JP2017013350A - Recording method and ink set - Google Patents

Abstract

An object of the present invention is to provide a recording method capable of giving a recorded matter with high glossiness.
A first drying step in which a pretreatment liquid is applied to a recording medium and dried at a drying temperature T1, and an ink composition is attached to the recording medium to which the pretreatment liquid has been applied. A second drying step of drying at a drying temperature T2, and a third drying step of applying a post-treatment liquid to the recording medium to which the ink composition is adhered and drying at a drying temperature T3. The pretreatment liquid includes a resin having a glass transition temperature Tg1, the ink composition includes a resin having a glass transition temperature Tg2, and the post-treatment liquid includes a resin having a glass transition temperature Tg3. A recording method that satisfies the following relationships (1) and (2).
Tg1 <Tg2 <Tg3 (1)
T1 <T2 <T3 (2)
[Selection figure] None

Description

  The present invention relates to a recording method and an ink set.

  The ink jet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields. Among them, various studies have been made on ejection stability and the like. For example, Patent Document 1 discloses an inkjet that has excellent ejection stability, improves feathering resistance to plain paper, and can obtain images and printed matter with high scratch resistance even on a recording medium that hardly absorbs ink. For the purpose of providing an ink, an inkjet ink containing a pigment, water, a water-soluble solvent, and polymer fine particles, wherein the polymer fine particles have a shell structure composed of a core portion and a shell portion, and the shell portion is An inkjet ink containing a monomer having a predetermined functional group is disclosed.

JP 2006-206665 A

  However, there are many required properties in addition to clogging resistance and abrasion resistance of the obtained recorded matter. For example, a method for obtaining a recorded matter having higher glossiness is also desired.

  SUMMARY An advantage of some aspects of the invention is that it provides a recording method capable of providing a recorded matter with high glossiness.

  The present inventors diligently studied to solve the above problems. As a result, it has been found that the above problem can be solved by having a predetermined drying step, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A first drying step in which a pretreatment liquid is applied to a recording medium and dried at a drying temperature T1;
A second drying step in which an ink composition is attached to the recording medium coated with the pretreatment liquid and dried at a drying temperature T2.
A third drying step of applying a post-treatment liquid to the recording medium to which the ink composition is adhered and drying at a drying temperature T3;
The pretreatment liquid includes a resin having a glass transition temperature Tg1,
The ink composition includes a resin having a glass transition temperature Tg2,
The post-treatment liquid includes a resin having a glass transition temperature Tg3;
A recording method that satisfies the following relationships (1) and (2).
Tg1 <Tg2 <Tg3 (1)
T1 <T2 <T3 (2)
[2]
The recording method according to [1], wherein the following relations (3) to (5) are satisfied.
T1 <Tg1 (3)
T2 <Tg2 (4)
T3 <Tg3 (5)
[3]
The recording method according to [1] or [2], wherein the following relationship (6) is satisfied.
T1 <Tg1 <T2 <Tg2 <T3 <Tg3 (6)
[4]
The recording method according to any one of [1] to [3], wherein at least one of the following relationships (7), (8), and (9) is satisfied.
| T1-Tg1 | ≧ 10 (7)
| T2-Tg2 | ≧ 10 (8)
| T3-Tg3 | ≧ 10 (9)
[5]
The recording method according to any one of [1] to [4], wherein the following relationship (10) is satisfied.
T1 ≧ 50 ° C. (10)
[6]
At least one of the resin having a glass transition temperature Tg1, the resin having a glass transition temperature Tg2, and the resin having a glass transition temperature Tg3 is a resin having a core-shell structure, [1] to [5] ] The recording method according to any one of the above.
[7]
The recording method according to [6] above, wherein in the resin having the core-shell structure, the glass transition temperature Tg _{core of the core} is lower than T1, and the glass transition temperature Tg _{shell of the shell} is higher than T2.
[8]
The recording method according to any one of [1] to [7], wherein the recording medium is a non-absorbable recording medium.

  Hereinafter, the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is.

〔Recording method〕
The recording method of the present embodiment includes a first drying step in which a pretreatment liquid is applied to a recording medium and dried at a drying temperature T1, and ink is applied to the recording medium to which the pretreatment liquid is applied. A second drying step in which the composition is adhered and dried at a drying temperature T2, and a third drying step in which a post-treatment liquid is applied to the recording medium to which the ink composition is adhered and dried at a drying temperature T3. The pretreatment liquid includes a resin having a glass transition temperature Tg1, the ink composition includes a resin having a glass transition temperature Tg2, and the post-treatment liquid has a glass transition temperature Tg3. Including the resin, the following relationships (1) and (2) are satisfied.
Tg1 <Tg2 <Tg3 (1)
T1 <T2 <T3 (2)

  From the viewpoint of ensuring abrasion resistance, it was known to add a large amount of resin to the ink composition. However, adding a large amount of resin impairs ejection stability and clogging. . On the other hand, in this embodiment, the discharge stability and the clogging property can be improved by making the temperature of each drying step and the glass transition temperature of each resin have a predetermined relationship. . At the same time, according to the recording method of the present embodiment, the three-layer coating film having different Tg can be formed on the obtained recorded matter, thereby improving the abrasion resistance and glossiness of the obtained recorded matter. it can. Hereinafter, each step will be described.

[First drying step]
The first drying step is a step in which a pretreatment liquid is applied to the recording medium and dried at a drying temperature T1. The means for attaching the pretreatment liquid is not particularly limited, and for example, roller coating, spray coating, and inkjet coating can be used. Moreover, it does not specifically limit as a drying method, For example, a heating, ventilation, leaving, etc. are mentioned. In the first drying step, the pretreatment liquid can be simultaneously dried while adhering the pretreatment liquid to the recording medium. Specifically, there is a method in which a pretreatment liquid is attached to a recording medium from an ink jet nozzle, and at the same time, the recording medium is heated with a platen heater or the like.

  Drying temperature T1 becomes like this. Preferably it is 20-55 degreeC, More preferably, it is 25-50 degreeC, More preferably, it is 30-45 degreeC. When the drying temperature T1 is within the above range, the ejection stability and clogging properties are further improved, and the resulting printed matter tends to be further improved in abrasion resistance and glossiness.

[Recording medium]
Examples of the recording medium include an absorptive recording medium, a low-absorbing recording medium, and a non-absorbing recording medium. Of these, non-absorbable recording media are preferable.

  The absorbent recording medium is not particularly limited. For example, plain paper such as electrophotographic paper having high ink permeability, ink jet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl alcohol ( Art paper, coated paper, etc. used for general offset printing with relatively low ink permeability, such as PVA) and polyvinyl pyrrolidone (PVP). Examples include cast paper.

  Although it does not specifically limit as a low absorptive recording medium, For example, the coated paper by which the coating layer for accepting oil-based ink was provided in the surface is mentioned. The coated paper is not particularly limited, and examples thereof include printing paper such as art paper, coated paper, and matte paper.

  The non-absorbable recording medium is not particularly limited. For example, films and plates of plastics such as polyvinyl chloride, polyethylene, polypropylene, and polyethylene terephthalate (PET), and metals such as iron, silver, copper, and aluminum are used. Examples thereof include a plate, a metal plate produced by vapor deposition of these various metals, a plastic film, a plate made of an alloy such as stainless steel or brass.

Here, the “low-absorbing recording medium” or “non-absorbing recording medium” refers to a recording medium having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec in the Bristow method. . This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method". Note that the low-absorbency recording medium refers to a recording medium having the water absorption amount of 5 mL / m ² or more and 10 mL / m ² or less. On the other hand, an absorptive recording medium refers to a recording medium having a water absorption amount of more than 10 mL / m ² .

(Pretreatment liquid)
The pretreatment liquid includes a resin having a glass transition temperature Tg1, and may include a flocculant, water, a solvent, and a surfactant as necessary. When the flocculant in the pretreatment liquid interacts with the ink composition, the ink composition is thickened or insolubilized. Thereby, landing interference and bleeding of the ink composition to be subsequently attached can be prevented, and lines and fine images can be drawn uniformly.

(Resin having glass transition temperature Tg1)
The glass transition temperature Tg1 is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, further preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. Further, the glass transition temperature Tg1 is preferably 55 ° C. or lower, more preferably 60 ° C. or lower, and further preferably 65 ° C. or lower. When the glass transition temperature Tg1 is within the above range, the ejection stability and clogging properties are further improved, and the resulting recorded product tends to be further improved in abrasion resistance and glossiness.

  Although it does not specifically limit as resin which has glass transition temperature Tg1, For example, acrylic resin, vinyl acetate resin, vinyl chloride resin, butadiene resin, styrene resin, polyester resin, crosslinked acrylic resin, crosslinked styrene resin, benzoguanamine resin, phenol resin , A silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluororesin, a water-soluble resin, and a copolymer obtained by combining monomers constituting these resins. The copolymer is not particularly limited, and examples thereof include styrene acrylate resin, styrene methacrylate resin, and styrene acrylate methacrylate resin. Among these, styrene acrylate resin, styrene methacrylate resin, styrene acrylate methacrylate resin, and resin having a core-shell structure are preferable. The styrene content of the resin is preferably 20 to 50% by mass, more preferably 25 to 45% by mass. Furthermore, the total of the acrylate content and the methacrylate content of the resin (when only one of acrylate or methacrylate is included) is preferably 50 to 80% by mass, more preferably 55 to 75% by mass. It is.

  By using a resin having a core-shell structure, it is possible to further improve the abrasion resistance of the obtained recorded matter. The core-shell structure refers to a structure in which a core polymer is formed inside the voids of the shell polymer. Accordingly, not only a structure in which the surface of the core polymer is covered with the shell polymer but also a structure in which the core polymer is filled in part of the voids of the three-dimensional network structure formed by the shell polymer is included.

  The structural unit constituting the core polymer is not particularly limited. For example, aromatic monomers, hydrophilic (meth) acrylate monomers, hydrophobic (meth) acrylate monomers, (meth) acrylamide monomers Or the thing derived from the N-substituted derivative and at least any one of a carboxylic acid monomer is mentioned. The said monomer may be used individually by 1 type, or may use 2 or more types together. Here, “hydrophobic” means that the solubility in 100 mL of water (20 ° C.) is less than 0.3 g.

  The aromatic monomer is not particularly limited, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, vinyl toluene, chlorostyrene, and divinylbenzene.

  The hydrophilic (meth) acrylate monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, α-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( Examples thereof include poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, ethoxy (poly) ethylene glycol (meth) acrylate, and (poly) propylene glycol (meth) acrylate. Among these, methyl (meth) acrylate and ethyl (meth) acrylate are preferable. Here, “hydrophilic” means that the solubility in 100 mL of water (20 ° C.) is 0.3 g or more.

  Although it does not specifically limit as a hydrophobic (meth) acrylate monomer, For example, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (Meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate, cetyl (meth) acrylate, neopentyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclope Thenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate.

  Although it does not specifically limit as a (meth) acrylamide monomer or its N-substituted derivative, For example, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, diacetone acrylamide, N, N-dimethylacrylic (meth) Examples include (meth) acrylamides such as amides or N-substituted derivatives thereof.

  Although it does not specifically limit as a carboxylic acid monomer, For example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid etc. are mentioned. Among these, (meth) acrylic acid is preferable. Here, the “carboxylic acid monomer unit” refers to a polymerizable monomer unit having a carboxyl group and a polymerizable unsaturated group.

  The structural unit constituting the shell polymer is not particularly limited, and examples thereof include those similar to the structural unit constituting the core polymer. The core polymer and the shell polymer are different in structural unit or combination of structural units.

  The shell preferably includes a structural unit derived from a carboxylic acid monomer, more preferably includes a structural unit derived from a carboxylic acid monomer and a hydrophilic (meth) acrylate monomer. It is more preferable that the structural unit derived from a body, a hydrophilic (meth) acrylate monomer, and an aromatic monomer is included.

In the resin having a core-shell structure, the glass transition temperature Tg _{core of the core} is preferably lower than T1, and the glass transition temperature Tg _{shell of the shell} is preferably higher than T2. By using a resin having such a core-shell structure, the ejection stability and clogging properties are further improved, and the resulting recorded product tends to have improved abrasion resistance and glossiness.

The core - when using a resin having a shell structure, Tg of the resin, Tg _n of various homopolymer (unit: K) and, by the following FOX equation from the mass fraction of the monomer (W _n) Can be calculated. In addition, what was described in various literature (for example, polymer handbook etc.) can be used for Tg of a homopolymer.
_{1 / Tg = W 1 / Tg} 1 + W 2 / Tg 2 + W n / Tg n
Where W _n ; mass fraction of each monomer
Tg _n ; Tg of the homopolymer of each monomer (unit: K)
Tg: Tg of copolymer (unit: K)
n: natural number

  The content of the resin having a glass transition temperature Tg1 is preferably 1.5 to 12.5% by mass, more preferably 2.5 to 10% by mass, and still more preferably based on the total amount of the pretreatment liquid. Is 5.0-7.5 mass%. When the content of the resin having the glass transition temperature Tg1 is within the above range, the ejection stability and the clogging property are further improved, and the resulting recorded product tends to be further improved in abrasion resistance and glossiness.

(Flocculant)
Although it does not specifically limit as an aggregating agent, For example, a polyvalent metal salt and an organic acid are mentioned, It is preferable that an aggregating agent contains at least any one of these. When the flocculant contains at least one of a polyvalent metal salt and an organic acid, betalam and bleed tend to be further suppressed.

  Although it does not specifically limit as a polyvalent metal salt, For example, the polyvalent metal salt of an inorganic acid or the polyvalent metal salt of an organic acid is preferable. Such a polyvalent metal salt is not particularly limited, but examples thereof include alkaline earth metals belonging to Group 2 of the periodic table (eg, magnesium, calcium), and transition metals belonging to Group 3 of the periodic table (eg, lanthanum). And salts of earth metals (eg, aluminum) and lanthanides (eg, neodymium) from group 13 of the periodic table. As these polyvalent metal salts, carboxylate (formic acid, acetic acid, benzoate, etc.), sulfate, nitrate, chloride, and thiocyanate are suitable. Among them, preferably, calcium salt or magnesium salt of carboxylic acid (formic acid, acetic acid, benzoate, etc.), calcium salt or magnesium salt of sulfuric acid, calcium salt or magnesium salt of nitric acid, calcium chloride, magnesium chloride, and thiocyanic acid. A calcium salt or a magnesium salt is mentioned. In addition, a polyvalent metal salt may be used individually by 1 type, and may use 2 or more types together.

  The organic acid is not particularly limited, and examples thereof include acetic acid, phosphoric acid, oxalic acid, malonic acid, and citric acid. Among these, monovalent or divalent or higher carboxylic acids are preferable. By including such a carboxylic acid, the aggregation effect of the polymer fine particles (A) is further improved, and as a result, the color developability tends to be more excellent. In addition, an organic acid may be used individually by 1 type, and may use 2 or more types together.

(water)
Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the ink is stored for a long period of time. This tends to improve the storage stability.

(solvent)
Examples of the solvent include, but are not limited to, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso- Propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monobutyl ether , Diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono-n -Butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl Methyl A , Triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tripropylene glycol dimethyl ether, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, alcohols or glycols such as tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfora And 1,1,3,3-tetramethylurea.

[Second drying step]
The second drying step is a step in which the ink composition is attached to the recording medium to which the pretreatment liquid has been applied, and is dried at the drying temperature T2. The attaching method is not particularly limited, and examples thereof include a method in which an ink composition is ejected from an ink jet nozzle and attached onto a recording medium. As a means for ejecting the ink composition, a conventionally known method can be used, and examples include means for ejecting droplets by utilizing vibration of a piezoelectric element, that is, means for forming ink droplets by mechanical deformation of an electrostrictive element. . Moreover, it does not specifically limit as a drying method, For example, a heating, ventilation, leaving, etc. are mentioned. In the second drying step, the ink composition can be simultaneously dried while adhering the ink composition to the recording medium. Specifically, there is a method in which an ink composition is attached to a recording medium from an inkjet nozzle, and at the same time, the recording medium is heated with a platen heater or the like.

  Drying temperature T2 becomes like this. Preferably it is 45-85 degreeC, More preferably, it is 50-80 degreeC, More preferably, it is 55-75 degreeC. When the drying temperature T2 is within the above range, the ejection stability and clogging properties are further improved, and the rub resistance and glossiness of the obtained recorded matter tend to be further improved.

(Ink composition)
The ink composition includes a resin having a glass transition temperature Tg2, and may include a coloring material, water, a solvent, and a surfactant as necessary. As a solvent and surfactant, the thing similar to what was illustrated in the pretreatment liquid can be illustrated.

(Resin having glass transition temperature Tg2)
Glass transition temperature Tg2 becomes like this. Preferably it is 55-95 degreeC, More preferably, it is 60-90 degreeC, More preferably, it is 65-85 degreeC. When the glass transition temperature Tg2 is within the above range, the ejection stability and clogging properties are further improved, and the resulting recorded product tends to be further improved in abrasion resistance and glossiness.

  Although it does not specifically limit as resin which has glass transition temperature Tg2, For example, acrylic resin, vinyl acetate resin, vinyl chloride resin, butadiene resin, styrene resin, polyester resin, crosslinked acrylic resin, crosslinked styrene resin, benzoguanamine resin, phenol resin , A silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluororesin, a water-soluble resin, and a copolymer obtained by combining monomers constituting these resins. The copolymer is not particularly limited, and examples thereof include styrene acrylate resin, styrene methacrylate resin, and styrene acrylate methacrylate resin. Among these, styrene acrylate resin, styrene methacrylate resin, styrene acrylate methacrylate resin, and resin having a core-shell structure are preferable. Moreover, the styrene content of the resin is preferably 55 to 90% by mass, and more preferably 60 to 85% by mass. Furthermore, the total of the acrylate content and methacrylate content of the resin (when only one of acrylate or methacrylate is included) is preferably 10 to 45% by mass, more preferably 15 to 40% by mass. It is.

  By using a resin having a core-shell structure, it is possible to further improve the abrasion resistance of the obtained recorded matter. Examples of the resin having a core-shell structure include mourning similar to that used in the first drying step.

  The content of the resin having a glass transition temperature Tg2 is preferably 0.10 to 5.0 mass%, more preferably 0.50 to 3.0 mass%, based on the total amount of the ink composition, More preferably, it is 0.75-2.0 mass%. When the content of the resin having the glass transition temperature Tg2 is within the above range, the ejection stability and the clogging property are further improved, and the rub resistance and the glossiness of the obtained recorded matter are further improved.

[Third drying step]
The third drying step is a step of applying a post-treatment liquid to the recording medium to which the ink composition is adhered and drying it at a drying temperature T3. The means for attaching the post-treatment liquid is not particularly limited, and for example, roller coating, spray coating, and inkjet coating can be used. Moreover, it does not specifically limit as a drying method, For example, a heating, ventilation, leaving, etc. are mentioned. In the third drying step, the post-treatment liquid can be simultaneously dried while adhering the post-treatment liquid to the recording medium. Specifically, there is a method in which a post-treatment liquid is attached to a recording medium from an ink jet nozzle, and at the same time, the recording medium is heated with a platen heater or the like.

  Drying temperature T3 becomes like this. Preferably it is 65-95 degreeC, More preferably, it is 70-90 degreeC, More preferably, it is 75-85 degreeC. When the drying temperature T3 is within the above range, the ejection stability and clogging properties are further improved, and the rubbing resistance and glossiness of the resulting recorded product tend to be further improved.

(Post-treatment liquid)
The post-treatment liquid includes a resin having a glass transition temperature Tg3, and may include water, a solvent, and a surfactant as necessary. As a solvent and surfactant, the thing similar to what was illustrated in the pretreatment liquid can be illustrated.

(Resin having glass transition temperature Tg3)
The glass transition temperature Tg3 is preferably 70 to 110 ° C, more preferably 75 to 105 ° C, and further preferably 80 to 100 ° C. When the glass transition temperature Tg3 is within the above range, the ejection stability and clogging properties are further improved, and the resulting recorded product tends to be further improved in abrasion resistance and glossiness.

  Although it does not specifically limit as resin which has glass transition temperature Tg3, For example, acrylic resin, vinyl acetate resin, vinyl chloride resin, butadiene resin, styrene resin, polyester resin, crosslinked acrylic resin, crosslinked styrene resin, benzoguanamine resin, phenol resin , A silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluororesin, a water-soluble resin, and a copolymer obtained by combining monomers constituting these resins. The copolymer is not particularly limited, and examples thereof include styrene acrylate resin, styrene methacrylate resin, and styrene acrylate methacrylate resin. Among these, styrene acrylate resin, styrene methacrylate resin, styrene acrylate methacrylate resin, styrene acrylate acrylamide resin, and resin having a core-shell structure are preferable. The styrene content of the resin is preferably 70 to 95% by mass, and more preferably 75 to 90% by mass. Furthermore, the total of the acrylate content and methacrylate content of the resin (when only one of acrylate or methacrylate is included) is preferably 1 to 30% by mass, more preferably 5 to 25% by mass. It is. The acrylamide content of the resin is preferably 3 to 15% by mass, more preferably 5 to 10% by mass.

  By using a resin having a core-shell structure, it is possible to further improve the abrasion resistance of the obtained recorded matter. Examples of the resin having a core-shell structure include mourning similar to that used in the first drying step.

  The content of the resin having a glass transition temperature Tg3 is preferably 1.5 to 12.5% by mass, more preferably 2.5 to 10% by mass, and still more preferably based on the total amount of the post-treatment liquid. Is 5.0-7.5 mass%. When the content of the resin having the glass transition temperature Tg3 is within the above range, the ejection stability and clogging properties are further improved, and the resulting recorded product tends to be more resistant to abrasion and gloss.

[Temperature]
The recording method of this embodiment satisfies the following relationships (1) and (2). By satisfying the following relations (1) and (2), since the resin having a low Tg is formed, it is possible to superimpose, whereby the abrasion resistance and the glossiness are further improved. In particular, the lower low Tg layer improves adhesion, and the upper high Tg layer improves abrasion resistance. Moreover, by making a layer structure into 3 layers, the smoothness of the coating film obtained improves, and glossiness improves as a result.
Tg1 <Tg2 <Tg3 (1)
T1 <T2 <T3 (2)

The recording method of the present embodiment preferably satisfies the following relationships (3) to (5). By satisfying the following relationships (3) to (5), that is, the drying temperature is lower than the Tg of the resin, the stability of the resin can be relatively maintained even when the nozzle is heated, and the discharge stability Tend to be more improved.
T1 <Tg1 (3)
T2 <Tg2 (4)
T3 <Tg3 (5)

Furthermore, the recording method of the present embodiment preferably satisfies the following relationship (6). In particular, in the first drying process to the third drying process, it is preferable to satisfy the following relationship (6) when each liquid is simultaneously dried while the liquid is adhered to the recording medium. By satisfying the following relationship (6), in the second drying step, it becomes possible to further soften the resin applied in the first drying step, and as a result, the obtained recorded matter has rub resistance and glossiness. There is a tendency to improve more (the same applies to the third drying step). In addition, since it is not necessary to raise the temperature of the first drying step too much, the discharge stability and clogging properties tend to be improved (the same applies to the second step).
T1 <Tg1 <T2 <Tg2 <T3 <Tg3 (6)

The recording method of the present embodiment preferably satisfies at least one of the following relationships (7), (8), and (9). By satisfying at least one of the following relationships (7), (8), and (9), the ejection stability and clogging properties are further improved, and the rub resistance and glossiness of the obtained printed matter are further improved. There is a tendency.
| T1-Tg1 | ≧ 10 (7)
| T2-Tg2 | ≧ 10 (8)
| T3-Tg3 | ≧ 10 (9)

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[material]
The main materials used in the following examples and comparative examples are as follows.

[Pretreatment liquid]
[Flocculant]
Calcium acetate (solvent)
1,2-hexanediol 2-pyrrolidone [Surfactant]
BYK348 (Bic Chemie Japan, silicone surfactant)
〔resin〕
Resin A (Tg32 ℃)
Resin D (Tg31 ℃)
Resin G (Tg40 ℃)
Resin K (Tg56 ℃)

[Ink composition]
[Color material]
PB15-3
〔solvent〕
1,2-hexanediol 2-pyrrolidone [Surfactant]
BYK348 (Bic Chemie Japan, silicone surfactant)
Surfynol DF110D (manufactured by Nisshin Chemical Industry Co., Ltd., acetylene glycol surfactant)
〔resin〕
Resin B (Tg64 ℃)
Resin E (Tg83 ℃)
Resin H (Tg72 ℃)
Resin I (core Tg-10 ° C, shell Tg 70 ° C)
Resin L (Tg90 ℃)
Resin N (Tg90 ℃)

[Post-treatment liquid]
〔solvent〕
1,2-hexanediol 2-pyrrolidone [Surfactant]
BYK348 (Bic Chemie Japan, silicone surfactant)
Surfynol DF110D (manufactured by Nisshin Chemical Industry Co., Ltd., acetylene glycol surfactant)
〔resin〕
Resin C (Tg82 ℃)
Resin F (Tg102 ℃)
Resin M (Tg100 ° C)
Resin J (core Tg 40 ° C, shell Tg 80 ° C)

[Method of synthesizing resins A to H and K to N]
To a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, in a nitrogen atmosphere, 0.5 parts by weight of potassium persulfate and 80 parts by weight of pure water were added and dissolved, and the internal temperature was increased while stirring. Heated to 70 ° C. On the other hand, each component shown in Tables 1 and 2 (the unit of numerical values represents parts by weight) was mixed and stirred to prepare an emulsion. The emulsion was gradually dropped into the flask using a dropping funnel over 3 hours to carry out an emulsion polymerization reaction. NaOH was added to a part of the obtained polymer emulsion to form a polymer emulsion prepared to a solid content of 40% by weight and a pH of 8.
Resins of monomer components shown below were synthesized.

[Synthesis of Core Shell Resin I]
A reaction vessel was equipped with a dropping device, thermometer, water-cooled reflux condenser, and stirrer, and 100 parts of ion-exchanged water was added and 0.2 parts of polymerization initiator potassium persulfate was added at 70 ° C. in a nitrogen atmosphere while stirring. Then, a monomer solution containing 0.05 part of sodium lauryl sulfate, 3 parts of styrene, 27 parts of n-butyl acrylate and 0.02 part of t-dodecyl mercaptan in 7 parts of ion-exchanged water is dropped at 70 ° C. for reaction. To produce core particles. Thereafter, 2 parts of a 10% ammonium persulfate solution was added and stirred, and further 30 parts of ion exchange water, 0.2 part of potassium lauryl sulfate, 15 parts of methyl methacrylate, 45 parts of styrene, 10 parts of acrylic acid, t-dodecyl mercaptan A reaction solution consisting of 5 parts was added at 70 ° C. with stirring, followed by polymerization reaction, neutralized with sodium hydroxide, adjusted to pH 8 to 8.5, and filtered through a 0.3 μm filter. An aqueous dispersion of polymer particles was prepared.

[Synthesis of core-shell resin J]
It was produced in the same manner as the core-shell resin I except that the monomer addition ratio was changed to the composition shown in Table 3 below.

[Measurement method of Tg]
Differential scanning calorimetry (DSC) based on JIS K7121 was performed, and a model “DSC6220” manufactured by Seiko Electronics Co., Ltd. was used. In the case of the core-shell resin, the glass transition temperature Tg (° C.) of the polymer constituting the core part and the polymer constituting the shell part were respectively determined.

[Preparation]
Each material was mixed with the composition shown in the following Tables 4 to 6 and sufficiently stirred to obtain a pretreatment liquid, an ink composition, and a posttreatment liquid. In Tables 4 to 6 below, the numerical unit is mass%, and the total is 100.0 mass%. The resin described in Table 7 was used.

[Clogging]
An ink jet printer (trade name: PX-H8000, manufactured by Seiko Epson Corporation) was filled with the ink composition, and after confirming that the ink composition could be ejected from the nozzle of the head, the cap was left open for one month. . Thereafter, cleaning was performed three times to determine how many nozzles were missing.
A: No missing nozzle B: Nozzle missing 1-5 C: Nozzle missing 6-20 D: Nozzle missing 21 or more

[Abrasion resistance]
An inkjet printer (trade name PX-G930, manufactured by Seiko Epson Corporation) was filled with the pretreatment liquid, the ink composition, and the posttreatment liquid. A pretreatment liquid is applied to a recording medium (Clearproof Film, manufactured by Seiko Epson Corporation) by ink jet and dried, and then an ink composition is applied thereon by ink jet and dried. Finally, the post treatment liquid is ink jetted. The recorded matter was obtained by applying and drying. Specifically, a fill pattern that can be recorded with a resolution of 720 dpi horizontal and 720 dpi vertical and with a duty of 100% was used for an abrasion resistance test. Table 4 shows the temperature conditions in each step.

Thereafter, the recorded surface of the recorded material left for 1 hour in a laboratory at room temperature (25 ° C.) was loaded using a Gakushin type friction fastness tester AB-301 (trade name, manufactured by Tester Sangyo Co., Ltd.). The rubbing resistance was evaluated by confirming the state of peeling of the recording surface and the state of ink transfer to the cotton cloth when rubbed 20 times with a cotton cloth under 200 g.
A: Ink peeling and ink transfer to a cotton cloth were not observed even after rubbing 20 times.
B: Ink peeling or ink transfer to cotton cloth was observed after rubbing 11 to 15 times.
C: After rubbing 6 to 10 times, ink peeling or ink transfer to a cotton cloth was observed.
D: After rubbing 1 to 5 times, ink peeling or ink transfer to a cotton cloth was observed.

[Coagulation unevenness]
For the evaluation of the aggregation unevenness, the same recorded material as that used in the above-mentioned abrasion resistance test was used. Ink aggregation within the solid pattern of the recorded matter was visually observed and evaluated according to the following evaluation criteria. This evaluation was performed in a laboratory at room temperature (25 ° C.).
A: Aggregation unevenness was not recognized in the solid pattern.
B: Some aggregation unevenness was observed in the solid pattern.
C: Aggregation unevenness was substantially recognized as a whole in the solid pattern.

[Glossy]
The ink composition was filled in an ink jet printer (trade name PX-G930, manufactured by Seiko Epson Corporation), and recorded on a recording medium (clear proof film, manufactured by Seiko Epson Corporation). Specifically, a filled pattern that can be recorded with a resolution of 720 dpi horizontal and 720 dpi vertical and 100% duty was used.
A: 60 ° gloss 80 or more B: 60 ° gloss 20 or more and less than 80 C: 60 ° gloss 20 or less

Claims (8)

A first drying step in which a pretreatment liquid is applied to a recording medium and dried at a drying temperature T1;
A second drying step in which an ink composition is attached to the recording medium coated with the pretreatment liquid and dried at a drying temperature T2.
A third drying step of applying a post-treatment liquid to the recording medium to which the ink composition is adhered and drying at a drying temperature T3;
The pretreatment liquid includes a resin having a glass transition temperature Tg1,
The ink composition includes a resin having a glass transition temperature Tg2,
The post-treatment liquid includes a resin having a glass transition temperature Tg3;
A recording method that satisfies the following relationships (1) and (2).
Tg1 <Tg2 <Tg3 (1)
T1 <T2 <T3 (2) The recording method according to claim 1, wherein the following relations (3) to (5) are satisfied.
T1 <Tg1 (3)
T2 <Tg2 (4)
T3 <Tg3 (5) The recording method according to claim 1 or 2, wherein the following relationship (6) is satisfied.
T1 <Tg1 <T2 <Tg2 <T3 <Tg3 (6) The recording method according to claim 1, wherein at least one of the following relationships (7), (8), and (9) is satisfied.
| T1-Tg1 | ≧ 10 (7)
| T2-Tg2 | ≧ 10 (8)
| T3-Tg3 | ≧ 10 (9) The recording method according to claim 1, wherein the following relationship (10) is satisfied.
T1 ≧ 50 ° C. (10)   6. The resin according to claim 1, wherein at least one of the resin having a glass transition temperature Tg1, the resin having a glass transition temperature Tg2, and the resin having a glass transition temperature Tg3 is a resin having a core-shell structure. The recording method according to claim 1. The recording method according to claim 6, wherein in the resin having the core-shell structure, the glass transition temperature Tg _{core of the core} is lower than T1, and the glass transition temperature Tg _{shell of the shell} is higher than T2.   The recording method according to claim 1, wherein the recording medium is a non-absorbable recording medium.