JP2017115127A - Ink, inkjet printer, inkjet printing method, and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink which has good storage stability and allows an image excellent in fixability and adhesion to an impermeable recording medium to be obtained.SOLUTION: The ink contains water, an organic solvent, a polysiloxane surfactant, and acrylic-silicone resin particles. The polysiloxane surfactant has an HLB value of 8 or less. In a preferred embodiment, the ink further contains at least one kind selected from polyurethane resin particles, fluororesin particles, vinyl chloride resin particles, polyester resin particles, acrylic-styrene copolymer resin particles, and polyvinyl alcohol resin particles.SELECTED DRAWING: None

Description

  The present invention relates to an ink, an inkjet printing apparatus, an inkjet printing method, and a printed matter.

  In order to improve durability such as light resistance, water resistance, and abrasion resistance in industrial applications such as advertising and billboards, for example, non-permeable recording media such as plastic films are used. Various inks used in the field have been developed.

As such an ink, for example, a solvent-based ink using an organic solvent as a solvent, an ultraviolet curable ink mainly containing a polymerizable monomer, and the like are widely used. However, there is a concern that the solvent-based ink may affect the environment due to evaporation of the organic solvent. The UV curable ink may have a limited choice of polymerizable monomers used from the viewpoint of safety.
Accordingly, water-based inks that have a low environmental burden and can be directly recorded on a non-permeable recording medium have been proposed (see, for example, Patent Documents 1 and 2).

  An object of the present invention is to provide an ink that has good storage stability and can provide an image having excellent fixability and adhesion to a non-permeable recording medium.

  The ink of the present invention as means for solving the above problems contains water, an organic solvent, a polysiloxane surfactant, and acrylic-silicone resin particles, and the HLB value of the polysiloxane surfactant is 8 or less. It is.

  According to the present invention, it is possible to provide an ink that has good storage stability and can provide an image having excellent fixability and adhesion to a non-permeable recording medium.

FIG. 1 is a perspective explanatory view showing an example of a serial type image forming apparatus. FIG. 2 is a perspective explanatory view showing an example of a main tank of the apparatus of FIG. FIG. 3 is a schematic view showing an example of the heating means of the apparatus of FIG. FIG. 4 is an external perspective view illustrating an example of a liquid (ink) discharge head. FIG. 5 is a cross-sectional explanatory diagram in a direction orthogonal to the nozzle arrangement direction of the liquid ejection head shown in FIG. 6 is a cross-sectional view taken along the line A-A ′ of FIG. 5. FIG. 7 is a B-B ′ cross-sectional view of FIG. 5. FIG. 8 is an explanatory cross-sectional view in a direction parallel to the nozzle arrangement direction of the liquid ejection head shown in FIG. FIG. 9 is an explanatory plan view of the nozzle plate of the liquid discharge head shown in FIG. FIG. 10 is an explanatory plan view of each member constituting the flow path member of the liquid ejection head shown in FIG. FIG. 11 is an explanatory plan view of each member constituting the common liquid chamber member of the liquid discharge head shown in FIG. FIG. 12 is a block diagram showing a liquid circulation system according to this embodiment. FIG. 13 is an explanatory plan view of an essential part showing an example of an apparatus for ejecting liquid. FIG. 14 is an explanatory side view of a main part showing an example of an apparatus for ejecting liquid. FIG. 15 is an explanatory plan view of a main part showing another example of the liquid discharge unit.

(ink)
The ink according to the present invention contains water, an organic solvent, a polysiloxane surfactant, and acryl-silicone resin particles, and the polysiloxane surfactant has an HLB value of 8 or less, and, if necessary, other Contains ingredients.
The ink of the present invention is generally excellent in fixability to a non-permeable recording medium because a solvent-based ink is fixed while the non-permeable recording medium is swollen by an organic solvent in the ink. In the final printed matter, since the ink film stays on the recording medium, the fixing property of the ink film to the recording medium is insufficient and there is a problem that the high-speed recording property is inferior. It is. In addition, assuming outdoor use, the scratch resistance of printed matter is required to have properties such as tough scratch resistance and image hardness that cannot be compared with those for indoor use. However, this is based on the knowledge that conventional water-based inks have a problem that sufficient properties comparable to solvent-based inks are not obtained.

In addition, the present inventors have found the following.
Among the components contained in the ink, the selection of the surfactant affects the fixability of the ink to the non-permeable recording medium to be recorded, and therefore plays a very important role. The present inventors have found that the fixability of the ink is remarkably improved by adding a compound having an HLB value of 8 or less among the polysiloxane surfactants to the ink. Although the reason for this is not clear, it is presumed that when the HLB value is 8 or less, the hydrophobicity increases, and the affinity with various non-permeable recording media is improved.
In addition, by improving the fixability of the ink to the impermeable recording medium, it is possible to suppress the phenomenon (beading) in which adjacent ink droplets coalesce and contract after landing even during high-speed recording. It has been found that a quality image can be obtained. Further, it has been found that the improvement of the fixing speed can also improve the drying property and the adhesion, so that the transfer to the backing paper can be suppressed when the recording medium is taken up after recording.

  However, if the HLB value is 8 or less, the balance between water solubility and oil solubility may be biased toward oil solubility. In such a case, in a water-based ink in which water exceeds 30% by mass of the total components of the ink, the surfactant becomes difficult to dissolve in the ink, and phase separation that separates into an oil phase and an aqueous phase is likely to occur. . As a result, the storage stability of the ink may be reduced.

  Therefore, the present inventors have found that when a predetermined amount of acrylic-silicone resin particles is added to the ink, the polysiloxane surfactant can be stabilized in the ink. Thereby, the phase separation of the ink can be eliminated within the use temperature range assumed as the ink for inkjet recording.

<Polysiloxane surfactant>
Examples of the polysiloxane surfactant include compounds having a hydrophilic group or a hydrophilic polymer chain in the side chain of a compound having a polysiloxane structure (silicone compound) such as polydimethylsiloxane, and polydimethylsiloxane. Examples thereof include a compound having a hydrophilic group or a hydrophilic polymer chain at the end of a compound having a siloxane structure (silicone compound). In addition, the said polysiloxane surfactant should just have a polysiloxane structure in the structure, and is the meaning also including a polysiloxane type surfactant.

Examples of the hydrophilic group and the hydrophilic polymer chain include polyether groups (polyethylene oxide, polypropylene oxide, copolymers thereof, and the like), polyglycerin (C ₃ Η ₆ O (CH ₂ CH (OH)). CH _{2 O)} n -H, etc.), pyrrolidones, betaines ^{_{(C 3 Η 6 n + (}} C 2 H 4) 2 -CH 2 COO - , etc.), sulfate _{(C 3 H 6 O (C} 2 H 4 O) _n -SO ₃ Na, etc.), phosphate _{(C 3 Η 6 O (C} 2 H 4 O) n -P (= O) OHONa etc.), quaternary salt ^{_{(C 3 H 6 n + (}} C 2 H 4 ) ₃ Cl- ^{and the} like. However, in said chemical formula, n represents an integer greater than or equal to 1. Among these, it is preferable to have a polyether group.
Also, polydimethylsiloxane having a polymerizable vinyl group at the terminal and other monomers copolymerizable (hydrophilic monomers such as (meth) acrylic acid or salts thereof may be used for at least a part of the monomers. And a vinyl copolymer having a silicone compound chain such as polydimethylsiloxane in the side chain obtained by copolymerization.
Among these, a compound having a polysiloxane structure and a compound having a hydrophilic polymer chain is preferable, and it is more preferable that the hydrophilic polymer chain contains a polyether group, and the polysiloxane surfactant is a hydrophobic group. A nonionic surfactant having methylpolysiloxane and having a polyoxyethylene structure as a hydrophilic group is particularly preferred.

  The HLB value of the polysiloxane surfactant is 8 or less, preferably 4.5 or more and 7.0 or less. When the HLB value is 8 or less, excellent ink fixing properties can be ensured even when ink-jet recording is performed on various non-permeable recording media. Further, the HLB value is 4.5 or more and 7.0 or less. If it exists, the temperature which does not produce phase separation of ink can be raised.

Here, the HLB value means the balance between the hydrophilic group and the lipophilic group of the surfactant. The HLB value takes a value of 0 to 20, and the closer to 0, the higher the lipophilicity is, and the closer to 20. The higher the hydrophilicity. The HLB value is defined by the following equation (Griffin method).
HLB value = 20 × (sum of hydrophilic part formula weight / molecular weight)

  Examples of the polysiloxane surfactant include polyether-modified silicone, polyoxyalkylene group-containing silicone compound, and the like.

  Commercially available products can be used as the polysiloxane surfactant. Examples of the commercially available products include Silface SAG005 (HLB value: 7.0), Silface SAG008 (HLB value: 7.0), ( As described above, manufactured by Nissin Chemical Industry Co., Ltd., FZ2110 (HLB: 1.0), FZ2166 (HLB value: 5.8), SH-3772M (HLB value: 6.0), L7001 (HLB value: 7.4) ), SH-3773M (HLB value: 8.0), (manufactured by Toray Dow Co., Ltd.), KF-945 (HLB value: 4.0), KF-6017 (HLB value: 4.5), ( As described above, Shin-Etsu Chemical Co., Ltd.), FormBan MS-575 (manufactured by Ultra Additives Inc., HLB value: 5.0) and the like can be mentioned.

  The content of the polysiloxane surfactant is preferably 0.1% by mass or more and 4.0% by mass or less, and more preferably 1.0% by mass or more and 2.0% by mass or less based on the total amount of the ink. When the content is 0.1% by mass or more and 4.0% by mass or less, it is possible to improve the fixability of the ink to various non-permeable recording media and to improve the image quality such as gloss.

<Acrylic-silicone resin particles>
The acrylic-silicone resin particles preferably contain other resin particles in order to suppress the occurrence of separation of the polysiloxane surfactant in the ink and to improve other properties.

  The acrylic-silicone resin particles are silicone-modified acrylic resin particles that can be obtained by polymerizing an acrylic monomer and a silane compound in the presence of an emulsifier and, if necessary, a silane coupling agent.

  Examples of the acrylic monomer include acrylics such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acryloylmorpholine, and N, N′-dimethylaminoethyl acrylate. Examples include acid ester monomers, amide-based acrylates such as N-methylolacrylamide and methoxymethylacrylamide. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the silane compound include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyl. Examples include diethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, and trifluoropropyltrimethoxysilane. These may be used individually by 1 type and may use 2 or more types together.

Examples of the emulsifier include alkylbenzene sulfonic acid or its salt, dialkyl sulfosuccinic acid ester or its salt, alkyl naphthalene sulfonic acid or its salt, formalin condensate of alkyl naphthalene sulfonate, higher fatty acid salt, sulfonic acid of higher fatty acid ester Salt, polyoxypropylene-polyoxyethylene condensate of ethylenediamine, sorbitan fatty acid ester or salt thereof, aromatic to aliphatic phosphate ester or salt thereof, dodecylbenzenesulfonate, dodecylsulfate, laurylsulfate, dialkylsulfosuccinic acid Salt, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl propenyl phenyl ether sulfate, alkyl phenyl ether disulfonate, polyoxyethylene alkyl phosphate Polyoxyethylene alkyl ether acetate, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, lauryl alcohol ethoxylate, lauryl ether sulfate ester, lauryl ether phosphate ester, sorbitan fatty acid ester, fatty acid diethanolamide, naphthalene sulfonic acid And the formalin condensate. These may be used individually by 1 type and may use 2 or more types together.
Here, examples of the salt include a sodium salt and an ammonium salt.

A reactive emulsifier having an unsaturated double bond can also be used as the emulsifier.
Examples of the reactive emulsifier include ADEKA rear soap SE, NE, PP (manufactured by ADEKA Corporation), LATEMUL S-180 (manufactured by Kao Corporation), Eleminol JS-2, and Eleminol RS-30 (Sanyo Chemical Industries, Ltd.). Product), Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

  Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) ) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Hydrochloride of silyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane Etc.

  The volume average particle size of the acrylic-silicone resin particles is preferably 10 nm to 300 nm, and more preferably 40 nm to 200 nm. When the volume average particle size is 10 nm or more, the viscosity of the resin emulsion can be prevented from becoming high when synthesized, and the discharge stability can be improved. When the volume average particle size is 300 nm or less, the acrylic-silicone resin particles in the nozzle of the printer It is possible to prevent clogging and discharge failure.

  The silicone content derived from the acrylic-silicone resin particles is preferably 0.01% by mass or more and 0.04% by mass or less based on the total amount of the ink. When the content is 0.01% by mass or more, a coating film having excellent scratch resistance and marker resistance can be obtained, and when it is 0.04% by mass or less, storage stability can be improved.

  The glass transition temperature (Tg) of the acrylic-silicone resin particles is preferably 0 ° C. or lower, more preferably −15 ° C. or higher and 0 ° C. or lower. Adhesiveness can be improved as the glass transition temperature is 0 ° C. or lower.

  The minimum film-forming temperature of the acrylic-silicone resin particles is preferably 20 ° C. or lower. When the minimum film-forming temperature is 20 ° C. or lower, fixability can be improved. That is, when the recording portion is rubbed or traced with a marker, the recording medium can be prevented from being removed due to the pigment being removed.

  Commercially available products can be used as the acrylic-silicone resin particles. For example, AQ914 (manufactured by Daicel FineChem, Inc., solid content concentration: 24% by mass, Tg: 50 ° C.), SA-6360 (manufactured by DIC Corporation). , Solid content concentration: 50% by mass, Tg: 21 ° C., Cymac 480 (manufactured by Toagosei Co., Ltd., solid content concentration: 30% by mass, Tg: 0 ° C.), AE980 (manufactured by Etec Corporation, solid content concentration: 50 % By mass, Tg: −14 ° C.), AE981A (manufactured by Etec Co., Ltd., solid content concentration: 50 mass%, Tg: −15 ° C.), AE982 (manufactured by Etec Co., Ltd., solid content concentration: 50 mass%, Tg: 0) ° C).

  The content of the acrylic-silicone resin particles is preferably 0.5% by mass or more and 5% by mass or less, and more preferably 0.8% by mass or more and 2.5% by mass or less with respect to the total amount of the ink.

[Mass ratio (B / A)]
The mass ratio (B / A) between the content A (mass%) of the polysiloxane surfactant and the content B (mass%) of the acrylic-silicone resin particles is 0.6 or more and 1.8 or less. Is preferable, and 0.8 or more and 1.5 or less are more preferable. When the mass ratio (B / A) is 0.6 or more and 1.8 or less, the temperature at which the separation of the polysiloxane surfactant can be increased, and the ink has excellent image quality such as gloss. Can provide.

<Other resin particles>
Examples of the other resin particles include polyurethane resin particles, fluorine resin particles, vinyl chloride resin particles, polyester resin particles, acrylic-styrene copolymer resin particles, polyvinyl alcohol resin particles, epoxy resin particles, polyamide resin particles, Examples include ether resin particles, polyolefin resin particles, polystyrene resin particles, polyvinyl ester resin particles, addition synthetic resin particles such as unsaturated carboxylic acid resins, and natural polymers such as celluloses, rosins, and natural rubber. These may be used individually by 1 type and may use 2 or more types together. Among these, polyurethane resin particles, fluororesin particles, vinyl chloride resin particles, polyester resin particles, acrylic-styrene copolymer resin particles, and polyvinyl alcohol resin particles are preferable.

<< Polyurethane resin particles >>
The polyurethane resin particles can be imparted with high image gloss and scratch resistance. Furthermore, surprisingly, by using the polysiloxane surfactant, the acrylic-silicone resin particles, and the polyurethane resin particles in combination, not only the scratch resistance of the coating film formed after recording, but also the solvent resistance is achieved. It can be greatly improved.

  Examples of the polyurethane resin particles include polyether-based polyurethane resin particles, polycarbonate-based polyurethane resin particles, and polyester-based polyurethane resin particles.

  There is no restriction | limiting in particular as said polyurethane resin particle, According to the objective, it can select suitably, For example, the polyurethane resin particle etc. which are obtained by making a polyol and polyisocyanate react are mentioned.

-Polyol-
Examples of the polyol include polyether polyol, polycarbonate polyol, and polyester polyol. These may be used individually by 1 type and may use 2 or more types together.

--Polyether polyol--
Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide using at least one compound having two or more active hydrogen atoms as a starting material.

  Examples of the compound having two or more active hydrogen atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane. Diol, glycerin, trimethylolethane, trimethylolpropane and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These may be used individually by 1 type and may use 2 or more types together.

  The polyether polyol is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of obtaining a binder for ink that can impart very excellent scratch resistance, polyoxytetramethylene glycol, polyoxy Propylene glycol is preferred. These may be used individually by 1 type and may use 2 or more types together.

--Polycarbonate polyol--
Examples of the polycarbonate polyol that can be used for the production of the polyurethane resin particles include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1, 2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol , Bisphenol-A, bisphe Relatively low molecular weight dihydroxy compounds such as polyol-F, 4,4′-biphenol; polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol; polyhexamethylene adipate, polyhexamethylene succinate, poly Examples thereof include polyester polyols such as caprolactone. These may be used individually by 1 type and may use 2 or more types together.

--Polyester polyol--
Examples of the polyester polyol include those obtained by esterifying low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and copolymers thereof. Examples include polyester. These may be used individually by 1 type and may use 2 or more types together.

Examples of the low molecular weight polyol include ethylene glycol and propylene glycol. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, anhydrides or ester-forming derivatives thereof. These may be used individually by 1 type and may use 2 or more types together.

-Polyisocyanate-
Examples of the polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene Examples thereof include aliphatic or alicyclic diisocyanates such as diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate. These may be used individually by 1 type and may use 2 or more types together. Among these, since the ink of the present invention is also used for outdoor applications such as posters and signboards, it requires a coating film having very high long-term weather resistance. Formula diisocyanates are preferred.

Furthermore, the use of at least one alicyclic diisocyanate makes it easy to obtain the desired coating strength and scratch resistance.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate.
As content of the said alicyclic diisocyanate, 60 mass% or more is preferable with respect to the isocyanate compound whole quantity.

[Production method of polyurethane resin particles]
The polyurethane resin particles can be obtained by a conventionally used production method, and examples thereof include the following methods.
First, in the absence of a solvent or in the presence of an organic solvent, the polyol and the polyisocyanate are reacted at an equivalent ratio in which an isocyanate group becomes excessive to produce an isocyanate-terminated urethane prepolymer.
Next, the anionic group in the isocyanate-terminated urethane prepolymer is neutralized with a neutralizing agent as necessary, and then reacted with a chain extender, and finally the organic solvent in the system is removed as necessary. Can be obtained.

Examples of the organic solvent that can be used in the production of the polyurethane resin particles include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; Examples include amides such as formamide, N-methylpyrrolidone, and N-ethylpyrrolidone. These may be used individually by 1 type and may use 2 or more types together.
Examples of the chain extender include polyamines and other active hydrogen group-containing compounds.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamines; Polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; Hydrazines such as hydrazine, N, N′-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Succinic dihydrazide, Adipic dihydrazide And dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the other active hydrogen group-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone Kind; water etc. are mentioned. These may be used singly or in combination of two or more as long as the storage stability of the ink is not lowered.

  The polyurethane resin particles are preferably polycarbonate polyurethane resin particles from the viewpoint of water resistance, heat resistance, abrasion resistance, weather resistance, and image scratch resistance due to the high cohesive strength of carbonate groups. When the polycarbonate-based polyurethane resin particles are used, an ink suitable for a printed material used in a harsh environment such as an outdoor application can be obtained.

  Commercially available products may be used as the polyurethane resin particles. For example, U-coat UX-485 (polycarbonate-based polyurethane resin particles), U-coat UWS-145 (polyester-based polyurethane resin particles), and Permarin UA-368T (polycarbonate-based polyurethane). Resin particles), Permarin UA-200 (polyether polyurethane resin particles) (manufactured by Sanyo Chemical Industries, Ltd.), and the like. These may be used individually by 1 type and may use 2 or more types together.

<< Fluoropolymer particle >>
The fluororesin particles can improve high image gloss, scratch resistance, and weather resistance. Furthermore, surprisingly, when the polysiloxane surfactant, the acrylic-silicone resin particles, and the fluororesin particles are used in combination, not only the scratch resistance of the coating film formed after recording, but also solvent resistance and weather resistance. The performance can be greatly improved.
The said fluororesin particle | grains should just have a fluorine in the structure, and are the meaning containing a fluorine resin particle.

Examples of the fluororesin particles include fluororesin particles having a structural unit derived from fluoroolefin and a structural unit containing a fluorine substituent, fluororesin particles having a structural unit derived from fluoroolefin and a structural unit derived from vinyl ether. .
Examples of the fluororesin particles having a structural unit derived from the fluoroolefin and a structural unit containing a fluorine substituent include 4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole and fluoroolefin And copolymer resin particles.

As the structural unit derived from the fluoroolefin is not particularly limited and may be appropriately selected depending on the purpose, for _{example, -CF 2 CF 2 -, -} CF 2 CF (CF 3) -, - CF 2 CFCl- Etc.

There is no restriction | limiting in particular as a structural unit derived from the said vinyl ether, According to the objective, it can select suitably, For example, the following structural unit etc. are mentioned.

  The glass transition temperature (Tg) of the fluororesin particles is preferably from 100 ° C. to 300 ° C., more preferably from 150 ° C. to 250 ° C. When the glass transition temperature is 100 ° C. or higher and 300 ° C. or lower, an image formed on a non-permeable recording medium with an ink containing fluororesin particles and at least one type of resin particles other than fluororesin particles is generally used. When dried in a range of 50 ° C. or more and 150 ° C. or less, which is a low drying temperature, the shape of the fluororesin particles can be maintained, and therefore uniform with resin particles other than one or more types of fluororesin particles Rather than hindering the formation of the film, rather the fluororesin particles behave like fillers, whereby the strength of the resin formed by resin particles other than one or more types of fluororesin particles can be improved. From such a viewpoint, the glass transition temperature of the fluororesin particles used is preferably higher than the drying temperature of the printed material, more preferably 20 ° C. or higher, and particularly preferably 50 ° C. or higher.

As said fluororesin particle | grains, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available products include Teflon (registered trademark) AF series, trade name: AF1600 (Tg: 160 ° C.), trade name: AF 2400 (Tg: 240 ° C.) ), Trade name: Lumiflon FE4400 (Asahi Glass Co., Ltd., Tg: 48 ° C.).

  As a mass ratio (fluororesin particles / resin particles other than fluororesin particles) of the content (mass%) of the fluororesin particles and the total content (mass%) of resin particles other than the fluororesin particles, 0.05 It is preferably 4.0 or less, more preferably 0.1 or more and 2.0 or less, and particularly preferably 0.2 or more and 1.5 or less. When the mass ratio (fluororesin particles / resin particles other than fluororesin particles) is 0.05 or more and 4.0 or less, the fluororesin is obtained without deteriorating the characteristics of the film formed by the resin particles other than the fluororesin particles. Appropriate properties of the particles can be imparted to the image.

  The fluororesin particles are preferably added to the ink in an emulsion state. The emulsion of the fluororesin particles can be obtained by phase inversion emulsification or suspension polymerization of tetrafluoroethylene (TFE), phase inversion emulsification of polytetrafluoroethylene (PTFE), or the like.

In the phase inversion emulsification, phase inversion emulsification is performed by mixing a fluororesin particle solution obtained by dissolving fluororesin particles in an organic solvent such as tetrafluoroethylene (TFE) with water and a surfactant. In the present invention, it is preferable to carry out dispersion by adding a surfactant or the like to the solution containing the fluororesin particles and gradually adding water to the solution. By using this method, the average particle size of the resulting aqueous dispersion can be reduced to 500 nm or less, and recording can be performed without causing nozzle clogging due to the fluororesin particles when used in an inkjet recording method. .
The phase inversion emulsification means that the amount of water exceeding the amount of the organic solvent contained in the solution is added to the organic solvent solution of the fluororesin to change the system from the organic solvent phase to the aqueous phase. .

In the fluororesin particle solution in which the fluororesin particles are dissolved in an organic solvent such as tetrafluoroethylene (TFE), the content of the fluororesin particles is 10% by mass or more and 70% by mass with respect to the total fluororesin particle solution. % Or less, more preferably 20% by mass or more and 60% by mass or less, and particularly preferably 30% by mass or more and 50% by mass or less. When the content is 70% by mass or less, an increase in viscosity can be suppressed when mixed with water in the subsequent dispersion step, the volume average particle size of the resulting aqueous dispersion can be reduced, and storage stability can be improved. It can be improved. Further, if it is 10% by mass or more, it is possible to prevent the concentration of the fluororesin from further decreasing in the subsequent dispersion step, and it is not necessary to remove a large amount of the organic solvent in the solvent removal step.
The apparatus for dissolving the fluororesin particles in an organic solvent is not particularly limited as long as it has a tank into which a liquid can be charged and can be appropriately stirred, and can be appropriately selected according to the purpose.
Moreover, when the said fluororesin particle | grains are hard to melt | dissolve, you may heat.

  As temperature in the said dispersion | distribution process, 40 degrees C or less is preferable, 30 degrees C or less is more preferable, 20 degrees C or less is more preferable, 15 degrees C or less is especially preferable. When the temperature is 40 ° C. or less, the average particle size of the obtained aqueous dispersion can be 500 nm or less even when the content of a surfactant or the like is small. The temperature of the dispersing step is preferably kept at 40 ° C. or lower throughout this step, but the liquid temperature is likely to rise due to shear heat by stirring, etc., and it may be difficult to maintain the temperature of the system. Even in such a case, it is preferable to control to 40 ° C. or less (so as not to exceed 40 ° C.) until the addition of 0.8 times the amount of water of the organic solvent contained in the fluororesin particle solution is completed. It is more preferable to control to 40 ° C. or less until the addition of an amount of water is completed, and it is particularly preferable to control to 40 ° C. or less until 1.1 times the amount of water has been added.

<< Vinyl chloride resin particles >>
The vinyl chloride resin particles can improve high image gloss and scratch resistance. Surprisingly, the combined use of the polysiloxane surfactant, the acrylic-silicone resin particles, and the vinyl chloride resin particles greatly suppresses fluctuations in ink characteristics during long-term storage and improves the viscosity stability over time. can do.

  The vinyl chloride resin particles are preferably vinyl chloride-ethylene copolymer resin particles and vinyl chloride-acrylic copolymer resin particles from the viewpoint of ensuring miscibility with pigments and other resin particles contained in the ink. From the viewpoint of excellent adhesion to a nonpolar recording medium, vinyl chloride-ethylene copolymer resin particles are more preferable.

  There is no restriction | limiting in particular as said vinyl chloride resin particle, A commercial item can be used, Commercially available vinyl chloride resin particle, Commercially available vinyl chloride-acrylic copolymer resin particle, Commercially available vinyl chloride-ethylene copolymer Examples include resin particles. These may be used individually by 1 type and may use 2 or more types together.

Examples of the commercially available vinyl chloride resin particles include product number 985 (solid content concentration: 40% by mass, anionic) in the Vinyblan (registered trademark) series manufactured by Nissin Chemical Industry Co., Ltd.
Examples of the commercially available vinyl chloride-acrylic copolymer resin particles include a product number 278 (solid content concentration: 43 mass%, anionic), 700 (in the Vinyblan (registered trademark) series manufactured by Nissin Chemical Industry Co., Ltd.), 700 ( Solid content concentration: 30% by mass, anionic), 701 (solid content concentration: 30% by mass, anionic), 711 (solid content concentration: 30% by mass, anionic), 721 (solid content concentration: 30% by mass, Anionic), 700FS (solid content concentration: 30% by mass, anionic), 701RL35 (solid content concentration: 30% by mass, anionic), 701RL (solid content concentration: 30% by mass, anionic), 701RL65 (solid content) (Concentration: 30% by mass, anionic). These may be used individually by 1 type and may use 2 or more types together.
Examples of the commercially available vinyl chloride-ethylene copolymer resin particles include, for example, product number 1010 (solid content concentration: 50 ± 1% by mass, anionic) in Sumielite (registered trademark) series manufactured by Sumika Chemtex Co., Ltd. 1210 (solid content concentration: 50 ± 1 mass%, anionic), 1320 (solid content concentration: 50 ± 1 mass%, anionic), and the like. These may be used individually by 1 type and may use 2 or more types together.
Other commercially available products include the product number E15 / 48A (solid content concentration: 50% by mass, anion) of the VINNOL series manufactured by Wacker Chemie AG, which is a vinyl chloride copolymer resin particle in which a hydroxyl component is introduced into a vinyl chloride resin. ), E22 / 48A (solid content concentration: 30% by mass, anionic). These may be used individually by 1 type and may use 2 or more types together.

<< Polyester resin particles >>
The polyester resin particles can improve high image gloss and scratch resistance. Surprisingly, the weather resistance of the recorded image can be greatly improved by using the polysiloxane-based surfactant, the acrylic-silicone resin particles, and the polyester resin particles in combination.

  The polyester resin particles preferably do not contain a hydrophilic component remaining in the dried film such as an emulsifier and a sulfonate in order to obtain weather resistance of the image.

As said polyester resin particle, what was synthesize | combined suitably may be used and a commercial item may be used.
As said commercial item, for example, product number KZA-1449 (solid content concentration: 30 mass%, anionic property), KZA-3556 (solid content concentration: 30 mass) in the emulsion Elite (registered trademark) series manufactured by Unitika Ltd. %, Anionic), KZA-0134 (solid content concentration: 30% by mass, anionic), part number A-124GP (solid content concentration: 25% by mass), A-125S among Pes Resin A series manufactured by Takamatsu Yushi Co., Ltd. (Solid content concentration: 30 mass%), A-160P (solid content concentration: 25 mass%), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

<< Acrylic-styrene copolymer resin particles >>
The acrylic-styrene copolymer resin particles can improve high image gloss and scratch resistance. Surprisingly, by using the polysiloxane surfactant, the acrylic-silicone resin particles, and the acrylic-styrene copolymer resin particles in combination, the ejection reliability during recording can be greatly improved.

  The acrylic-styrene copolymer resin particles can prevent clogging with a nozzle and can further improve ejection stability.

As said acryl-styrene copolymer resin particle, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available products include Rikabond series Rikabond ET-700 (manufactured by Japan Coating Resin Co., Ltd.), Polymaron series (manufactured by Arakawa Industrial Co., Ltd.), J-140A, QE-1042 (manufactured by Seiko PMC Co., Ltd.), and the like. Is mentioned.

<< Polyvinyl alcohol resin particles >>
The polyvinyl alcohol resin particles can improve water resistance and solvent resistance, and can also improve fixability to a permeable recording medium. Furthermore, surprisingly, by using the polysiloxane surfactant, the acrylic-silicone resin particles, and the polyvinyl alcohol resin particles in combination, the stability of the pigment dispersion state can be improved, weather resistance, and Storage stability can be greatly improved.

  The polyvinyl alcohol resin particles can be produced by polymerizing a vinyl acetate monomer and saponifying the obtained polyvinyl acetate resin. In the saponification step, the acetate group of polyvinyl acetate is substituted with a hydroxyl group using an alkali catalyst in a methanol solvent. At this time, the water resistance of the polyvinyl alcohol resin film obtained is affected by the amount of hydroxyl groups substituted. The hydroxyl portion is hydrophilic and the acetic acid portion is hydrophobic, and has excellent surface activity.

As said polyvinyl alcohol resin particle, what was synthesize | combined suitably may be used and a commercial item may be used.
As said commercial item, brand name: Poval JF-04, brand name: Poval JF-05, brand name: Poval JF-17 (above, Nippon Vineyard Poval Co., Ltd. product) etc. are mentioned.

The resin particles are preferably mixed with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is used as a dispersion medium to obtain an ink.
Considering the ease of work of preparing water-based inks by blending with organic solvents, coloring materials, and water, and dispersing them as uniformly as possible in the ink, the resin particles are stably dispersed using water as a dispersion medium. It is preferable to add to the ink in the state of a resin emulsion.

  The resin particles are easily formed into a film by dissolving in an organic solvent added to the ink, and a film-like recording layer is formed. As the organic solvent and water evaporate, film formation of the resin particles is promoted. Therefore, when the ink of the present invention is used, recording without a heating step can be performed.

  In dispersing the resin particles using water as a dispersion medium, the resin particles include forced emulsification type resin particles using a dispersant, so-called self-emulsification type resin particles having an anionic group in the molecular structure, and the like. Can be mentioned. Among these, self-emulsifying resin particles having an anionic group in the molecular structure are preferable from the viewpoint of increasing the strength of the printed matter.

  The acid value of the anionic group of the self-emulsifying resin particles is preferably 5 mgKOH / g or more and 100 mgKOH / g or less, preferably 5 mgKOH / mg or more and 50 mgKOH / g from the viewpoint of water dispersibility, scratch resistance and chemical resistance. mg or less is more preferable.

  Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. Among these, a carboxylate group or a sulfonate group partially or wholly neutralized with a basic compound or the like is preferable from the viewpoint of maintaining good water dispersion stability. In order to introduce the anionic group into the resin, a monomer having the anionic group may be used.

Examples of the method for producing an aqueous dispersion of resin particles having an anionic group include a method of adding a basic compound that can be used for neutralization of an anionic group to the aqueous dispersion.
Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine and morpholine; alkanolamines such as monoethanolamine; metal base compounds containing Na, K, Li, Ca and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the method for producing an aqueous dispersion using the forced emulsification type resin particles include a method using a surfactant such as a nonionic surfactant and an anionic surfactant. These may be used individually by 1 type and may use 2 or more types together. Among these, from the viewpoint of water resistance, a method using a nonionic surfactant is preferable.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, Examples include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, and polyalkylene glycol (meth) acrylate. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the anionic surfactant include alkyl sulfate salts, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ethers. Examples thereof include carboxylate, fatty acid salt, naphthalenesulfonic acid formalin condensate, alkylamine salt, quaternary ammonium salt, alkylbetaine, and alkylamine oxide. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

  In the case of producing an aqueous dispersion using the forced emulsification type resin particles, the content of the surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. 0.1 mass% or more and 30 mass% or less are preferable with respect to the total amount of particles, and 5 mass% or more and 20 mass% or less are more preferable. If the content is in the range of 0.1% by mass or more and 30% by mass or less, the resin particles are preferably formed into a film, and an ink having excellent adhesion and water resistance can be obtained without causing the printed matter to block. Preferably used.

The volume average particle diameter of the resin particles is preferably 10 nm to 1,000 nm, more preferably 10 nm to 500 nm, and particularly preferably 10 nm to 200 nm, considering use in an ink jet printing apparatus. When the volume average particle size is 10 nm or more and 1,000 nm or less, the contact site between the organic solvent and the resin particle surface is increased, the film-forming property of the resin particle is enhanced, and a tough continuous resin film is formed. Therefore, a printed matter with high strength can be obtained.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  Examples of the qualitative and quantitative determination of the resin particles include, for example, “Testing method and evaluation result of each dynamic characteristic of plastic material (22); Takeo Yasuda, Plastics: Japan Plastic Industry Federation /“ Plastics ”Editorial Committee. It can be confirmed by the procedure detailed in the above. Specifically, it can be confirmed by analyzing by infrared spectroscopic analysis (IR), thermal analysis (DSC, TG / DTA), pyrolysis gas chromatography (PyGC) nuclear magnetic resonance (NMR) and the like.

The glass transition temperature of the resin particles can be measured using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.). Specifically, measurement is performed under the conditions of the following continuous temperature programs 1 to 4, and the value measured by the temperature program 3 is set as the glass transition temperature. The reason for performing the measurement in the temperature program and using the measurement value of the temperature program 3 is to ensure the reproducibility of the measurement value.
Temperature program:
1. 30 ° C. or more and 250 ° C. or less: temperature rising rate 30 ° C./min, holding time 1 minute 2. 250 or more and −100 ° C. or less: cooling rate 30 ° C./min, holding time 30 minutes −100 to 250 ° C .: heating rate 5 ° C./min, holding time 1 minute 4. 250 to 30 ° C .: cooling rate 30 ° C./min, holding time 2 minutes

  When the ink of the present invention is heated, the residual solvent can be reduced and the adhesion can be improved. In particular, when the minimum film-forming temperature of the resin particles (hereinafter also referred to as “MFT”) exceeds 80 ° C., it is preferable to heat from the viewpoint that the image fastness can be improved without defective film formation of the resin. . The heating is preferably performed after recording after applying ink to the recording medium.

When adjusting the minimum film-forming temperature of the resin emulsion in order to obtain the ink of the present invention, for example, it is adjusted by controlling the glass transition temperature (hereinafter also referred to as “Tg”) of the resin particles. In the case where the resin particles are a copolymer, it can be adjusted by changing the ratio of the monomers forming the copolymer. The minimum film-forming temperature refers to the minimum temperature at which a transparent continuous film is formed when the resin particles are cast thinly on a metal plate such as aluminum and the temperature is raised, In the temperature range below the minimum film-forming temperature, the emulsion is in the form of a white powder. The minimum film-forming temperature is measured by a commercially available minimum film-forming temperature measuring device such as “film-forming temperature test device” (manufactured by Imoto Seisakusho Co., Ltd.), “TP-801 MFT tester” (manufactured by Tester Sangyo Co., Ltd.), etc. can do.
In addition, since the minimum film-forming temperature varies depending on the volume average particle diameter of the resin particles, the minimum film-forming temperature of the resin particles can be set to a target value by a control factor of the volume average particle diameter of the resin particles.

  The content of the other resin particles is preferably 3% by mass or more and 10% by mass or less, and more preferably 4% by mass or more and 8% by mass or less with respect to the total amount of the ink.

<Organic solvent>
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, A water-soluble organic solvent etc. are mentioned. Water-soluble means, for example, that 5 g or more is dissolved in 100 g of water at 25 ° C.

  Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 3-methoxy-3-methylbutanol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, 6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, etc. Polyhydric alcohols, ethylene glycol monoethyl ether, ethylene Polyol alcohol alkyl ethers such as recall monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monophenyl ether, ethylene Polyhydric alcohol aryl ethers such as glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone Nitrogen-containing heterocyclic compounds such as formamide, N-methylformamide, N, N-dimethylformua Amides such as de, monoethanolamine, diethanolamine, amines such as triethylamine, dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, and the like ethylene carbonate. These may be used individually by 1 type and may use 2 or more types together.

Moreover, when containing a polyurethane resin particle as another resin particle, it is preferable to contain the compound represented by following General formula (1) as an organic solvent.
Since the compound represented by the general formula (1) has high resin solubility, it can penetrate into the recording medium and improve the drying speed during recording, and the film forming property of the resin particles is improved. Therefore, the drying property can be further improved, and it can be suitably used without blocking even in a short drying time.
(In the general formula (1), R _{1, R 2,} and R ₃ each independently. Representing a hydrocarbon group which may number 1 to 8 carbons have an ether bond)

In the general formula (1), R ₁ , R ₂ , and R ₃ represent a hydrocarbon group having 1 to 8 carbon atoms that may have an ether bond.
Examples of the hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group.
Examples of the hydrocarbon group having 1 to 8 carbon atoms having an ether bond include a methoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.
Among these, from the viewpoint of ejection stability, R ₁ is preferably a pentyl group, hexyl group, or octyl group, more preferably a pentyl group or hexyl group, and R ₂ and R ₃ are preferably methyl groups.

  Examples of the compound represented by the general formula (1) include N, N-dimethyl-β-butoxypropionamide, N, N-dimethyl-β-pentoxypropionamide, N, N-dimethyl-β-hex. Soxypropionamide, N, N-dimethyl-β-heptoxypropionamide, N, N-dimethyl-β-2-ethylhexoxypropionamide, N, N-dimethyl-β-octoxypropionamide, N, N- Diethyl-β-butoxypropionamide, N, N-diethyl-β-pentoxypropionamide, N, N-diethyl-β-hexoxypropionamide, N, N-diethyl-β-heptoxypropionamide, N, N -Diethyl-β-octoxypropionamide and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the organic solvent is preferably 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, with respect to the total amount of ink, from the viewpoints of ink drying properties and ejection reliability. .

  The content of the compound represented by the general formula (1) is preferably 5% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 25% by mass or less with respect to the total amount of the ink. When the content is 5% by mass or more, the drying property of the ink can be improved, and when it is 30% by mass or less, the storage stability can be improved.

<Water>
There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, ultrapure water, etc. are mentioned. . These may be used individually by 1 type and may use 2 or more types together.

  The content of the water is preferably 15% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 40% by mass or less with respect to the total amount of the ink. When the content is 15% by mass or more, high viscosity can be prevented and ejection stability can be improved. When the content is 60% by mass or less, wettability to a non-permeable recording medium is preferable. Image quality can be improved.

<Other ingredients>
Examples of the other components include coloring materials, surfactants other than polysiloxane surfactants, antiseptic / antifungal agents, rust inhibitors, pH adjusters, rubbers such as hindered phenols and hindered phenol amines, and plastics. Examples include colorless anti-aging agents.

<Color material>
There is no restriction | limiting in particular as said coloring material, According to the objective, it can select suitably, A pigment, dye, etc. are mentioned. Among these, a pigment is preferable.
Examples of the pigment include inorganic pigments and organic pigments.

  As the inorganic pigment, for example, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, it is manufactured by a known method such as a contact method, a furnace method, or a thermal method. And carbon black. These may be used individually by 1 type and may use 2 or more types together.

Examples of the organic pigment include azo pigments (for example, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments). , Quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acidic dye chelates), nitro pigments, nitroso pigments, aniline black, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
In addition, use of hollow resin particles and inorganic hollow particles is also possible.
Of these pigments, those having good affinity with the solvent are preferably used.

  As the pigment, for black, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11) And metals such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1). These may be used individually by 1 type and may use 2 or more types together.

  For color, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155; I. Pigment orange 5, 13, 16, 17, 36, 43, 51; C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219; I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63; I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; I. Acid Red 52, 80, 82, 249, 254, 289; I. Acid Blue 9, 45, 249; C.I. I. Acid Black 1, 2, 24, 94; C.I. I. Food black 1, 2; I. Direct yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173; I. Direct Red 1, 4, 9, 80, 81, 225, 227; I. Direct blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202; I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195; I. Reactive red 14, 32, 55, 79, 249; I. Reactive black 3, 4, 35 etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

In order to obtain an ink by dispersing a pigment, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing, a dispersing agent is used. Method, etc.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of making it dispersible in water by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon) Is mentioned.
As a method for coating the surface of the pigment with a resin and dispersing it, a method in which the pigment is included in microcapsules and dispersible in water can be mentioned. This can be paraphrased as a resin-coated pigment. In this case, it is not necessary that all pigments blended in the ink are coated with a resin, and within a range where the effects of the present invention are not impaired, uncoated pigments and partially coated pigments are dispersed in the ink. It may be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular type dispersant or high-molecular type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and naphthalenesulfonic acid Na formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

<Pigment dispersion>
An ink can be obtained by mixing a material such as water or an organic solvent with a pigment. Further, it is also possible to produce an ink by mixing a pigment, other water, a dispersant, and the like into a pigment dispersion and mixing a material such as water or an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. For dispersion, a disperser is preferably used.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of maximum number because the pigment dispersion stability is good and the image quality such as ejection stability and image density is also high. 500 nm or less is preferable and 20 nm or more and 150 nm or less are more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1% by mass. % To 50% by mass is preferable, and 0.1% to 30% by mass is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

The number average particle diameter of the pigment is not particularly limited and may be appropriately selected depending on the intended purpose, but the maximum frequency is preferably 20 nm or more and 150 nm or less in terms of the maximum number. When the number average particle size is 20 nm or more, dispersion operation and classification operation are facilitated, and when it is 150 nm or less, not only pigment dispersion stability as ink is improved, but also ejection stability is excellent. Image quality such as image density is also high, which is preferable.
The number average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  The content of the color material is preferably 0.1% by mass or more and 15% by mass or less, and preferably 1% by mass or more and 10% by mass or less based on the total amount of ink from the viewpoint of image density, fixability, and ejection stability. Is more preferable. When the content is from 0.1% by mass to 15% by mass, the ejection reliability is high and an image with high saturation can be obtained.

  The content of the pigment is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 10% by mass or less based on the total amount of the ink. Particularly preferred. When the content is 0.1% by mass or more and 15% by mass or less, image density, fixability, and ejection stability can be improved.

<Surfactants other than polysiloxane surfactants>
The ink of the present invention may be used in combination with a surfactant other than the polysiloxane surfactant from the viewpoint of ensuring wettability to the recording medium.

The surfactant other than the polysiloxane surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include amphoteric surfactants, nonionic surfactants and anionic surfactants. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, nonionic surfactants are preferable from the viewpoints of dispersion stability and image quality.
Depending on the composition, a fluorine-based surfactant or a silicone-based surfactant can be used in combination or singly.

  Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene. Examples include sorbitan fatty acid esters and ethylene oxide adducts of acetylene alcohol. These may be used individually by 1 type and may use 2 or more types together.

  The content of the surfactant other than the polysiloxane surfactant is preferably 0.1% by mass or more and 5% by mass or less. When the content is 0.1% by mass or more, wettability to a non-permeable recording medium can be secured, so that the image quality can be improved, and when it is 5% by mass or less, the ink is less likely to foam. Excellent discharge stability can be obtained.

<Antifoaming agent>
There is no restriction | limiting in particular as an antifoamer, For example, a silicone type antifoamer, a polyether type | system | group antifoamer, a fatty-acid ester type | system | group antifoamer etc. are mentioned. These may be used alone or in combination of two or more. Among these, a silicone type antifoaming agent is preferable from the viewpoint of excellent foam breaking effect.

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

<Rust preventive>
There is no restriction | limiting in particular as a rust preventive agent, For example, acidic sulfite, sodium thiosulfate, etc. are mentioned.

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

[Ink production method]
As the method for producing the ink, for example, the water, the organic solvent, the polysiloxane surfactant, the acrylic-silicone resin particles, and, if necessary, the other components are produced by stirring and mixing. be able to. As the stirring and mixing, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using a normal stirrer blade, a magnetic stirrer, a high-speed disperser, or the like can be used.

There is no restriction | limiting in particular as a physical property of an ink, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, pH, etc. are the following ranges.
The viscosity at 25 ° C. of the ink is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less from the viewpoint of improving the printing density and character quality and obtaining good discharge properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. Measurement conditions are 25 ° C., standard cone rotor (1 ° 34 ′ × R24), sample liquid amount 1.2 mL, rotation speed 50 rpm, and measurement is possible for 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less and more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is suitably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12 and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

  The ink of the present invention can be suitably used for inkjet recording.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used. Good image formation is possible even with a non-permeable substrate.
The non-permeable base material is a base material having a surface with low water permeability and absorbability, and includes materials that do not open to the outside even if there are many cavities inside, more quantitatively. In the Bristow method, the water absorption amount from the start of contact to 30 msec ^1/2 is 10 mL / m ² or less.
As said non-permeable base material, plastic films, such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, a polypropylene, polyethylene, a polycarbonate film, can be used conveniently, for example.

In addition, even when the recording medium is colored (colored recording medium) by applying a white ink before the color ink during color recording, the color of the recording medium can be made white. The color development can be improved.
Representative examples of the colored recording medium include colored paper, the film, fabrics, clothes, ceramics, and the like.

<Ink container>
The ink container contains the ink of the present invention in a container.
The ink storage container is configured to store the ink in a container and further include other members appropriately selected as necessary.

  The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, an ink bag formed of an aluminum laminate film, a resin film, etc. What has at least etc. is mentioned.

<Recording apparatus and recording method>
The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, such as a printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier complex machine, and a three-dimensional modeling apparatus.
In the present invention, the recording apparatus and the recording method are an apparatus capable of ejecting ink, various treatment liquids, and the like to a recording medium, and a method of performing recording using the apparatus. The recording medium means a medium on which ink or various processing liquids can be temporarily attached.
The recording apparatus can include not only a head portion that ejects ink but also means for feeding, transporting, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, a means for heating and drying the printing surface and the back surface of the recording medium. Although it does not specifically limit as a heating means and a drying means, For example, a warm air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording apparatus and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, what forms patterns, such as a geometric pattern, etc. includes what forms a three-dimensional image.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise specified.
Furthermore, this recording apparatus can use not only a desktop type but also a wide recording apparatus that can print on an A0 size recording medium, for example, a continuous paper wound up in a roll shape as a recording medium. Also included are continuous paper printers.
An example of the recording apparatus will be described with reference to FIGS. FIG. 1 is a perspective view of the apparatus. FIG. 2 is an explanatory perspective view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial type image forming apparatus. A mechanism unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), yellow (Y) is packaged, for example, an aluminum laminate film It is formed by a member. The ink storage unit 411 is stored in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404. Thus, the ink discharge ports 413 of the main tank 410 and the discharge heads 434 for the respective colors communicate with each other via the supply tubes 436 for the respective colors, and ink can be discharged from the discharge heads 434 to the recording medium.

The ink jet printing method of the present invention includes an ink discharge step, preferably includes a heating step, and further includes other steps as necessary.
The inkjet printing apparatus preferably includes an ink discharge unit, a heating unit, and an ink storage unit that stores ink, and further includes other units as necessary.
The ink jet printing method of the present invention can be preferably carried out by the ink jet printing apparatus, and the ink ejection step can be suitably carried out by the ink ejection means. The heating step can be suitably performed by the heating means. Moreover, the said other process can be suitably performed by the said other means.
In addition, it is preferable to include a printing process in which either thermal energy or mechanical energy is applied to the ink to discharge the ink for printing.

<< Ink Ejecting Step and Ink Ejecting Means >>
The ink ejection step is a step of applying a stimulus to the ink of the present invention and ejecting the ink to print on a recording medium.
The ink ejecting means ejects ink having pressure generating means for applying a stimulus to the ink and applying pressure.
There is no restriction | limiting in particular as said ink discharge means, For example, an discharge head etc. are mentioned.
Examples of the ejection head include an ink ejection head (inkjet head).

  As the ink jet head, a piezoelectric element is used as a pressure generating means for pressurizing ink in the ink flow path, and a diaphragm that forms the wall surface of the ink flow path is deformed to change the volume in the ink flow path to eject ink droplets. A so-called piezo type (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-59911). The volume of the ink flow path is changed by disposing the diaphragm and the electrode that form the wall surface of the ink flow path to face each other and deforming the vibration plate by an electrostatic force generated between the vibration plate and the electrode. In this case, an electrostatic type (see Japanese Patent Laid-Open No. Hei 6-71882) that discharges ink droplets is included.

  The stimulus can be generated by, for example, the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose. For example, heat (temperature), pressure, vibration, light Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  The ink ejection mode is not particularly limited and varies depending on the type of the stimulus. For example, when the stimulus is “heat”, the ink corresponding to the recording signal is applied to the ink in the recording head. A method of applying energy using, for example, a thermal head, generating bubbles in the ink by the thermal energy, and ejecting and ejecting the ink as droplets from the nozzle holes of the recording head by the pressure of the bubbles Is mentioned. When the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element is bent, and the pressure chamber For example, a method in which the volume is reduced and the ink is ejected and ejected as droplets from the nozzle holes of the recording head.

  The size of the ink droplets to be ejected is preferably 3 pL or more and 40 pL or less, for example, and the ejection jet speed is preferably 5 m / s or more and 20 m / s or less, and the drive frequency is 1 kHz or more is preferable, and the resolution is preferably 300 dpi or more.

  A plurality of nozzles for discharging the ink; individual liquid chambers communicating with the nozzles; a common liquid chamber for supplying liquid to the individual liquid chambers; and for causing ink to flow into the individual liquid chambers. An inflow channel, a circulation channel leading to the individual liquid chamber, a circulation common liquid chamber leading to the circulation channel, an outflow channel for allowing ink to flow out of the individual liquid chamber, and the individual liquid chambers It is preferable to include pressure generating means for applying pressure to the liquid. Further, it is preferable that a circulation unit that circulates the ink from the inflow channel toward the outflow channel is further provided, and the circulation process is operated during non-printing.

  By using the printing head as described above, the ink in the nozzle portion can be circulated, the stay of the deteriorated ink in the head can be suppressed, and the ejection stability can be improved. In addition, the ink circulation as described above causes phase separation of the surfactant in the ink by stirring the ink even in the case of the aqueous ink to which the surfactant having a low HLB value that easily causes phase separation with water is added. Can be suppressed.

Hereinafter, an example of an ink discharge head used in the ink jet printing method of the present invention will be described.
Embodiments of the present invention will be described below with reference to the accompanying drawings. An example of a liquid discharge head according to an embodiment of the present invention will be described with reference to FIGS. 4 is an external perspective view illustrating an example of the liquid discharge head, FIG. 5 is a cross-sectional explanatory view in a direction orthogonal to the nozzle arrangement direction of the liquid discharge head illustrated in FIG. 4, and FIG. 6 is a cross-sectional view taken along line AA ′ of FIG. 7 is a cross-sectional view taken along line BB ′ of FIG. 5, FIG. 8 is a cross-sectional explanatory view in a direction parallel to the nozzle arrangement direction of the liquid discharge head shown in FIG. 4, and FIG. 9 is a nozzle plate of the liquid discharge head shown in FIG. FIG. 10 is an explanatory plan view of each member constituting the flow path member of the liquid discharge head shown in FIG. 4, and FIG. 11 is an illustration of each member constituting the common liquid chamber member of the liquid discharge head shown in FIG. It is a plane explanatory view.
The ink discharge head preferably has an inflow channel for allowing ink to flow into the individual liquid chamber and an outflow channel for allowing ink to flow out of the individual liquid chamber.

In this liquid discharge head, a nozzle plate 1, a flow path plate 2, and a vibration plate member 3 as a wall surface member are laminated and joined. A piezoelectric actuator 11 that displaces the diaphragm member 3, a common liquid chamber member 20, and a cover 29 are provided.
The nozzle plate 1 has a plurality of nozzles 4 that discharge liquid.
The flow path plate 2 forms an individual liquid chamber 6 that communicates with the nozzle 4, a fluid resistance portion 7 that communicates with the individual liquid chamber 6, and a liquid introduction portion 8 that communicates with the fluid resistance portion 7. The flow path plate 2 is formed by laminating and joining a plurality of plate-like members 41 to 45 from the nozzle plate 1 side, and laminating and joining these plate-like members 41 to 45 and the vibration plate member 3. A member 40 is configured.

The diaphragm member 3 has a filter portion 9 as an opening through the liquid introduction portion 8 and the common liquid chamber 10 formed by the common liquid chamber member 20.
The diaphragm member 3 is a wall surface member that forms the wall surface of the individual liquid chamber 6 of the flow path plate 2. The diaphragm member 3 has a two-layer structure (not limited), and is formed of a first layer that forms a thin portion and a second layer that forms a thick portion from the flow path plate 2 side. A deformable vibration region 30 is formed in a portion corresponding to the chamber 6.

Here, a plurality of nozzles 4 are arranged in a staggered manner on the nozzle plate 1 as shown in FIG.
As shown in FIG. 10A, the plate-like member 41 constituting the flow path plate 2 includes a through groove portion (meaning a groove-shaped through hole) 6a constituting the individual liquid chamber 6, a fluid resistance portion 51, Through groove portions 51 a and 52 a constituting the circulation flow path 52 are formed.
Similarly, as shown in FIG. 10B, the plate-like member 42 is formed with a through groove portion 6 b that constitutes the individual liquid chamber 6 and a through groove portion 52 b that constitutes the circulation channel 52.
Similarly, as shown in FIG. 10C, the plate-like member 43 is formed with a through groove portion 6 c constituting the individual liquid chamber 6 and a through groove portion 53 a having the nozzle arrangement direction constituting the circulation channel 53 as the longitudinal direction. Has been.
Similarly, as shown in FIG. 10 (d), the plate-like member 44 includes a through groove portion 6 d constituting the individual liquid chamber 6, a through groove portion 7 a constituting the fluid resistance portion 7, and a through groove portion 8 a constituting the liquid introduction portion 8. And the through-groove part 53b which makes the nozzle arrangement direction which comprises the circulation flow path 53 a longitudinal direction is formed.
Similarly, as shown in FIG. 10 (e), the plate-like member 45 includes a through groove portion 6 e constituting the individual liquid chamber 6 and a through groove portion 8 b (filter) having the nozzle arrangement direction constituting the liquid introduction portion 8 as the longitudinal direction. And a through-groove portion 53c having a nozzle arrangement direction constituting the circulation flow path 53 as a longitudinal direction.

As shown in FIG. 10 (f), the diaphragm member 3 is formed with a vibration region 30, a filter portion 9, and a through groove portion 53 d whose longitudinal direction is the nozzle arrangement direction constituting the circulation flow channel 53. .
Thus, a complicated flow path can be formed with a simple configuration by configuring the flow path member by laminating and joining a plurality of plate-like members.

With the above configuration, the flow path member 40 including the flow path plate 2 and the vibration plate member 3 includes the fluid resistance portion 51, the circulation flow path 52, and the circulation along the surface direction of the flow path plate 2 leading to each individual liquid chamber 6. A circulation channel 53 in the thickness direction of the channel member 40 that communicates with the channel 52 is formed. The circulation channel 53 communicates with a circulation common liquid chamber 50 described later.
On the other hand, the common liquid chamber member 20 is formed with a common liquid chamber 10 to which liquid is supplied from a supply / circulation mechanism 494 and a circulation common liquid chamber 50.

As shown in FIG. 11A, the first common liquid chamber member 21 constituting the common liquid chamber member 20 includes a piezoelectric actuator through hole 25a, a through groove portion 10a serving as a downstream common liquid chamber 10A, and a circulation. A groove portion 50 a having a bottom that becomes the common liquid chamber 50 is formed.
Similarly, as shown in FIG. 11B, the second common liquid chamber member 22 is formed with a piezoelectric actuator through hole 25b and a groove portion 10b that becomes the upstream common liquid chamber 10B.
Referring also to FIG. 4, the second common liquid chamber member 22 has a through hole 71 a serving as a supply port portion through one end portion of the common liquid chamber 10 in the nozzle arrangement direction and the supply port 71.
Similarly, the first common liquid chamber member 21 and the second common liquid chamber member 22 are provided with the other end of the circulation common liquid chamber 50 in the nozzle arrangement direction (the end opposite to the through hole 71a) and the circulation port 81. Through holes 81a and 81b are formed.
In addition, in FIG. 11, the groove part with the bottom is shown with surface coating (the same applies to the following drawings).

As described above, the common liquid chamber member 20 is constituted by the first common liquid chamber member 21 and the second common liquid chamber member 22, and the first common liquid chamber member 21 is joined to the diaphragm member 3 side of the flow path member 40. Then, the second common liquid chamber member 22 is laminated and joined to the first common liquid chamber member 21.
Here, the first common liquid chamber member 21 forms a downstream common liquid chamber 10 </ b> A that is a part of the common liquid chamber 10 that communicates with the liquid introduction unit 8, and a circulation common liquid chamber 50 that communicates with the circulation channel 53. ing. The second common liquid chamber member 22 forms an upstream common liquid chamber 10 </ b> B that is the remaining part of the common liquid chamber 10.

At this time, the downstream common liquid chamber 10A, which is a part of the common liquid chamber 10, and the circulating common liquid chamber 50 are arranged side by side in a direction orthogonal to the nozzle arrangement direction, and the circulating common liquid chamber 50 is arranged in the common liquid chamber 10. It is arranged at the position projected inside.
Thereby, the dimension of the circulation common liquid chamber 50 is not restricted by the dimension required for the flow path including the individual liquid chamber 6, the fluid resistance portion 7 and the liquid introduction portion 8 formed by the flow path member 40.

  The circulation common liquid chamber 50 and a part of the common liquid chamber 10 are arranged side by side, and the circulation common liquid chamber 50 is arranged at a position projected into the common liquid chamber 10, thereby orthogonal to the nozzle arrangement direction. The width of the head in the direction can be suppressed, and the enlargement of the head can be suppressed. The common liquid chamber member 20 forms a common liquid chamber 10 and a circulation common liquid chamber 50 to which liquid is supplied from a head tank or a liquid cartridge.

  On the other hand, a piezoelectric actuator 11 including an electromechanical conversion element as a driving unit that deforms the vibration region 30 of the diaphragm member 3 is disposed on the opposite side of the diaphragm member 3 from the individual liquid chamber 6.

  As shown in FIG. 8, the piezoelectric actuator 11 has a piezoelectric member 12 bonded on a base member 13, and the piezoelectric member 12 is grooved by half-cut dicing so that a required number of piezoelectric members 12 is provided. The columnar piezoelectric elements 12A and 12B are formed in a comb shape at a predetermined interval.

Here, the piezoelectric element 12A of the piezoelectric member 12 is a piezoelectric element that is driven by giving a drive waveform, and the piezoelectric element 12B is used as a mere support without giving a drive waveform. However, all the piezoelectric elements 12A and 12B are driven. It can also be used as a piezoelectric element.
The piezoelectric element 12 </ b> A is joined to a convex portion 30 a that is an island-shaped thick portion formed in the vibration region 30 of the diaphragm member 3. Further, the piezoelectric element 12 </ b> B is joined to the convex portion 30 b which is a thick portion of the diaphragm member 3.

  The piezoelectric member 12 is formed by alternately laminating piezoelectric layers and internal electrodes. The internal electrodes are drawn out to end faces, external electrodes are provided, and the flexible wiring member 15 is connected to the external electrodes.

  In the liquid discharge head configured as described above, for example, by lowering the voltage applied to the piezoelectric element 12A from the reference potential, the piezoelectric element 12A contracts, the vibration region 30 of the diaphragm member 3 descends, and the volume of the individual liquid chamber 6 decreases. As the liquid expands, the liquid flows into the individual liquid chamber 6.

Thereafter, the voltage applied to the piezoelectric element 12A is increased to extend the piezoelectric element 12A in the stacking direction, and the vibration region 30 of the diaphragm member 3 is deformed in the direction toward the nozzle 4 to contract the volume of the individual liquid chamber 6. As a result, the liquid in the individual liquid chamber 6 is pressurized, and the liquid is discharged from the nozzle 4.
Then, by returning the voltage applied to the piezoelectric element 12A to the reference potential, the vibration region 30 of the diaphragm member 3 is restored to the initial position, and the individual liquid chamber 6 expands to generate a negative pressure. The liquid is filled into the individual liquid chamber 6 from the chamber 10. Therefore, after the vibration of the meniscus surface of the nozzle 4 is attenuated and stabilized, the operation for the next discharge is started.

  Note that the driving method of the head is not limited to the above example (pulling-pushing), and it is also possible to perform striking or pushing depending on the direction to which the driving waveform is given. In the above-described embodiment, the laminated piezoelectric element is described as the pressure generating means for applying the pressure fluctuation to the individual liquid chamber 6, but the present invention is not limited to this, and a thin film piezoelectric element can also be used. . Furthermore, a heating resistor can be provided in the individual liquid chamber 6 to generate a bubble by generating heat by generating heat from the heating resistor, or to generate a pressure variation using electrostatic force. .

  Next, an example of a liquid circulation system using the liquid discharge head according to the present embodiment will be described with reference to FIG.

FIG. 12 is a block diagram showing a liquid circulation system according to this embodiment.
As shown in FIG. 12, the liquid circulation system includes a main tank, a liquid discharge head, a supply tank, a circulation tank, a compressor, a vacuum pump, a liquid feed pump, a regulator (R), a supply side pressure sensor, a circulation side pressure sensor, and the like. It is configured. The supply side pressure sensor is connected between the supply tank and the liquid discharge head and on the supply flow path side connected to the supply port 71 (see FIG. 4) of the liquid discharge head. The circulation side pressure sensor is connected between the liquid discharge head and the circulation tank and on the circulation flow path side connected to the circulation port 81 (see FIG. 4) of the liquid discharge head.

  One of the circulation tanks is connected to the supply tank via a first liquid feed pump, and the other of the circulation tanks is connected to the main tank via a second liquid feed pump. As a result, the liquid flows from the supply tank through the supply port 71 into the liquid discharge head, is discharged from the circulation port, is discharged to the circulation tank, and is further sent from the circulation tank to the supply tank by the first liquid feed pump. The liquid circulates by being carried out.

  In addition, a compressor is connected to the supply tank, and the supply side pressure sensor is controlled to detect a predetermined positive pressure. On the other hand, a vacuum pump is connected to the circulation tank, and control is performed so that a predetermined negative pressure is detected by the circulation side pressure sensor. Thereby, the negative pressure of the meniscus can be kept constant while circulating the liquid through the liquid ejection head.

  In addition, when the liquid droplets are ejected from the nozzles of the liquid ejection head, the amount of liquid in the supply tank and the circulation tank decreases, so the liquid is appropriately transferred from the main tank to the circulation tank using the second liquid feed pump. It is desirable to replenish. The timing of liquid replenishment from the main tank to the circulation tank depends on the detection result of the liquid level sensor etc. provided in the circulation tank, such as liquid replenishment when the ink level in the circulation tank falls below a predetermined level. Can be controlled.

  Next, liquid circulation in the liquid discharge head will be described. As shown in FIG. 4, a supply port 71 communicating with the common liquid chamber and a circulation port 81 communicating with the circulation common liquid chamber 50 are formed at the end of the common liquid chamber member 20. The supply port 71 and the circulation port 81 are connected to a supply tank / circulation tank (see FIG. 12) for storing liquid via tubes. Then, the liquid stored in the supply tank is supplied to the individual liquid chamber 6 via the supply port 71, the common liquid chamber 10, the liquid introduction portion 8, and the fluid resistance portion 7.

Furthermore, while the liquid in the individual liquid chamber 6 is discharged from the nozzle 4 by driving the piezoelectric element 12, part or all of the liquid remaining in the individual liquid chamber 6 without being discharged is circulated in the fluid resistance portion 51. It is circulated to the circulation tank through the flow paths 52 and 53, the circulation common liquid chamber 50, and the circulation port 81.
The circulation of the liquid can be performed not only when the liquid discharge head is operating but also when the operation is stopped. Circulation during operation stop is preferable because the liquid in the individual liquid chamber is always refreshed and aggregation and sedimentation of components contained in the liquid can be suppressed.

  Further, an example of a recording apparatus using the ejection head will be described.

Next, an example of an apparatus for ejecting liquid according to the present invention will be described with reference to FIGS. FIG. 13 is an explanatory plan view of a main part showing an example of a device for discharging a liquid, and FIG. 14 is an explanatory side view of a main part of an example of an apparatus for discharging a liquid.
This apparatus is a serial type apparatus, and the carriage 403 reciprocates in the main scanning direction by the main scanning moving mechanism 493. The main scanning movement mechanism 493 includes a guide member 401, a main scanning motor 405, a timing belt 408, a driving pulley 406, a driven pulley 407, and the like. The guide member 401 spans the left and right side plates 491A and 491B and holds the carriage 403 so as to be movable. The carriage 403 is reciprocated in the main scanning direction by the main scanning motor 405 via the timing belt 408 spanned between the driving pulley 406 and the driven pulley 407.

  The carriage 403 is equipped with a liquid discharge unit 440 on which the liquid discharge head 404 according to the present invention is mounted. The liquid discharge head 404 of the liquid discharge unit 440 discharges, for example, yellow (Y), cyan (C), magenta (M), and black (K) liquids. The liquid ejection head 404 is mounted with a nozzle row composed of a plurality of nozzles arranged in the sub-scanning direction orthogonal to the main scanning direction, and the ejection direction facing downward.

  The liquid is supplied and circulated in the liquid discharge head 404 by a supply / circulation mechanism 494 for supplying the liquid stored outside the liquid discharge head 404 to the liquid discharge head 404. In this example, the supply / circulation mechanism 494 includes a supply tank, a circulation tank, a compressor, a vacuum pump, a liquid feed pump, a regulator (R), and the like. The supply-side pressure sensor is connected between the supply tank and the liquid discharge head and on the supply flow path side connected to the supply pipe port 71 of the liquid discharge head. The circulation side pressure sensor is connected between the liquid discharge head and the circulation tank and on the circulation flow path side connected to the circulation port 81 of the liquid discharge head.

This apparatus includes a transport mechanism 495 for transporting the paper 410. The transport mechanism 495 includes a transport belt 412 serving as transport means, and a sub-scanning motor 416 for driving the transport belt 412.
The conveyance belt 412 adsorbs the paper 410 and conveys it at a position facing the liquid ejection head 404. The transport belt 412 is an endless belt and is stretched between the transport roller 413 and the tension roller 414. The adsorption can be performed by electrostatic adsorption or air suction.

  The transport belt 412 rotates in the sub-scanning direction when the transport roller 413 is rotationally driven by the sub-scanning motor 416 via the timing belt 417 and the timing pulley 418.

Further, on one side of the carriage 403 in the main scanning direction, a maintenance / recovery mechanism 420 that performs maintenance / recovery of the liquid ejection head 404 is disposed on the side of the transport belt 412.
The maintenance / recovery mechanism 420 includes, for example, a cap member 421 for capping the nozzle surface (surface on which the nozzle is formed) of the liquid ejection head 404, a wiper member 422 for wiping the nozzle surface, and the like.

The main scanning movement mechanism 493, the supply / circulation mechanism 494, the maintenance / recovery mechanism 420, and the transport mechanism 495 are attached to a housing including the side plates 491A and 491B and the back plate 491C.
In this apparatus configured as described above, the paper 410 is fed and sucked onto the transport belt 412, and the paper 410 is transported in the sub-scanning direction by the circular movement of the transport belt 412.
Therefore, the liquid ejection head 404 is driven in accordance with the image signal while moving the carriage 403 in the main scanning direction, thereby ejecting liquid onto the stopped paper 410 to form an image.

Thus, since this apparatus includes the liquid discharge head used in the present invention, a high-quality image can be stably formed.
Next, another example of the liquid discharge unit used in the present invention will be described with reference to FIG. FIG. 15 is an explanatory plan view of a main part showing another example of the liquid discharge unit.

The liquid discharge unit includes a casing portion composed of side plates 491A and 491B and a back plate 491C, a main scanning moving mechanism 493, a carriage 403, and a liquid discharge head 404 among members constituting the liquid discharge device. It consists of
Note that a liquid discharge unit in which at least one of the above-described maintenance / recovery mechanism 420 and supply / circulation mechanism 494 is further attached to, for example, the side plate 491B of the liquid discharge unit may be configured.

  In the present application, the “liquid ejection head” is a functional component that ejects and ejects liquid from a nozzle.

As energy generation sources for discharging liquid, piezoelectric actuators (laminated piezoelectric elements and thin film piezoelectric elements), thermal actuators using electrothermal transducers such as heating resistors, electrostatic actuators consisting of a diaphragm and counter electrode are used. To be included.
A “liquid ejection unit” is a unit in which functional parts and mechanisms are integrated with a liquid ejection head, and is an assembly of parts related to liquid ejection. For example, the “liquid discharge unit” includes a combination of at least one of a supply / circulation mechanism, a carriage, a maintenance / recovery mechanism, and a main scanning movement mechanism with a liquid discharge head.

Here, the term “integrated” refers to, for example, a liquid discharge head, a functional component, and a mechanism that are fixed to each other by fastening, adhesion, engagement, etc., and one that is held movably with respect to the other. Including. Further, the liquid discharge head, the functional component, and the mechanism may be configured to be detachable from each other.
For example, there is a liquid discharge unit in which a liquid discharge head and a supply / circulation mechanism are integrated. Also, there are some in which a liquid discharge head and a supply / circulation mechanism are integrated by being connected to each other by a tube or the like. Here, a unit including a filter may be added between the supply / circulation mechanism of these liquid discharge units and the liquid discharge head.
In addition, there is a liquid discharge unit in which a liquid discharge head and a carriage are integrated.

  In addition, there is a liquid discharge unit in which the liquid discharge head and the scanning movement mechanism are integrated by holding the liquid discharge head movably on a guide member that constitutes a part of the scanning movement mechanism.

  Also, there is a liquid discharge unit in which a cap member that is a part of the maintenance / recovery mechanism is fixed to a carriage to which the liquid discharge head is attached, and the liquid discharge head, the carriage, and the maintenance / recovery mechanism are integrated. .

Some liquid discharge units have a liquid discharge head and a supply mechanism integrated by connecting a tube to a liquid discharge head to which a supply / circulation mechanism or a flow path component is attached. The liquid from the liquid storage source is supplied to the liquid discharge head via this tube.
The main scanning movement mechanism includes a guide member alone. The supply mechanism includes a single tube and a single loading unit.

  In the present invention, the “apparatus for ejecting liquid” is an apparatus that includes a liquid ejection head or a liquid ejection unit and that drives the liquid ejection head to eject liquid. The apparatus for ejecting liquid includes not only an apparatus capable of ejecting liquid to an object to which liquid can adhere, but also an apparatus for ejecting liquid toward the air or liquid.

This “apparatus for discharging liquid” may include means for feeding, transporting, and discharging a liquid to which liquid can adhere, as well as a pre-processing apparatus and a post-processing apparatus.

Further, the “apparatus for ejecting liquid” is not limited to an apparatus in which significant images such as characters and figures are visualized by the ejected liquid. For example, what forms a pattern etc. which does not have a meaning in itself, and what forms a three-dimensional image are also included.
The above-mentioned “applicable liquid” means that the liquid can be attached at least temporarily and adheres and adheres, or adheres and penetrates. Specific examples include recording media such as paper, recording paper, recording paper, film, and cloth, electronic parts such as electronic substrates and piezoelectric elements, powder layers (powder layers), organ models, and test cells. Yes, unless specifically limited, includes everything that the liquid adheres to.

  The material of the above-mentioned “material to which liquid can adhere” is not limited as long as liquid such as paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics can be adhered even temporarily.

  In addition, the “device for ejecting liquid” includes a device in which the liquid ejection head and the device to which the liquid can adhere move relatively, but is not limited thereto. Specific examples include a serial type apparatus that moves the liquid discharge head, a line type apparatus that does not move the liquid discharge head, and the like.

In the present invention, a “liquid ejection head” is a functional component that ejects and ejects liquid from a nozzle.
The liquid to be ejected is not particularly limited as long as it has a viscosity and surface tension that can be ejected from the head. However, the liquid has a viscosity of 30 mPa · s or less at room temperature, normal pressure, or by heating and cooling. It is preferable. More specifically, solvents such as water and organic solvents, colorants such as dyes and pigments, functional materials such as polymerizable compounds, resins, and surfactants, and biocompatible materials such as DNA, amino acids, proteins, and calcium. , Edible materials such as natural pigments, solutions, suspensions, emulsions, and the like. These include, for example, inkjet inks, surface treatment liquids, components of electronic elements and light emitting elements, and electronic circuit resist patterns. It can be used in applications such as forming liquids and three-dimensional modeling material liquids.

  In addition, the terms “image formation”, “recording”, “printing”, “printing”, “printing”, “modeling” and the like in the terms of the present application are all synonymous.

<< Heating step and heating means >>
The heating step is a step of heating a recording medium on which an image is recorded, and can be performed by a heating unit.
As the ink jet printing method, high image quality recording can be performed on a non-permeable recording medium as the recording medium, but the image quality is higher, the scratch resistance, and the formation of an image with high adhesion to the recording medium, and In order to be able to cope with high-speed recording conditions, it is preferable to heat the non-permeable recording medium after recording. When a heating step is included after recording, film formation of the resin particles contained in the ink is promoted, so that the image hardness of the printed matter can be improved.

  The heating temperature is preferably high in terms of drying property and film forming temperature, more preferably 40 ° C. or more and 100 ° C. or less, and particularly preferably 50 ° C. or more and 90 ° C. or less. When the heating temperature is 40 ° C. or higher and 120 ° C. or lower, damage to the impermeable recording medium due to heat can be prevented, and occurrence of non-ejection due to warming of the ink head can be suppressed.

FIG. 3 is a schematic view showing an example of the heating means of the apparatus of FIG. As shown in FIG. 3, the recording head is driven in accordance with the image signal while moving the carriage 133, thereby ejecting ink droplets onto the stopped recording medium 142 to record an image. On the image formed on the recording medium 142 conveyed on the conveying belt 151 that is stretched between the conveying roller 157 and the tension roller 158 and on the guide member 153 that even lowers the recording medium, Drying is performed by blowing hot air 202 by a heating fan 201 as a generating unit.
A heater group 203 is provided on the opposite side of the conveyance belt 151 from the recording medium 142, and the recording medium 142 on which an image is formed can be heated.

<Other processes and other means>
Examples of the other steps include a stimulus generation step and a control step.
Examples of the other means include stimulus generation means and control means.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor. Examples include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal conversion element such as a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  An example of the inkjet printing method of the present invention includes a step of applying a clear ink containing no pigment or an ink containing a white pigment as a color material (white ink) to a recording medium, and a color color material The recording method may also include a recording step of recording using ink. At this time, the clear ink or the white ink can be applied to the entire surface of the recording medium, or may be applied to a part of the recording medium. When applying to a part of the recording medium, for example, it may be applied to the same part as the part where recording is performed, or may be applied to a part which is partly common with the part where recording is performed.

  When the white ink is used, it is also effective to use the following recording method. White ink is applied to a recording medium, and recording is performed thereon with ink of a color other than white. According to this method, for example, even when a transparent film is used, the white ink is adhered to the surface of the recording medium, so that the recording visibility can be ensured. Since the ink of the present invention has good drying properties, high gloss, scratch resistance, etc. even for non-permeable recording media, white ink is used for non-permeable recording media such as transparent films in order to improve visibility. It is possible to apply.

  Also, it is possible to obtain a similar image with excellent visibility by applying white ink after recording on a transparent film. If clear ink is used instead of white ink, it can also function as a protective layer.

The ink of the present invention is not limited to the ink jet printing method and can be widely used. Besides the inkjet printing method, for example, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method , Smoothing coating method, micro gravure coating method, reverse roll coating method, 4 to 5 roll coating method, dip coating method, curtain coating method, slide coating method, die coating method, spray coating method and the like.
As an example of the embodiment, when the white ink is applied to the entire surface of the recording medium, the coating is performed by a coating method other than the inkjet printing method, and when recording with ink of a color other than white, the recording is performed by the inkjet printing method. Embodiments are possible.
As another embodiment, recording using white ink and recording using ink of a color other than white can be performed by an inkjet printing method.
The same applies when clear ink is used instead of white ink.

(Printed matter)
The printed matter of the present invention has a recording medium and an image containing a polysiloxane surfactant and acrylic-silicone resin particles on the recording medium, and the HLB value of the polysiloxane surfactant is 8 or less. It has other members as needed.
The printed matter can be suitably obtained by an inkjet printing apparatus and an inkjet printing method.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Preparation Example 1 of Pigment Dispersion)
<Preparation of self-dispersing black pigment dispersion>
After pre-mixing the following prescription mixture, it was circulated and dispersed for 7 hours in a disk-type bead mill (Shinmaru Enterprises Co., Ltd., KDL type, media: 0.3 mm diameter zirconia ball used), self-dispersing black pigment dispersion (Pigment solid content concentration: 15% by mass) was obtained.
Carbon black pigment (trade name: Monarch 800, manufactured by Cabot Corporation) 15 parts by mass Anionic surfactant (trade name: Pionein A-51-B, manufactured by Takemoto Yushi Co., Ltd.) 2 parts by mass Ion exchange water ... 83 parts by mass

(Preparation Example 2 of Pigment Dispersion)
<Preparation of self-dispersing cyan pigment dispersion>
In Preparation Example 1 of Pigment Dispersion, the same procedure as in Preparation Example 1 of Pigment Dispersion was performed except that the carbon black pigment was changed to Pigment Blue 15: 3 (trade name: LIONOL BLUE FG-7351, manufactured by Toyo Ink Co., Ltd.). Thus, a self-dispersing cyan pigment dispersion (pigment solid content concentration: 15% by mass) was obtained.

(Preparation Example 3 of Pigment Dispersion)
<Preparation of self-dispersing magenta pigment dispersion>
In the same manner as in Pigment Dispersion Preparation Example 1, except that the carbon black pigment was changed to Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.). A dispersion type magenta pigment dispersion (pigment solid content concentration: 15% by mass) was obtained.

(Preparation Example 4 of Pigment Dispersion)
<Preparation of self-dispersing yellow pigment dispersion>
In Preparation Example 1 of Pigment Dispersion, the same procedure as in Preparation Example 1 of Pigment Dispersion was carried out except that the carbon black pigment was changed to Pigment Yellow 74 (trade name: First Yellow 531; manufactured by Daiichi Seika Kogyo Co., Ltd.). A self-dispersing yellow pigment dispersion (pigment solid content concentration: 15% by mass) was obtained.

(Preparation Example 5 of Pigment Dispersion)
<Preparation of resin dispersion type black pigment dispersion>
-Preparation of polymer solution A-
After sufficiently replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube, and dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, 12. 0 g, polyethylene glycol methacrylate 4.0 g, styrene macromer (trade name: AS-6, manufactured by Toa Gosei Co., Ltd.) 4.0 g, and mercaptoethanol 0.4 g were mixed and heated to 65 ° C. Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxylethyl methacrylate, 36.0 g of styrene macromer, 3.6 g of mercaptoethanol, azobismethyl A mixed solution of 2.4 g of valeronitrile and 18.0 g of methyl ethyl ketone was dropped into the flask over 2.5 hours. After dropping, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18.0 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added and further aging was performed for 1 hour. After completion of the reaction, 364.0 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution A having a concentration of 50% by mass.

-Preparation of resin dispersed black pigment dispersion-
After sufficiently stirring 28 g of the polymer solution A, 42 g of carbon black (trade name: FW100, manufactured by Degussa), 13.6 g of a 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of water, a roll mill was used. And kneaded. The obtained paste was put into 200 g of pure water and stirred sufficiently. Then, the ethyl ethyl ketone and water were distilled off with an evaporator, and the obtained dispersion was added to a polymer having an average pore size of 5.0 μm to remove coarse particles. Pressure-filtering with a vinylidene fluoride membrane filter (trade name: Durapore SVLP04700, manufactured by Merck & Co., Inc.) to obtain a resin-dispersed black pigment dispersion having a pigment solid content concentration of 15% by mass and a solid content concentration of 20% by mass. .

(Preparation example 1 of polyurethane resin particles)
<Preparation of polycarbonate polyurethane resin emulsion>
Polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate (number average molecular weight (Mn): 1,200) 1,500 mass) in a reaction vessel into which a stirrer, a reflux condenser, and a thermometer were inserted. Part, 2,2-dimethylolpropionic acid (hereinafter also referred to as “DMPA”) 220 parts by mass, and N-methylpyrrolidone (hereinafter also referred to as “NMP”) 1,347 parts by mass The solution was charged under an air stream and heated to 60 ° C. to dissolve DMPA.
Next, 1,445 parts by mass of 4,4′-dicyclohexylmethane diisocyanate and 2.6 parts by mass of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C., and the urethanization reaction was carried out over 5 hours. A urethane prepolymer was obtained. The reaction mixture was cooled to 80 ° C., 149 parts by mass of triethylamine was added thereto, 4,340 parts by mass was extracted from the mixture, 5,400 parts by mass of water, and 15 parts by mass of triethylamine with vigorous stirring. Into the mixed solution.
Next, 1,500 parts by mass of ice is added, and 626 parts by mass of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution is added to carry out a chain extension reaction so that the solid content concentration becomes 30% by mass. The solvent was distilled off to obtain a polycarbonate-based polyurethane resin emulsion.
About the obtained polycarbonate-type polyurethane resin emulsion, when measured with the "film-forming temperature test apparatus" (made by Imoto Seisakusho Co., Ltd.), the minimum film-forming temperature was 55 degreeC.

(Preparation example 2 of polyurethane resin particles)
<Preparation of polyether polyurethane resin emulsion>
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 100.2 parts by mass of polyether polyol (“PTMG1000”, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 1,000), 1,2 parts by mass of 2,2-dimethylolpropionic acid, 48.0 parts by mass of isophorone diisocyanate, 77.1 parts by mass of methyl ethyl ketone as an organic solvent, and dibutyltin dilaurate as a catalyst (hereinafter also referred to as “DMTDL”) The reaction was carried out using 0.06 parts by mass.
After continuing the said reaction for 4 hours, 30.7 mass parts of methyl ethyl ketone was supplied as a dilution solvent, and also reaction was continued.
When the weight average molecular weight of the reactant reaches a range of 20,000 to 60,000, 1.4 parts by mass of methanol is added to complete the reaction, thereby obtaining an organic solvent solution of urethane resin. It was.
The carboxyl group which the said urethane resin has was neutralized by adding 13.4 mass parts of 48 mass% potassium hydroxide aqueous solution to the organic solvent solution of the said urethane resin. Subsequently, after 715.3 parts by mass of water was added and sufficiently stirred, aging and solvent removal were performed to obtain a polyether polyurethane resin emulsion having a solid content concentration of 30% by mass.
For the obtained polyether-based polyurethane resin emulsion, the minimum film-forming temperature was measured in the same manner as in Preparation Example 1 for the polycarbonate-based polyurethane resin emulsion. As a result, the minimum film forming temperature was 43 ° C.

(Preparation example 3 of polyurethane resin particles)
<Preparation of polyester polyurethane resin emulsion>
In Preparation Example 2 of the polyurethane resin particles, polyether polyol (“PTMG1000”, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 1,000) was changed to polyester polyol (“Polylite OD-X-2251”, manufactured by DIC Corporation). A polyester polyurethane resin emulsion having a solid content concentration of 30% by mass was obtained in the same manner as in Preparation Example 2 of the polyurethane resin particles except that the weight average molecular weight was changed to 2,000).
With respect to the obtained polyester-based polyurethane resin emulsion, the minimum film-forming temperature was measured in the same manner as in Preparation Example 1 for the polycarbonate-based polyurethane resin emulsion. As a result, the minimum film forming temperature was 74 ° C.

(Example A1)
Self-dispersing black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-silicone resin emulsion 4 (trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): −14 ° C.) 2.0% by mass, polycarbonate polyurethane resin emulsion ( (Solid content concentration: 30% by mass) 23.3% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0% by mass, 1,2-butanediol 3.0% by mass, 2,3-butanediol 3.0% by mass, 3-methoxy-3-methylbutanol 3.0% by mass, 2-methyl-2,4-pentanediol 3.0% by mass, dip Pyrylene glycol monomethyl ether 4.0% by mass, as a preservative, trade name: Proxel LV (manufactured by Avicia) 0.1% by mass, and high-purity water are added so as to be the remaining amount, and mixed and stirred, so that the average pore size is 0 Ink A1 was prepared by filtering with a 2 μm polypropylene filter (trade name: Betafine polypropylene pleated filter PPG series, 3M).

(Examples A2 to A12 and Comparative Examples A1 to A2)
In Example A1, Examples A2 to A12 and Comparative Examples A1 to A2 were the same as Example A1, except that the compositions and contents described in Table A-1 to Table A-3 below were changed. Inks A2 to A14 were prepared.

In Table A-1 to Table A-3, the trade names of the components and the names of the manufacturing companies are as follows.
Polyoxyalkylene group-containing silicone compound 1: manufactured by Toray Dow Co., Ltd., trade name: FZ2110, HLB value: 1.0
Polyether-modified silicone 1: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-945, HLB value: 4.0
Polyether-modified silicone 2: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6017, HLB value: 4.5
Polyether-modified silicone 3: Ultra Additives Inc. Product name: FormBan MS-575, HLB value: 5.0
Polyoxyalkylene group-containing silicone compound 2: manufactured by Toray Dow Co., Ltd., trade name: FZ2166, HLB value: 5.8
-Polyether-modified silicone 4: manufactured by Toray Dow Co., Ltd., trade name: SH-3772M, HLB value: 6.0
Polyether-modified silicone 5: manufactured by Nissin Chemical Industry Co., Ltd., trade name: Silface SAG005, HLB value: 7.0
Polyether-modified silicone 6: manufactured by Toray Dow Co., Ltd., trade name: L7001, HLB value: 7.4
Polyether-modified silicone 7: manufactured by Toray Dow Co., Ltd., trade name: SH-3773M, HLB value: 8.0
Polyether modified silicone 8: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353, HLB value: 10.0
Acrylic-silicone resin emulsion 1: manufactured by Daicel FineChem, Inc., trade name: AQ914, solid content concentration: 24% by mass, Tg: 50 ° C.
Acrylic-silicone resin emulsion 2: manufactured by DIC Corporation, trade name: SA-6360, solid content concentration: 50% by mass, Tg: 21 ° C.
Acrylic-silicone resin emulsion 3: manufactured by Toagosei Co., Ltd., trade name: Saimak 480, solid content concentration: 30% by mass, Tg: 0 ° C.
Acrylic-silicone resin emulsion 4: Trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, Tg: −14 ° C.
Acrylic-silicone resin emulsion 5: Trade name: AE981A, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, Tg: −15 ° C.
Acrylic-silicone resin emulsion 6: Trade name: AE982, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, Tg: 0 ° C.
-Antiseptic: Avicia Co., Ltd., trade name: Proxel LV

  Next, “storage stability”, “fixability (beading)”, “scratch resistance”, “solvent resistance”, “image glossiness”, and “adhesion” were evaluated as follows. . The results are shown in Table A-4.

  Considering the use for outdoor use, the evaluation of “fixing (beading)” and “scratch resistance” was considerably stricter than the case of recording on general paper.

<Storage stability (appearance evaluation)>
The obtained inks A1 to A14 of Examples A1 to A12 and Comparative Examples A1 to A2 were packed in a 30 mL capacity container (trade name: Glass Vial SV-30, manufactured by Nidec Rika Glass Co., Ltd.), 50 ° C, 60 ° C, and Each was stored at 70 ° C. for 7 days, visually observed, and “storage stability” was evaluated based on the following criteria. It is desirable in practical use that the evaluation is B or more.
[Evaluation criteria]
A: Phase separation does not occur during storage at 70 ° C. B: Phase separation does not occur during storage at 60 ° C., but phase separation occurs during storage at 70 ° C. C: Phase separation does not occur during storage at 50 ° C., but storage at 60 ° C. Phase separation D: Phase separation during storage at 50 ° C

[Formation of solid image]
Next, the obtained inks A1 to A14 of Examples A1 to A12 and Comparative Examples A1 to A2 were filled into an ink jet printer (device name: IPSiO GXe5500 remodeling machine, manufactured by Ricoh Co., Ltd.), and a polyvinyl chloride film (CPPVWP1300). A solid image was recorded at an ink adhesion amount of 0.6 g / cm ² on a recording medium (manufactured by Sakurai Co., Ltd., hereinafter also referred to as “PVC film”). After recording, the solid image was dried for 1 hour on a hot plate (NINOS ND-1, manufactured by ASONE CORPORATION) set at 80 ° C.
The IPSiO GXe5500 remodeling machine has been remodeled from the IPSiO GXe5500 machine so that a record corresponding to a recording speed of 30 m ² / hr can be reproduced with a printing width of 150 cm in A4 size, and the pot plate is installed and recorded. It was modified so that later heating conditions (heating temperature, heating time) could be changed.

<Fixability (Beading)>
Recording unevenness of the solid image formed on the PVC film recording medium was visually observed, and “fixability (beading)” was evaluated based on the following evaluation criteria. It is desirable in practical use that the evaluation is B or more.
[Evaluation criteria]
A: Very good (no beading)
B: Good (slight beading was observed)
C: Normal (there was beading)
D: Defect (there was significant beading)

<Abrasion resistance>
The solid image formed on the PVC film recording medium is rubbed with a dry cotton (Kanakin No. 3) under a load of 400 g, the state of the image is visually observed, and “scratch resistance” is based on the following evaluation criteria. Was evaluated. It is desirable in practical use that the evaluation is B or more.
[Evaluation criteria]
AA: The image did not change even after rubbing 50 times or more A: Some scratches remained after rubbing 50 times but did not affect the image B: The image changed even after rubbing 31 to 49 times C: Image did not change even after rubbing 30 times or less

<Solvent resistance>
The solid image formed on the PVC film recording medium was immersed in an aqueous 60% by mass ethanol solution at room temperature (25 ° C.) for 24 hours, and then naturally dried at room temperature (25 ° C.) for 24 hours, and then X-Rite 938 (X -Made by Rite), the image density was measured, the amount of decrease in the image density value in the image density after immersion with respect to the initial density of the image before immersion was calculated, and based on the following evaluation criteria, "Sex" was evaluated. It is desirable in practical use that the evaluation is B or more.
〔Evaluation criteria〕
A: A decrease in image density value is less than 10% A: A decrease in image density value is 10% or more and less than 20% B: A decrease in image density value is 20% or more and less than 30% C: A decrease in image density value is 30% or more

<Image glossiness>
The 60 ° glossiness of the solid image formed on the PVC film recording medium was measured four times with a gloss meter (manufactured by BYK Gardener, 4501), and the average gloss value was determined. Based on the following evaluation criteria, The “image gloss” was evaluated. It is desirable in practical use that the evaluation is B or more.
〔Evaluation criteria〕
AA: Gloss value is 100 or more A: Gloss value is 90 or more and less than 100 B: Gloss value is 80 or more and less than 90 C: Gloss value is less than 80

<Adhesion>
For the solid image formed on the PVC film recording medium, the number of remaining squares of 100 test squares was counted by a cross-cut peel test using a cloth adhesive tape (manufactured by Nichiban Co., Ltd., 123LW-50). Based on the criteria, “adhesion” to the recording medium was evaluated. It is desirable in practical use that the evaluation is B or more.
〔Evaluation criteria〕
AA: The number of remaining cells is 98 or more A: The number of remaining cells is 90 or more and less than 98 B: The number of remaining cells is 70 or more and less than 90 C: The number of remaining cells is less than 70

Example A1 and Example A2 are preferable examples of the present invention, and are excellent in adhesion to a PVC film recording medium, and can provide high image glossiness even when printed on a non-permeable recording medium. It can be seen that an image having scratch resistance and solvent resistance can be obtained.
Example A3 and Example A4 are examples in which the HLB value of the polysiloxane surfactant is slightly high, and the fixability was inferior to that of Example A1.
Example A5 and Example A6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability was inferior to that of Example A1.
Example A7 is an example in which the addition amount of the polysiloxane surfactant is slightly smaller, and the fixability and solvent resistance were inferior to those of Example A1.
Example A8 is an example in which the addition amount of the polysiloxane surfactant is slightly larger, and the storage stability is inferior to that of Example A1.
Example A9 and Example A10 are examples in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., resulting in poor adhesion compared to Example A1.
Example A11 is an example in which the content of the acrylic-silicone resin particles is slightly insufficient as compared with the polysiloxane surfactant, and the storage stability is inferior to that of Example A1.
Example A12 is an example in which the content of acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, and the image glossiness is inferior to that of Example A1.

  On the other hand, Comparative Examples A1 to A2 are examples that are not inks containing all of the polysiloxane surfactant having an HLB value of 8 or less and acrylic-silicone resin particles, and Comparative Example A1 is the same as Example A1. In comparison, the fixability and solvent resistance were particularly inferior. Comparative Example A2 was particularly inferior in storage stability and adhesion compared to Example A1.

  From the results of Table A-4, it can be seen that the ink of the present invention is suitable for outdoor use. Further, the inks of Examples A1 to A12 were excellent in fixability, storage stability, scratch resistance, solvent resistance, image glossiness, and adhesion.

(Evaluation of effects due to differences in printing devices)
<Test Example 1>
The ink A6 of Example A6 was filled in a print recording apparatus (IPSiO GXe5500 (manufactured by Ricoh Co., Ltd.)) and left for 24 hours in an environment of temperature: 35 ° C. and humidity: 30% RH. During the standing, the circulation mechanism was operated once every hour for 2 minutes. Also, the circulation mechanism was operated for 1 minute before printing.
Next, after standing, in an environment of temperature: 35 ° C. and humidity: 30% RH, the recording medium is a polyvinyl chloride film (CPPVWP1300, manufactured by Sakurai Co., Ltd., hereinafter also referred to as “PVC film”). Thus, a solid image was obtained at an ink adhesion amount of 0.6 g / cm ² . After recording, the solid image was dried for 1 hour on a hot plate (device name: NINOS ND-1, manufactured by AS ONE Corporation) set at 80 ° C. The IPSiO GXe5500 remodeling machine is remodeled into a device provided with a head portion capable of circulating ink and a mechanism capable of circulating ink as shown in FIGS.

  Using the obtained solid image, “image density”, “density uniformity of solid image”, and “isolated dot diameter” were evaluated as follows. The results are shown in Table A-5 below.

(Image density)
Using the obtained solid image, the OD value was measured at any four locations using an apparatus name: X-Rite 938 (manufactured by X-Rite), the average value of the measured values, and the maximum value (Max) and the minimum The difference value (Max-Min) of the value (Min) was calculated.

(Density uniformity of solid image)
Using the obtained solid image, “density uniformity of solid image” was evaluated based on the following evaluation criteria. Note that B and above are levels that are not problematic in actual use.
〔Evaluation criteria〕
A: The solid image is uniform B: There is a slight density unevenness when the solid image is viewed closely C: The density of the solid image has a large unevenness D: The density of the solid image has a large unevenness, and a part of the recording medium You can see the white background of

(Isolated dot diameter)
Using the ink A6 of Example A6, a nozzle check pattern was printed with the same apparatus and conditions, and an isolated dot observation image with a diameter of 450 times was taken with a digital microscope. Got. Next, the obtained image was binarized with image processing software, and the diameter of the isolated dot was calculated. Note that the number of observation images of isolated dots is 28 dots.

<Test Example 2>
A solid image was obtained in the same manner as in Test Example 1 except that the print recording apparatus (IPSiO GXe5500 (manufactured by Ricoh Co., Ltd.)) was changed to IPSiO GXe5500 (manufactured by Ricoh Co., Ltd.). Note that the IPSiO GXe5500 does not circulate ink because there is no mechanism for circulating ink.

  Using the obtained solid image, “image density”, “density uniformity of solid image”, and “isolated dot diameter” were evaluated in the same manner as in Test Example 1. The results are shown in Table A-5 below.

  From the results of Table A-5, Test Example 1 using a printing apparatus having a mechanism for circulating ink in the head is compared with Test Example 2 using a printing apparatus having no mechanism for circulating ink in the head. It can be seen that the image density is high, there is little variation in density depending on the location of the solid image, and the isolated dot diameter is large. This is because the phase separation of the surfactant was suppressed even when the ink using the surfactant having a low HLB value was allowed to stand at a high temperature because the ink A6 used in Test Example 1 was circulated and stirred. it is conceivable that.

(Example B1)
Self-dispersing black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-silicone resin emulsion 4 (trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50 mass%, glass transition temperature (Tg): −14 ° C.) 2.0 mass%, fluororesin emulsion 1 (Mitsui -DuPont Fluorochemical Co., Ltd., trade name: Teflon (registered trademark) AF1600, solid content concentration: 30% by mass, Tg: 160 ° C) 23.3% by mass, 1,2-propanediol 12.0% by mass, 1 , 3-propanediol 10.0% by mass, 1,2-butanediol 3.0% by mass, 2,3-butanediol 3.0% by mass, 3-methoxy-3-methyl 3.0% by mass of tanol, 3.0% by mass of 2-methyl-2,4-pentanediol, 4.0% by mass of dipropylene glycol monomethyl ether, and trade name as a preservative: Proxel LV (manufactured by Avicia) 0.1 By adding mass% and high-purity water to the remaining amount, mixing and stirring, and filtering with a polypropylene filter (trade name: Betafine polypropylene pleated filter PPG series, 3M) having an average pore size of 0.2 μm Ink B1 was produced.

(Examples B2-B12 and Comparative Examples B1-B2)
In Example B1, Examples B2 to B12 and Comparative Examples B1 to B2 were the same as Example B1, except that the compositions and contents described in Table B-1 to Table B-3 below were changed. Inks B2 to B14 were prepared.

In Table B-1 to Table B-3, the trade names of the components and the names of the manufacturing companies are as follows.
Fluororesin emulsion 1: Mitsui DuPont Fluoro Chemical Co., Ltd., trade name: Teflon (registered trademark) AF160, solid content concentration: 30% by mass, Tg: 160 ° C.
Fluoropolymer emulsion 2: Mitsui DuPont Fluoro Chemical Co., Ltd., trade name: Teflon (registered trademark) AF2400, solid content concentration: 30% by mass, Tg: 240 ° C.
・ Fluorine resin emulsion 3: manufactured by Asahi Glass Co., Ltd., trade name: Lumiflon FE4400, solid content concentration: 30% by mass, Tg: 48 ° C.
In addition, the coloring materials, polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives in Table B-1 to Table B-3 are the coloring materials in Table A-1 to Table A-3, The same polysiloxane surfactant, styrene-acrylic resin particles, organic solvent, and preservative were used.

  Next, “storage stability”, “fixing property (beading)”, “scratch resistance”, “solvent resistance”, “image gloss”, “adhesion”, and “weather resistance” are performed as follows. "Sex" was evaluated. The results are shown in Table B-4. The evaluations of “storage stability”, “fixability (beading)”, “scratch resistance”, “solvent resistance”, “image gloss”, and “adhesion” were the same as in Example A1. And evaluated.

[Formation of solid image]
In Examples A1 to A12 and Comparative Examples A1 to A2, a solid image was formed in the same manner as in Examples A1 to A12 and Comparative Examples A1 to A2 except that the inks A1 to A14 were changed to the inks B1 to B14. .

<Weather resistance>
The weather resistance (xenon lamp method) was implemented by a fading test based on JIS K5600-7-7: 2008. Using a highly accelerated weathering tester (device name: Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.), the solid part of the produced solid image was applied for 500 hours using a xenon lamp, and the illumination intensity was 180 W. / M ² , ultraviolet light was exposed, the image density after exposure was measured, the color difference ΔE of the image density after exposure to the image density before exposure was calculated, and “weather resistance” was evaluated based on the following evaluation criteria . It is desirable in practical use that the evaluation is B or more.
[Evaluation criteria]
AA: ΔE is less than 35 A: ΔE is 35 or more and less than 40 B: ΔE is 40 or more and less than 50 C: ΔE is 50 or more

Example B1 and Example B2 are preferred examples of the present invention, and are excellent in adhesion to a PVC film recording medium. A high image glossiness can be obtained even when printed on a non-permeable recording medium, It can be seen that an image having scratch resistance, solvent resistance, and weather resistance can be obtained.
Example B3 and Example B4 are examples in which the HLB value of the polysiloxane surfactant is slightly high, and the fixability was inferior to that of Example B1.
Example B5 and Example B6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability was inferior to that of Example B1.
Example B7 is an example in which the addition amount of the polysiloxane surfactant is slightly less, and the fixability and solvent resistance are inferior to those of Example B1.
Example B8 is an example in which the addition amount of the polysiloxane surfactant is slightly larger, and the storage stability is inferior to that of Example B1.
Example B9 and Example B10 are examples in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., resulting in poor adhesion and weather resistance compared to Example B1.
Example B11 is an example in which the content of acrylic-silicone resin particles is slightly insufficient as compared with the polysiloxane surfactant, and the storage stability is inferior to that of Example B1.
Example B12 is an example in which the content of acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, resulting in inferior image glossiness and weather resistance compared to Example B1.

  On the other hand, Comparative Examples B1 to B2 are examples that are not inks containing all of the polysiloxane surfactant having an HLB value of 8 or less and acrylic-silicone resin particles, and Comparative Example B1 is the same as Example B1. In comparison, the fixability and solvent resistance were particularly inferior. Comparative Example B2 was particularly inferior in storage stability and adhesion compared to Example B1.

  From the results shown in Table B-4, it can be seen that the ink of the present invention is suitable for outdoor use. Further, the inks of Examples B1 to B12 were excellent in fixability, storage stability, scratch resistance, solvent resistance, image glossiness, adhesion, and weather resistance.

(Example C1)
Self-dispersing black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-silicone resin emulsion 4 (trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): −14 ° C.) 2.0% by mass, vinyl chloride-ethylene copolymer Polymer resin emulsion (manufactured by Sumika Chemtex Co., Ltd., trade name: Sumilite 1210, solid content concentration: 50% by mass) 14.0% by mass, 1,2-propanediol 12.0% by mass, 1,3-propane Diol 10.0% by mass, 1,2-butanediol 3.0% by mass, 2,3-butanediol 3.0% by mass, 3-methoxy-3-methylbutanol 3.0% by mass %, 2-methyl-2,4-pentanediol 3.0% by mass, dipropylene glycol monomethyl ether 4.0% by mass, trade name as preservative: 0.1% by mass of Proxel LV (manufactured by Avicia), and high purity water Was added to the remaining amount, mixed and stirred, and filtered with a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M) to produce ink C1. did.

(Examples C2-C12 and Comparative Examples C1-C2)
In Example C1, Examples C2 to C12 and Comparative Examples C1 to C2 were the same as Example C1, except that the compositions and contents described in Table C-1 to Table C-3 below were changed. Inks C2 to C14 were prepared.

In Tables C-1 to C-3, the trade names of the components and the names of the manufacturing companies are as follows.
-Vinyl chloride-ethylene copolymer resin emulsion: manufactured by Sumika Chemtex Co., Ltd., trade name: Sumilite 1210, solid content concentration: 50% by mass
Vinyl chloride-acrylic copolymer resin emulsion: manufactured by Nissin Chemical Industry Co., Ltd., trade name: Vini Blanc 711, solid content concentration: 30% by mass
-Vinyl chloride resin emulsion: Wacker Chemie AG, trade name: VINNOL E15 / 48A, solid content: 50% by mass
Moreover, the coloring material in Table C-1 to Table C-3, the polysiloxane surfactant, the styrene-acrylic resin particles, the organic solvent, and the preservative are the coloring material in Table A-1 to Table A-3, The same polysiloxane surfactant, styrene-acrylic resin particles, organic solvent, and preservative were used.

  Next, “storage stability”, “viscosity stability with time”, “fixing property (beading)”, “scratch resistance”, “image glossiness”, and “adhesion” are evaluated as follows. did. The results are shown in Table C-4. “Storage stability”, “fixability (beading)”, “scratch resistance”, “image gloss”, and “adhesion” were evaluated in the same manner as in Example A1.

<Viscosity stability over time>
The inks of Examples C2 to C12 and Comparative Examples C1 to C2 were sealed in a 50 mL glass vial (manufactured by Nidec Rika Glass Co., Ltd.), stored in a constant temperature bath at 70 ° C. for 14 days, and then the viscosity of the ink was measured. The viscosity change rate of the viscosity of the ink after storage with respect to the viscosity of the ink before storage was calculated, and the “viscosity stability with time” was evaluated based on the following evaluation criteria. It is desirable in practical use that the evaluation is B or more.
[Evaluation criteria]
A: Viscosity change rate is less than 5% B: Viscosity change rate is 5% or more and less than 10% C: Viscosity change rate is 10% or more

Examples C1 and C2 are preferred examples of the present invention, which have excellent adhesion to a PVC film recording medium, and can provide high image glossiness even when printed on a non-permeable recording medium. It can be seen that an image having scratch resistance, solvent resistance, and viscosity stability over time can be obtained.
Example C3 and Example C4 are examples in which the HLB value of the polysiloxane surfactant is slightly high, and the fixability is inferior to that of Example C1.
Example C5 and Example C6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability was inferior to that of Example C1.
Example C7 is an example in which the addition amount of the polysiloxane surfactant is slightly smaller, and the fixability and solvent resistance were inferior to those of Example C1.
Example C8 is an example in which the addition amount of the polysiloxane surfactant is slightly larger, and the storage stability and the viscosity stability with time were inferior to those of Example C1.
Example C9 and Example C10 are examples in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., resulting in poor adhesion compared to Example C1.
Example C11 is an example in which the content of the acrylic-silicone resin particles is slightly insufficient compared to the polysiloxane surfactant, and the storage stability and the viscosity stability with time are inferior to those of Example C1. became.
Example C12 is an example in which the content of acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, and the image glossiness is inferior to that of Example C1.

  On the other hand, Comparative Examples C1 to C2 are examples that are not inks containing all of the polysiloxane surfactant having an HLB value of 8 or less and acrylic-silicone resin particles, and Comparative Example C1 is the same as Example C1. In comparison, the fixability and the viscosity stability over time were particularly inferior. Comparative Example C2 was particularly inferior in storage stability and adhesion compared to Example C1.

  From the results of Table C-4, it can be seen that the ink of the present invention is suitable for outdoor use. Further, the inks of Examples C1 to C12 were excellent in fixability, storage stability, scratch resistance, viscosity stability with time, image glossiness, and adhesion.

(Example D1)
Self-dispersing black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-silicone resin emulsion 4 (trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): −14 ° C.) 2.0% by mass, polyester resin emulsion 1 (Unitika) (Trade name: KZA-1449, solid concentration: 30% by mass), 23.3% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0% by mass, 1 , 2-butanediol 3.0% by mass, 2,3-butanediol 3.0% by mass, 3-methoxy-3-methylbutanol 3.0% by mass, 2-methyl-2,4-pen Tandiol 3.0% by mass, Dipropylene glycol monomethyl ether 4.0% by mass, Trade name: Proxel LV (manufactured by Avicia) 0.1% by mass as preservative, and high purity water are added so as to be the remaining amount, and mixed. The ink D1 was produced by stirring and filtering with a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, 3M).

(Examples D2-D12 and Comparative Examples D1-D2)
In Example D1, Examples D2 to D12 and Comparative Examples D1 to D2 were the same as Example D1, except that the compositions and contents described in Table D-1 to Table D-3 below were changed. Inks D2 to D14 were prepared.

In Tables D-1 to D-3, the trade names of the components and the names of the manufacturing companies are as follows.
Polyester resin emulsion 1: manufactured by Unitika Ltd., trade name: KZA-1449, solid content concentration: 30% by mass
Polyester resin emulsion 2: manufactured by Takamatsu Yushi Co., Ltd., trade name: A-125S, solid content concentration: 30% by mass
Polyester resin emulsion 3: manufactured by Takamatsu Yushi Co., Ltd., trade name: A-160P, solid content concentration: 25% by mass
Moreover, the coloring material in Table D-1 to Table D-3, the polysiloxane surfactant, the styrene-acrylic resin particles, the organic solvent, and the preservative are the coloring material in Table A-1 to Table A-3, The same polysiloxane surfactant, styrene-acrylic resin particles, organic solvent, and preservative were used.

  Next, in the same manner as in Example B1, “storage stability”, “fixability (beading)”, “scratch resistance”, “weather resistance”, “image glossiness”, and “adhesion” were evaluated. did. The results are shown in Table D-4.

Examples D1 and D2 are preferable examples of the present invention, and have excellent adhesion to a PVC film recording medium, and can provide high image glossiness even when printed on a non-permeable recording medium. It can be seen that an image having scratch resistance and weather resistance can be obtained.
Example D3 and Example D4 are examples in which the HLB value of the polysiloxane surfactant is slightly high, and the fixability was inferior to that of Example D1.
Example D5 and Example D6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability was inferior to that of Example D1.
Example D7 is an example in which the addition amount of the polysiloxane surfactant is slightly less, and the fixing property and the solvent resistance are inferior to those of Example D1.
Example D8 is an example in which the amount of the polysiloxane surfactant added is slightly larger, and the storage stability and weather resistance were inferior to those of Example D1.
Example D9 and Example D10 are examples in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., resulting in poor adhesion as compared to Example D1.
Example D11 is an example in which the content of acrylic-silicone resin particles is slightly insufficient as compared with the polysiloxane surfactant, and results in poor storage stability and weather resistance compared to Example D1. .
Example D12 is an example in which the content of acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, and the image glossiness is inferior to that of Example D1.

  On the other hand, Comparative Examples D1 to D2 are examples that are not inks that include all of the polysiloxane surfactant having an HLB value of 8 or less and acrylic-silicone resin particles, and Comparative Example D1 is the same as Example D1. In comparison, the fixability and weather resistance were particularly inferior. Comparative Example D2 was particularly inferior in storage stability and adhesion compared to Example D1.

  From the results of Table D-4, it can be seen that the ink of the present invention is suitable for outdoor use. Further, the inks of Examples D1 to D12 were excellent in fixability, storage stability, scratch resistance, image glossiness, adhesion, and weather resistance.

(Example E1)
Self-dispersing black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-silicone resin emulsion 4 (trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): −14 ° C.) 2.0% by mass, acrylic-styrene resin emulsion 1 (Japan Coating Resin Co., Ltd., trade name: Ricabond ET-700, solid content concentration: 33.0% by mass) 21.2% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0% by weight, 1,2-butanediol 3.0% by weight, 2,3-butanediol 3.0% by weight, 3-methoxy-3-methylbutanol 3. 0% by mass, 3.0% by mass of 2-methyl-2,4-pentanediol, 4.0% by mass of dipropylene glycol monomethyl ether, trade name: 0.1% by mass as a preservative, Proxel LV (manufactured by Avicia), Ink E1 was added by adding high-purity water to the remaining amount, mixing and stirring, and filtering with a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, 3M). Was made.

(Examples E2-E12 and Comparative Examples E1-E2)
In Example E1, Examples E2 to E12 and Comparative Examples E1 to E2 were the same as Example E1, except that the compositions and contents described in Table E-1 to Table E-3 below were changed. Inks E2 to E14 were prepared.

In Tables E-1 to E-3, the trade names of the components and the names of the manufacturing companies are as follows.
-Acrylic-styrene resin emulsion 1: manufactured by Japan Coating Resin Co., Ltd., Rikabond ET-700, solid content concentration: 33.0% by mass
Acrylic-styrene resin emulsion 2: manufactured by Seiko PMC Co., Ltd., trade name: J-140A, solid content concentration: 41% by mass
Acrylic-styrene resin emulsion 3: manufactured by Seiko PMC Co., Ltd., trade name: QE-1042, solid content concentration: 40.5% by mass
Further, the coloring materials, polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives in Table E-1 to Table E-3 are the coloring materials in Table A-1 to Table A-3, The same polysiloxane surfactant, styrene-acrylic resin particles, organic solvent, and preservative were used.

  Next, “storage stability”, “fixability (beading)”, “scratch resistance”, “ejection reliability”, “image gloss”, and “adhesion” were evaluated as follows. . The results are shown in Table E-4. “Storage stability”, “fixability (beading)”, “scratch resistance”, “image gloss”, and “adhesion” were evaluated in the same manner as in Example A1.

<Discharge reliability>
The inks of Examples E1 to E12 and Comparative Examples E1 to E2 were filled in the inkjet printer (device name: IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.), recorded, and the ink was stably ejected. After confirmation, the recording head was left for 4 weeks in a 50 ° C., 40% RH environment with the recording head removed from the home position. Thereafter, the ink jet printer was moved to a room temperature (25 ° C.) environment, waited for the temperature to drop to room temperature (25 ° C.), the main body was turned on, recording was performed again, and the ink re-discharge state was visually observed. At that time, when the ejection was not stable, the number of cleaning operations of a predetermined recording head was examined, and “ejection reliability” was evaluated based on the following evaluation criteria.
[Evaluation criteria]
A: Re-ejection after being left is extremely stable, and the cleaning operation of the recording head is unnecessary. B: Re-ejection after being left unsettled is unstable, but returns after cleaning the recording head. Re-ejection is unstable and does not return even if the print head is cleaned

Example E1 and Example E2 are preferred examples of the present invention, and are excellent in adhesion to a PVC film recording medium. A high image glossiness can be obtained even when printed on a non-permeable recording medium, It can be seen that an image having scratching and ejection reliability can be obtained.
Example E3 and Example E4 are examples in which the HLB value of the polysiloxane surfactant is slightly high, and the fixability is inferior to that of Example E1.
Example E5 and Example E6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability was inferior to that of Example E1.
Example E7 is an example in which the amount of polysiloxane surfactant added is slightly smaller, and results in inferior fixability and ejection reliability compared to Example E1.
Example E8 is an example in which the amount of polysiloxane surfactant added is slightly larger, and the storage stability and ejection reliability were inferior to Example E1.
Example E9 and Example E10 are examples in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., resulting in poor adhesion compared to Example E1.
Example E11 is an example in which the content of acrylic-silicone resin particles is slightly insufficient compared to the polysiloxane surfactant, and results in poor storage stability and ejection reliability compared to Example E1. It was.
Example E12 is an example in which the content of acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, and the image glossiness is inferior to that of Example E1.

  On the other hand, Comparative Examples E1 to E2 are examples that are not inks containing all of the polysiloxane surfactant having an HLB value of 8 or less and the acrylic-silicone resin particles, and Comparative Example E1 is the same as Example E1. In comparison, the fixability and ejection reliability were particularly inferior. Comparative Example E2 was particularly inferior in storage stability and adhesion compared to Example E1.

  From the results shown in Table E-4, it can be seen that the ink of the present invention is suitable for outdoor use. Further, the inks of Examples E1 to E12 were excellent in fixability, storage stability, scratch resistance, ejection reliability, image glossiness, and adhesion.

(Example F1)
Self-dispersing black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-silicone resin emulsion 4 (trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50 mass%, glass transition temperature (Tg): −14 ° C.) 2.0 mass%, polyvinyl alcohol resin emulsion 1 ( Nippon Vinegar Poval Co., Ltd., trade name: Poval JF-17, solid content concentration: 30% by mass) 23.3% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10 0.0 mass%, 1,2-butanediol 3.0 mass%, 2,3-butanediol 3.0 mass%, 3-methoxy-3-methylbutanol 3.0 mass%, 2- Methyl-2,4-pentanediol (3.0% by mass), dipropylene glycol monomethyl ether (4.0% by mass), trade name: Proxel LV (manufactured by Avicia) (0.1% by mass), and high purity water The mixture was stirred and mixed, and filtered with a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M Corporation) to prepare ink F1.

(Examples F2-F12 and Comparative Examples F1-F2)
In Example F1, Examples F2 to F12 and Comparative Examples F1 to F2 were the same as Example F1 except that the compositions and contents described in Table F-1 to Table F-3 below were changed. Inks F2 to F14 were prepared.

In Table F-1 to Table F-3, the trade names of the components and the manufacturing company names are as follows.
・ Polyvinyl alcohol resin emulsion 1: Nippon Vinegar-Poval Co., Ltd., trade name: Poval JF-17, solid content: 30% by mass
-Polyvinyl alcohol resin emulsion 2: Nippon Vinegar-Poval Co., Ltd., trade name: Poval JF-04, solid content concentration: 30% by mass
-Polyvinyl alcohol resin emulsion 3: Nippon Vinegar-Poval Co., Ltd., trade name: Poval JF-05, solid content concentration: 30% by mass
Further, the coloring materials, polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives in Table F-1 to Table F-3 are the coloring materials in Table A-1 to Table A-3, The same polysiloxane surfactant, styrene-acrylic resin particles, organic solvent, and preservative were used.

  Next, in the same manner as in Example B1, “storage stability”, “fixability (beading)”, “scratch resistance”, “solvent resistance”, “image gloss”, “adhesion”, and “Weather resistance” was evaluated. The results are shown in Table F-4.

Example F1 and Example F2 are preferable examples of the present invention, and are excellent in adhesion to a PVC film recording medium, and can obtain high image glossiness even when printed on a non-permeable recording medium, and weather resistance. It can be seen that an image having the property, solvent resistance, fixing property, storage stability, and scratch resistance can be obtained.
Example F3 and Example F4 are examples in which the HLB value of the polysiloxane surfactant is slightly high, and the fixability was inferior to that of Example F1.
Example F5 and Example F6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability was inferior to that of Example F1.
Example F7 is an example in which the amount of the polysiloxane surfactant added is slightly smaller, and the fixability is inferior to that of Example F1.
Example F8 is an example in which the amount of polysiloxane surfactant added is slightly larger, and the storage stability and weather resistance were inferior to those of Example F1.
Example F9 and Example F10 are examples in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., resulting in poor adhesion as compared to Example F1.
Example F11 is an example in which the content of acrylic-silicone resin particles is slightly insufficient as compared with the polysiloxane surfactant, and the storage stability is inferior to that of Example F1.
Example F12 is an example in which the content of the acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, and the image glossiness is inferior to that of Example F1.

  On the other hand, Comparative Examples F1 to F2 are examples that are not inks containing all of the polysiloxane surfactant having an HLB value of 8 or less and acrylic-silicone resin particles, and Comparative Example F1 is the same as Example F1. In comparison, the fixability and solvent resistance were particularly inferior. Comparative Example F2 was particularly inferior in storage stability and adhesion compared to Example F1.

  From the results shown in Table F-4, it can be seen that the ink of the present invention is suitable for outdoor use. Inks of Examples F1 to F12 were excellent in fixability, storage stability, scratch resistance, solvent resistance, image glossiness, adhesion, and weather resistance.

(Example G1)
Self-dispersing black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-silicone resin emulsion 4 (trade name: AE980, manufactured by Etec Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): −14 ° C.) 2.0% by mass, polycarbonate polyurethane resin emulsion ( (Solid content concentration: 30% by mass) 23.3% by mass, 22.0 parts by mass of N, N-dimethyl-β-butoxypropionamide, 3.0% by mass of 1,2-butanediol, 2,3-butanediol 3 0.0 mass%, 3-methoxy-3-methylbutanol 3.0 mass%, 2-methyl-2,4-pentanediol 3.0 mass%, dipropylene glycol Monomethyl ether 4.0% by mass, trade name as preservative: 0.1% by mass of Proxel LV (manufactured by Avicia), and high purity water were added so as to remain, mixed and stirred, and the average pore size was 0.2 μm. Ink G1 was produced by filtering with a polypropylene filter (trade name: Betafine polypropylene pleated filter PPG series, 3M).

(Examples G2 to G12 and Comparative Examples G1 to G2)
In Example G1, Examples G2 to G12 and Comparative Examples G1 to G2 were the same as Example G1, except that the compositions and contents described in Table G-1 to Table G-3 below were changed. Inks G2 to G14 were prepared.

In Tables G-1 to G-3, the trade names of the components and the names of the manufacturing companies are as follows.
N, N-dimethyl-β-butoxypropionamide: Idemitsu Kosan Co., Ltd. N, N-dimethyl-β-heptoxypropionamide: Idemitsu Kosan Co., Ltd. N, N-diethyl-β-butoxypropionamide: Idemitsu Kosan Co., Ltd., N, N-diethyl-β-butoxypropionamide: Idemitsu Kosan Co., Ltd. Also, coloring materials, polysiloxane surfactants, and styrene-acrylic resin particles in Table G-1 to Table G-3 , Polyurethane resin particles, organic solvents, and preservatives include coloring materials, polysiloxane surfactants, styrene-acrylic resin particles, polyurethane resin particles, organic solvents, and preservatives in Table A-1 to Table A-3. Similar ones were used.

  Next, “storage stability”, “fixing property (beading)”, “scratch resistance”, “solvent resistance”, “image gloss”, “adhesion”, and “drying” are performed as follows. "Sex" was evaluated. The results are shown in Table G-4. The evaluations of “storage stability”, “fixability (beading)”, “scratch resistance”, “solvent resistance”, “image gloss”, and “adhesion” were the same as in Example A1. And evaluated.

<Drying>
The obtained inks G1 to G14 of Examples G1 to G12 and Comparative Examples G1 to G2 were filled in the inkjet printer (device name: IPSiO GXe5500 remodeled machine, manufactured by Ricoh Co., Ltd.), and a polyvinyl chloride film (CPPVWP1300, Sakurai) A solid image was recorded on a recording medium (manufactured by Co., Ltd., hereinafter also referred to as “PVC film”) at an ink adhesion amount of 0.6 g / cm ² . After recording, the solid image was dried on a hot plate (NINOS ND-1, manufactured by ASONE Corporation) set at 50 ° C. The filter paper was pressed against the solid portion of the solid image after drying, and the transfer of the ink onto the filter paper was visually observed, and “dryability” was evaluated based on the following evaluation criteria.
[Evaluation criteria]
A: No transfer to filter paper under drying conditions at 50 ° C. for 5 minutes or less B: No transfer to filter paper under drying conditions at 50 ° C. for more than 5 minutes and 8 minutes or less C: Drying conditions at 50 ° C. for more than 8 minutes to 10 minutes or less D: No transfer to filter paper D: Transfer to filter paper does not disappear even under drying conditions at 50 ° C for more than 10 minutes

Examples G1 and G2 are preferred examples of the present invention, which have excellent adhesion to the PVC film recording medium, provide high image gloss when printed on a non-permeable recording medium, It can be seen that an image having scratching properties, solvent resistance, and drying properties can be obtained.
Example G3 is an example in which the HLB value of the polysiloxane surfactant is slightly high, and the fixing property and the drying property were inferior to those of Example G1.
Example G4 is an example in which the HLB value of the polysiloxane surfactant is slightly high, and the fixability is inferior to that of Example G1.
Example G5 and Example G6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability was inferior to that of Example G1.
Example G7 is an example in which the amount of polysiloxane surfactant added is slightly smaller, and results in inferior fixability, solvent resistance, and drying properties compared to Example G1.
Example G8 is an example in which the addition amount of the polysiloxane surfactant is slightly larger, and the storage stability and the drying property were inferior to those of Example G1.
Example G9 is an example in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., resulting in poor adhesion and drying compared to Example G1.
Example G10 is an example in which the Tg of the acrylic-silicone resin emulsion is higher than 0 ° C., and the adhesion was inferior to that of Example G1.
Example G11 is an example in which the content of acrylic-silicone resin particles is slightly insufficient as compared with the polysiloxane surfactant, and the storage stability is inferior to that of Example G1.
Example G12 is an example in which the content of acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, and the image glossiness is inferior to that of Example G1.

  On the other hand, Comparative Examples G1 to G2 are examples that are not inks containing all of the polysiloxane surfactant having an HLB value of 8 or less and acrylic-silicone resin particles, and Comparative Example G1 is the same as Example G1. In comparison, the fixability and solvent resistance were particularly inferior. Comparative Example G2 was particularly inferior in storage stability and adhesion compared to Example G1.

  From the results of Table G-4, it can be seen that the ink of the present invention is suitable for outdoor use. The inks of Examples G1 to G12 were excellent in fixability, storage stability, scratch resistance, solvent resistance, image glossiness, adhesion, and drying properties.

(Test Examples A to G)
<Evaluation of effects in heat drying>
Ink A1 of Example A1, Ink B1 of Example B1, Ink C1 of Example C1, Ink D1 of Example D1, Ink E1 of Example E1, Ink F1 of Example F1, and Ink G1 of Example G1 As shown in Table H-1 to Table H-7 below, the fixing property (beading), and the resistance to resistance were the same as in Example A1 except that the heating conditions after recording (heating temperature, heating time) were changed. The rubbing property was evaluated, and the drying property was evaluated in the same manner as in Example G1. The results are shown in Tables H-1 to H-7.
Test Examples A1-8, B1-8, C1-8, D1-8, E1-8, F1-8, and G1-8 are ink A1, ink B1, ink C1, ink D1, ink E1, and ink. A solid image was recorded using F1 and ink G1 in the same manner as in Example A1, and dried by heating after recording (left at 25 ° C. for 24 hours).

As an aspect of this invention, it is as follows, for example.
<1> containing water, an organic solvent, a polysiloxane surfactant, and acrylic-silicone resin particles,
The ink is characterized in that the polysiloxane surfactant has an HLB value of 8 or less.
<2> In the above <1>, further containing at least one selected from polyurethane resin particles, fluororesin particles, vinyl chloride resin particles, polyester resin particles, acrylic-styrene copolymer resin particles, and polyvinyl alcohol resin particles The ink described.
<3> The ink according to any one of <1> to <2>, wherein the organic solvent contains a compound represented by the following general formula (1).
(In the general formula (1), R _{1, R 2,} and R ₃ each independently. Representing a hydrocarbon group which may number 1 to 8 carbons have an ether bond)
<4> The ink according to any one of <1> to <3>, wherein the polysiloxane surfactant has an HLB value of 4.5 or more and 7.0 or less.
<5> The ink according to any one of <1> to <4>, wherein a content of the polysiloxane surfactant is 1.0% by mass or more and 2.0% by mass or less.
<6> The ink according to any one of <1> to <5>, wherein a glass transition temperature of the acrylic-silicone resin particles is 0 ° C. or lower.
<7> The mass ratio (B / A) between the content A (mass%) of the polysiloxane surfactant and the content B (mass%) of the acrylic-silicone resin particles is 0.8 or more. The ink according to any one of <1> to <6>, which is 5 or less.
<8> The ink according to any one of <1> to <7>, wherein a content of silicone derived from the acrylic-silicone resin particles is 0.01% by mass or more and 0.04% by mass or less.
<9> The ink according to any one of <1> to <8>, wherein a minimum film-forming temperature of the acrylic-silicone resin particles is 20 ° C. or lower.
<10> The ink according to any one of <1> to <9>, wherein the content of the acrylic-silicone resin particles is 0.5% by mass or more and 5% by mass or less.
<11> The ink according to any one of <1> to <10>, wherein a glass transition temperature of the fluororesin particles is 100 ° C. or higher and 300 ° C. or lower.
<12> The ink according to any one of <1> to <11>, wherein the content of the organic solvent is 10% by mass or more and 60% by mass or less.
<13> The ink according to any one of <3> to <12>, wherein the content of the compound represented by the general formula (1) is 5% by mass or more and 30% by mass or less.
<14> The ink according to any one of <1> to <13>, further including a coloring material.
<15> The ink according to <14>, wherein the color material is a pigment.
<16> an ink storage unit that stores the ink according to any one of <1> to <15>;
An ink jet printing apparatus comprising: an ejection head that applies a stimulus to the ink and ejects the ink.
<17> An ink discharge head, wherein the discharge head includes an individual liquid chamber, an inflow channel for allowing ink to flow into the individual liquid chamber, and an outflow channel for allowing ink to flow out of the individual liquid chamber. The inkjet printing apparatus according to <16>, wherein
<18> The inkjet printing apparatus according to <17>, further including a circulation unit that circulates the ink from the inflow channel toward the outflow channel.
<19> An inkjet printing method comprising an ink ejection step of applying a stimulus to the ink according to any one of <1> to <15> and ejecting the ink to print on a recording medium. .
<20> Using an ink discharge head having an inflow channel for allowing ink to flow into the individual liquid chamber and an outflow channel for allowing ink to flow out of the individual liquid chamber, either thermal energy or mechanical energy Further comprising a printing step of causing the ink to act on the ink and discharging the ink to print,
The inkjet printing method according to <19>, wherein the ink according to any one of <1> to <15> is used as the ink.
<21> The inkjet printing method according to <20>, further including a circulation step of circulating ink from the inflow channel toward the outflow channel during non-printing.
<22> The inkjet printing method according to any one of <19> to <21>, including a heating step of heating the recording medium.
<23> The inkjet printing method according to <22>, wherein a heating temperature in the heating step is 40 ° C. or higher and 100 ° C. or lower.
<24> a recording medium, and an image containing a polysiloxane surfactant and acrylic-silicone resin particles on the recording medium,
The printed matter is characterized in that the polysiloxane surfactant has an HLB value of 8 or less.

  The ink according to any one of <1> to <15>, the ink jet printing apparatus according to any one of <16> to <18>, and the ink jet printing according to any one of <19> to <23>. The printed matter described in <24>, the method, can solve the conventional problems and achieve the object of the present invention.

JP 2005-220352 A JP 2011-094082 A

142: Recording medium 6: Individual liquid chamber

Claims (16)

Containing water, organic solvent, polysiloxane surfactant, and acrylic-silicone resin particles,
An ink wherein the polysiloxane surfactant has an HLB value of 8 or less.   The ink according to claim 1, further comprising at least one selected from polyurethane resin particles, fluorine resin particles, vinyl chloride resin particles, polyester resin particles, acrylic-styrene copolymer resin particles, and polyvinyl alcohol resin particles. The ink according to claim 1, wherein the organic solvent contains a compound represented by the following general formula (1).
(In the general formula (1), R _{1, R 2,} and R ₃ each independently. Representing a hydrocarbon group which may number 1 to 8 carbons have an ether bond)   The ink according to any one of claims 1 to 3, wherein the polysiloxane surfactant has an HLB value of 4.5 or more and 7.0 or less.   The ink according to any one of claims 1 to 4, wherein a content of the polysiloxane surfactant is 1.0% by mass or more and 2.0% by mass or less.   The ink according to any one of claims 1 to 5, wherein a glass transition temperature of the acrylic-silicone resin particles is 0 ° C or lower.   The mass ratio (B / A) between the content A (mass%) of the polysiloxane surfactant and the content B (mass%) of the acrylic-silicone resin particles is 0.8 to 1.5. The ink according to any one of claims 1 to 6. An ink containing portion for containing the ink according to claim 1;
An inkjet printing apparatus comprising: an ejection head that applies a stimulus to the ink and ejects the ink.   The ink discharge head has an individual liquid chamber, an inflow channel for allowing ink to flow into the individual liquid chamber, and an outflow channel for allowing ink to flow out from the individual liquid chamber. Item 9. The inkjet printing apparatus according to Item 8.   The inkjet printing apparatus according to claim 9, further comprising a circulation unit that circulates the ink from the inflow channel toward the outflow channel.   8. An ink jet printing method comprising: an ink ejection step of applying a stimulus to the ink according to claim 1 and ejecting the ink to print on a recording medium. Using an ink discharge head having an inflow channel for allowing ink to flow into the individual liquid chamber and an outflow channel for allowing ink to flow out of the individual liquid chamber, either thermal energy or mechanical energy is used as the ink. Further comprising a printing step of causing the ink to discharge and printing the ink,
The inkjet printing method according to claim 11, wherein the ink according to claim 1 is used as the ink.   The inkjet printing method according to claim 12, further comprising a circulation step of circulating ink from the inflow channel toward the outflow channel during non-printing.   The inkjet printing method according to claim 11, further comprising a heating step of heating the recording medium.   The inkjet printing method according to claim 14, wherein a heating temperature in the heating step is 40 ° C or higher and 100 ° C or lower. A recording medium, and an image containing a polysiloxane surfactant and acrylic-silicone resin particles on the recording medium,
The printed matter, wherein the polysiloxane surfactant has an HLB value of 8 or less.