the addition amount of an organic solvent and/or water according to the used polymer emulsion.
The liquid dispersant for use in the ink jet recording method of the present disclosure preferably has a pH of from 4 to 10 and more preferably from 5 to 9. When the pH is too small, the recording medium tends to deteriorate over a prolonged preservation time. With regard to the upper limit of the pH, a strong alkali is not preferable considering safe handling and an applicator that contacts with the liquid.
The processing liquid for use in the ink jet recording method of the present disclosure can be attached to a recording medium by application by a roller or discharging from a head but the attachment method is not limited thereto. Specific examples of devices of drying the processing liquid after the attachment thereof include, but are not limited to, heat air drying and heat roller drying. It is preferable that ink should be attached before the processing liquid becomes dry and forms a film. In the ink jet recording method of the present disclosure, the cationic ink coloring material is agglomerated by charges (anion) having a reverse polarity to that of the cationic ink and then the coloring material is attracted by the electrostatic mutual function between the rest of the charges (anion) and the charges (cation) of the core portion, thereby boosting the agglomeration effect. Therefore, if the liquid dispersant becomes dry and forms a film first, the charges are canceled before the coloring material is attracted, which weakens the agglomeration effect of the coloring material.
Ink
The cationic ink for use in the ink jet recording method of the present disclosure contains a coloring agent and water. A cationic coloring material is preferably used as the coloring material. Specific examples of the cationic coloring materials include, but are not limited to, dyes or pigments to which a cation group such as a quaternary ammonium group, a quaternary phosphonium group, a quaternary cyclic amine, or a quaternary aromatic amine is directly introduced, dyes or pigments to which a polymer containing a cation group is adsorbed, and dyes or pigments encapsulated by a polymer containing a cation group. Both free acid cation groups and neutralized salt cation groups can be suitably used.
Specific examples of the color pigments specified above include, but are not limited to, phthalocyanine blue, phthalocyanine green, quinacridone, anthraquinone, perylene, (thio)indigoid, heterocyclic yellow, and pyranthrone.
Specific examples of the phthalocyanine blue include, but are not limited to, copper phthalocyanine blue and derivatives thereof (Pigment Blue 15, etc.). Specific examples of the quinacridones include, but are not limited to, Pigment Orange 48, Pigment Orange 49, Pigment Red 122, Pigment Red 192, Pigment red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19, and Pigment Violet 42. Specific examples of the anthraquinone include, but are not limited to, Pigment Red 43, Pigment Red 194 (perinone red), Pigment Red 216 (brominated pyranthrone red), and Pigment Red 226 (pyranthrone red)). Specific examples of the perylene include, but are not limited to, Pigment Red 123 (vermilion), Pigment Red 149 (scarlet), Pigment Red 179 (maroon), Pigment Red 190 (Red), Pigment Violet, Pigment Red 189 (yellow shade red), and Pigment Red 224. Specific examples of the thioindigoid include, but are not limited to, Pigment Orange 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36, and Pigment Violet 38. Specific examples of the heterocyclic yellow include, but are not limited to, Pigment Yellow 117 and Pigment Yellow 138.
Other coloring pigments are specified in “The Colour Index, third edition (published in 1982 by The Society of Dyers and Colourists. Among the pigments specified above, carbon black is used as the black pigment.
Such a pigment having a cation group can be prepared by a known method in which a pigment is modified by a surface modifier in a liquid medium followed by introduction of quaternary ammonium salt (refer to, for example, a method described in Japanese Unexamined Patent Application Publication (Translation of PCT Application) No. 2002-538280.
Specific examples of the cationic dyes include, but are not limited to, C.I. Basic Yellow 11, 13, 19, 28, 29, 33, C.I. Basic Orange 21, C.I. Basic Red 1, 2, 9, 12, 13, 24, 39, 51, C.I. Basic Violet 1, 3, 7, 10, 11, 15, 16, 20, 27, 35, 39, C.I. Basic Blue 1, 3, 5, 9, 21, 24, 25, 26, 28, 45, 47, 54, 65, 92, 100, 124, 147.
The ink for use in the ink jet recording method of this embodiment must be cationic but there is no specific limit to the combination of dyes and pigments and dispersion processing method.
The ink for use in the ink jet recording method of the present disclosure may contain an aqueous organic solvent, a surface active agent, a penetrating agent, a pH adjustment agent, and a corrosion control agent in addition to the coloring materials and water described above. There is no specific limitation on the selection of the water-soluble organic solvents and any known water-soluble organic solvents can be suitably used. Specific examples thereof include, but are not limited to, polyols, polyol alkyl ethers, polyol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonates, and ethylene carbonate.
Specific examples of the polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-prpopane diol, 1,3-butane diol, 2,3-butane diol, 1,4-butane diol, 3-methyl-1,3-butane diol 1,5-pentane diol, tetraethylene glycol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, 2-methyl-2,4-pentane diol, polyethylene glycol, glycerol, 1,2,6-hexane triol, 1,2,4-butane triol, 1,2,3-butane triol, and petriol.
Specific examples of the polyol alkyl ethers include, but are not limited to, 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. Specific examples of the polyol aryl ethers include, but are not limited to, ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Specific examples of the nitrogen-containing heterocyclic compounds include, but are not limited to, 2-pyrolidone, N--methyl-2-pyrolidone, N-hydroxyethyle-2-pyrolidone, 1,3-dimethyl imidazoline, and ε-caprolactam.
Specific examples of the amides include, but are not limited to, formamide, N-methyl formamide, and N,N-dimethylformamide Specific examples of the amines include, but are not limited to, monoethanol amine, diethanol amine, triethanol amine, monoethyl amine, diethylamine, and triethyl amine. Specific examples of the sulfur-containing compounds include, but are not limited to, dimethyl sulphoxide, sulfolane, and thiodiethanol.
These water-soluble organic solvents can be used alone or in combination. Among these, in terms of the solubility and the prevention of deterioration of jet characteristics caused by moisture evaporation, suitable solvents are glycerine, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butane diol, 2,3-butane diol, 1,4-butane diol, 3-methyl-1,3-butane diol 1,5-pentane diol, tetraethylene glycol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, 2-methyl-2,4-pentane diol, polyethylene glycol, 1,2,6-hexane triol, 1,2,4-butane triol, thiodiglycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrolidone.
The content of the water-soluble organic solvent in the ink is preferably from 15% to 40% by weight and more preferably from 20% to 35%. When the content is too small, the nozzle tends to become dry, thereby causing unsatisfactory discharging of droplets. When the content is too large, the viscosity of the ink tends to increase beyond the suitable viscosity range.
As the surface active agents, for example, anionic surface active agents, cationic surface active agents, nonionic surface active agents, amphoteric surface active agents, and fluorine-containing surface active agents can be used. These charge transport materials may be used alone or in combination.
Specific examples of the anion surface active agent include, but are not limited to, alkyl aryl, alkyl naphthalene sulfonic acid salts, alkyl phosophoric acid salts, alkyl sulfuric acid salts, alkyl sulphonic acid salts, alkyl ether sulfuric acid salts, allkyl sulpho succinic acid salts, alkyl ester sulfuric acid salts, alkyl benzene sulfonic acid salts, alkyl diphenyl ether disulphonic acid salts, alkyl aryl ether phosphoric acid salts, alkyl aryl ether sulfuric acid salts, alkyl aryl ether ester sulfuric acid salts, olefin sulfonic acid salts, alkane olefin sulfocnic acid salts, polyoxyethylene alkyl ether phosphoric acid salts, polyoxyethylene alkyl ether sulfuric acid ester salts, ether carboxylate, sulfosuccinic acid salts, α-sulfoalicyclic acid esters, aliphatic acid salts, condensation products of a higher aliphatic acid and an amino acid, and naphthene acid salts.
Specific examples of the nonion surface active agent include, but are not limited to, acetylene glycol-based surface active agents, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, and polyoxyethylene sorbitane aliphatic acid esters.
Specific examples of the cationic surface active agents include, but are not limited to, alkyl amine salts, dialkyl amine salts, aliphatic amine salts, benzalkonium salts, quaternary amonium salts, alkyl pyridinium salts, imidazolinium salts, sulfonium salts, and phosphonium salts.
Specific examples of the amphoteric surface active agents include, but are not limited to, imidazoline derivatives such as imidazolinium betaine, dimethyl alkyl lauryl betaine, alkyl glycine, and alkyl di(aminoethyhl) glycine.
Diol compounds having 7 to 17 carbon atoms can be used as the penetrating agents mentioned above. By adding a penetrating agent, penetration to a recording medium is improved. Therefore, quality images can be formed without contamination caused by friction during paper transfer or by attachment of ink to a transfer belt when the recording face of a recording medium is reversed in duplicate mode. Specific examples of the diols include, but are not limited to, 2-ethyl-1,3-hexane diol and 2,2,4-trimethyl 1,3-pentane diol. The content of the diol compound in the ink is preferably from 1% to 5% by weight. When the content is too small, a satisfactory penetrating property is not easily obtained. By contrast, when the content is too large, the stability during preservation may deteriorate.
There is no specific limitation on the selection of the pH adjusting agent and any pH adjusting agent that can adjust pH to be 7 or higher without an adverse impact on ink can be used. Specific examples of such pH adjusting agents include, but are not limited to, amines such as diethanol amine and triethanol amine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and carbonates of alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate.
Specific examples of the corrosion control (anti-corrosion) agents include, but are not limited to, acid sulfite, thiosodium sulfate, ammonium thiodiglycolate, diisopropyl ammonium nitride, pentaerythritol quaternary nitdride, dicyclohexyl ammonium nitride, and benzotriazole.
The viscosity of the ink for use in the ink jet recording method of the present disclosure is preferably from 5 mPa·s to 20 mPa·s at 25° C. and more preferably from 6 mPa·s to 12 mPa·s. When the viscosity is too large, the stability about discharging is not easily secured.
The surface tension of the ink for use in the ink jet recording method of the present disclosure is preferably from 23 mN/m to 40 mN/m at 20° C. When the surface tension is too weak, bleeding on a recording image may become apparent or discharging may not be stabilized. When the surface tension is too strong, ink penetration to a recording medium tends to be unsatisfactory, resulting in a long drying time for ink.
pH of the ink for use in the ink jet recording method of the present disclosure is preferably from 7 to 10. When the Ink is preserved for a long period of time, the properties thereof tend to change. In particular, when the ink is heated and preserved, the viscosity of the ink increases and pH thereof lowers. It is preferable to reduce such changes. In the case of this ink, it is preferable that the change of the viscosity is within 5% and the pH change is within −5% after two week's preservation of the ink at 60° C.
There is no specific limitation on the method of attaching ink for use in the ink jet recording method of the present disclosure to a recording medium by discharging. Any method of attaching the ink to the surface on which the processing liquid described above is attached can be suitably used. Preferably, attachment of the ink is conducted before the processing liquid becomes dry. If the ink is attached after the processing liquid becomes dry, satisfactory agglomeration effect is not easily obtained as described above, resulting in poor characteristics with regard to the image density, bleeding, feathering, etc. Therefore, it is preferable that the ink is attached immediately after the processing liquid is attached and thereafter the entire is dried.
EXAMPLES
Next, the present disclosure is described in detail with reference to Examples but not limited thereto.
Processing Liquid
Synthesis Example 1
Synthesis of Emulsion of Amphoteric Polymer Having Cationic Core Portion and Anionic Shell Portion
Place 50 g of ethanol in a flask equipped with a stirrer, a dripping funnel, a condenser, and a thermometer; Heat the system to 80° C. in a nitrogen atmosphere; Mix the following composition 2-1 and place it in the dripping funnel; Drip the composition 2-1 to the flask in three hours.
Composition 2-1:
















Azobis isobutyl nitrile
10 g



Methyl methacrylate
60 g



Butyl acrylate
100 g 



Acrylic acid
40 g










Subsequent to dropping, continue reaction for two more hours at 80° C. while stirring; Thereafter, cool down the product to 50° C.; Add 80 g of dimethylaminoethyl methacrylate to the product; Dilute the resultant with 660 g of deionized water to obtain anionic polymerizable aqueous polymer B;
Place 500 g of the thus-obtained anionic polymerizable aqueous polymer B in a flask; Add 1 g of sodium ascorbate and 1 g of 5% aqueous solution of ferrous sulfate; Heat the system to 80° C. in a nitrogen atmosphere; Place the following composition 2-2 and the composition 2-3 in the dripping funnel: Simultaneously drop them to the flask in two hours;
Composition 2-2:
















Methyl methacrylate
100 g 



Butyl acrylate
50 g



Styrene
50 g










Composition 2-3:

















35% Hydrogen peroxide solution
1 g



Deionized water
5 g










And subsequent to dropping, keep the resultant at 80° C. for three hours while stirring followed by dilution with 247 g of deionized water to obtain an emulsion of an amphoteric polymer having a cationic core portion and an anionic shell portion; Adjust the emulsion with deionized water such that the solid portion concentration is 30%.
Synthesis Example 2
Synthesis of Amphoteric Polymer Emulsion Which Does Not Take Core-Shell Form
Place 120 g of isoparaffin having a boiling point of 190° C. and 7.5 g of sorbitan monooleate in a reaction container equipped with a stirrer and a temperature controller; Add 200 g of a liquid mixture of the following composition followed by stirring and emulsifying by a Homogenizer;













Demineralized water
165 g


Solution of Acryloyloxy ethyltrimethyl ammonium chloride
 35 g


(99.7 mol %)/acrylamide-2-methyl propane sulfonic acid soda


(0.3 mol %)









Add 0.2 g of isopropyl alcohol to the thus-obtained emulsion; Add 0.04 g of dimethylazobis isobutylate to the resultant in nitrogen atmosphere to complete the reaction at 50° C.; And thereafter, admix 7.5 g of polyoxyethylene nonylphenyl ether to obtain an emulsion of an amphoteric polymer; and adjust the emulsion with deionized water such that the solid portion density is 30%.
Preparation of Processing Liquid
Processing liquid is prepared by stirring and uniformly mixing the materials of Preparation Examples A to I shown in Table 1. The blend amount of each material in Tables 1-1 and 1-2 is represented in parts by weight.









TABLE 1-1









Processing Liquid (Liquid Dispersant)












Mfg.
Mfg.
Mfg.
Mfg.



Example
Example
Example
Example



A
B
C
D
















Polymer
Synthesis
15


15



Example 1



Synthesis

15



Example 2



Aquabrid


15



Asi-91


Water-
1,3-butane diol
15
15
15
15


soluble
1,5-pentane


organic
diol


solvent


Surface
SOFTANOL
1
1
1


active
EP7025


agent
BYK347



1



Zonyl FS3000


Water
Deionized
69
69
69
69



water















Total
100
100
100
100


















TABLE 1-2









Processing Liquid (Liquid Dispersant)












Mfg.
Mfg.
Mfg.
Mfg.



Example
Example
Example
Example



F
G
H
I
















Polymer
Synthesis
15
15
15
15



Example 1



Synthesis



Example 2



Aquabrid



Asi-91


Water-
1,3-butane diol



30


soluble
1,5-pentane
20


organic
diol


solvent


Surface
SOFTANOL


1


active
EP7025


agent
BYK347



Zonyl FS3000
1
1

1


Water
Deionized
64
84
84
54



water















Total
100
100
100
100









The product names shown in Tables 1-1 and 1-2 represent as follows:

    AQUABRID Asi-91: Anionic polymer emulsion
    SOFTANOL EP7025: Nonion-based surface active agent
    BYK347: Silicone-based surface active agent
    Zonyl FS300: Fluorine-containing surface active agent

Preparation of Processing Liquid



Characteristics of the obtained processing liquid are evaluated as follows: The results are shown in Tables 4-1, 4-2, 4-2, 4-3, 4-4, 4-5, 4-6, 4-7, 5-1, 5-2, and 5-3.
Dynamic Absorptivity
The transfer (attached) amount of each processing liquid is measured using a dynamic scanning absorptometer (K350 Series D type, manufactured by KYOWA SEIKO INC.). The transfer amount (ml/m2) to plain paper (My Paper, manufactured by NBS RICOH CO., LTD.) for a contact time of 100 ms is obtained. Measuring is conducted at 23° C. and 50% RH.
Ink
Preparation Example 1
Mix a solution in which 14.0 g of N-(4-aminophenyl) nitrous acid pyridinium is added in 200 ml of adjusted deionized water of a cationic pigment with 100 g of carbon black having a surface area of 200 m2/g and a DBPA of 117 ml/100 g followed by heating at 70° C.; Add 38.0 ml of 10% nitrous acid to the mixture to conduct reaction at 80° C. for two hours;
And conduct centrifugal separation of the thus-obtained dispersion body followed by ultrafiltration and membrane filtration until the filtrate is colorless (0.8μ filter). —C6H4NC5H5+ group is bonded to the cationic pigment product and the corresponding pair anion group is NO3−.
Manufacturing Examples of Ink
Stir and uniformly mix each material of Manufacturing Examples 1 to 4 shown in Table 2; and thereafter filter the mixture with a membrane filter having an average opening diameter of 0.8 μm to manufacture ink. The blend amount of each material in Table 2 is represented in parts by weight.









TABLE 2









Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4

















Pigment
6






dispersant



body of



Preparation



Example 1



*1



C.I. Basic

3



Blue 9



C.I. Basic


3



Red 2


Coloring
C.I. Basic



2.5


material
Yellow 11


Water-
Glycerin
12
15
15
15


soluble
1,5-pentane


organic
diol


solvent
1,3-butane
24
30
30
30



diol



2-pyrolidone
2
2
5
5


Penetrating
2-ethyl-1,3-
2
2
2
2


agent
hexane diol


Surface
Zonyl FS300
1
1
1
1


active
*2


agent


Water
Deionized
53
47
47
47.5



water















Total
100
100
100
100





*1: represents the blend ratio of the solid portion


*2: represent fluorine-based surface active agent






Evaluation of Ink

Characteristics of the obtained ink are evaluated as follows: The results are shown in Table 3.
Viscosity
Measure the viscosity of the ink at 25° C. using R type viscometer (manufactured by TOKI SANGYO CO., LTD.).
Surface Tension
Measure the viscosity of the ink at 20° C. to 26° C. using a static surface tensiometer (BVP-Z, manufactured by KYOWA INTERFACE SCIENCE Co., Ltd.).
pH
Measure pH of the ink at 25° C. using a pH meter (HM30R, manufactured by DKK-TOA CORPORATION).
Preservability
Place ink in a polypropylene bin (50 ml) and preserve it at 50° C. for one month; Take it out from the bin, leave it for one day, and measure the viscosity change; and evaluate the preservability according to the following criteria:

    G (Good): between ±3% (not inclusive) change from the initial viscosity
    F (Fair): ±3% to ±6% (not inclusive) change from the initial viscosity
    P (Poor): ±6% or more change from the initial viscosity











TABLE 3









Ink












Mfg.
Mfg.
Mfg.
Mfg.



Example 1
Example 2
Example 3
Example 4















Viscosity
7.8
7.6
7.2
7.2


mPa · s


Surface
25.8
25.3
25.4
25.6


tension


mN/m


pH
9
9
9
9


Preservability
G
G
G
G









Image Evaluation

Application of Processing Liquid

Apply the thus-obtained processing liquid to plain paper (My paper. manufactured by NBS RICOH CO., LTD.) using a bar coater (No. 5). The applied amount is 3 g/m2 in a wet state.
Image Output
Set the paper to which the processing liquid is applied in an ink jet printer IPSiO GX5000 (manufactured by RICOH CO., LTD.) quickly and conduct recording using each ink shown in Examples 1 to 7 and Comparative Examples 1 to 3 in Tables 4-1, 4-2, 4-3, 4-4, 4-5, 4-6, 4-7, 5-1, 5-2, and 5-3 with a definition of 600 dpi. The attached amount of ink is 9.5 g/m2 in a wet state. Example 7 is conducted in the same manner as in Example 1 except that a process of drying the processing liquid attached to plain paper for 10 seconds at 120° C. is provided between the process of ejecting (discharging) and attaching the processing liquid to the plain paper and the process of attaching the ink. The output images are evaluated as follows: The results are shown in Tables 4-1, 4-2, 4-3, 4-4, 4-5, 4-6, 4-7, 5-1, 5-2, and 5-3.
Image Feathering
Feathering of the recorded image is observed with naked eyes and evaluated according to the following criteria.
Evaluation Criteria


    G (Good): Vivid images without feathering
    F (Fair): Feathering occurs locally
    B (Bad): Feathering occurs to a degree that the contour of texts is not clear.

Image Density



Dry the recorded image sufficiently, measure the image density using a reflection type color spectrodensitometer (manufactured by X-RITE CORPORATION), and evaluate the image density according to the following criteria:
Evaluation Criteria
Black Ink


    G (Good): 1.4 or higher
    F (Fair): 1.3 to less than 1.4
    B (Bad): Less than 1.3

Cyan Ink

    G (Good): 1.3 or higher
    F (Fair): 1.2 to less than 1.3
    B (Bad): Less than 1.2

Magenta ink

    G (Good): 1.2 or higher
    F (Fair): 1.1 to less than 1.2
    B (Bad): Less than 1.1

Yellow Ink

    G (Good): 1.0 or higher
    F (Fair): 0.9 to less than 1.0
    B (Bad): Less than 0.9

Strike-through



Dry the recorded image sufficiently, measure the strike-through density of images using a reflection type color spectrodensitometer (manufactured by X-RITE CORPORATION), and evaluate according to the following criteria:
Evaluation Criteria


    G (Good): Less than 0.10
    F (Fair): 0.1 to less than 0.15
    B (Bad): 0.15 or higher

Scratch



Leave the recorded image at 25° C. and 50% RH for five hours, scratch the solid image portion with cotton cloth ten times, observe the transfer state of the pigment to the cotton cloth with naked eyes, and evaluate the image according to the following criteria:
Evaluation Criteria


    G (Good): No transfer of pigment to cotton cloth observed by naked eyes
    F (Fair): Transfer of pigment to cotton cloth slightly observed
    B (Bad): Transfer of pigment to cotton cloth apparently observed

Marker Resistance



Leave the recorded image at 25° C. and 50% RH for ten minutes, follow the text portion by a fluorescent marker (PROPUS2, manufactured by MITSUBISHI PENCIL CO., LTD.), observe the degree of contamination caused by scratch by the marker with naked eyes, and evaluate the image according to the following criteria.
Evaluation Criteria


    G (Good): no contamination observed by loss of color
    F (Fair): Slight contamination observed by loss of color
    B (Bad): Contamination observed along the marker.

Bleed



Record a pattern containing black texts in a color solid portion, observe bleeding at the boundary of color and black, and evaluate the image according to the following criteria.
Evaluation Criteria


    G (Good): No bleeding observed at the color boundary
    F (Fair): Slight bleeding observed by loss of color depending on the color
    B (Bad): Bleeding observed clearly at most color boundaries.

Duplex Printing Property



Set the paper to which the processing liquid is applied in an ink jet printer IPSiO GX5000 (manufactured by RICOH CO., LTD.) quickly and conduct duplex recording using each ink shown in Examples 1 to 7 and Comparative Examples 1 to 3 with a definition of 600 dpi; In the recording, reverse the paper immediately after an image is recorded on one side; And conduct this operation for 10 sheets in a row and scratch ink thereon when reversing the paper and evaluate the paper contamination according to the following criteria:
Evaluation Criteria


    G (Good): No ink contamination observed when reversing recording medium
    F (Fair): Slight but not apparent ink contamination observed for one or two sheets when reversing recording medium
    B (Bad): Ink contamination caused by scratching during reversing sheet apparently observed when reversing recording medium.

Discharging Misplacement



Set the paper to which the processing liquid is applied in an ink jet printer IPSiO GX5000 (manufactured by RICOH CO., LTD.) quickly and conduct dot recording using each ink shown in Examples 1 to 7 and Comparative Examples 1 to 3 with a definition of 600 dpi at 28° C. and 10% RH; And observe the recorded portion with a microscope and evaluate dot misplacement.
Evaluation Criteria


    G (Good): No dot misplacement observed
    F (Fair): Dot misplacement slightly observed but not apparent in terms of recording
    B (Bad): Dot misplacement observed significantly and streaks on the recorded image apparent











TABLE 4-1









Example 1



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example A


Core
Cation


portion


Shell
Anion


portion


Dynamic absorptivity
20


characteristics







Evaluation of recorded images











Image density
G
G
G
G


Strike-through
G
G
G
G


Feathering
G
G
G
G


Scratch
G
G
G
G


Marker resistance
G
G
G
G


Duplex printing
G
G
G
G


property


Bleeding
—
G
G
G


Discharging
G
G
G
G


misplacement


















TABLE 4-2









Example 2



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example D


Core
Cation


portion


Shell
Anion


portion


Dynamic absorptivity
17


characteristics







Evaluation of recorded images











Image density
G
G
G
G


Strike-through
G
G
G
G


Feathering
G
G
G
G


Scratch
G
G
G
G


Marker resistance
G
G
G
G


Duplex printing
G
G
G
G


property


Bleeding
—
G
G
G


Discharging
G
G
G
G


misplacement


















TABLE 4-3









Example 3



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example F


Core
Cation


portion


Shell
Anion


portion


Dynamic absorptivity
24


characteristics







Evaluation of recorded images











Image density
F
F
F
F


Strike-through
G
G
G
G


Feathering
G
G
G
G


Scratch
G
G
G
G


Marker resistance
G
G
G
G


Duplex printing
G
G
G
G


property


Bleeding
—
G
G
G


Discharging
G
G
G
G


misplacement


















TABLE 4-4









Example 4



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example G


Core
Cation


portion


Shell
Anion


portion


Dynamic absorptivity
10


characteristics







Evaluation of recorded images











Image density
G
G
G
G


Strike-through
G
G
G
G


Feathering
F
F
F
F


Scratch
G
G
G
G


Marker resistance
G
G
G
G


Duplex printing
G
G
G
G


property


Bleeding
—
G
G
G


Discharging
G
G
G
G


misplacement


















TABLE 4-5









Example 5



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example H


Core
Cation


portion


Shell
Anion


portion


Dynamic absorptivity
7


characteristics







Evaluation of recorded images











Image density
G
G
G
G


Strike-through
G
G
G
G


Feathering
F
F
F
F


Scratch
G
G
G
G


Marker resistance
G
G
G
G


Duplex printing
G
G
G
G


property


Bleeding
—
F
F
F


Discharging
G
G
G
G


misplacement


















TABLE 4-6









Example 6



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example I


Core
Cation


portion


Shell
Anion


portion


Dynamic absorptivity
30


characteristics







Evaluation of recorded images











Image density
G
G
G
G


Strike-through
F
F
F
F


Feathering
G
G
G
G


Scratch
F
F
F
F


Marker resistance
F
F
F
F


Duplex printing
G
G
G
G


property


Bleeding
—
G
G
G


Discharging
G
G
G
G


misplacement


















TABLE 4-7









Example 7



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example A


Core
Cation


portion


Shell
Anion


portion


Dynamic absorptivity
20


characteristics







Evaluation of recorded images











Image density
G
G
G
G


Strike-through
G
G
G
G


Feathering
G
G
G
G


Scratch
G
G
G
G


Marker resistance
G
G
G
G


Duplex printing
G
G
G
G


property


Bleeding
—
G
G
G


Discharging
G
G
G
G


misplacement


















TABLE 5-1









Comparative Example 1



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example B


Core portion
—


Shell
—


portion


Dynamic absorptivity
15


characteristics







Evaluation of recorded image











Image density
G
G
G
G


Strike-through
F
F
F
F


Feathering
G
G
G
G


Scratch
B
B
B
B


Marker resistance
B
B
B
B


Duplex printing property
F
F
F
F


Bleeding
—
F
F
F


Discharging
G
G
G
G


misplacement


















TABLE 5-2









Comparative Example 2



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
Manufacturing Example C


Core portion
—


Shell
—


portion


Dynamic absorptivity
25


characteristics







Evaluation of recorded image











Image density
F
F
F
F


Strike-through
F
F
F
F


Feathering
F
F
F
F


Scratch
B
B
B
B


Marker resistance
B
B
B
B


Duplex printing property
F
F
F
F


Bleeding
—
F
F
F


Discharging
G
G
G
G


misplacement


















TABLE 5-3









Comparative Example 3



Ink












Manufacturing
Manufacturing
Manufacturing
Manufacturing



Example 1
Example 2
Example 3
Example 4



Cation
Cation
Cation
Cation












Processing liquid
—


Core portion
—


Shell
—


portion


Dynamic absorptivity
—


characteristics







Evaluation of recorded image











Image density
F
B
B
B


Strike-through
B
B
B
B


Feathering
F
F
F
F


Scratch
F
F
F
F


Marker resistance
F
F
F
F


Duplex printing property
F
F
F
F


Bleeding
—
F
F
F


Discharging
G
G
G
G


misplacement

## Claims

1. An ink jet recording method comprising the steps of:
attaching a processing liquid in which an amphoteric polymer comprising a core portion having a cation group and a shell portion having an anion group that covers the core portion is dispersed in a dispersion medium to a surface of a recording medium; and
discharging and attaching cationic ink comprising a coloring material d water to the surface of the recording medium where the processing liquid is attached,
wherein an amount of the processing liquid attached to the recording medium as measured by a dynamic scanning absorptometer is from 10 ml/m2 to 25 ml/m2 for a contact time of 100 ms, and
wherein the step of attaching a processing liquid is performed prior to the step of discharging and attaching cationic ink.

2. The ink jet recording method according to claim 1, wherein the coloring material of the cationic ink comprises a cation group.

3. The ink jet recording method according to claim 1, wherein the processing liquid further comprises an aqueous organic solvent and a surface active agent.

4. The ink jet recording method according to claim 3, wherein the surface active agent is a silicone-based surface active agent.

5. The ink jet recording method according to claim 1, wherein the amphoteric polymer is manufactured by polymerizing a first polymerizable compound with a second polymerizable compound, reacting with a third polymerizable compound, and polymerizing with both the second polymerizable compound and the third polymerizable compound.

6. The ink jet recording method according to claim 5, wherein the first polymerizable compound is a compound having at least one kind of anionic group, the second polymerizable compound is a compound free from a cationic group and an anionic group, and the third polymerizable compound is a compound having at least one kind of cationic group.