JP2002225414A - Recording method for printing on recording medium with two liquids - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording method, which is excellent in the fixing properties to and the abrasion resistance against a recording medium and with which a favorable image can be realized. SOLUTION: This recording method can be realized by performing printing by adhering an ink composition and reacting liquid to a recording medium and by consisting of a process for adhering the reacting liquid onto the recording medium, a process for recording an image by adhering the ink composition onto the recording medium and a process for cleansing the recording medium printed through the adhesion of the reacting liquid and the ink composition under the condition that the ink composition includes a colorant, resin emulsion particles, a water-soluble organic solvent and water and the reacting liquid includes a reacting agent, which develops an agglomerate through the contact with the ink composition, and cationic inorganic fine particles and/or cationic polymer fine particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording method for printing by depositing an ink composition and a reaction solution on a recording medium and then washing the recording medium with a polar solvent.

2. Description of the Related Art An aqueous ink composition generally comprises water as a main component, and further contains a coloring component and a wetting agent such as glycerin. As the recording medium used for the aqueous ink composition, one that can absorb the ink composition to some extent and allow the colorant to permeate, such as paper, is used. As a recording method for printing using the aqueous ink composition,
2. Description of the Related Art In recent years, an inkjet recording method has attracted attention. The ink jet recording method is a recording method in which small droplets of an ink composition are made to fly and adhere to a recording medium to perform printing.

On the other hand, when printing or coating is performed on a recording medium such as plastic or metal which does not basically absorb the aqueous ink composition, a solvent using an organic solvent (especially a lipophilic organic solvent) is generally used. A system ink composition and a paint are used. Solvent-based ink compositions and paints are excellent in fixability, abrasion resistance, durability and the like when printed on a non-absorbable recording medium. However, certain organic solvents can be toxic to animals and plants. Therefore, its use,
Attention should be paid to disposal, which may be inconvenient to handle.

[0004] Even when printing and painting on a non-absorbent recording medium, the recording method using the aqueous ink composition is preferable from the viewpoints of safety, environment, convenience of use, and the like. However, in printing on a non-absorbable recording medium, it is required that the colorant component of the aqueous ink composition be firmly fixed on the surface of the recording medium. In general, it has been proposed to add a resin as a binder to an aqueous ink composition in order to improve the fixability of a colorant to a recording medium. This resin fixes a colorant on the recording medium as a binder.

[0005] In printing on a recording medium such as a plastic metal, the durability, light resistance and weather resistance of the printed matter are generally required in many cases. As means for improving the light fastness of the ink composition, it is conceivable to add an ultraviolet absorber or a light stabilizer to the ink composition. However, since most of the ultraviolet absorbers and light stabilizers are oil-soluble, it has been difficult to allow a sufficient amount of the water-soluble ink composition to be present. Further, as a means for improving the weather resistance of the ink composition, as a low molecular weight lightfastness imparting agent,
It is conceivable to add certain polymeric binders into the ink composition. However, it may be difficult to maintain the initial image quality of the print under severe conditions, such as when the print is exposed to rain and dew in the field or comes into contact with seaside seawater.

In the ink jet recording method, it is necessary to improve the dispersion stability and the ejection stability of the ink composition in order to realize good image formation.

When printing characters, printing is usually performed using a real image. However, a mirror image may be printed on a recording medium depending on the use and environment of use of the printed matter. For example, a wall material, a packaging material, a transfer paper, or the like may be used by mirror-printing a design on a transparent or translucent recording medium.
In addition, the manufacture of a seal is performed based on a composition on which a mirror image is printed. Further, the backlight-only sheet has a mirror image printed on the back surface of the sheet, and irradiates light from the back surface of the mirror-image printed sheet when used. Therefore, even in mirror image printing, there is a demand for a printing method which is excellent in fixability, abrasion resistance, and light resistance and has good image quality.

[0008]

SUMMARY OF THE INVENTION The present inventors have recently developed a reaction liquid comprising an ink composition containing a colorant and resin emulsion particles, cationic inorganic fine particles and / or cationic polymer fine particles, and a reactant. An image is formed on a recording medium using the two liquids described above, and thereafter, the printed portion (image portion) is formed into a film by washing with a polar solvent. As a result, the fixability and abrasion resistance of the colorant in the recording medium are reduced. , Light resistance and weather resistance were improved, and the image quality of the printed matter could be improved more than expected. The present invention is based on such findings.

Accordingly, the present invention provides a colorant for a recording medium which is excellent in fixability, abrasion resistance, light resistance, and weather resistance;
It is an object of the present invention to provide a recording method capable of realizing a good image.

The recording method according to the present invention is a recording method in which an ink composition and a reaction liquid are adhered to a recording medium to perform printing, wherein the step of adhering the reaction liquid onto the recording medium comprises the steps of: Adhering the ink composition on a recording medium to record an image, and washing the recording medium printed with the reaction liquid and the ink composition adhered with a polar solvent, the method comprising: An ink composition comprising a colorant, resin emulsion particles, a water-soluble organic solvent, and water, wherein the reaction solution is capable of forming an aggregate when contacted with the ink composition; It contains inorganic fine particles and / or cationic polymer particles, a water-soluble organic solvent, and water.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The recording method according to the present invention comprises a step of depositing a reaction liquid on a recording medium, a step of depositing an ink composition to record an image, and a step of depositing the reaction liquid and the ink composition. Washing the printed recording medium with the polar solvent.

A Reaction Solution 1. Reactant The reaction liquid according to the present invention comprises a reactant, where the “reactant” is capable of disrupting the state of dispersion and / or dissolution of the colorant, resin emulsion particles, and the like in the ink composition and causing aggregation. Things. Examples include polyvalent metal salts, polyamines, and polyamine derivatives.

The polyvalent metal salt is composed of divalent or higher polyvalent metal ions and anions bonded to these polyvalent metal ions, and is soluble in water. Specific examples of polyvalent metal ions include Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Z
divalent metal ions such as n ²⁺ and Ba ²⁺ , Al ³⁺ , F
^Examples include trivalent metal ions such as e ³⁺ and Cr ³⁺ . Examples of anions include Cl ⁻ , NO ^{3 −} , I ⁻ , Br ⁻ , and ClO.
^3, and CH ₃ COO ^- and the like, such as.

In particular, a metal salt composed of Ca ²⁺ or Mg ²⁺ gives favorable results from the two viewpoints of the pH of the reaction solution and the quality of the obtained printed matter.

The concentration of these polyvalent metal salts in the reaction solution may be appropriately determined within a range in which the effect of preventing printing quality and clogging can be obtained, but is preferably about 0.1 to 40% by weight, and more preferably about 0.1 to 40% by weight. Is about 5 to 25% by weight.

According to a preferred embodiment of the present invention, the polyvalent metal salt contained in the reaction solution comprises a divalent or higher polyvalent metal ion,
It is composed of nitrate ions or carboxylate ions bound to these polyvalent metal ions, and is soluble in water.

Here, the carboxylate ion is preferably derived from a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms or a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms. Preferred examples of the saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid,
Isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid and the like. Particularly, formic acid and acetic acid are preferable.

The hydrogen atom on the saturated aliphatic hydrocarbon group of the monocarboxylic acid may be substituted with a hydroxyl group. A preferred example of such a carboxylic acid is lactic acid.

Further, preferred examples of the carbocyclic monocarboxylic acid having 6 to 10 carbon atoms include benzoic acid and naphthoic acid, and more preferably benzoic acid.

The polyallylamine and the polyallylamine derivative which can be used in the reaction solution are cationic polymers which are soluble in water and positively charged in water. For example,
What is represented by the following formula is mentioned.

[0021]

Embedded image [In the above formula, X- represents a chloride ion, a bromide ion, an iodide ion, a nitrate ion, a phosphate ion, a sulfate ion, an acetate ion, etc.] In addition to the above, a polymer obtained by copolymerizing allylamine and diallylamine or diallylmethylammonium Copolymers of chloride and sulfur dioxide can be used.

The content of these polyallylamine and polyallylamine derivative is 0.5 to 10% by weight of the reaction solution.
It is preferred that

[0023] 2. Cationic inorganic fine particles and / or
Cationic Polymer Fine Particles The reaction solution in the present invention comprises cationic inorganic fine particles and / or
Or it comprises cationic polymer fine particles.

In the present invention, the cationic inorganic fine particles are obtained by treating the inorganic fine particles by various methods to cationize. As a preferable specific example of the processing,
A method of cationizing the inorganic fine particles by hydration treatment or treatment with a cationic substance may be mentioned. Specific examples of the method of treating the inorganic fine particles with a cationic substance to cationize include a method of treating the surface of the inorganic fine particles with a cationic substance and a method of dispersing and stabilizing the inorganic fine particles with a cationic substance.

As the inorganic fine particles, fine particles of various inorganic substances can be used, and preferable specific examples thereof include inorganic colloid particles. Inorganic colloid particles have a diameter of 1
In the range of about to 500 ^nm, it refers to those comprising 10 3 to 10 ⁹ about atoms. The inorganic colloid particles are dispersed in the liquid using the liquid as a dispersant to form a colloid solution. Specific examples of the inorganic fine particles include silica (including amorphous silica and amorphous silica), colloidal silica, silicic anhydride, hydrated silicic acid, finely divided silica, silica gel, alumina, boehmite, pseudo boehmite, aluminum hydroxide,
Examples thereof include silicic acids called calcium silicate, aluminum silicate, barium sulfate, alumina sol, calcium carbonate, and white carbon. In addition, specific examples of the inorganic colloid particles preferably include colloidal silica and alumina.

Specific examples of the cationic substance include alumina sol (also referred to as alumina hydrate), basic aluminum chloride, a cationic surfactant, and a polycation compound.

Specific examples of the cationic surfactant include:
Primary fatty amine salt; secondary fatty amine salt; tertiary fatty amine salt; tetraalkylammonium salt, trialkylbenzylammonium salt, alkylpyridinium salt, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium Quaternary ammonium salts such as salts, N, N-dialkylmorpholinium salts, polyethylene polyamine fatty acid amide salts, salts of urea condensates of polyethylene polyamine fatty acid amides, and quaternary ammonium salts of urea condensates of polyethylene polyamine fatty acid amide ;

Specific examples of the polycation compound include a polyamine, a polyamine derivative, a polyamine sulfone, a polyamine sulfone derivative and the like.

The average primary particle diameter of the cationic inorganic fine particles is in the range of 0.1 nm to 200 nm, and preferably in the range of 1 nm to 100 nm. More preferably, 1n
m to 50 nm. When the average primary particle diameter of the cationic inorganic fine particles is within the above range, the coloring component of the ink composition can be firmly fixed to the recording medium. Specific preferred examples of the cationic inorganic fine particles include alumina sol and cationic colloidal silica. As the alumina sol, a commercially available product can be used. Specific examples thereof include Cataloid AS-3 (manufactured by Catalyst Chemical Industry Co., Ltd .: primary particle size: about 10 nm), and alumina sol 100
(Nissan Chemical Co., Ltd.), alumina sol 200 (Nissan Chemical Co., Ltd.), alumina sol 520 (Nissan Chemical Co., Ltd.) and the like.

Commercially available cationic colloidal silica can be used, and specific examples thereof include Snowtex-
UP-AK (manufactured by Nissan Chemical Industries: primary particle size 10 to 20 n)
m), Snowtex-AK (manufactured by Nissan Chemical Industries, Ltd .: primary particle size: 10 to 20 nm), and Cataloid-SN (manufactured by Catalyst Chemical Industry Co., Ltd .: primary particle size: 40 to 50 nm).

As the cationic polymer fine particles, those obtained by various methods are used, and preferably, those obtained by treating polymer fine particles with a cationic substance to cationize or polymerizing cationic monomers are used. Specific examples of the method of treating the polymer fine particles with a cationic substance to cationize include a method of treating the surface of the polymer fine particles with a cationic substance and a method of dispersing and stabilizing the polymer fine particles with a cationic substance. The cationic substance may be the same as that used for the cationic inorganic fine particles.

The average primary particle diameter of the cationic polymer fine particles is in the range of 0.1 nm to 200 nm, preferably in the range of 1 nm to 100 nm. When the average primary particle diameter of the cationic inorganic fine particles is within the above range, the coloring component of the ink composition can be firmly fixed to the recording medium. As the polymer fine particles, polymer fine particles synthesized by various methods can be used. Specific examples of the polymer fine particles include a group of acrylic resin, polyester resin, epoxy resin, styrene-butadiene copolymer, polybutadiene, polyolefin, polystyrene, polyamide, ethylene-vinyl acetate copolymer, polysiloxane, and polyurethane. Preferably, a resin composed of a polymer selected from the group consisting of an acrylic resin, a polyester resin, a polyamide, a polysiloxane, and a polyurethane is preferable.

In the present invention, fine particles composed of a polymer obtained by polymerizing a cationic monomer can be used as the cationic polymer fine particles. Preferred examples of the cationic monomer include those represented by the following formula (I). Then, cationic polymer fine particles can be obtained by copolymerizing the monomer represented by the formula (I) and a vinyl monomer. The monomer represented by the formula (I) and the vinyl monomer are known ones disclosed in JP-A-9-99632.
Therefore, specific examples of these monomers, the method of copolymerization, and the like may be the same as those described in this publication.

[0034]

Embedded image [Wherein R ¹ represents a hydrogen atom or a methyl group;
Represents an oxygen atom or an NH group, R ² and R ³ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁴ may be a hydrogen atom or may be substituted Represents a linear or branched alkyl group having 1 to 4 carbon atoms, n represents an integer of 2 to 5, and Y ⁻ represents a salt-forming anion. The inorganic fine particles and / or the cationic polymer fine particles are used in an amount of 0.1 to the total amount of the reaction solution.
It comprises in the range of 1 to 30% by weight, preferably in the range of 1 to 20% by weight.

[0035] 3. Water-Soluble Organic Solvent and Water The reaction solution in the present invention uses a water-soluble organic solvent and water as main solvents. Specific examples of the water-soluble organic solvent,
A high-boiling water-soluble organic solvent may be used. The high-boiling water-soluble organic solvent prevents the reaction solution from drying. Preferred examples of the high-boiling water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, and 1,2,6-hexanetriol, which partially overlap with the polyol described below. Polyhydric alcohols such as thioglycol, hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
Alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; urea; 2-pyrrolidone; Examples thereof include methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and triethanolamine.

According to a preferred embodiment of the present invention, the high-boiling water-soluble organic solvent is preferably at least glycerin, more preferably a combination of glycerin, triethylene glycol monobutyl ether and 1,2-hexanediol, or glycerin. Preferred is a combination with triethylene glycol monobutyl ether or 1,2-hexanediol.

According to another embodiment of the present invention, preferred examples of the water-soluble organic solvent include a low-boiling water-soluble organic solvent. Preferred examples of the low boiling water-soluble organic solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol,
sec-butanol, tert-butanol, iso-
Butanol, n-pentanol and the like. Particularly, a monohydric alcohol is preferable. Low boiling water-soluble organic solvents
The cleaning with water in the method of the present invention has the effect of making the cleaning easier.

The addition amount of the water-soluble organic solvent is preferably from 0.5 to 10% by weight, more preferably from 1.5 to 6% by weight, based on the total amount of the reaction solution.

[0039] 4. Other Components The reaction solution of the present invention may contain other components other than the above-described components. According to a preferred embodiment of the present invention, the reaction solution may further contain a saccharide. Addition of a saccharide is effective in improving reliability such as clogging and ejection stability when the reaction liquid is used in an ink jet recording apparatus. Preferred examples of saccharides include monosaccharides, disaccharides, oligosaccharides, (including trisaccharides and tetrasaccharides) and polysaccharides. Specific examples of the saccharide include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucosyl, sorbitol, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like. These saccharides may be added as one kind or a mixture of two or more kinds.

The amount of saccharide added is 1 to 1 with respect to the total amount of the reaction solution.
0% by weight.

According to a preferred embodiment of the present invention, the reaction solution may contain various surfactants such as an anionic surfactant, a cationic surfactant and an amphoteric surfactant.

The surfactant is preferably a compound represented by the following formula (III) and / or a lower alcohol ether of a polyhydric alcohol.

[0043]

Embedded image [In the above formula, 0 ≦ m + n ≦ 50, R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group (preferably having 1 to carbon atoms)
Specific examples of the compound represented by the above formula (III) include Olfin Y, Surfynol 82, Surfynol 44
0, Surfynol 465 and Surfinol 485 (all manufactured by Air Products and Ch
electronics. Inc. ). These may be used alone or in combination of two or more.

The addition amount of the surfactant is 0.01 to 5% by weight based on the total amount of the reaction solution.

According to a preferred embodiment of the present invention, the reaction solution contains an alkanolamine for pH adjustment. A preferred specific example of the alkanolamine is triethanolamine. The addition amount of triethanolamine is preferably about 0.5 to 2% by weight based on the total amount of the reaction solution.

B Ink Composition The ink composition used in the method according to the present invention comprises at least a colorant, resin emulsion particles, a water-soluble organic solvent, and water. In the present invention, the ink composition means a black ink composition when performing monochrome printing, and a color ink composition when performing color printing, specifically, a yellow ink composition and a magenta ink composition. , And a cyan ink composition, and in some cases, a black ink composition.

[0047] 1. Colorant The colorant according to the present invention is one in which a pigment or pigment and / or dye is included in a polymer, and the inclusion is in the form of fine particles.

1) Pigment The pigment is not particularly limited, and any of an inorganic pigment and an organic pigment can be used. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method can be used. As organic pigments, azo pigments (azo lakes, insoluble azo pigments,
Condensed azo pigments, chelating azo pigments and the like), polycyclic pigments (for example, phthalocyanine pigment, perylene pigment, perinone pigment, anthraquinone pigment, quinacridone pigment,
Dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinoflurone pigments, etc., dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like can be used.

As a specific example of the pigment, carbon black No. 2300, no. 900,
MCF88, no. 33, no. 40, no. 45, N
o. 52, MA7, MA8, MA100, No2200
B, etc. are Raven 5750 and 52 manufactured by Columbia Corporation.
50, 5000, 3500, 1255, 700
Etc. are Regal 400R, 3
30R, 660R, Mogul L, 700, Mo
network 800, 880, 900, 100
0, 1100, 1300, and 1400 are Color Black FW1 and FW manufactured by Degussa.
2, FW2V, FW18, FW200, Col
or Black S150, S160, S17
0, Printex 35, U, V, 140U,
Special Black 6,5,4A, 4
And the like. Examples of the pigment used for the yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 12,
13, 14, 16, 17, 73, 74, 75, 83, 9
3, 95, 97, 98, 109, 110, 114, 12
8, 129, 138, 150, 151, 154, 15
5, 180, 185 and the like. Examples of the pigment used for the magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57
(Ca), 57: 1, 112, 122, 123, 16
8, 184, 202 and the like. Further, as the pigment used for the cyan ink, C.I. I. Pigment Blue 1, 2, 3, 15: 3, 15: 4, 16, 22, 6
0, C.I. I. Bat Blue 4, 60.

The particle size of these pigments is about 5 to 500 nm, preferably about 5 to 200 nm, more preferably 5 to 200 nm.
About 100 nm.

2) Dyes : Direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, etc. are usually used for ink jet recording. Various dyes can be used.

The content of the colorant is preferably about 1 to 20% by weight, more preferably 1 to 20% by weight based on the total amount of the ink composition.
It is in the range of 10% by weight. When the content of the coloring agent is in the above range, good ejection stability can be obtained in the ink jet recording method.

3) Dispersant According to a preferred embodiment of the present invention, when a pigment is used as the colorant, it is preferable to add the pigment to the ink as a pigment dispersion in which the pigment is dispersed in an aqueous medium with a dispersant. As a dispersant used for preparing a pigment dispersion, a dispersant generally used for preparing a pigment dispersion, for example, a polymer dispersant or a surfactant can be used. It will be apparent to those skilled in the art that the surfactant contained in this pigment dispersion will also function as the surfactant of the ink composition. Preferred examples of the polymer dispersant include natural polymers, and specific examples thereof include proteins such as glue, gelatin, casein, and albumin; natural gums such as gum arabic and tragacanth; glucosides such as savonin; Alginic acid and alginic acid derivatives such as propylene glycol alginate, triethanolamine alginate and ammonium alginate; cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose and ethylhydroxycellulose.

Preferred examples of the polymer dispersant include synthetic polymers, such as polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, and acetic acid. Acrylic resins such as vinyl-acrylate copolymer and acrylic acid-acrylate copolymer; styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-
Styrene-acrylic resin such as acrylate copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylate copolymer; styrene-maleic acid copolymer Styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate- Examples include vinyl acetate-based copolymers such as maleic ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and salts thereof. Among them, a copolymer of a monomer having a hydrophobic group and a monomer having a hydrophilic group, and a polymer composed of a monomer having both a hydrophobic group and a hydrophilic group in a molecular structure are preferable.

The amount of the dispersant added is about 0.1 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the ink composition.
% By weight.

4) Pigments Incorporated in Polymer and / or
According to a preferred embodiment by the dye present invention, as the coloring agent are those pigments and / or dyes include a polymer, and it is preferred that the inclusions are added to those in the form of fine particles in the ink. Such a coloring agent is sometimes called a microcapsule-type coloring agent (hereinafter, this name is appropriately used in the present specification).

The microcapsule type colorant is prepared by mixing a dye or pigment in a polymer, microencapsulating the dye or pigment with a polymer, or dissolving the dye or pigment in a monomer and emulsion-polymerizing. And microemulsification.

Methods for encapsulating a dye or a pigment with a polymer include an interfacial polymerization method, an in-situ polymerization method, a coacervation method, a liquid drying method, a melt dispersion cooling method, a spray drying method, and a liquid curing coating method. Law. Specifically, Japanese Patent Application Laid-Open No. 9-279073,
0-176130, JP-A-5-239392 and the like.

The following are specific examples of the microcapsule type coloring agent.

A ) Aqueous Dispersion of Pigment In the present invention, “aqueous dispersion of a pigment” refers to a polymer obtained by mixing a pigment with a polymerizable surfactant having both nonionic and anionic hydrophilicity and a monomer. Refers to microscopic and stable encapsulated particles of pigment incorporated by coalescence. “Aqueous dispersion of pigment” is one in which fine and stable encapsulated particles of pigment are stably dispersed in an aqueous medium. The polymerizable surfactant having both anionic and nonionic hydrophilicity according to the present invention is adsorbed on the surface of pigment particles, and is stable in dispersibility even under subsequent polymerization conditions (that is, it is possible to prevent aggregation of particles). Is advantageous in that it is easy to form encapsulated particles. The pigment in the aqueous dispersion of the pigment may be the same as described above.

The aqueous dispersion of the pigment has excellent dispersion stability. Although the reason is not clear, the encapsulation as described above allows the dispersant to be more mechanically and firmly fixed than when the dispersant is simply adsorbed to the surface of the pigment particles by van der Waals force. it is conceivable that. It should be noted that the above-mentioned theory is used only for explaining the content of the present invention, and the scope of the present invention is not limited only by the theory.

In the present invention, when an aqueous dispersion of a pigment is used as a coloring agent, its content is preferably about 1 to 20% by weight based on the ink composition.
More preferably, it is about 1 to 10% by weight. It is preferable that the content of the aqueous dispersion of the pigment be 1% by weight or more, since a sufficient print density can be obtained.
On the other hand, when the content of the pigment dispersion is 20% by weight or less, the viscosity of the ink composition falls within a range suitable for an inkjet recording ink, and the ejection stability can be maintained. The amount of the pigment to be added is preferably in the range of about 5 to 50% by weight, more preferably in the range of about 5 to 30% by weight, based on the total amount of the aqueous dispersion of the pigment. The particle size of the aqueous dispersion of the pigment is about 5 to 500 nm, preferably 5 to 200 nm.
nm.

Examples of the polymerizable surfactant having both anionic and nonionic hydrophilicity include the following formula (II):
The compound represented by is preferred. The polymerizable surfactant represented by the following formula (II) is described in JP-A-5-320276,
This is disclosed in JP-A-10-316909.

[0064]

Embedded image [In the above formula, R represents a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms, n represents a number of 2 to 20, M represents an alkali metal atom (preferably lithium, sodium or potassium), Represents an ammonium salt or an alkanolamine] By appropriately adjusting the values of R and n in the formula (II), it is possible to correspond to the degree of hydrophilicity or hydrophobicity of the pigment surface. Preferred examples of the polymerizable surfactant represented by the formula (II) include a compound represented by the following formula. These may be used alone or as a mixture of two or more.

[0065]

Embedded image In the present invention, a commercially available polymerizable surfactant can also be used. For example, Aqualon HS series (Aqualon HS-05, H
S-10, HS-20, HS-1025), Aqualon RN series (RN-10, RN-20, RN-30,
RN-50, RN-2025), New Frontier Series (New Frontier N-177E, S-51)
0), Asahi Denka Co., Ltd. Adecaria Soap SE series, Adecaria Soap NE series (NE-10, NE
-20, NE-30, NE-40, NE-50).

According to a preferred embodiment of the present invention, the polymerizable surfactant can be homopolymerized, but is preferably a copolymer. The amount of the polymerizable surfactant to be added is preferably in the range of about 10 to 150% by weight, more preferably in the range of about 20 to 100% by weight, based on the pigment. When the amount is 10% by weight or more, the dispersion stability of the ink composition can be improved. Also,
By setting the addition amount to 150% by weight or less, the generation of a polymerizable surfactant not adsorbed to the pigment can be suppressed, and the generation of a polymer other than the capsule particles can be prevented. Discharge stability can be improved.

As the monomer used in the present invention, any monomer having a high copolymerizability with a polymerizable surfactant can be used. However, equation (1)
Is a monomer having a high electron-donating property, and therefore, a monomer having a high electron-accepting property is preferred in the invention. Specific examples of monomers having a high electron-accepting property include fumaric acid diesters such as acrylonitrile, fumaronitrile, and dibutyl fumarate; maleic acid diesters such as maleic acid dibutyl ester; maleimides such as N-phenylmaleimide; And vinylidene chloride. These may be used alone or as a mixture of two or more.

Further, examples of the monomer used in the present invention include acrylic acid, acrylic ester, methacrylic acid, and methacrylic ester. Specifically, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, butoxyethyl acrylate, benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, Dicyclobenthyl acrylate, dicyclopentynyloxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl Phthalic acid, caprolactone acrylate, glycidyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2
-Ethylhexyl methacrylate, butoxymethyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate,
Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, tetrahydrofurfuryl methacrylate, iribornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, glycerol methacrylate, 21-methacryloyloxy Ethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, caprolactone methacrylate, glycidyl methacrylate, sulfoethyl methacrylate, butyl acrylamide sulfonic acid, phosphoethyl methacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene Glycol diacrylate, polyethylene Glycol diacrylate, allyl acrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, bis (acryloxyneopentyl glycol) adipate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate Acrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxy) phenyl] propane, 2,2-bis [4- (acrylic Roxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy / diethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy / polyethoxy) phenyl] propa , Hydroxy Viva phosphate neopentyl glycol diacrylate,
1,4-butanediol diacrylate, dicyclopentanyl diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, tetrabromopisphenol A diacrylate, triacrylate Glycerol diacrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, provylene glycol dimethacrylate , Polypropylene glue Over dimethacrylate, 1,
3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [ 4- (methacryloxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4-
(Methacryloxyethoxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxypolyethoxy) phenyl] propane, tetrabromobisphenol A dimethacrylate, dicyclopentanyl dimethacrylate, dipentaerythritol hexamethacrylate, Glycerol dimethacrylate, hydroxypentivalate neopentyl glycol dimethacrylate, dipentaerythritol monohydroxypentamethacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, triglycerol dimethacrylate, trimethylolpropane trimethacrylate, And the like.

The amount of the monomer is preferably in the range of about 2 to 15 mole ratio, more preferably in the range of about 3 to 12 mole ratio, based on the polymerizable surfactant. Capsule pigment particles formed with an addition amount of 2 mol ratio or more have excellent dispersion stability in an aqueous medium. In addition, when the amount is 15 mole ratio or less, the monomer can be sufficiently dissolved in the polymerizable surfactant adsorbing layer, and the generation of water-insoluble polymer can be suppressed, and the ionic repulsion can be relatively reduced. Since the decrease in the amount of the group can be suppressed, the dispersion stability of the ink composition can be improved.

The polymerization initiator used in the present invention includes potassium persulfate, ammonium persulfate, sodium persulfate, 2,2, azobis- (2-methylpropionamidine) dihydrochloride, and 4,4, azobis- (4 Cyanovaleric acid) and the like.

The aqueous dispersion of the pigment according to the present invention can be produced as follows.

The immobilization of the polymerizable surfactant on the pigment, that is, microencapsulation of the pigment is performed by adding the pigment and the polymerizable surfactant to an aqueous organic solvent and / or water, and using an ultrasonic wave, a ball mill or a sand grinder. After wet pulverization by, for example, adding a monomer and / or a polymerization initiator to be copolymerized while continuing the pulverization treatment as needed, and performing a polymerization reaction at 40 to 100 ° C. for 10 to 60 hours. Thereby, microencapsulated pigment particles can be obtained. The amount of polymerization initiator added is
The amount is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the monomer.

Next, after removing coarse particles from the obtained microencapsulated pigment particles by centrifugation or filtration, alcohols, glycols,
An aqueous dispersion of a pigment can be obtained by adding and adjusting a water-soluble organic solvent such as an amide, a water-soluble polymer, a surfactant, and a fungicide. More preferably, it can be produced by the production method described in JP-A-10-316909.

B) UV absorbing activity and / or photostability
According to a preferred embodiment of the colorants present invention having an activity, as a coloring agent, a dye or pigment includes a polymer having an ultraviolet absorbing activity and / or light stabilizing activity, and its inclusions in particulate form It is preferable to add the ink to the ink. In the present invention, the polymer has a site having an ultraviolet absorbing activity and / or a light stabilizing activity in a molecular chain. The ink with this coloring agent added
It is considered that light resistance can be imparted to the printed image of the recording medium. Dyes or pigments as colorants may be the same as described above.

According to a preferred embodiment of the present invention, the polymer is a polymer or copolymer containing a monomer having a site having an ultraviolet absorbing activity and / or a light stabilizing activity as a polymerization component, or a polymer having an ultraviolet ray. It means that a site having an absorption activity and / or a light stabilization activity is graft-polymerized.

According to a preferred embodiment of the present invention, the site having the ultraviolet absorbing activity and / or the light stabilizing activity includes an aromatic monocyclic hydrocarbon group, a condensed polycyclic aromatic hydrocarbon group, and a heterocyclic monocyclic hydrocarbon group. A group selected from the group consisting of a ring group and a condensed heterocyclic group, and having absorptivity in the region of 200 to 400 nm. Further, the ultraviolet absorbing activity and / or
Alternatively, specific examples of the site having a light stabilizing activity include those having a benzotriazole skeleton, a benzophenone skeleton, a salicylate skeleton, a cyanoacrylate structure, a hindered phenol skeleton, or a hindered amine skeleton.

The specific structures of these skeletons include those represented by the following formulas.

[0078]

Embedded image In the present invention, the polymer having a site having an ultraviolet absorbing activity and / or a light stabilizing activity in a molecular chain is:
A monomer having a site having an ultraviolet absorbing activity and / or a light stabilizing activity can be used as a polymerization component and a homopolymer obtained by polymerizing the monomer or a copolymer obtained by copolymerizing with another monomer can be obtained. Alternatively, a polymer having a site having an ultraviolet absorbing activity and / or a light stabilizing activity in a molecular chain may be obtained by graft-polymerizing a site having an ultraviolet absorbing activity and / or a light stabilizing activity to the polymer. Can also be obtained by The monomer having a site having an ultraviolet absorbing activity and / or a light stabilizing activity, which is preferably used in such a production method, includes a site having an ultraviolet absorbing activity and / or a light stabilizing activity, And a monomer having a saturated bond. Further specific examples of such a monomer include a benzotriazole ultraviolet absorber having an ethylenically unsaturated bond, a benzophenone ultraviolet absorber having an ethylenically unsaturated bond, a salicylate ultraviolet absorber having an ethylenically unsaturated bond, Examples include a cyanoacrylate-based ultraviolet absorber having an ethylenically unsaturated bond, a hindered phenol-based ultraviolet absorber having an ethylenically unsaturated bond, and a hindered amine-based light stabilizer having an ethylenically unsaturated bond. Further, the ethylenically unsaturated bonds of these monomers may be provided as methacryloyl, acroyl, vinyl, allyl groups.

The following are specific examples of such a monomer. First, as a specific example of a monomer having an ultraviolet absorption site having a benzophenone skeleton,
Examples include those represented by the following formulas.

[0080]

Embedded image Further, specific examples of the monomer having an ultraviolet absorbing portion having a benzotriazole skeleton include those represented by the following formula.

[0081]

Embedded image Further, specific examples of the monomer having an ultraviolet absorbing site having a hindered phenol skeleton include those represented by the following formula.

[0082]

Embedded image Further, specific examples of the monomer having a light stable site having a hindered amine skeleton include the following.

[0083]

Embedded image As a monomer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability, a commercially available monomer can be used. Examples of commercially available products include RUVA-93 available from Otsuka Chemical Co., Ltd. as a monomer having an ultraviolet absorbing site having a benzotriazole skeleton.
(2- (2′-hydroxy-5-methylacryloxyethylphenyl) -2H-benzotriazole). As a monomer having a light stabilizing site having a hindered amine skeleton, ADK STAB LA-82 (1, 2, 2, 6, available from Asahi Denka Kogyo KK)
6-pentamethyl-4-piperidyl methacrylate),
LA-87 (2,2,6,6-tetramethyl-4-piperidyl methacrylate).

Further, monomers copolymerized with the above-mentioned monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-butyl (meth) acrylate. Amyl (meth) acrylate,
Isoamyl (meth) acrylate, n-hexyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylates such as acrylate, 2-hydroxylethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl methacrylate, and glycidyl acrylate; and vinyl esters such as vinyl acetate; acrylonitrile, methacrylonitrile, and other styrene; Aromatic vinyl such as 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene, etc. And vinylidene halides such as vinylidene chloride and vinylidene fluoride; ethylene, propylene, isopropylene, butadiene, vinylpyrrolidone, vinyl chloride, vinyl ether, vinyl ketone, chloroprene and the like, and acrylic acid, methacrylic acid, and maleic acid containing a carboxyl group Or an ethylenically unsaturated carboxylic acid such as a monoalkyl ester, itaconic acid or a monoalkyl ester thereof, fumaric acid or a monoalkyl ester thereof; N-containing amino group such as acrylamide having an amide group, N, N-dimethylacrylamide, etc. -Methylaminoethyl methacrylate, N-methylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,
Alkylamino esters of acrylic acid or methacrylic acid such as diethylaminoethyl methacrylate and diethylaminoethyl methacrylate; N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, N, N-dimethylaminopropyl Unsaturated amides having an alkylamino group such as acrylamide, and monovinylpyridines such as vinylpyridine, and vinylethers having an alkylamino group such as dimethylaminoethyl vinyl ether; vinylimidazole and the like, vinylsulfonic acid, styrenesulfonic acid, and the like. Examples thereof include those having a sulfone group, such as salts thereof, 2-acryloylamino-2-methylpropanesulfonic acid, and salts thereof. These monomers can be used alone or in combination of two or more. As copolymers obtained from these monomers, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer,
Polyethylene, polypropylene, polystyrene, poly (meth) acrylate, styrene- (meth) acrylate copolymer, styrene-maleic acid copolymer, styrene-itaconate copolymer, polyvinyl acetate, polyester, polyurethane And polyamide.

According to a preferred embodiment of the present invention, the polymer having a site having an ultraviolet absorbing activity and / or a light stabilizing activity in a molecular chain is preferably thermoplastic.

Further, as the polymer to which the above-mentioned monomer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability is graft-polymerized, a homopolymer or a copolymer of the above-mentioned monomers can be mentioned.

The colorant having an ultraviolet absorbing activity and / or a light stabilizing activity is preferably produced by an emulsion polymerization method. In the emulsion polymerization method, specifically, a dye or a pigment is dispersed in a monomer component constituting a polymer, and a monomer having a site having ultraviolet absorbing activity or photostable activity, a polymerization catalyst and an emulsifier are present. It is carried out by emulsion polymerization in water.

According to a preferred embodiment of the present invention, the colorant having an ultraviolet absorbing activity and / or a light stabilizing activity is
Those having a functional group of either a carboxyl group or a sulfonic acid group are preferable, and those having an amide group, a hydroxyl group, or an amino group are more preferable. These groups may be present in the structure of the monomer in the above-mentioned production method, or may be added to the surface of the fine particles by graft polymerization or the like after obtaining the fine particles.

According to a preferred embodiment of the present invention, the colorant having ultraviolet absorbing activity and / or light stabilizing activity preferably has a particle size of about 5 nm to 500 nm, more preferably about 5 nm to 200 nm. is there.

The content of the dye or pigment in the colorant having the ultraviolet absorbing activity and / or the light stabilizing activity may be appropriately determined as long as the color developability is not impaired. Therefore, the content is 0.1% in the coloring agent for imparting polymer.
It is preferably about 1 to 99% by weight, more preferably 5 to 9% by weight.
The range is 0% by weight.

The ink composition according to the present invention may contain other dyes and / or pigments in addition to the above-mentioned colorants. In particular, when used in combination with a resin emulsion particle having a film forming ability described later, it is advantageous in that an image having more excellent color development, water resistance, abrasion resistance, and light resistance can be realized.

Further, according to a preferred embodiment of the present invention, the polymer containing a dye or a pigment preferably has a film-forming ability. According to a preferred embodiment of the present invention, the polymer preferably has a glass transition point of 30 ° C. or lower when in the form of a colorant. Here, the minimum film forming temperature refers to a temperature at which a continuous film is formed when a colorant dispersed in water is thinly cast on a metal plate such as aluminum and the temperature is increased. According to this aspect, the ink composition according to the present invention reliably forms a film at room temperature, and as a result, it is possible to improve the quick drying property, the touch property, the abrasion resistance, and the water resistance of the printed matter.

[0093] 2. Resin emulsion particles The ink composition of the present invention contains resin emulsion particles. In the present invention, “resin emulsion particles” refer to fine particles of a polymer component, that is, polymer fine particles. The “resin emulsion particles” are preferably made of a polymer having a film forming ability.
"Resin emulsion" refers to an aqueous dispersion in which the continuous phase is water and the dispersed particles are resin emulsion particles.
"Resin emulsion" is "polymer emulsion",
It is sometimes called "aqueous emulsion".

In the present invention, a specific example of the polymer component constituting the resin emulsion particles is styrene-
(Meth) acrylic acid copolymer, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, poly (meth) acrylic acid ester, styrene-butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer , Chloroprene copolymer, polyolefin,
Examples include polystyrene, polyvinyl acetate, polyamide, ethylene-vinyl acetate copolymer, vinyl acetate-acrylate copolymer, and polyurethane. In the present invention, the resin emulsion particles promote the fixability of the colorant to the surface of the recording medium by the interaction with the reactant in the above-described reaction solution, particularly with a polyvalent metal ion or polyallylamine or a derivative of polyallylamine. Having.

The amount of the resin emulsion particles is about 0.1 to 30% by weight, preferably 5 to 30% by weight, based on the total amount of the ink composition.

In the present invention, the resin emulsion is preferably formed such that the ratio of the resin emulsion particles to water is about 1: 1 to 4, preferably about 1: 1 to 3. According to a preferred embodiment of the present invention, the resin emulsion particles are preferably composed of a polymer component having both a hydrophilic portion and a hydrophobic portion. The average molecular weight of the resin emulsion particles is about 5,000 or more, preferably about 10,000 or more. The average molecular weight of the resin emulsion particles is measured by dissolving the polymer obtained after removing the water component of the resin emulsion in an organic solvent such as tetrahydrofuran and performing gel permeation chromatography (GPC). Calibration of molecular weight is performed using monodisperse polystyrene.

The average particle size of the resin emulsion particles is 40
It is preferably about 0 nm or less, more preferably 100 to 2 nm.
It is about 00 nm, more preferably about 10 to 100 nm. The average particle size of the resin emulsion particles may be measured by a general method. Particularly, a value measured by a laser scattering method is preferably used.

According to a preferred embodiment of the present invention, the glass transition point of the resin emulsion particles is about 30 ° C. or less, preferably about 25 ° C. or less, more preferably about 20 ° C. or less.
It is preferred that According to a preferred embodiment of the present invention, the minimum film forming temperature of the resin emulsion containing the resin emulsion particles is about 30 ° C. or less, preferably room temperature (about 25 ° C.) or less, more preferably about 20 ° C. or less. Is preferred. If the film formation of the resin emulsion can be performed at about 30 ° C. or less, the film formation on the printing surface automatically proceeds at room temperature or less without heating and drying the printed recording medium, and the colorant dye It is preferable because the pigment is firmly fixed to the recording medium.

On the other hand, the resin emulsion particles are preferred when the heating and drying steps are not particularly required in the recording method according to the present invention.
The minimum film formation temperature of the resin emulsion is 30 ° C as described above.
It is not limited only to resin emulsion particles having a degree of less than or equal to, and those having a higher value can be preferably used. Those skilled in the art should understand that heating at the minimum film forming temperature of the resin emulsion forms a film and fixes the colorant component to the recording medium.

Here, the “minimum film forming temperature” means that a resin emulsion obtained by dispersing resin emulsion particles in water is thinly cast on a metal plate such as aluminum and the temperature is raised. The lowest temperature at which a transparent continuous film is formed. In a temperature region lower than the minimum film forming temperature, a white powder is formed.

The term “film-forming property” means that when a resin emulsion particle is dispersed in water to form a resin emulsion, a water component, which is a continuous phase of the resin emulsion, is evaporated to form a polymer film. Means to be done.
The ink composition to which the resin emulsion particles are added has a property that a polymer film is similarly formed when water or an aqueous organic solvent is removed from the periphery of the resin emulsion particles (polymer fine particles). Become. The polymer film plays a role in firmly fixing the colorant in the ink composition on the surface of the recording medium. It is considered that this makes it possible to realize an image having excellent abrasion resistance, water resistance, and weather resistance.

According to a preferred embodiment of the present invention, the resin emulsion particles of the present invention have a surface of any of a carboxyl group, a sulfonic group, an amide group, an amino group and a hydroxyl group in both a single particle structure and a core-shell structure. It preferably has at least one functional group. In the case of a core-shell structure, these functional groups are preferably present in the shell layer. In particular, it preferably has a carboxyl group. These groups, in the production method described below,
It may be present in the structure of the monomer, or may be added to the surface of the resin emulsion particles by graft polymerization or the like after the particles are obtained.

Although the existence of such a functional group seems to be preferable from the following expected mechanism, the following theory is merely a hypothesis, and the present invention is not limited to this. Such a hydrophilic group such as a carboxyl group, a sulfonic group, an amide group, an amino group, or a hydroxyl group on the surface of the resin emulsion particle is formed on the surface of a non-absorbable recording medium such as a plastic, rubber, metal, or ceramic by a hydroxyl group ( Since a hydrogen bond can be formed with the (OH group), the coloring material can be firmly fixed to the non-absorbing recording medium in the recording method of the present invention. In particular, the resin emulsion particle structure is a core-shell structure, and the shell layer has a carboxyl group, a sulfonic acid group, an amide group, an amino group,
When a hydrophilic group such as a hydroxyl group is contained, the proportion of the hydrophilic group present on the particle surface increases, so that the effect is further exhibited. Further, the ink composition containing the resin emulsion particles having these groups does not wet the surface of the nozzle plate of the recording head of the inkjet printer that has been subjected to the water-repellent treatment. As a result, the ejection stability is excellent without occurrence of ejection failure or flight bend due to the wetting of the nozzle plate surface of the ink. Further, the ink composition containing the resin emulsion particles having these groups has excellent storage stability.

According to a preferred embodiment of the present invention,
Resin emulsion particles have high cohesiveness with divalent metal salts
Are preferred. Specifically, resin emulsion particles
Is a resin emulsion having 0.1% by weight of the fine particles.
3 volumes and 1 volume of 1 mol / l divalent metal salt aqueous solution
When light is brought into contact with
1 × 10 is 50% of the initial value⁴Seconds or less, preferably
Is 1 × 10³Seconds or less, more preferably 1 × 10²And
When they come into contact with divalent metal ions,
Decrease the clarity of the resulting solution. The amount of this floating matter
Measure with transmittance. Where the divalent metal ion and
Is Ca²⁺, Cu²⁺, Ni²⁺, Mg ²⁺, Zn
²⁺, Ba²⁺Which form a salt with it
Is Cl⁻, NO^3-, I⁻, Br⁻, CLO
₃ ⁻, And CH₃COO⁻Is mentioned.

Further, according to a particularly preferred embodiment of the present invention, the resin emulsion particles of the present invention preferably have a carboxyl group on the surface. Thereby, the divalent metal salt has higher cohesiveness. Specifically, the resin emulsion particles consist of 3 volumes of a resin emulsion having 0.1% by weight of the fine particles and 1 m
When 1 volume of an aqueous solution of a divalent metal salt having an ol / l concentration is brought into contact, the time at which the transmittance of light having a wavelength of 700 nm becomes 50% of the initial value is 1 × 10 ⁴ seconds or less, preferably 1 × 10 ² seconds. In the following, more preferably, contact with the divalent metal ion for 10 seconds or less causes agglomeration to form suspended matter and lower the transparency of the solution. The amount of the suspended matter is measured based on the light transmittance. It is considered that such high cohesiveness is obtained in combination with the fact that the resin emulsion particles have relatively many carboxyl groups on the surface. The ink composition containing the resin emulsion particles having a large amount of carboxyl groups on the surface as described above has no affinity for the nozzle plate of a water-repellent ink jet recording head. Therefore, the use of resin emulsion particles having a relatively large amount of carboxyl groups achieves better abrasion resistance and water resistance. Furthermore, due to the high hydrophilicity of the surface of the resin emulsion particles, the ink composition has an advantage that excellent storage stability can be obtained.

According to a preferred embodiment of the present invention, a resin emulsion obtained by dispersing resin emulsion particles in water at a concentration of 10% by weight has a contact angle of 7 on a Teflon (registered trademark) plate.
It is preferably about 0 ° or more, more preferably about 80 ° or more. Further, the surface tension of the resin emulsion in which the resin emulsion particles are dispersed in water so as to have a concentration of 35% by weight has a surface tension of 40 × 10 ⁻³ N / m (40 dyne).
/ Cm, 20 ° C), preferably about 50 × 10 ⁻³ N /
It is preferably about m or more. By using the resin emulsion particles as described above, in the ink jet recording method, flight bending can be further prevented, and good printing can be performed.

According to another preferred embodiment of the present invention, the resin emulsion particles contain 1 to 10% by weight of a structure derived from an unsaturated vinyl monomer having a carboxyl group, and have two or more polymerizable double bonds. It preferably has a structure crosslinked by one or more crosslinkable monomers, and contains 0.2 to 4% by weight of a structure derived from the crosslinkable monomer. Due to the use of a cross-linkable polymer obtained by copolymerizing cross-linkable monomers having two or more polymerizable double bonds, more preferably three or more at the time of polymerization and three-dimensionally cross-linking, the nozzle plate surface may be changed depending on the ink composition. Further, it becomes difficult to get wet, the bending of the flight can be further prevented, and the ejection stability can be further improved.

In the present invention, a resin emulsion particle having a single particle structure can be used. On the other hand, in the present invention, it is also possible to use resin emulsion particles having a core-shell structure composed of a core portion and a shell portion surrounding the core portion. In the present invention, the “core-shell structure” means “a form in which two or more kinds of polymers having different compositions exist in a phase separated state in a particle”. Therefore,
Not only a form in which the shell part completely covers the core part, but also a part in which the shell part partially covers the core part may be used.
Further, a part of the shell polymer may form a domain or the like in the core particle. Further, a layer having a multilayer structure of three or more layers including layers having different compositions may be further provided between the core part and the shell part.

According to a preferred embodiment of the present invention, the resin emulsion particles preferably have a core portion formed of a polymer having an epoxy group and a shell portion formed of a polymer having a carboxyl group. Epoxy and carboxyl groups have the property of reacting with each other,
These two groups are present separately in a core part and a shell part. Due to the decrease of water or the water-soluble organic solvent, the resin emulsion particles (that is, polymer fine particles) are united with each other and deformed by the pressure accompanying film formation. Thereby, the epoxy group of the core and the carboxyl group of the shell are combined to form a network structure. Thereby, there is obtained an advantage that a film having higher strength can be formed. The amount of the unsaturated vinyl monomer having an epoxy group is 1 to 10
% By weight. Here, the reaction between some epoxy groups and carboxyl groups before film formation is permissible in the present invention as long as the film-forming ability is not lost. In the present invention, the property that a reactive functional group coexists in such a resin emulsion particle and that the group reacts during film formation without adding a curing agent to form a network structure is referred to as “self-crosslinking property”. Call.

The resin emulsion according to the present invention comprises water,
It is obtained by mixing a monomer, an emulsifier, and a polymerization initiator to cause an emulsion polymerization reaction, and then adjusting the pH to a desired pH by adding a pH adjuster. In the present invention, the resin emulsion particles forming the dispersed phase of the resin emulsion are composed of monomers (particularly, unsaturated vinyl monomers).
And an emulsion polymerization reaction using an emulsifier and a polymerization initiator.

In the present invention, a monomer, preferably, an unsaturated vinyl monomer is used. Specific examples of the unsaturated vinyl monomer include acrylic ester monomers, methacrylic ester monomers, aromatic vinyl monomers, vinyl ester monomers, vinyl cyanide compound monomers, and halogenated ester monomers generally used in emulsion polymerization. Monomers, olefin monomers and diene monomers. Further, specific examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate , Octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate,
Acrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
Methacrylates such as n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and the like; Vinyl esters such as vinyl acetate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; halogenated monomers such as vinylidene chloride and vinyl chloride; styrene, 2-methylstyrene, vinyl toluene,
Aromatic vinyl monomers such as t-butylstyrene, chlorostyrene, vinylanisole and vinylnaphthalene; olefins such as ethylene, propylene and isopropylene; dienes such as butadiene and chloroprene; vinyls such as vinyl ether, vinyl ketone and vinylpyrrolidone Monomers. For a monomer having no carboxyl group, the use of an unsaturated vinyl monomer having a carboxyl group is essential, and preferred examples thereof include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. The use of methacrylic acid is preferred.

Further, in the present invention, it is preferable to have a structure in which a molecule derived from the above monomer is crosslinked by a crosslinking monomer having two or more polymerizable double bonds. Examples of the crosslinkable monomer having two or more polymerizable double bonds include polyethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butylene glycol diacrylate, 1,6-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4-acryloxypropyloxyphenyl) propane,
Diacrylate compounds such as 2,2'-bis (4-acryloxydiethoxyphenyl) propane; triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylol methane triacrylate; ditrimethylol tetraacrylate Tetraacrylate compounds such as tetramethylolmethanetetraacrylate and pentaerythritol tetraacrylate; hexaacrylate compounds such as dipentaerythritol hexaacrylate;
Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,4-butylene glycol dimethacrylate, 1,6
-Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate,
Dimethacrylate compounds such as 2,2'-bis (4-methacryloxydiethoxyphenyl) propane; trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate; methylenebisacrylamide and divinylbenzene.

Further, by adding a sulfonic acid group-containing monomer, an acrylamide or a hydroxyl group-containing monomer in addition to the above-mentioned monomers, the printing stability can be further improved. Specific examples of acrylamides include acrylamide and N, N'-dimethylacrylamide. Specific examples of the monomer having a sulfonic acid group include vinylsulfonic acid and its salts, styrenesulfonic acid and its salts, and 2-acryloylamino-2-methylpropanesulfonic acid and its salts. These can be used alone or in combination of two or more. Further, specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and these may be used alone or in combination of two or more. can do.

Examples of the emulsifier include anionic surfactants such as alkyl allyl sulfonate or sulfate, alkyl sulfonate or sulfate, dialkyl sulfosuccinate, polyoxyethylene nonyl phenyl ether, polyoxyethylene stearate, and the like. Nonionic surfactants such as polyoxyethylene alkyl allyl ether and sorbitan monolaurate are included.

Examples of the polymerization initiator include potassium persulfate and ammonium persulfate. Other components include a polymerization adjuster, a chain transfer agent, a molecular weight regulator and the like.

The resin emulsion particles are produced by mixing a monomer, an emulsifier, a polymerization initiator, and other optional components and performing an emulsion polymerization reaction. The amounts of these components added can be determined as appropriate. Further, the above-mentioned components are put into a reaction vessel and mixed to carry out an emulsion polymerization reaction. The emulsion polymerization reaction temperature is 60 to 90 ° C, preferably 70 to 80 ° C.
It is about.

The above-mentioned resin emulsion particles having a core-shell structure are produced by a known method, generally by multi-stage emulsion polymerization or the like. For example, JP
It can be manufactured by the method disclosed in JP-A-76004. Examples of the unsaturated vinyl monomer used for the polymerization include those described above.

The introduction of an epoxy group into the above-mentioned core portion is achieved by converting an unsaturated vinyl monomer having an epoxy group into
Glycidyl acrylate, glycidyl methacrylate,
Examples include a method of copolymerizing allyl glycidyl ether or the like with another unsaturated vinyl monomer, or a method of simultaneously adding an epoxy compound to prepare core particles by polymerizing one or more unsaturated vinyl monomers to form a composite. Can be. The former method is preferred from the viewpoint of easiness of polymerization and polymerization stability.

In the present invention, the resin emulsion particles obtained by the above emulsion polymerization are adjusted to a desired pH by adding a pH adjuster.

As the pH adjuster used in the present invention, monovalent alkali metal hydroxides and organic amines are preferably used.

When a desired pH is adjusted by adding a monovalent alkali metal hydroxide, the pH is adjusted so as to be in the range of about 7 to 10, preferably in the range of about 7 to 9. Therefore, the addition amount of the monovalent alkali metal hydroxide,
The amount of the resin emulsion particles that falls within the above-mentioned pH range is added.

The method for producing the resin emulsion is as follows. Water, an emulsifier is charged, a polymerization initiator is added, and a resin emulsion is added to a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, a thermometer, and the like adjusted to a predetermined temperature, and reacted to form a resin emulsion. obtain. To this, a monovalent metal hydroxide is added so as to have a desired pH. This produces a resin emulsion according to the present invention.

Further, as the resin emulsion satisfying the above conditions in the present invention, a known resin emulsion can be used. For example, Japanese Patent Publication No. 62-1426
JP-A-3-56573, JP-A-3-79678
JP-A-3-160068, JP-A-4-18462
And the like.

According to another embodiment of the present invention, resin emulsion particles having a specific function can be added to the ink, and specific examples thereof include the following. The resin emulsion particles described below have a specific function, but may be otherwise the same as the resin emulsion particles described above.

1) Resin Emer Having Fluoroalkyl Group
According to a preferred embodiment of the Rujon particles present invention, resin emulsion particles having a fluoroalkyl group may be added to the ink. When the ink composition to which the resin emulsion particles are added adheres to the recording medium, the resin emulsion particles form a film and fix the colorant on the recording medium. As a result, it is considered that abrasion resistance and weather resistance are imparted to the printed portion. The reason why such an effect occurs is not clear, but can be inferred as described below. Since the resin emulsion particles have a fluoroalkyl group, the coloring agent fixed to the recording medium is further coated with the fluorine atom, and it is considered that the resin emulsion particles impart weather resistance to the printed matter. Note that the above mechanism is merely an assumption, and the present invention is not construed as being limited to this mechanism.

The fluoroalkyl group in the resin emulsion particles has 1 to 13 carbon atoms, and is preferably
A straight-chain or branched-chain alkyl group having 3 to 13 has 3 to 41, preferably 3 to 27 fluorine atoms. Preferred specific examples of such a fluoroalkyl group include —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ ,
_{-C 4 F 9, -C 5 F} 11, -C 6 F 13, -C 7 F
_{15, -C 8 F 17, -C} 9 F 19, -C 10 F 21,
_{-C 11 F 23, -C 12 F} 25, -C 13 F 2 7, -
_{CF 2 H, -C 2 F 4} H, -C 3 F 6 H, -CF 2 CF
HCF _{3 and the} like.

The monomer having a fluoroalkyl group is
Those selected from the group consisting of those represented by the following formulas are preferred.

[0128]

Embedded image [Where n is 1 or more and m is 1 to 20]
Specific examples of the monomer having a fluoroalkyl group include trifluoroethyl methacrylate, heptadecafluorodecyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,4,4,4-
Hexafluorobutyl methacrylate, perfluorooctylethyl methacrylate and the like can be mentioned.

2) Chelate- Formable Resin Emulsion
According to a preferred embodiment of the particles present invention, the ink composition comprises a polymer having a ligand structure capable of forming a chelate with a metal ion, added resin emulsion particles having a property of aggregation to form a chelate with a metal ion Is preferably performed. When the ink composition to which the resin emulsion particles are added adheres to the recording medium, the resin emulsion particles form a film and fix the colorant on the recording medium. As a result, it is possible to impart abrasion resistance to the printed portion. The reason why such an effect occurs is not clear, but can be inferred as described below. The resin emulsion particles are composed of a polymer having a ligand structure capable of forming a chelate with a metal ion, and have a property of aggregating when a chelate is formed with a metal ion. For this reason, when the resin emulsion particles and the reaction solution having metal ions come into contact, the formation of aggregates is remarkably promoted and the film formability is enhanced, and as a result, the printed matter is not imparted with abrasion resistance. It is thought. Note that the above mechanism is merely an assumption, and the present invention is not construed as being limited to this mechanism.

In the present invention, the “ligand structure capable of forming a chelate with a metal ion” contained in the resin emulsion particle means that the resin emulsion particle has a plurality of atoms for supplying electrons for forming a coordination bond, and this atom is an appropriate one. It refers to a structure that exists at an interval and, as a result, forms a metal chelate compound in such a manner that these multiple atoms sandwich a metal ion.

According to a preferred embodiment of the present invention, preferable examples of such a “ligand structure” include a β-diketone structure, a polyamine structure, an iminodiacetic acid structure, a sarcosine structure, an ethanol amino acid structure, a glycine structure, and a xanthogen structure. Acid structure, amidoxime structure, amine structure, pyridine structure, imidazole structure, phosphonic acid structure, phosphinic acid structure, phosphoric acid structure, Schiff base structure, oxime structure, hydroxam structure, aminopolycarboxylic acid structure, thiol structure, polythioalcohol structure , A 2-pyrrolidone structure, and a 2-oxazolidone structure.

Further, according to a specific embodiment of the present invention, for example, “a ligand structure capable of forming a chelate with a metal ion”
May be a structure represented by the following formula.

[0133]

Embedded image [In the above formula, P is a polymer structural moiety, and R is an alkyl group (preferably a C ₁ -C ₂₀ alkyl group, more preferably a C ₁ -C ₁₀ alkyl group, most preferably a methyl group) or Represents an allyl group (for example, a phenyl group, a naphthyl group, a tolyl group)] The structure in the case where the ligand structure of the above formula forms a metal chelate with, for example, a divalent metal is considered as follows.

[0134]

Embedded image [In the above formula, Mt represents a divalent metal, and P and R are as defined above.] According to a preferred embodiment of the present invention, a polymer having a ligand structure capable of forming a chelate with a metal ion And a monomer having a ligand structure capable of forming a chelate with a metal ion, such as 2-acetoacetoxyethyl methacrylate,
Methacryloylacetone, methacrylyldiacetylmethane, 4- (1,3-dioxypentyl) phenyl-4-
(6-Acryloyloxyhexyloxy) benzoate, acryloyl acetylacetone, diethyl acryloylmalonate, diethyl methacryloylmalonate, 2- (methacryloxy) ethyl acetate, and the like.

3) UV absorbing ability and / or light stabilization
Resin Emulsion Particles Having Function According to a preferred embodiment of the present invention, it is preferable that the ink composition is added with resin emulsion particles having an ultraviolet absorbing ability and / or a light stabilizing ability. When the ink composition to which the resin emulsion particles are added adheres to the recording medium, the resin emulsion particles form a film and fix the colorant on the recording medium. As a result, it is considered that light resistance and weather resistance are imparted to the printed portion. The reason why such an effect occurs is not clear, but can be inferred as described below. Since the resin emulsion particles have ultraviolet absorbing ability and / or light stabilizing ability, they impart ultraviolet absorbing ability and / or light stabilizing ability to the colorant fixed to the recording medium. It is thought that it may provide weather resistance. More specifically, when the coloring material is a pigment, a film in which the pigment is dispersed is formed. The ultraviolet light is blocked by this film and does not reach the pigment therein, so that the image has light resistance. Note that the above mechanism is merely an assumption, and the present invention is not construed as being limited to this mechanism.

In the present invention, the ultraviolet absorbing ability and the ultraviolet absorbing agent and the light stabilizing ability and the light stabilizer are
It follows the definitions understood in the art.
In other words, from its mechanism of action, the ultraviolet absorbing ability and the ultraviolet absorber generally convert the strong energy possessed by ultraviolet rays into thermal energy gradually by keto-enol type tautomerism, and release and stabilize it. Light stabilizing ability and light stabilizer mean those which are stabilized by scavenging radicals, decomposing hydroperoxides, scavenging heavy metals, and quenching singlet oxygen. In the present invention, any one of them may be present, but according to a preferred embodiment of the present invention, both of them are preferably present.

In the present invention, specific examples of such resin emulsion particles include two embodiments. According to the first embodiment, resin emulsion particles obtained by physically mixing an ultraviolet absorber and / or a light stabilizer with a constituent polymer can be used.

The ultraviolet absorber and light stabilizer usable in the present invention include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a hindered phenol ultraviolet absorber, a salicylate ultraviolet absorber, and a cyanoacrylate ultraviolet absorber. Examples thereof include those selected from the group consisting of ultraviolet absorbers, nickel complex-based ultraviolet absorbers, and hindered amine-based light stabilizers.

According to the second embodiment, there are resin emulsion particles composed of a polymer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability. Examples of the site having an ultraviolet absorbing ability that can be used in this embodiment include a benzophenone skeleton, a benzotriazole skeleton, a hindered phenol skeleton, a salicylate skeleton, and a cyanoacrylate skeleton. Is mentioned.

Incidentally, resin emulsion particles having an ultraviolet absorbing ability and / or a light stabilizing ability are described in JP-A-11-1.
No. 2519.
Therefore, the production of the resin emulsion particles is disclosed in
It may be the same as that disclosed in 1-112519.

[0141] 4. Water-soluble organic solvent and water The ink composition of the present invention uses water and a water-soluble organic solvent as main solvents. As the water-soluble organic solvent, a high-boiling organic solvent is preferable. Preferred specific examples of the high-boiling organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, and glycerin. , Trimethylolethane, polyhydric alcohols such as trimethylolpropane; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
Alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; urea, 2-pyrrolidone, N-methyl -2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethanolamine and the like.

Among them, it is preferable to use a water-soluble organic solvent having a boiling point of 180 ° C. or higher. Use of a water-soluble organic solvent having a boiling point of 180 ° C. or more results in water retention and wettability of the ink composition. As a result, even if the ink composition is stored for a long period of time, there is no aggregation or increase in viscosity of the colorant, and excellent storage stability can be realized. Further, an ink composition that maintains fluidity and redispersibility for a long time even when left in an open state (a state where it is exposed to air at room temperature) can be realized. Further, in the ink jet recording method, nozzle clogging does not occur at the time of restarting during printing or after printing is interrupted, and high ejection stability can be obtained.

Examples of the water-soluble organic solvent having a boiling point of 180 ° C. or more include ethylene glycol (boiling point: 197 ° C .; hereinafter, the boiling point is shown in parentheses) and propylene glycol (187).
° C), diethylene glycol (245 ° C), pentamethylene glycol (242 ° C), trimethylene glycol (214 ° C), 2-butene-1,4-diol (235 ° C).
° C), 2-ethyl-1,3-hexanediol (243
° C), 2-methyl-2,4-pentanediol (197
C), N-methyl-2-pyrrolidone (202 C), 1,
3-dimethyl-2-imidazolidinone (257 to 260
C), 2-pyrrolidone (245 C), glycerin (29
0 ° C.), tripropylene glycol monomethyl ether (243 ° C.), dipropylene glycol monoethyl glycol (198 ° C.), dipropylene glycol monomethyl ether (190 ° C.), dipropylene glycol (2
32 ° C.), triethylene glycol monomethyl ether (249 ° C.), tetraethylene glycol (327
° C), triethylene glycol (288 ° C), diethylene glycol monobutyl ether (230 ° C), diethylene glycol monoethyl ether (202 ° C), and diethylene glycol monomethyl ether (194 ° C). In particular, among these water-soluble organic solvents, those having a boiling point of 200 ° C. or higher are preferred. These water-soluble organic solvents can be used alone or in combination of two or more.

As the water-soluble organic solvent, a low-boiling organic solvent is also preferably used. As a preferred example,
Methanol, ethanol, n-propyl alcohol, i
so-propyl alcohol, n-butanol, sec-
Butanol, tert-butanol, iso-butanol, n-pentanol and the like. Particularly, a monohydric alcohol is preferable.

The content of these water-soluble organic solvents is preferably about 0.5 to 40% by weight, more preferably 2 to 20% by weight, based on the ink composition.

[0146] 5. Other Ingredients The ink composition according to the present invention contains the above-described components, but may further include other components. According to a preferred embodiment of the present invention, the ink composition comprises:
Sugars, tertiary amines, alkali hydroxides, or alginic acid derivatives may be added. Addition of sugar and tertiary amine results in wetting. Further, the addition of the tertiary amine and the alkali hydroxide brings about a stable dispersion of the colorant and the resin emulsion particles in the ink composition in the ink.

Examples of sugars include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldone. Acid, glucitol, (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a sugar in a broad sense, and is used to include a substance widely existing in nature such as alginic acid, α-cyclodextrin, and cellulose. In addition, derivatives of these saccharides include reducing sugars of the aforementioned saccharides [(for example, sugar alcohol (general formula HOCH ₂ (CHOH) _n C
H ₂ OH (where n represents an integer of 2 to 5)], an oxidized sugar (eg, aldonic acid, uronic acid, etc.),
Examples include amino acids and thiosugars. Particularly, sugar alcohols are preferable, and specific examples include maltitol and sorbitol. The added amount of these saccharides is 0.1 to 40
% By weight, more preferably 1 to 30% by weight
It is about.

Examples of the tertiary amine include trimethylamine, triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, triisopropenolamine, butyldiethanolamine and the like. These may be used alone or in combination. The amount of these tertiary amines added to the ink composition is
Preferably about 0.1 to 10% by weight, more preferably,
0.5 to 5% by weight.

Examples of the alkali hydroxide include potassium hydroxide, sodium hydroxide and lithium hydroxide, and the addition amount thereof is preferably about 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. It is about.

Preferred examples of the alginic acid derivative include:
Alginic acid alkali metal salts (eg, sodium salt, potassium salt), alginic acid organic salts (eg, triethanolamine salt), and alginic acid ammonium salts are exemplified. The amount of the alginic acid derivative added to the ink composition is preferably about 0.01 to 1% by weight, and more preferably about 0.05 to 0.5% by weight.

The reason why a good image can be obtained by adding the alginic acid derivative is not clear, but the polyvalent metal salt present in the reaction solution reacts with the alginic acid derivative in the ink composition to change the dispersion state of the colorant. This is considered to be caused by promoting the fixation of the colorant to the recording medium.

[0152] The ink composition used in the method according to the present invention may further contain a surfactant. As examples of the surfactant, the same surfactant as that used in the preparation of the resin emulsion particles described above can be suitably used.

In addition, if necessary, a pH adjuster, a preservative, a fungicide and the like can be added to the ink composition in order to improve the storage stability.

Method for Producing Ink Composition The ink composition according to the present invention can be produced by dispersing and mixing the above components by an appropriate method.

(1) When a pigment is used as a colorant, first, a pigment, a polymer dispersant and water are dispersed in a suitable dispersing machine (eg, ball mill, sand mill, attritor, roll mill, azide mill, Henschel mixer, colloid mill). , An ultrasonic homogenizer, a jet mill, an ang mill, etc.) to prepare a uniform pigment dispersion,
To this, water, a water-soluble organic solvent, sugar, a pH adjuster, a preservative, a fungicide and the like are added and sufficiently dissolved, and then the resin emulsion particles are added, and the mixture is sufficiently dispersed at room temperature using a suitable dispersing machine. The stirred ink solvent is gradually dropped, and further sufficiently stirred. After sufficient stirring, filtration is performed to remove coarse particles and foreign substances that cause clogging, thereby obtaining a target ink composition.

(2) When a microcapsule type colorant is used as a colorant, the microcapsule type colorant, water, a water-soluble organic solvent and the like are supplied to the above-mentioned dispersing machine and mixed, and then mixed with the resin emulsion particles. And stir well. After sufficient stirring, filtration is performed to remove coarse particles and foreign substances that cause clogging, thereby obtaining a target ink composition.

Recording Method According to the recording method of the present invention, the colorant is firmly fixed on the recording medium, and as a result, the fixability and the abrasion resistance of the printed matter are improved, and the light resistance of the printed portion of the printed matter is improved. And weather resistance.

The reason why such an effect occurs is not clear, but can be inferred as described below. On the surface of a non-absorptive recording medium such as plastic, rubber, metal, ceramics, etc., the reaction liquid and the ink composition first come into contact with each other, so that the reaction agent in the reaction liquid and the colorant in the ink composition and the resin emulsion particles And destroy the dispersion state,
It is thought to agglomerate it. Further, it is considered that the cationic inorganic fine particles or cationic polymer fine particles in the reaction liquid strongly aggregate the coloring components in the ink composition like the reactants.

The printed portion formed on the recording medium by contacting the reaction liquid with the ink composition initially comprises a colorant, a reaction liquid, resin emulsion particles, and cationic inorganic fine particles or cationic polymer fine particles. The aggregate and water or a water-soluble organic solvent separated from the aggregate coexist. When the aggregate is formed, water and the water-soluble organic solvent are removed from between the aggregate and the surface of the recording medium, and as a result, the aggregate is adsorbed on the surface of the recording medium. Further washing with a polar solvent removes water or a water-soluble organic solvent present between the resin emulsion particles and the particles of the cationic inorganic fine particles and / or the cationic polymer fine particles. Accelerated to form an organic-inorganic composite film containing the colorant.

The formation of the organic-inorganic composite film is carried out by forming carboxyl groups, sulfone groups,
It is thought that the presence of hydrophilic groups such as amide groups, amino groups, and hydroxyl groups is largely involved. On the other hand, the presence of the cationic inorganic fine particles or cationic polymer fine particles fixes the colorant more firmly on the recording medium and increases the strength of the film as compared with the case where only the resin emulsion particles are contained in the ink. It is thought that what can be done.

In particular, when the cationic inorganic fine particles or cationic polymer fine particles and the resin emulsion particles are added to the ink, the colorant is firmly fixed on the surface of the recording medium more than the sum of the combined effects of the two. As a result, it is considered that the mechanical strength of the printed portion, such as abrasion resistance and abrasion resistance, was dramatically improved.

This mechanism has a remarkable effect when the recording medium is a non-absorbent recording medium. Note that the above mechanism is only an assumption, and the present invention is not construed as being limited to this mechanism.

In the present invention, "printing" may be either real image printing or mirror image printing, or both may be performed alternately or simultaneously. The order in which the reaction liquid and the ink composition are applied to the recording medium can be determined as appropriate. However, a method in which the reaction liquid is applied to the recording medium and then the ink composition is preferably applied to the recording medium is preferable.

Regarding the adhesion of the reaction liquid to the recording medium, either the method of selectively adhering the reaction liquid only to the place where the ink composition is applied or the method of adhering the reaction liquid to the entire recording medium is used. There may be. Which method is employed may be determined in consideration of the combination of the ink composition and the reaction liquid.

The means for attaching the reaction liquid to the recording medium and the means for attaching the ink composition to the recording medium are described in the printing industry,
Recording methods commonly used in the coatings industry are possible, for example, direct injection, spraying, coating, transfer and the like,
Preferably, an ink jet recording method of performing printing by discharging droplets onto a recording medium is preferable.

In the present invention, specific examples of the method for washing the recording medium after printing with a polar solvent include rinsing, rinsing, dipping, or mixing the recording medium or its surface with a polar solvent. Can be The washing method can be performed continuously or intermittently during printing.

As the polar solvent, those which do not remove the colorant and the resin emulsion particles adsorbed on the recording medium, and which are water-soluble and safe are preferably used. Specific examples of such polar solvents include water; alcohols having 5 or less carbon atoms, preferably methyl alcohol, ethyl alcohol,
Lower alcohols such as propyl alcohol; formula R (R ')
A sulfoxide represented by S ＝ O (wherein each of R and R ′ is a linear or branched alkyl group having 5 or less carbon atoms), preferably a sulfoxide such as dimethyl sulfoxide or diethyl sulfoxide; Amines of number 5 or less,
Preferably lower aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, preferably lower aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine,
Preferred are lower amines such as lower aliphatic tertiary amines such as trimethylamine and triethylamine; and mixtures thereof; water is particularly preferred.

According to the aspect of the present invention, a method of heating and drying the recording medium after washing the recording medium with a polar solvent can be used.

As the recording medium in the invention, those which are substantially non-absorbable with respect to the ink composition are preferably used.
"Substantially non-absorbable with respect to the ink composition" means that when the ink composition is applied to the recording medium, the recording medium is such that the ink composition does not penetrate the recording medium at all for a time of several seconds. means. Therefore, it is sufficient that the recording medium itself or at least the recording surface of the recording medium is substantially non-absorbable.

Specific examples of the recording medium to which the recording method according to the present invention can be applied include polyethylene terephthalate, polycarbonate, polysulfone, ABS resin, polyvinyl chloride, polystyrene, poly (meth) acrylate,
Polyvinyl acetate, AS resin, ACS resin, polyamide,
Recording media consisting of plastics and rubbers based on polyurethane, natural rubber, butadiene-styrene copolymer, nitrile rubber, chloroprene, polyisoprene, butyl rubber, etc .; consisting of metal surfaces such as brass, iron, aluminum, SUS, and copper Recording medium; or a recording medium in which a non-metallic base material has been subjected to a metal coating treatment by a method such as vapor deposition; a recording medium in which a paper base material has been subjected to a resin coating treatment; etc .; Recording medium; a recording medium made of a so-called ceramic material obtained by firing an inorganic material at a high temperature; and the like.

The recording method according to the present invention is used for a method of applying character information, image information, and design to a recording medium, preferably a non-absorbent recording medium (ie, a recording method, a printing method, a coating method, a dyeing method) and the like. be able to. In particular,
It can be used for a method of recording or printing character information, image information, design information, etc. on an industrial product, a signboard or a display plate, a coating method used for interior and exterior of building supplies and industrial products, and a method of dyeing a fiber.

The recording method of the present invention can print on various recording media. Specific examples of recording media include industrial products, industrial supplies, home appliances, building supplies, furniture,
Tableware, aircraft, vehicles, ships, cards, packaging containers, medical supplies, clothes, shoes, bags, office supplies, stationery, toys, signs, fibers, and the like. Specific examples include compact disc (CD) labels, wall surfaces, building materials such as building materials, displays such as power distribution and switches, wallpapers, umbrellas, tents, swimwear, rubber pools, vinyl pools, shoes, glasses, pottery,
Porcelain, tableware, tepra, surfboards, ships (eg, motor boats, fishing boats, tankers), vehicles (passenger cars, buses,
Trucks), railways (eg, trains, rails), aircraft (eg, airliners, fighters, Cessna, gliders), ski equipment (eg, skis, poles, boots, ski wear), snowboards (eg, snowboards, Wear), diving equipment (eg, wetsuit, aqua lang, snorkel, weight, fin), suitcase, furniture (eg, desk, table, chair), medical equipment (eg, syringe, catheter, infusion container) ), Cans (for example, design, content display), clocks (dial, design), home appliances (for example,
TVs, refrigerators, radios, personal computers, cassettes, CD players, vacuum cleaners, barcodes, card products (various membership cards, prepaid cards "telephone card, haika, oleca, creca", credit cards, bank cards) nail art, nameplate Can be printed on toys, dolls, mannequins and the like. In addition, these are listed as examples, and the present invention is not limited to the above-described recording medium.

Recording Apparatus A recording apparatus according to the present invention will be described with reference to the drawings.

FIG. 1 shows the configuration of a recording apparatus according to the present invention. A recording medium is carried from a supply source 1 containing a recording medium to a printing process including an inkjet recording mechanism 2. The reaction liquid and the ink composition are ejected from the recording head provided in the inkjet recording mechanism 2 onto the surface of the recording medium to form the printing surface 3. The recording head includes a nozzle for discharging a reaction liquid and a nozzle for discharging an ink composition, which are not shown in the drawing. The recording medium on which the printing surface 3 is formed is carried into a cleaning step. The recording medium on which the printing surface 3 is formed is washed by a washing mechanism 4 with a polar solvent. The cleaning mechanism 4 has means for collecting and separating a cleaning liquid not shown in the figure. After the cleaning, the recording medium is carried into a drying step. The recording medium is dried by the drying mechanism 5. The drying mechanism 5 may be a device that contacts and heats the recording medium, or may be a device that heats the recording medium without contacting it, such as irradiating infrared rays or blowing hot air. After drying, the recording medium is carried into the product storage 6 as a product. Note that this recording apparatus is performed by a roll or a conveyor not shown in the figure as a means for conveying the recording medium. According to the recording apparatus of the present invention, real image printing, mirror image printing, or mixed printing thereof can be realized.

FIG. 2 shows an embodiment of the recording apparatus according to the present invention. 2, the components having the same configuration as the mechanism in FIG. 1 are denoted by the same reference numerals as those in FIG.

The PET film is conveyed from the PET film roll 11 to a printing step provided with the ink jet recording mechanism 2. The reaction liquid and the ink composition are ejected from the recording head provided in the inkjet recording mechanism 2 onto the surface of the PET film to form the printing surface 3. The PET film on which the printing surface 3 is formed passes through the support table 12 and is carried into the cleaning step. The PET film on which the printing surface 3 is formed is washed with a polar solvent by a washing mechanism 4. After washing, the PET film is carried into a drying process. The PET film is dried by the drying mechanism 5. After drying, it is wound on a roll 13 as a printed PET film product. According to the recording apparatus of the present invention, a product can be obtained from a PET film on which a real image printing, a mirror image printing, or a mixed printing thereof is performed.

[0177]

The embodiments of the present invention will be described below, but these examples explain the contents of the present invention and do not limit the scope of the present invention.

Preparation of Reaction Solution A reaction solution was prepared according to the composition shown in Table 1 below. Table 1
The “cationic polymer fine particles” therein were prepared by the following method. Preparation of Cationic Polymer Fine Particles In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, a thermometer and a nitrogen inlet tube, 600 ml of ion-exchanged water, 50 g of styrene, 100 g of butyl acrylate, and 7 g of dimethylaminoethylbenzyl methacrylate were added.
After supplying 15 g of a 0% aqueous solution and raising the temperature to 80 ° C., the inside of the reaction system was replaced with nitrogen gas.

Next, 50 g of styrene, 100 g of butyl acrylate, and 15 g of a 70% aqueous solution of dimethylaminoethylbenzyl methacrylate were supplied to the reaction system at a constant rate over 4 hours to cause a reaction. At the same time, 40 g of a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride was supplied to the reaction system at a constant rate over 5 hours to cause a reaction. After cooling the reaction, 0.1 μl
The resulting mixture was filtered through an m filter to obtain an aqueous emulsion of cationic polymer fine particles. The glass transition point of the cationic polymer particles is −15 ° C., and the aqueous emulsion of the cationic polymer particles has a solid content of 35%,
The minimum film formation temperature was 5 ° C. The average particle diameter of the cationic polymer fine particles was 80 nm as measured by a light scattering particle size analyzer (Microtrack UPA; manufactured by Leeds & Northrop).

The glass transition point was measured by spreading a few g of the aqueous emulsion of cationic polymer fine particles into a thin film, drying the film at 70 ° C. for 1 hour or more, sampling the film, and measuring the differential scanning calorimetry. Device (D
SC) at a heating rate of 10 ° C./min.

The minimum film formation temperature was measured by spreading the aqueous emulsion of the cationic polymer fine particles thinly on an aluminum sample plate of a minimum film formation temperature measuring device and raising the temperature to form a transparent continuous film. The temperature obtained was taken as the minimum film formation temperature.

The measurement of the glass transition point of the resin emulsion particles and the measurement of the minimum film forming temperature of the resin emulsion, which will be described later, were performed according to these measuring methods.

[0183]

[Table 1] Preparation of Ink Composition An ink composition was prepared according to the composition shown in Table 1 below.
"Resin emulsions A to D" in Table 2 and "Pigment dispersion" in Table 3 were prepared by the following methods. Preparation of Resin Emulsion 100 ml of ion-exchanged water and 0.1 g of potassium persulfate were added to a reaction vessel equipped with a resin emulsion A stirrer, a reflux condenser, a dropping device, a thermometer and a nitrogen inlet tube, and the system was flushed with nitrogen gas. This was replaced and the temperature was raised to 70 ° C.

Next, 100 ml of ion-exchanged water, 1.0 g of sodium dodecylbenzenesulfonate, 30 g of styrene
g, butyl acrylate 55 g, methacrylic acid 5 g, and acrylamide 1 g were stirred to obtain an emulsion. This emulsion is dropped into the reaction vessel using a dropping funnel,
After reacting for an hour, the mixture was cooled to room temperature, and then the pH was adjusted with aqueous ammonia as a neutralizing agent, followed by filtration through a 0.4 μm filter to obtain a resin emulsion. The glass transition point of the resin emulsion particles was −15 ° C. The minimum film formation temperature of this resin emulsion is 5 ° C.
Met. The average particle size of the resin emulsion particles was 100 nm as measured by Microtrac UPA.

Resin emulsion B 900 g of ion-exchanged water was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and the internal temperature was raised to 70 ° C. while purging with nitrogen while stirring. The internal temperature was maintained at 70 ° C., and 4 g of potassium persulfate was used as a polymerization initiator.
Was added and dissolved. Next, 70 g of ion-exchanged water was
Sodium lauryl sulfate 1 g, styrene 53 g, butyl acrylate 59 g, glycidyl methacrylate 48 g
And t-dodecyl mercaptan 0.1 as a molecular weight modifier
An emulsion prepared by adding 6 g with stirring is dropped into the reaction vessel continuously over 1 hour. After completion of dropping, aging is performed for one hour.

Further, an emulsion prepared by previously adding 70 g of ion-exchanged water, 1 g of sodium lauryl sulfate, 1 g of acrylamide, 79 g of styrene, 80 g of butyl acrylate and 0.16 g of t-dodecyl mercaptan to the reaction vessel was continuously added to the reaction vessel. For 1 hour. After completion of dropping, aging is performed for one hour.

Subsequently, an aqueous solution in which 4 g of ammonium persulfate was dissolved as a polymerization initiator in 20 g of ion-exchanged water was added to the reaction vessel, and 300 g of ion-exchanged water, 2 g of sodium lauryl sulfate, 16 g of acrylamide, 298 g of styrene, 298 g of butyl acrylate were added in advance. 297 g, methacrylic acid 29 g, and t-dodecyl mercaptan 0.6
An emulsion prepared by adding 5 g with stirring is dropped into the reaction vessel continuously over 3 hours. After cooling the obtained resin emulsion to room temperature, ion-exchanged water and aqueous ammonia were added to adjust the solid content to 35% by weight and the pH to 8.
Passed through a 1 μm filter. Micro Truck UP
When measured using A, the average particle diameter was 90 nm.

The glass transition point of the obtained resin emulsion particles was 17 ° C. The minimum film forming temperature of the obtained resin emulsion was 24 ° C. 3 volumes of an aqueous emulsion having 0.1% by weight of particles of the resin emulsion, and 1 mol / l of a magnesium nitrate aqueous solution 1
The capacitor was brought into contact with the capacitor, and the time (half-life) at which the transmittance of 700 nm light became 50% of the initial value was 10 seconds. Also,
The contact angle of the aqueous emulsion prepared so as to contain 10% by weight of the particles of the resin emulsion on the Teflon plate was 108 °.

Resin emulsion C 200 ml of distilled water and 0.6 g of sodium dodecylbenzenesulfonate were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, a thermometer and a nitrogen inlet tube, and stirred in a nitrogen atmosphere. While heating to 70 ° C., 2 g of potassium persulfate was further added.

Meanwhile, 50 g of butyl acrylate, 40 g of styrene, 5 g of acrylamide, 5 g of acrylic acid, t-
0.1 g of dodecyl mercaptan and 5 g of monomer 2 (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (RUVA-93 manufactured by Otsuka Chemical Co.) having a skeleton capable of absorbing ultraviolet light 1 g of a monomer having a skeleton having an ability 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (ADEKA STAB LA-82 manufactured by Asahi Denka) and 2 g of ethylene glycol dimethacrylate are mixed and dissolved, and the mixture is dissolved in the reaction vessel. Dropped in. After further reacting at 70 ° C. for 6 hours,
After cooling to room temperature, ammonia water is added as a neutralizing agent to adjust the pH, and the solution is filtered through a 0.4 μm filter to disperse polymer fine particles having a portion having an ultraviolet absorbing ability and a light stabilizing ability in the structure. Was obtained.

The glass transition point of the obtained resin emulsion particles was 8 ° C. This resin emulsion has a glass transition point of 20 ° C., a minimum film forming temperature of 25 ° C., and a surface tension of 5 ° C.
8 × 10 ⁻³ N / m, contact angle 90 °, average particle diameter 0.1
μm (measured by Microtrac UPA), the half-life in the reaction with Mg ²⁺ ions was 70 seconds. The glass transition point of the resin emulsion particles was 20 ° C.

Resin Emulsion D A reaction vessel equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 900 g of ion-exchanged water and 4 g of sodium lauryl sulfate.
The internal temperature was heated to 70 ° C. The internal temperature was maintained at 70 ° C., and 2 g of potassium persulfate was added and dissolved as a polymerization initiator.

Then, 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 435 g of styrene, 20 g of acrylamide, 475 g of butyl acrylate, 30 g of methacrylic acid, 50 g of heptadecafluorodecyl methacrylate, and 4 g of ethylene glycol dimethacrylate were added with stirring. The prepared emulsion was continuously dropped into the reaction vessel over 3 hours. After completion of dropping, aging was performed for 3 hours. This was gradually dropped into the above reaction vessel with a dropping funnel. After cooling the obtained resin emulsion to normal temperature, ion-exchanged water and aqueous ammonia were added to adjust the solid content to 35% by weight and pH 8, and then passed through a 0.1 μm filter. The average particle size was 90 nm as measured by using Microtrac UPA. The glass transition point of the obtained resin emulsion particles was 9 ° C. The minimum film forming temperature of the obtained resin emulsion is 24 ° C.
Met. Three volumes of a resin emulsion having 0.1% by weight of the resin emulsion particles and 1 volume of a 1 mol / l aqueous solution of magnesium nitrate were brought into contact with each other, and 700 n
Time at which the transmittance of m light becomes 50% of the initial value (half-life)
Was 5 seconds. In addition, the resin emulsion particles
The contact angle on the Teflon plate of the resin emulsion prepared so as to contain 0% by weight was 110 °.

Resin Emulsion E A reaction vessel equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 900 g of ion-exchanged water and 4 g of sodium lauryl sulfate.
The internal temperature was heated to 70 ° C. The internal temperature was maintained at 70 ° C., and 2 g of potassium persulfate was added and dissolved as a polymerization initiator.

Then, 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 435 g of styrene, 475 g of butyl acrylate and 2-acryloylamino-
An emulsion prepared by adding 30 g of 2-methylpropanesulfonic acid, 50 g of methacryloyl diacetylmethane, and 4 g of diethylene glycol dimethacrylate with stirring was dropped into the reaction vessel continuously over 3 hours. After completion of dropping, aging was performed for 3 hours. This was gradually dropped into the above reaction vessel using a dropping funnel. After cooling the obtained resin emulsion to normal temperature, ion-exchanged water and aqueous ammonia were added to adjust the solid content to 35% by weight and the pH to 8,
Passed through a 0.1 μm filter. The average particle diameter was measured using Microtrac UPA to be 95 nm. The glass transition point of the obtained resin emulsion particles was 8 ° C. The minimum film forming temperature of the obtained resin emulsion was 20 ° C. 3 volumes of a resin emulsion having 0.1% by weight of the resin emulsion particles;
1 volume of a magnesium nitrate aqueous solution having a concentration of 1 mol / l was brought into contact with the solution, and light transmittance at 700 nm was 50% of an initial value.
(Half-life) was 6 seconds. The contact angle on the Teflon plate of the resin emulsion produced so as to contain 10% by weight of the resin emulsion particles is 115.
Was ゜.

Preparation of Microcapsule-Type Colorant As a microcapsule-type colorant, the following aqueous dispersions of the following pigments were prepared.

Aqueous dispersion of magenta pigment C.I. I. 100 g of CI Pigment Red 122 and 60 g of polymerizable surfactant SE-10N (manufactured by Asahi Denka) are added to 1,000 g of ion-exchanged water, irradiated with ultrasonic waves by an ultrasonic generator, and dispersed for 2 hours. For about 2 hours. This dispersion was charged into a reaction vessel equipped with an ultrasonic generator, a stirrer, a temperature controller, a reflux condenser, and a dropping funnel. Then, in advance, 5 g of benzyl methacrylate,
A monomer mixture obtained by mixing 15 g of butyl methacrylate, 10 g of dicyclopentanyl dimethacrylate, and 10 g of methacrylic acid, and 1 g of potassium persulfate were further added, and a polymerization reaction was performed at 60 ° C. for 48 hours. The target product was adjusted to pH 8 with potassium hydroxide and passed through a 0.4 μm filter to remove coarse particles. As a result, an intended aqueous dispersion of the magenta pigment was obtained. The average particle diameter was 80 nm as measured using Microtrac UPA.

Aqueous dispersion of cyan pigment C.I. I. Pigment Blue 15: 3 (100 g) and 60 g of a polymerizable surfactant SE-10N (manufactured by Asahi Denka) were added to 1,000 g of ion-exchanged water, and the mixture was irradiated with ultrasonic waves by an ultrasonic generator and dispersed for 2 hours. Further, the mixture was dispersed in a sand mill for about 2 hours. This dispersion, ultrasonic generator, stirrer,
Charge into a reaction vessel equipped with a temperature controller, reflux condenser and dropping funnel. Next, 10 g of 2-acrylamido-2-methylpropanesulfonic acid and 10 g of acrylonitrile
g, 10 g of benzyl methacrylate and 10 g of butyl methacrylate, and 1 g of potassium persulfate were further added, and a polymerization reaction was carried out at 60 ° C. for 48 hours. The target product was adjusted to pH 8 with potassium hydroxide and passed through a 0.4 μm filter to remove coarse particles. As a result, an aqueous dispersion of the intended cyan pigment was obtained. The average particle size was 90 nm as measured by using Microtrac UPA.

Aqueous dispersion of yellow pigment C.I. I. 100 g of CI Pigment Yellow 185 and 60 g of polymerizable surfactant SE-10N (manufactured by Asahi Denka) are added to 1,000 g of ion-exchanged water, irradiated with ultrasonic waves by an ultrasonic generator, and dispersed for 2 hours. For about 2 hours. This dispersion, ultrasonic generator, stirrer,
It was charged into a reaction vessel equipped with a temperature controller, a reflux condenser, and a dropping funnel. Next, in advance, a monomer mixture obtained by mixing 20 g of acrylonitrile and 20 g of dibutyl fumarate,
1 g of potassium persulfate was further added, and
The polymerization reaction was performed for an hour. The target product was adjusted to pH 8 with potassium hydroxide and passed through a 0.4 μm filter to remove coarse particles. As a result, an aqueous dispersion of the target yellow pigment was obtained. When measured using a Microtrac UPA, the average particle size was 70.
nm.

[0200]

[Table 2]

[0201]

[Table 3]

Printing Evaluation Test The ink composition and the reaction solution were used in the combinations shown in Table 4 below. The following printed materials were evaluated.
Using the recording apparatus of the present invention, the ink composition and the reaction liquid were printed on a PET (polyethylene terephthalate) film, an aluminum plate, an iron plate, an SBR sheet, and a glass plate, and washed with water. The results of each evaluation test were as described in Table 5 below.

Evaluation 1: Printability Using the recording apparatus of the present invention, first, the reaction liquid of the present invention was applied to the above-mentioned recording medium, and the ink of the present invention was applied to the applied portion to form an image. And further washed with water to obtain a printed matter. At this time, the state of the printed portion on the recording medium was visually observed and evaluated according to the following three grades. Evaluation A: The ink was uniformly applied, the image was clear, and the edge was sharp. Evaluation B: Due to the occurrence of ink repelling, the image lacked sharpness and the edges were not sharp. Evaluation C: At the time of cleaning, the ink was washed away,
The image was unclear.

Evaluation 2: Fixing Property (Adhesion) Using the recording apparatus of the present invention, first, the reaction liquid of the present invention was applied to the above-mentioned recording medium, and the ink of the present invention was applied to the applied portion to obtain a solid. An image was formed and washed with water to obtain a print. The obtained printed matter was left for 1 hour in an atmosphere of 25 ° C. and a humidity of 40%, and then subjected to an evaluation test.

An evaluation test was performed as follows. Make a 1cm square by making a notch using a sharp blade so that the solid printing part becomes a grid at 1mm intervals.
A scotch clear tape (trade name: manufactured by 3M Company) was applied thereon, and after applying a load of 9.8 N / mm ² , the tape was peeled off and the number of 1 mm × 1 mm grids left on the recording medium was removed. Was examined. The evaluation was performed according to the following criteria. Evaluation A: 95 or more pieces remained. Evaluation B: 90 or more pieces remained. Evaluation C: 60 to less than 90 remained. Evaluation D: Less than 60 pieces remained.

Evaluation 3: Color Bleed Using the recording apparatus of the present invention, first, the reaction liquid of the present invention was applied to the above-mentioned recording medium, and the ink of the present invention was applied to the applied portion to form an image. And further washed with water to obtain a printed matter. At this time, uneven color mixing at the color boundary of the obtained printed matter was visually evaluated based on the following criteria. Evaluation A: There was no mixing of colors and the boundary was clear. Evaluation B: Slight color mixing was observed. Evaluation C: Colors were mixed so that the boundaries between the colors were not clear.

Evaluation 4: Abrasion Resistance Using the recording apparatus of the present invention, first, the reaction liquid of the present invention was applied to the above-mentioned recording medium, and the ink of the present invention was applied to the applied portion to form an image. And further washed with water to obtain a printed matter. After leaving the obtained printed matter in an atmosphere of 25 ° C. and a humidity of 40% for 1 hour, a 9.8 N / mm ² load was applied to the yellow aqueous highlighter ZEBRA PEN2 (trade name) manufactured by Zebra Corporation to rub the printed part, The state of the image was visually observed and evaluated according to the following criteria. Evaluation A: The state was the same as before rubbing. Evaluation B: The printed portion was stained by rubbing, and the image was unclear.

[0208]

[Table 4]

[0209]

[Table 5]

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a recording apparatus according to the present invention.

FIG. 2 is a view showing one embodiment of a recording apparatus according to the present invention, in which the recording apparatus for printing a PET film is shown.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Supply source and recording head 2 Ink jet recording mechanism 3 Printing surface 4 Cleaning mechanism 5 Drying mechanism 6 Product storage tray 11 PET film roll 12 Support stand 13 Product roll

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41J 3/04 101Y F-term (Reference) 2C056 EA13 FB01 FB02 FB03 FB04 FC01 FC02 HA42 HA46 HA47 2H086 BA01 BA05 BA17 BA18 BA19 BA23 BA52 BA53 BA55 BA59 BA60 4J039 AB01 AB02 AB07 AD01 AD02 AD03 AD06 AD08 AD09 AD10 AD11 AD14 AD15 AE04 AE08 BA04 BA13 BA35 BA37 BC07 BC09 BC13 BC35 BC37 BC39 BC50 BC51 BC60 BD03 BE01 BE03 BE04 BE05 BE07 BE08 BE12 CA06 EA15 EA16 EA16 FA06 GA24

Claims (26)

[Claims] 1. A recording method for printing by adhering an ink composition and a reaction liquid to a recording medium, the method comprising: adhering the reaction liquid onto a recording medium; and applying the ink composition onto a recording medium. And a step of washing the recording medium printed by attaching the reaction liquid and the ink composition with a polar solvent, wherein the ink composition comprises a colorant. And a resin emulsion particle; a water-soluble organic solvent; and water; a reaction agent that forms an agglomerate when the reaction liquid comes into contact with the ink composition;
Alternatively, a recording method comprising cationic polymer fine particles, a water-soluble organic solvent, and water. 2. The recording according to claim 1, wherein the cationic inorganic fine particles are those obtained by hydrating inorganic fine particles to be cationized, or those obtained by treating inorganic fine particles with a cationic substance to be cationized. Method. 3. The recording method according to claim 2, wherein said inorganic fine particles are inorganic colloid particles. 4. The recording method according to claim 2, wherein the cationic substance is an alumina sol, basic alumina chloride, a cationic surfactant or a polycation compound. 5. The recording method according to claim 1, wherein said cationic inorganic fine particles are cationic alumina sol or cationic colloidal silica. 6. The recording method according to claim 1, wherein the cationic polymer fine particles are obtained by treating the polymer fine particles with a cationic substance to cationize or by polymerizing a cationic monomer. . 7. The cationic polymer fine particles include acrylic resin, polyester resin, epoxy resin, styrene-butadiene copolymer, polybutadiene, polyolefin, polystyrene, polyamide, ethylene-vinyl acetate copolymer, polysiloxane, And a polymer selected from the group of polyurethanes.
The recording method according to claim 6. 8. The recording method according to claim 7, wherein the cationic substance is an alumina sol, basic alumina chloride, a cationic surfactant, or a polycation compound. 9. The cationic polymer fine particles are fine particles composed of a polymer obtained by copolymerizing a cationic monomer represented by the following formula (I) and a vinyl monomer. Recording method described in 1. Embedded image [Wherein, R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom or an NH group, and R ² and R ³ each independently represent a straight-chain or branched-chain having 1 to 4 carbon atoms. R ⁴ represents a hydrogen atom or an optionally substituted carbon atom of 1
Represents to 4 linear or branched alkyl group, n represents an integer of 2 to 5, Y ^- represents an anion which forms a salt] 10. The recording method according to claim 1, wherein the recording medium is substantially non-absorbable with respect to the ink composition. 11. The recording medium is made of plastic, rubber,
The recording method according to claim 10, wherein the recording method is made of a metal or a ceramic. 12. The recording medium according to claim 1, wherein the surface of the recording medium is substantially non-absorbable, and the surface is made of plastic, rubber, metal, or ceramic.
The recording method according to any one of Items 1 to 9, 13. The method according to claim 1, wherein said colorant is a pigment.
3. The recording method according to any one of 2. 14. The colorant according to claim 1, wherein the colorant contains a pigment and / or a dye as a polymer, and the inclusion is in the form of fine particles. The described method. 15. The resin emulsion particles according to claim 1, wherein the resin emulsion particles comprise: 1) a polymer having film-forming ability; and 2) at least one selected from the group consisting of a carboxyl group, a sulfone group, an amide group, an amino group, and a hydroxyl group. 3) having a glass transition point of 20 ° C. or lower, 4) 3 volumes of a resin emulsion containing 0.1% by weight of the particles, and a divalent solution having a concentration of 1 mol / l. Having a reactivity with a divalent metal salt such that the time when the transmittance of light having a wavelength of 700 nm becomes 50% of the initial value is 1 × 10 ⁴ seconds or less when brought into contact with one volume of a metal salt aqueous solution 5) The recording method according to any one of claims 1 to 14, wherein the particle diameter is 5 to 200 nm. 16. The recording method according to claim 15, wherein a minimum film forming temperature of the resin emulsion containing the resin emulsion particles is 30 ° C. or less. 17. The recording method according to claim 1, wherein the step of depositing a droplet of the ink composition on the recording medium is performed after the step of depositing the reaction liquid on the recording medium. . 18. The ink jet recording method in which the step of adhering droplets of the ink composition on the recording medium or the step of adhering the reaction liquid to the recording medium is an ink jet recording method in which droplets are ejected and adhered to the recording medium to perform printing. The recording method according to claim 1. 19. The recording method according to claim 1, wherein the printing is a real image printing and / or a mirror image printing. 20. The recording medium may be an industrial product, an industrial product, a home appliance, a building product, furniture, tableware, an aircraft, a vehicle, a ship, a card, a packaging container, a medical product, clothes, shoes, bags, office supplies, stationery, 2. A toy, sign, or fiber.
20. The recording method according to any one of claims 19 to 19. 21. A recorded matter printed by the recording method according to any one of claims 1 to 20. 22. A method for applying character information, image information, and design to a recording medium by using the recording method according to claim 1. 23. A recording apparatus for performing the recording method according to any one of claims 1 to 20, wherein: a means for adhering the reaction liquid on a recording medium; Means for recording an image by depositing an ink composition; means for depositing the reaction liquid on a recording medium; and means for controlling means for recording an image by depositing the ink composition on a recording medium. And a means for washing the recording medium printed by attaching the reaction liquid and the ink composition with a polar solvent. 24. An ink jet recording means for controlling means for adhering the reaction liquid on a recording medium and means for recording an image by adhering the ink composition on a recording medium. An apparatus according to claim 1. 25. The recording apparatus according to claim 23, wherein the printing is a real image printing and / or a mirror image printing. 26. A recorded matter printed by the apparatus according to any one of claims 23 to 25.