JP6848324B2 - Inks, inkjet printing equipment, and inkjet printing methods - Google Patents

Description

The present invention relates to inks, inkjet printing devices, inkjet printing methods, and printed matter.

In industrial applications such as advertisements and signboards, in order to improve durability such as light resistance, water resistance, and abrasion resistance, for example, a non-permeable recording medium such as a plastic film is used, and the non-penetrating recording medium is used. Various inks used in the above have been developed.

As such inks, for example, solvent-based inks using an organic solvent as a solvent, ultraviolet curable inks containing a polymerizable monomer as a main component, and the like are widely used. However, the solvent-based ink is concerned about the influence on the environment due to the evaporation of the organic solvent. In the ultraviolet curable ink, the choice of the polymerizable monomer used may be limited from the viewpoint of safety.
Therefore, water-based inks that have a low environmental load and can be directly recorded on a non-penetrating 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 obtain an image having excellent fixability and adhesion to a non-penetrating recording medium.

The ink of the present invention as a means for solving the above-mentioned 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. Is.

According to the present invention, it is possible to provide an ink that has good storage stability and can obtain an image having excellent fixability and adhesion to a non-penetrating 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 the 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 explanatory view showing an example of a liquid (ink) ejection head. FIG. 5 is a cross-sectional explanatory view of the liquid discharge head shown in FIG. 4 in a direction orthogonal to the nozzle arrangement direction. FIG. 6 is a cross-sectional view taken along the line AA'of FIG. FIG. 7 is a cross-sectional view taken along the line BB'of FIG. FIG. 8 is a cross-sectional explanatory view of the liquid discharge head shown in FIG. 4 in a direction parallel to the nozzle arrangement direction. FIG. 9 is a plan explanatory view of the nozzle plate of the liquid discharge head shown in FIG. FIG. 10 is a plan explanatory view of each member constituting the flow path member of the liquid discharge head shown in FIG. FIG. 11 is a plan explanatory 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 the present embodiment. FIG. 13 is an explanatory plan view of a main part showing an example of a device for discharging a liquid. FIG. 14 is an explanatory side view of a main part showing an example of a device for discharging a liquid. FIG. 15 is an explanatory plan view of a main part showing another example of the liquid discharge unit.

(ink)
In the present invention, the ink 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, and if necessary, other inks are used. Containing ingredients.
In general, the solvent-based ink of the present invention has excellent fixability to a non-penetrating recording medium because the solvent-based ink is fixed while swelling the impermeable recording medium with the organic solvent in the ink. Then, since the ink coating film stays on the recording medium as the final printed matter, the fixing property of the ink coating film on the recording medium is insufficient, and there is a problem that the high-speed recording property is inferior. Is. Further, assuming outdoor use, the scratch resistance of printed matter is also required to have tough scratch resistance and image hardness that cannot be compared with those for indoor use. However, it is based on the finding that the conventional water-based ink does not have sufficient properties comparable to those of the solvent-based ink.

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

However, when 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 the water content exceeds 30% by mass of all the components of the ink, the surfactant becomes difficult to dissolve in the ink, and it becomes easy to cause phase separation that separates the oil phase and the aqueous phase. .. As a result, the storage stability of the ink may decrease.

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 operating temperature range assumed as the ink for inkjet recording.

<Polysiloxane surfactant>
Examples of the polysiloxane surfactant include a compound having a hydrophilic group or a hydrophilic polymer chain on the side chain of a compound having a polysiloxane structure (silicone-based compound) such as polydimethylsiloxane, and a poly such as 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-based compound). The polysiloxane surfactant may have a polysiloxane structure in its structure, and means that a polysiloxane-based surfactant is also included.

Examples of the hydrophilic group and the hydrophilic polymer chain include a polyether group (polyethylene oxide, polypropylene oxine, a copolymer thereof, etc.) and 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 ⁻ etc.) and the like. However, in the chemical formula, n represents an integer of 1 or more. Among these, it is preferable to have a polyether group.
Further, a hydrophilic monomer such as (meth) acrylic acid or a salt thereof may be used as at least a part of other monomers copolymerizable with polydimethylsiloxane having a polymerizable vinyl group at the terminal. A vinyl-based copolymer having a silicone-based compound chain such as polydimethylsiloxane in the side chain obtained by the copolymerization of (preferably) is also preferable.
Among these, a compound having a polysiloxane structure and having a hydrophilic polymer chain is preferable, a polyether group is more preferably contained as the hydrophilic polymer chain, and a polysiloxane surfactant is used as a hydrophobic group. A nonionic surfactant having a methylpolysiloxane and having a polyoxyethylene structure as a hydrophilic group is particularly preferable.

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 fixability can be ensured even when inkjet recording is performed on various impermeable recording media, and further, when the HLB value is 4.5 or more and 7.0 or less. If there is, it is possible to raise the temperature at which phase separation of the ink does not occur.

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

Examples of the polysiloxane surfactant include polyether-modified silicones and polyoxyalkylene group-containing silicone compounds.

As the polysiloxane surfactant, a commercially available product can be used, and examples of the commercially available product include Silface SAG005 (HLB value: 7.0), Sylface SAG008 (HLB value: 7.0), and (. As mentioned 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), (above, manufactured by Toray Dow Co., Ltd.), KF-945 (HLB value: 4.0), KF-6017 (HLB value: 4.5), ( As mentioned above, Shin-Etsu Chemical Industry Co., Ltd.), FormBan MS-575 (manufactured by Ultra Ads 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, the fixability of the ink to various impermeable recording media can be improved, and the image quality such as gloss can be improved.

<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 improve various 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 thereof include acid ester monomers, amide-based acrylates such as N-methylol acrylamide and methoxymethyl acrylamide. These may be used alone or in combination of two or more.

Examples of the silane compound include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyl. Examples thereof include diethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, and trifluoropropyltrimethoxysilane. These may be used alone or in combination of two or more.

Examples of the emulsifier include alkylbenzene sulfonic acid or a salt thereof, dialkyl sulfosuccinate or a salt thereof, alkylnaphthalene sulfonic acid or a salt thereof, a formalin condensate of alkylnaphthalene sulfonate, a higher fatty acid salt, and a sulfonic acid of a higher fatty acid ester. Salt, polyoxypropylene-polyoxyethylene condensate of ethylenediamine, sorbitan fatty acid ester or salt thereof, aromatic to aliphatic phosphate or salt thereof, dodecylbenzene sulfonate, dodecyl sulfate, lauryl sulfate, dialkyl sulfosuccinic acid Salt, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkylpropenylphenyl ether sulfate, alkylphenyl 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, formalin condensate of naphthalene sulfonic acid and the like. These may be used alone or in combination of two or more.
Here, examples of the salt include sodium salt, ammonium salt and the like.

As the emulsifier, a reactive emulsifier having an unsaturated double bond can also be used.
Examples of the reactive emulsifier include Adecaria Soap SE, NE, PP (manufactured by ADEKA Corporation), Latemul S-180 (manufactured by Kao Corporation), Eleminor JS-2, and Eleminor RS-30 (Sanyo Kasei Kogyo Co., Ltd.). ), Aqualon RN-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

Examples of the silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 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-triethoxysilyl-N-( 1,3-Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyl Examples thereof include triethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyandiapropyltriethoxysilane.

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

The content of silicone derived from the acrylic-silicone resin particles is preferably 0.01% by mass or more and 0.04% by mass or less with respect to the total amount of 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. When the glass transition temperature is 0 ° C. or lower, the adhesion can be improved.

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, the fixability can be improved. That is, it is possible to prevent the pigment from being removed and contaminating the recording medium by rubbing the recording portion or tracing with a marker.

Commercially available products can be used as the acrylic-silicone resin particles, for example, AQ914 (manufactured by Daicel FineChem Co., Ltd., solid content concentration: 24% by mass, Tg: 50 ° C.), SA-6360 (manufactured by DIC Co., Ltd.). , Solid content concentration: 50% by mass, Tg: 21 ° C., Cymac 480 (manufactured by Toa Synthetic Co., Ltd., solid content concentration: 30% by mass, Tg: 0 ° C.), AE980 (manufactured by E-Tech Co., Ltd., solid content concentration: 50) Mass%, Tg: -14 ° C), AE981A (manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, Tg: -15 ° C), AE982 (manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, Tg: 0) ℃) and the like.

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) of 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 is more preferable. When the mass ratio (B / A) is 0.6 or more and 1.8 or less, the temperature at which separation of the polysiloxane surfactant occurs can be raised, and the ink has excellent image quality such as gloss. Can be provided.

<Other resin particles>
Examples of the other resin particles include polyurethane resin particles, fluororesin particles, vinyl chloride resin particles, polyester resin particles, acrylic-styrene copolymer resin particles, polyvinyl alcohol resin particles, epoxy resin particles, polyamide resin particles, and poly. Examples thereof include ether resin particles, polyolefin resin particles, polystyrene resin particles, polyvinyl ester resin particles, additive synthetic resin particles such as unsaturated carboxylic acid resin, and natural polymers such as celluloses, rosins, and natural rubbers. These may be used alone or in combination of two or more. 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 impart high image glossiness 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 obtained. It can be greatly improved.

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

The polyurethane resin particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyurethane resin particles obtained by reacting a polyol with a polyisocyanate.

− Polyol −
Examples of the polyol include polyether polyols, polycarbonate polyols, polyester polyols and the like. These may be used alone or in combination of two or more.

--Polyether polyol ---
Examples of the polyether polyol include those obtained by addition polymerization of an 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, trimethylolglycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane. Examples thereof include diol, glycerin, trimethylolethane, and trimethylolpropane. These may be used alone or in combination of two or more.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These may be used alone or in combination of two or more.

The polyether polyol is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining an ink binder capable of imparting extremely excellent scratch resistance, polyoxytetramethylene glycol and polyoxy Propylene glycol is preferred. These may be used alone or in combination of two or more.

--Polycarbonate polyol ---
Examples of the polycarbonate polyol that can be used for producing the polyurethane resin particles include those obtained by reacting a carbonic acid ester with a polyol, and those obtained by reacting phosgene with bisphenol A and the like. These may be used alone or in combination of two or more.

Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like. These may be used alone or in combination of two or more.

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, resorcin , Bisphenol-A, Bisphenol-F, 4,4'-biphenol and other relatively low molecular weight dihydroxy compounds; Polyether polyols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol; Polyhexamethylene adipate, polyhexamethylene Examples thereof include polyester polyols such as succinate and polycaprolactone. These may be used alone or in combination of two or more.

--Polyester polyol ---
Examples of the polyester polyol include those obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, polyester obtained by ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymerization thereof. Examples include polyester. These may be used alone or in combination of two or more.

Examples of the low molecular weight polyol include ethylene glycol and propylene glycol. These may be used alone or in combination of two or more.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecandicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, anhydrides or ester-forming derivatives thereof. These may be used alone or in combination of two or more.

-Polyisocyanate-
Examples of the polyisocyanate include aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxyli. Examples thereof include aliphatic or alicyclic diisocyanates such as range isocyanate and 2,2,4-trimethylhexamethylene diisocyanate. These may be used alone or in combination of two or more. Among these, since the ink of the present invention is also used for outdoor applications such as posters and signboards, a coating film having extremely high long-term weather resistance is required, and from the viewpoint of the long-term weather resistance, an alicyclic ring is required. The formula diisocyanate is preferred.

Further, by using at least one kind of alicyclic diisocyanate, it becomes easy to obtain the desired coating film strength and scratch resistance.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate.
The content of the alicyclic diisocyanate is preferably 60% by mass or more with respect to the total amount of the isocyanate compound.

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

Examples of the organic solvent that can be used for producing the polyurethane resin particles include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethyl. Examples thereof include amides such as formamide, N-methylpyrrolidone and N-ethylpyrrolidone. These may be used alone or in combination of two or more.
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; Hydradins such as hydrazine, N, N'-dimethylhydrazine, and 1,6-hexamethylenebishydrazine; dihydrazide succinate, dihydrazide adipic acid , Glutarate dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide and other dihydrazides. These may be used alone or in combination of two or more.

Examples of the other active hydrogen group-containing compound include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol. Glycos such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc. Kind: Water and the like. These may be used alone or in combination of two or more as long as the storage stability of the ink is not deteriorated.

As the polyurethane resin particles, polycarbonate-based polyurethane resin particles are preferable from the viewpoints of water resistance, heat resistance, abrasion resistance, weather resistance, and scratch resistance of images due to the high cohesive force of carbonate groups. In the case of the polycarbonate-based polyurethane resin particles, an ink suitable for printed matter used in a harsh environment such as outdoor use can be obtained.

Commercially available products may be used as the polyurethane resin particles, for example, U-coat UX-485 (polyurethane-based polyurethane resin particles), U-coat UWS-145 (polyurethane-based polyurethane resin particles), and Permarin UA-368T (polyurethane-based polyurethane). Resin particles), Permarin UA-200 (polyether-based polyurethane resin particles) (all manufactured by Sanyo Kasei Kogyo Co., Ltd.) and the like. These may be used alone or in combination of two or more.

<< Fluororesin particles >>
The fluororesin particles can improve high image glossiness, 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 the solvent resistance and the weather resistance. The sex can also be greatly improved.
The fluororesin particles need only have fluorine in the structure, and means that the fluororesin particles are included.

Examples of the fluororesin particles include fluororesin particles having a fluoroolefin-derived structural unit and a structural unit containing a fluorine substituent, fluororesin particles having a fluoroolefin-derived structural unit and a vinyl ether-derived structural unit, and the like. ..
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-dioxol and fluoroolefin. Examples thereof include copolymer resin particles with.

The constituent unit derived from the fluoroolefin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, -CF ₂ CF _{2- , -CF 2} CF (CF ₃ )-, -CF ₂ CFCl- And so on.

The structural unit derived from the vinyl ether is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the following structural units.

The glass transition temperature (Tg) of the fluororesin particles is preferably 100 ° C. or higher and 300 ° C. or lower, and more preferably 150 ° C. or higher and 250 ° C. or lower. When the glass transition temperature is 100 ° C. or higher and 300 ° C. or lower, an image formed on a non-permeable recording medium by an ink containing fluororesin particles and resin particles other than at least one type of fluororesin particles is generally used. Since the fluororesin particles can maintain their shape as particles when dried in a range of 50 ° C. or higher and 150 ° C. or lower, which is a moderate drying temperature, the fluororesin particles are uniform due to resin particles other than one or more types of fluororesin particles. Rather than hindering the formation of the film, the fluororesin particles behave like a filler, so that the strength of the resin formed by the resin particles other than one or more kinds of fluororesin particles can be improved. From this point of view, the glass transition temperature of the fluororesin particles used is preferably higher than the drying temperature of the printed matter, more preferably 20 ° C. or higher, and particularly preferably 50 ° C. or higher.

As the fluororesin particles, those synthesized as appropriate may be used, or commercially available products may be used.
Examples of the commercially available product include, among the Teflon (registered trademark) AF series, trade name: AF1600 (Tg: 160 ° C), trade name: AF2400 (Tg: 240 ° C) (all manufactured by Mitsui-DuPont Fluorochemical Co., Ltd.). ), Product name: Lumiflon FE4400 (manufactured by Asahi Glass Co., Ltd., Tg: 48 ° C.) and the like.

The mass ratio (fluororesin particles / resin particles other than fluororesin particles) of the content (mass%) of the fluororesin particles to the total content (mass%) of the resin particles other than the fluororesin particles is 0.05. More than 4.0 is preferable, 0.1 or more and 2.0 or less is more preferable, and 0.2 or more and 1.5 or less is particularly preferable. When the mass ratio (fluororesin particles / resin particles other than fluororesin particles) is 0.05 or more and 4.0 or less, the fluororesin does not deteriorate the characteristics of the film formed by the resin particles other than the fluororesin particles. Suitable properties of the particles can be imparted to the image.

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

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

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 amount of the fluororesin particle solution. % Or less is preferable, 20% by mass or more and 60% by mass or less is more preferable, and 30% by mass or more and 50% by mass or less is particularly preferable. When the content is 70% by mass or less, in the next dispersion step, an increase in viscosity can be suppressed when mixed with water, the volume average particle size of the obtained aqueous dispersion can be reduced, and storage stability can be improved. Can be improved. Further, when it is 10% by mass or more, it is possible to prevent the concentration of the fluororesin from further decreasing by the next dispersion step, and it is not necessary to remove a large amount of organic solvent in the solvent removal step.
The device for dissolving the fluororesin particles in an organic solvent is provided with a tank into which a liquid can be charged, and is not particularly limited as long as it can be appropriately stirred, and can be appropriately selected depending on the intended purpose.
If the fluororesin particles are difficult to dissolve, they may be heated.

The temperature in the dispersion step is preferably 40 ° C. or lower, more preferably 30 ° C. or lower, further preferably 20 ° C. or lower, and particularly preferably 15 ° C. or lower. When the temperature is 40 ° C. or lower, the average particle size of the obtained aqueous dispersion can be 500 nm or less even if the content of the surfactant or the like is small. The temperature of the dispersion step is preferably maintained at 40 ° C. or lower throughout this step, but it may be difficult to maintain the temperature of the system because the liquid temperature tends to rise due to shear insulation by stirring or the like. Even in such a case, it is preferable to control the temperature to 40 ° C. or lower (not to exceed 40 ° C.) until 0.8 times the amount of water contained in the fluororesin particle solution is added. It is more preferable to control the temperature to 40 ° C. or lower until the amount of water added is completed, and it is particularly preferable to control the temperature to 40 ° C. or lower until the addition of 1.1 times the amount of water is completed.

<< Vinyl chloride resin particles >>
The vinyl chloride resin particles can improve high image glossiness and scratch resistance. Furthermore, 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 viscosity stability over time. can do.

As the vinyl chloride resin particles, vinyl chloride-ethylene copolymer resin particles and vinyl chloride-acrylic copolymer resin particles are preferable from the viewpoint of ensuring compatibility with pigments contained in the ink and other resin particles. Vinyl chloride-ethylene copolymer resin particles are more preferable because they have excellent adhesion to non-polar recording media.

The vinyl chloride resin particles are not particularly limited, and commercially available products can be used. Commercially available vinyl chloride resin particles, commercially available vinyl chloride-acrylic copolymer resin particles, and commercially available vinyl chloride-ethylene copolymer Examples include resin particles. These may be used alone or in combination of two or more.

Examples of the commercially available vinyl chloride resin particles include product number 985 (solid content concentration: 40% by mass, anionic) in the Viniblanc (registered trademark) series manufactured by Nisshin Chemical Industry Co., Ltd.
Examples of the commercially available vinyl chloride-acrylic copolymer resin particles include product numbers 278 (solid content concentration: 43% by mass, anionic) and 700 (solid content concentration: 43% by mass, anionic) in the Vinibran (registered trademark) series manufactured by Nisshin Chemical Industry Co., Ltd. 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), 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) and the like. These may be used alone or in combination of two or more.
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 the Sumi Elite (registered trademark) series manufactured by Sumika Chemtex Co., Ltd. Examples thereof include 1210 (solid content concentration: 50 ± 1% by mass, anionic) and 1320 (solid content concentration: 50 ± 1% by mass, anionic). These may be used alone or in combination of two or more.
Other commercially available products include product number E15 / 48A (solid content concentration: 50% by mass, anion) in the VINNOL series manufactured by Wacker Chemie AG, which is a vinyl chloride-based copolymer resin particle in which a hydroxyl component is introduced into a vinyl chloride resin. (Sex), E22 / 48A (solid content concentration: 30% by mass, anionic) and the like. These may be used alone or in combination of two or more.

<< Polyester resin particles >>
The polyester resin grains can improve high image glossiness and scratch resistance. Furthermore, 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 hydrophilic components such as emulsifiers and sulfonates that remain in the film after drying in order to obtain weather resistance of the image.

As the polyester resin particles, those synthesized as appropriate may be used, or commercially available products may be used.
Examples of the commercially available products include product numbers KZA-1449 (solid content concentration: 30% by mass, anionic) and KZA-3556 (solid content concentration: 30% by mass) in the emulsion Elitel (registered trademark) series manufactured by Unitica Co., Ltd. %, Anionic), KZA-0134 (Solid content concentration: 30% by mass, Anionic), Part number A-124GP (Solid content concentration: 25% by mass) of the Pesresin A series manufactured by Takamatsu Oil & Fat Co., Ltd., A-125S (Solid content concentration: 30% by mass), A-160P (solid content concentration: 25% by mass) and the like. These may be used alone or in combination of two or more.

<< Acrylic-Styrene Copolymer Resin Particles >>
The acrylic-styrene copolymer resin particles can improve high image glossiness and scratch resistance. Furthermore, surprisingly, the combined use of the polysiloxane surfactant, the acrylic-silicone resin particles, and the acrylic-styrene copolymer resin particles can greatly improve the ejection reliability at the time of recording.

The acrylic-styrene copolymer resin particles can prevent clogging at the nozzle and further improve discharge stability.

As the acrylic-styrene copolymer resin particles, those synthesized as appropriate may be used, or commercially available products 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 Kogyo Co., Ltd.), J-140A, QE-1042 (manufactured by Seiko PMC Corporation), and the like. Can be mentioned.

<< Polyvinyl alcohol resin particles >>
The polyvinyl alcohol resin particles can improve water resistance and solvent resistance, and can also improve fixability to a penetrating 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-dispersed state can be improved, and the weather resistance and weather resistance can be improved. 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 acetic acid group of polyvinyl acetate is replaced with a hydroxyl group using an alkaline catalyst in a methanol solvent. At this time, the water resistance of the obtained polyvinyl alcohol resin film is affected by the amount of hydroxyl groups substituted. The hydroxyl group part is hydrophilic and the acetic acid group part is hydrophobic, and it has excellent surface activity.

As the polyvinyl alcohol resin particles, those synthesized as appropriate may be used, or commercially available products may be used.
Examples of the commercially available product include trade name: Poval JF-04, trade name: Poval JF-05, and trade name: Poval JF-17 (all manufactured by Japan Vam & Poval Co., Ltd.).

It is preferable that the resin particles are mixed with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is dispersed as a dispersion medium to obtain an ink.
Considering the ease of adjusting the water-based ink by blending it with an organic solvent, coloring material, and water, and considering that the ink is dispersed as uniformly as possible in the ink, the resin particles are stably dispersed using water as a dispersion medium. It is preferable to add the resin emulsion to the ink in the state of the above.

The resin particles are easily formed into a film by being dissolved in an organic solvent added to the ink, and a film-like recording layer is formed. Film formation of resin particles is promoted as the organic solvent and water evaporate. Therefore, using the ink of the present invention, it is possible to perform recording without a heating step.

When 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-emulsifying 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, and 5 mgKOH / mg or more and 50 mgKOH / g, from the viewpoint of water dispersibility, scratch resistance, and chemical resistance. More preferably, mg or less.

Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. Among these, carboxylate groups and sulfonate groups that are partially or wholly neutralized with a basic compound or the like are 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 neutralizing the 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; and metal base compounds containing Na, K, Li, Ca and the like. These may be used alone or in combination of two or more.
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 alone or in combination of two or more. Among these, a method using a nonionic surfactant is preferable from the viewpoint of water resistance.

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, and polyoxyethylene propylene polyol. Examples thereof include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkyl alkanolamide, and polyalkylene glycol (meth) acrylate. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkyl amine are preferable. These may be used alone or in combination of two or more.

Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurilates, sulfosuccinates, ether sulfonates, and ethers. Examples thereof include carboxylates, fatty acid salts, sodium sulfonate formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, alkylamine oxides and the like. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

When an aqueous dispersion is produced 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, but the forced emulsification type resin It is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less with respect to the total amount of particles. When 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, an ink having excellent adhesion and water resistance can be obtained, and the printed matter does not block. It is preferably used.

The volume average particle diameter of the resin particles is preferably 10 nm or more and 1,000 nm or less, more preferably 10 nm or more and 500 nm or less, and particularly preferably 10 nm or more and 200 nm or less, considering that the resin particles are used in an inkjet printing apparatus. When the volume average particle diameter is 10 nm or more and 1,000 nm or less, the contact portion between the organic solvent and the surface of the resin particles increases, the film-forming property of the resin particles is enhanced, and a continuous coating film of a tough resin is formed. Therefore, a high-strength printed matter can be obtained.
The volume average particle size can be measured using, for example, a particle size analyzer (Microtrack MODEL UPA9340, manufactured by Nikkiso Co., Ltd.).

As the qualitative and quantitative analysis of the resin particles, for example, "Test method and evaluation result of each dynamic property of plastic material (22); by Takeo Yasuda, Plastics: Journal of Japan Plastic Industry Federation / Editorial Committee of" Plastics " It can be confirmed by the procedure as described in detail in. Specifically, it can be confirmed by analysis by infrared spectroscopic analysis (IR), thermal analysis (DSC, TG / DTA), thermal decomposition gas chromatography (PyGC), nuclear magnetic resonance (NMR), or 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, the 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 defined as the glass transition temperature. The measurement is performed in the temperature program and the measured value of the temperature program 3 is used in order to ensure the reproducibility of the measured value.
Temperature program:
1. 30 ° C or higher and 250 ° C or lower: heating rate 30 ° C / min, holding time 1 minute 2. 250 or higher and -100 ° C or lower: cooling rate 30 ° C / min, holding time 30 minutes 3. -100 or more and 250 ° C or less: heating rate 5 ° C / min, holding time 1 minute 4.250 or more and 30 ° C or less: cooling rate 30 ° C / minute, holding time 2 minutes

When the ink of the present invention is heated, the residual solvent can be reduced and the adhesiveness can be improved. In particular, when the minimum film-forming temperature of the resin particles (hereinafter, also referred to as "MFT") exceeds 80 ° C., heating is preferable from the viewpoint that the film-forming defect of the resin can be improved and the image fastness can be improved. .. Further, it is preferable that the heating is performed after the ink is applied to the recording medium and after the recording.

When adjusting the minimum film-forming temperature of the resin emulsion in order to obtain the ink of the present invention, for example, it should be adjusted by controlling the glass transition temperature of the resin particles (hereinafter, also referred to as “Tg”). When the resin particles are copolymers, the resin particles can be adjusted by changing the ratio of the monomers forming the copolymer. The minimum film-forming temperature is the minimum temperature at which a transparent continuous film is formed when resin particles are thinly cast on a metal plate such as aluminum and the temperature is raised. In the temperature range below the minimum film-forming temperature, the emulsion becomes 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.) and "TP-801 MFT tester" (manufactured by Tester Sangyo Co., Ltd.). can do.
Further, since the minimum film-forming temperature also changes depending on the volume average particle size of the resin particles, the minimum film-forming temperature of the resin particles can be set as a target value by a control factor of the volume average particle size 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>
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include water-soluble organic solvents. The term "water-soluble" means that, for example, 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, and 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, ethyl1,2,4-butanetriol, 1,2,3-butanetriol, petriol, etc. Polyvalent alcohols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, etc. Polyvalent alcohol aryl ethers such as alcohol alkyl ethers, ethylene glycol monophenyl ethers and ethylene glycol monobenzyl ethers, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3- Nitrogen-containing heterocyclic compounds such as dimethylimidazolidinone, ε-caprolactam and γ-butyrolactone, amides such as formamide, N-methylformamide, N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine and triethylamine, Examples thereof include sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. These may be used alone or in combination of two or more.

（ただし、前記一般式（１）中、Ｒ_１、Ｒ_２、及びＲ_３は、それぞれ独立に、エーテル結合を有していてもよい炭素数１以上８以下の炭化水素基を表す。） When polyurethane resin particles are contained as other resin particles, it is preferable to contain a compound represented by the following general formula (1) as an organic solvent.
Since the compound represented by the general formula (1) has high resin solubility, it can permeate into a recording medium to improve the drying rate at the time of 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.

(However, in the general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrocarbon group having 1 to 8 carbon atoms which may have an ether bond.)

In the general formula (1), the R _{1, R 2,} and R _3, represents a hydrocarbon group which may number 1 to 8 carbons have an ether bond.
Examples of the hydrocarbon group having 1 or more and 8 or less carbon atoms include a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and the like.
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, R ₁ is preferably a pentyl group, a hexyl group, and an octyl group, more preferably a pentyl group and a hexyl group, and R _{2 and R 3} are preferably a methyl group.

Examples of the compound represented by the general formula (1) include N, N-dimethyl-β-butoxypropionamide, N, N-dimethyl-β-pentoxypropionamide, and 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 alone or in combination of two or more.

The content of the organic solvent is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 60% by mass or less, based on the total amount of ink, from the viewpoint of ink drying property 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>
The water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ion-exchanged water, ultrafiltration water, reverse osmosis water, pure water such as distilled water, and ultrapure water. .. These may be used alone or in combination of two or more.

The water content 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 ink. When the content is 15% by mass or more, high viscosity can be prevented and discharge stability can be improved, and when it is 60% by mass or less, wettability to a non-permeable recording medium becomes preferable. Image quality can be improved.

<Other ingredients>
The other components include coloring materials, surfactants other than polysiloxane surfactants, antiseptic and fungicides, rust preventives, pH adjusters, and rubbers and plastics such as hindered phenol and hindered phenolamine. Examples include colorless anti-aging agents.

<Color material>
The coloring material is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include pigments and dyes. Of these, pigments are preferred.
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 produced by a known method such as a contact method, a furnace method, or a thermal method. Carbon black and the like. These may be used alone or in combination of two or more.

Examples of the organic pigment include azo pigments (including, for example, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments). , Kinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofuralone pigments, etc.), dye chelate (for example, basic dye type chelates, acidic dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. Can be mentioned. These may be used alone or in combination of two or more.
In addition, hollow resin particles and inorganic hollow particles can also be used.
Among these pigments, those having a good affinity with a solvent are preferably used.

Examples of the pigment for black include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, and iron (CI pigment black 11). , Metals such as titanium oxide, organic pigments such as aniline black (CI pigment black 1) and the like. These may be used alone or in combination of two or more.

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; C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51; C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Cadmium 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; C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63; C.I. I. Pigment Greens 1, 4, 7, 8, 10, 17, 18, 36 and the like. These may be used alone or in combination of two or more.

As the dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 52, 80, 82, 249, 254, 289; C.I. I. Acid Blue 9, 45, 249; C.I. I. Acid Black 1, 2, 24, 94; C.I. I. Hood Black 1, 2; C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173; C.I. I. Direct Red 1, 4, 9, 80, 81, 225, 227; C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202; C.I. I. Dilekdo Black 19, 38, 51, 71, 154, 168, 171, 195; C.I. I. Reactive Red 14, 32, 55, 79, 249; C.I. I. Reactive Black 3, 4, 35 and the like can be mentioned. These may be used alone or in combination of two or more.

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin coating pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effects of the present invention are not impaired. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low molecular weight dispersant and a high molecular weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonate Na formalin condensate can also be suitably used as a dispersant.
The dispersant may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with a pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
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. It is preferable to use a disperser for dispersion.
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 the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac 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 mass is used. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
If necessary, the pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifuge, or the like.

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 in terms of the maximum number is preferably 20 nm or more and 150 nm or less. When the number average particle size is 20 nm or more, the dispersion operation and the classification operation become easy, and when it is 150 nm or less, not only the pigment dispersion stability as an ink is improved, but also the ejection stability is excellent. Image quality such as image density is also high, which is preferable.
The number average particle size can be measured using, for example, a particle size analyzer (Microtrack MODEL UPA9340, manufactured by Nikkiso Co., Ltd.).

The content of the coloring material is preferably 0.1% by mass or more and 15% by mass or less, and 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 0.1% by mass or more and 15% by mass or less, 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 1% by mass or more and 10% by mass or less with respect to the total amount of ink. Especially preferable. When the content is 0.1% by mass or more and 15% by mass or less, the 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. For example, an amphoteric surfactant, a nonionic surfactant, an anionic surfactant and the like can be selected. Can be mentioned. These may be used alone or in combination of two or more. Among these, nonionic surfactants are preferable from the viewpoint of dispersion stability and image quality.
Further, depending on the composition, a fluorine-based surfactant or a silicone-based surfactant may be used in combination or alone.

Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include sorbitan fatty acid ester and ethylene oxide adduct of acetylene alcohol. These may be used alone or in combination of two or more.

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, the wettability to the impermeable recording medium can be ensured, so that the image quality can be improved, and when the content is 5% by mass or less, the ink is less likely to foam. Excellent discharge stability can be obtained.

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

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

<Rust inhibitor>
The rust preventive is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

<pH adjuster>
The pH adjusting agent 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 manufacturing method]
As a 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 mixed by stirring. 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 stirring blade, a magnetic stirrer, a high-speed disperser and the like can be used.

The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, 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, or the like can be used, but good image formation can be achieved even if a non-permeable base material is used.
The non-permeable base material is a base material having a surface having low water permeability and low absorbability, and includes a material that does not open to the outside even if there are many cavities inside, and more quantitatively. , A base material having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^{1/2 in the Bristow method.}
As the non-permeable base material, for example, a plastic film such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, polypropylene, polyethylene, or a polycarbonate film can be preferably used.

Further, even if the recording medium is colored by applying white ink before the color ink during color recording (colored recording medium), the color of the recording medium can be aligned with white, and the color ink can be used. Color development can be improved.
Typical examples of the colored recording medium include colored paper, the film, fabrics, clothes, and ceramics.

<Ink container>
The ink container contains the ink of the present invention in the container.
The ink container includes the ink contained in the container, and further includes other members appropriately selected as needed.

The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. For example, an ink bag made of an aluminum laminate film, a resin film, or the like can be used. At least those who have it can be mentioned.

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method of recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, and other devices called pretreatment devices and posttreatment devices. ..
The recording device and recording method may include a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the print surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot 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 device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form a three-dimensional image are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous line printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanical unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage section 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed 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 behind 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. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

The inkjet printing method of the present invention preferably includes an ink ejection step and a heating step, and further includes other steps as necessary.
The inkjet printing apparatus preferably has an ink ejection means, a heating means, and an ink accommodating portion for accommodating ink, and further includes other means as needed.
The inkjet printing method of the present invention can be suitably carried out by the inkjet printing apparatus, and the ink ejection step can be suitably carried out by the ink ejection means. The heating step can be preferably performed by the heating means. In addition, the other steps can be preferably performed by the other means.
Further, it is preferable to include a printing step in which either thermal energy or mechanical energy is applied to the ink to eject the ink for printing.

<< Ink ejection process and ink ejection means >>
The ink ejection step is a step of applying a stimulus to the ink of the present invention, ejecting the ink, and printing on a recording medium.
The ink ejection means applies a stimulus to the ink and ejects the ink having a pressure generating means for applying pressure.
The ink ejection means is not particularly limited, and examples thereof include an ejection head.
Examples of the ejection head include an ink ejection head (inkjet head) and the like.

As the inkjet head, a piezoelectric element is used as a pressure generating means for pressurizing the ink in the ink flow path to deform a vibrating plate forming the wall surface of the ink flow path to change the volume inside the ink flow path and eject ink droplets. The so-called piezo type (see JP-A-2-51734) and the so-called thermal type that heats ink in the ink flow path using a heat generating resistor to generate bubbles (Japanese Patent Laid-Open No. 61-59911). (Refer to the publication), the vibrating plate forming the wall surface of the ink flow path and the electrode are arranged facing each other, and the vibrating plate is deformed by the electrostatic force generated between the vibrating plate and the electrode to change the internal volume of the ink flow path. In any case is included, such as an electrostatic type in which ink droplets are ejected (see JP-A-6-71882).

The stimulus can be generated by, for example, the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected depending on the intended purpose. For example, heat (temperature), pressure, vibration, and light. And so on. These may be used alone or in combination of two or more. Among these, heat and pressure are preferable.

The mode of ejecting the ink is not particularly limited and differs depending on the type of the stimulus and the like. For example, when the stimulus is "heat", the heat corresponding to the recording signal is generated with respect to the ink in the recording head. A method in which energy is applied using, for example, a thermal head, bubbles are generated in the ink by the heat energy, and the ink is ejected as droplets from the nozzle hole of the recording head by the pressure of the bubbles. Can be mentioned. When the stimulus is "pressure", for example, by applying a voltage to the piezoelectric element adhered to a position called a pressure chamber in the ink flow path in the recording head, the piezoelectric element is bent and the pressure chamber is formed. Examples thereof include a method in which the volume is reduced and the ink is ejected as droplets from the nozzle hole of the recording head.

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

Further, because the recording head causes the ink to flow into the plurality of nozzles for ejecting the ink, the individual liquid chambers communicating with the nozzles, the common liquid chamber for supplying the liquid to the individual liquid chambers, and the individual liquid chambers. The inflow flow path, the circulation flow path leading to the individual liquid chamber, the circulation common liquid chamber leading to the circulation flow path, the outflow flow path for discharging ink from the individual liquid chamber, and the individual liquid chamber. It is preferable to provide a pressure generating means for applying pressure to the liquid. Further, it is preferable to further have a circulation means for circulating the ink from the inflow channel to the outflow channel, and to operate the circulation step during non-printing.

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

Hereinafter, an example of an ink ejection head used in the inkjet printing method of the present invention will be described.
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. An example of the liquid discharge head according to the embodiment of the present invention will be described with reference to FIGS. 4 to 11. 4 is an external perspective explanatory view showing 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 shown in FIG. 4, and FIG. 6 is a cross-sectional view taken along the line AA'of FIG. 7 is a cross-sectional view taken along the line BB'of FIG. 5, FIG. 8 is an explanatory cross-sectional 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. 10 is a plan explanatory view of each member constituting the flow path member of the liquid discharge head shown in FIG. 4, and FIG. 11 is a plan explanatory view of each member constituting the common liquid chamber member of the liquid discharge head shown in FIG. It is a plan explanatory view.
The ink ejection head preferably has an inflow flow path for allowing ink to flow into the individual liquid chambers and an outflow flow path for causing ink to flow out of the individual liquid chambers.

In this liquid discharge head, a nozzle plate 1, a flow path plate 2, and a diaphragm 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 for discharging a liquid.
The flow path plate 2 forms an individual liquid chamber 6 leading to the nozzle 4, a fluid resistance portion 7 communicating with the individual liquid chamber 6, and a liquid introduction portion 8 communicating with the fluid resistance portion 7. Further, the flow path plate 2 is formed by laminating and joining a plurality of plate-shaped members 41 to 45 from the nozzle plate 1 side, and laminating and joining these plate-shaped members 41 to 45 and the diaphragm member 3 to form a flow path. The 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-walled portion from the flow path plate 2 side and a second layer that forms a thick-walled portion, and the first layer is an individual liquid. A deformable vibration region 30 is formed in a portion corresponding to the chamber 6.

Here, as shown in FIG. 9, a plurality of nozzles 4 are arranged in a staggered pattern on the nozzle plate 1.
As shown in FIG. 10A, the plate-shaped 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 and a fluid resistance portion 51. Through groove portions 51a and 52a forming the circulation flow path 52 are formed.
Similarly, as shown in FIG. 10B, the plate-shaped member 42 is formed with a through groove portion 6b forming the individual liquid chamber 6 and a through groove portion 52b forming the circulation flow path 52.
Similarly, as shown in FIG. 10C, the plate-shaped member 43 is formed with a through groove portion 6c constituting the individual liquid chamber 6 and a through groove portion 53a having the nozzle arrangement direction forming the circulation flow path 53 as the longitudinal direction. Has been done.
Similarly, as shown in FIG. 10D, the plate-shaped member 44 has a through groove portion 6d forming the individual liquid chamber 6, a through groove portion 7a forming the fluid resistance portion 7, and a through groove portion 8a forming the liquid introduction portion 8. And the through groove portion 53b having the nozzle arrangement direction forming the circulation flow path 53 as the longitudinal direction is formed.
Similarly, as shown in FIG. 10E, the plate-shaped member 45 has a through groove portion 6e constituting the individual liquid chamber 6 and a through groove portion 8b (filter) having the nozzle arrangement direction constituting the liquid introduction portion 8 as the longitudinal direction. (It becomes the liquid chamber on the downstream side), and a through groove portion 53c having a longitudinal direction of the nozzle arrangement forming the circulation flow path 53 is formed.

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 53d whose longitudinal direction is the nozzle arrangement direction constituting the circulation flow path 53. ..
In this way, by forming the flow path member by laminating and joining a plurality of plate-shaped members, it is possible to form a complicated flow path with a simple structure.

With the above configuration, the flow path member 40 composed of the flow path plate 2 and the diaphragm member 3 has a fluid resistance portion 51, a circulation flow path 52, and circulation along the surface direction of the flow path plate 2 leading to each individual liquid chamber 6. A circulation flow path 53 in the thickness direction of the flow path member 40 leading to the flow path 52 is formed. The circulation flow path 53 leads to the circulation common liquid chamber 50, which will be 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 the 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 has a through hole 25a for a piezoelectric actuator, a through groove portion 10a serving as a downstream common liquid chamber 10A, and circulation. A groove portion 50a having a bottom that serves as a common liquid chamber 50 is formed.
Similarly, as shown in FIG. 11B, the second common liquid chamber member 22 is formed with a through hole 25b for the piezoelectric actuator and a groove portion 10b serving as the upstream common liquid chamber 10B.
Further, with reference to FIG. 4, the second common liquid chamber member 22 is formed with a through hole 71a which is an end portion of the common liquid chamber 10 in the nozzle arrangement direction and a supply port portion through which the supply port 71 is passed.
Similarly, the first common liquid chamber member 21 and the second common liquid chamber member 22 are provided with the other end (the end opposite to the through hole 71a) of the circulation common liquid chamber 50 in the nozzle arrangement direction and the circulation port 81. Through holes 81a and 81b are formed.
In addition, in FIG. 11, the groove portion having a bottom is shown by applying a surface coating (the same applies to the following figures).

As described above, the common liquid chamber member 20 is composed of 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 10A which is a part of the common liquid chamber 10 leading to the liquid introduction portion 8 and a circulation common liquid chamber 50 leading to the circulation flow path 53. ing. Further, the second common liquid chamber member 22 forms the upstream common liquid chamber 10B which is the rest of the common liquid chamber 10.

At this time, the downstream common liquid chamber 10A and the circulation common liquid chamber 50, which are a part of the common liquid chamber 10, are arranged side by side in the direction orthogonal to the nozzle arrangement direction, and the circulation common liquid chamber 50 is the common liquid chamber 10. It is placed at the position projected inside.
As a result, the dimensions of the circulation common liquid chamber 50 are not restricted by the dimensions 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.

Then, 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 in the common liquid chamber 10 so as to be orthogonal to the nozzle arrangement direction. The width of the head in the direction can be suppressed, and the increase in size of the head can be suppressed. The common liquid chamber member 20 forms a circulation common liquid chamber 50 with a common liquid chamber 10 to which liquid is supplied from a head tank or a liquid cartridge.

On the other hand, on the side of the diaphragm member 3 opposite to the individual liquid chamber 6, a piezoelectric actuator 11 including an electromechanical conversion element as a driving means for deforming the vibration region 30 of the diaphragm member 3 is arranged.

As shown in FIG. 8, the piezoelectric actuator 11 has a piezoelectric member 12 joined on a base member 13, and the piezoelectric member 12 is grooved by half-cut dicing to obtain a required number for one piezoelectric member 12. The columnar piezoelectric elements 12A and 12B are formed in a comb-teeth shape at predetermined intervals.

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 column without giving a drive waveform, but all the piezoelectric elements 12A and 12B are driven. It can also be used as a piezoelectric element.
Then, the piezoelectric element 12A is joined to the convex portion 30a which is an island-shaped thick portion formed in the vibration region 30 of the diaphragm member 3. Further, the piezoelectric element 12B is joined to the convex portion 30b which is a thick portion of the diaphragm member 3.

The piezoelectric member 12 is formed by alternately stacking piezoelectric layers and internal electrodes. The internal electrodes are pulled out to their end faces to provide external electrodes, and the flexible wiring member 15 is connected to the external electrodes.

In the liquid discharge head configured in this way, 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 vibrating plate member 3 descends, and the volume of the individual liquid chamber 6 As the liquid expands, the liquid flows into the individual liquid chamber 6.

After that, 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 vibrating plate 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, the individual liquid chamber 6 expands, and a negative pressure is generated. The liquid is filled from the chamber 10 into the individual liquid chamber 6. Therefore, after the vibration of the meniscus surface of the nozzle 4 is attenuated and stabilized, the operation for the next ejection is started.

The driving method of this head is not limited to the above example (pull-pushing), and pulling or pushing may be performed depending on the driving waveform. Further, in the above-described embodiment, the laminated piezoelectric element has been described as the pressure generating means for giving 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. .. Further, it is possible to use a heat-generating resistor arranged in the individual liquid chamber 6 to generate air bubbles by the heat generated by the heat-generating resistor to cause pressure fluctuation, or to generate pressure fluctuation by 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 the present 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 to 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 is connected to 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 the first liquid feed pump, and the other of the circulation tanks is connected to the main tank via the 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 and is discharged to the circulation tank, and further, the liquid is sent from the circulation tank to the supply tank by the first liquid feed pump. The liquid circulates by being pumped.

Further, a compressor is connected to the supply tank, and the pressure sensor on the supply side is controlled so that a predetermined positive pressure is detected. On the other hand, a vacuum pump is connected to the circulation tank, and the circulation side pressure sensor is controlled to detect a predetermined negative pressure. As a result, the negative pressure of the meniscus can be kept constant while circulating the liquid through the liquid discharge head.

Further, when droplets are discharged from the nozzle of the liquid discharge head, the amount of liquid in the supply tank and the circulation tank decreases. Therefore, the liquid from the main tank to the circulation tank is appropriately used from the main tank to the circulation tank. 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 provided in the circulation tank, such as replenishing the liquid when the liquid level height of the ink in the circulation tank falls below the specified height. Can be controlled.

Next, the circulation of the liquid 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 each connected to a supply tank / circulation tank (see FIG. 12) for storing liquid via a tube. 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 section 8, and the fluid resistance section 7.

Further, 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 that remains 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.
It should be noted that the circulation of the liquid can be carried out not only when the liquid discharge head is operated but also when the operation is stopped. By circulating during the suspension of operation, the liquid in the individual liquid chamber is constantly refreshed, and the aggregation and sedimentation of the components contained in the liquid can be suppressed, which is preferable.

Further, an example of a recording device using the discharge head will be described.

Next, an example of the device for discharging the liquid according to the present invention will be described with reference to FIGS. 13 and 14. FIG. 13 is a plan view of a main part showing an example of a device for discharging a liquid, and FIG. 14 is a side explanatory view of a main part showing an example of a device for discharging a liquid.
This device is a serial type device, and the carriage 403 is reciprocated 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 drive pulley 406, a driven pulley 407, and the like. The guide member 401 is bridged over the left and right side plates 491A and 491B to movably hold the carriage 403. Then, the carriage 403 is reciprocated in the main scanning direction by the main scanning motor 405 via the timing belt 408 bridged between the drive pulley 406 and the driven pulley 407.

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

The liquid is supplied and circulated in the liquid discharge head 404 by the 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. Further, the supply side pressure sensor is connected between the supply tank and the liquid discharge head and is connected to 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 is connected to the circulation flow path side connected to the circulation port 81 of the liquid discharge head.

This device includes a transport mechanism 495 for transporting the paper 410. The transport mechanism 495 includes a transport belt 412, which is a transport means, and a sub-scanning motor 416 for driving the transport belt 412.
The transport belt 412 attracts the paper 410 and transports it at a position facing the liquid discharge head 404. The transport belt 412 is an endless belt, and is hung between the transport roller 413 and the tension roller 414. Adsorption can be performed by electrostatic adsorption, air suction, or the like.

Then, the transport belt 412 orbits in the sub-scanning direction by rotationally driving the transport roller 413 via the timing belt 417 and the timing pulley 418 by the sub-scanning motor 416.

Further, on one side of the carriage 403 in the main scanning direction, a maintenance / recovery mechanism 420 for maintaining / recovering the liquid discharge head 404 is arranged on the side of the transport belt 412.
The maintenance / recovery mechanism 420 is composed of, for example, a cap member 421 that caps the nozzle surface (the surface on which the nozzle is formed) of the liquid discharge head 404, a wiper member 422 that wipes 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 device configured in this way, the paper 410 is fed onto the transport belt 412 and sucked, and the paper 410 is conveyed in the sub-scanning direction by the circumferential movement of the transport belt 412.
Therefore, by driving the liquid discharge head 404 in response to the image signal while moving the carriage 403 in the main scanning direction, the liquid is discharged to the stopped paper 410 to form an image.

As described above, since this device includes the liquid discharge head used in the present invention, it is possible to stably form a high-quality image.
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.

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

In the present application, the "liquid discharge head" is a functional component that discharges and ejects a liquid from a nozzle.

Piezoelectric actuators (laminated piezoelectric elements and thin-film piezoelectric elements), thermal actuators that use electrothermal conversion elements such as heat-generating resistors, and electrostatic actuators that consist of a vibrating plate and counter electrodes are used as energy sources for discharging liquids. Includes what to do.
The "liquid discharge unit" is a liquid discharge head integrated with functional parts and a mechanism, and is an aggregate of parts related to liquid discharge. 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, "integration" means, for example, a liquid discharge head and a functional component, a mechanism in which the mechanism is fixed to each other by fastening, adhesion, engagement, etc., or one in which one is movably held with respect to the other. Including. Further, the liquid discharge head, the functional component, and the mechanism may be detachably attached to each other.
For example, as a liquid discharge unit, there is a liquid discharge head in which a supply / circulation mechanism is integrated. In addition, there are some that are connected to each other by a tube or the like to integrate the liquid discharge head and the supply / circulation mechanism. Here, a unit including a filter can be added between the supply / circulation mechanism of these liquid discharge units and the liquid discharge head.
Further, as a liquid discharge unit, there is a liquid discharge head and a carriage integrated.

Further, as a liquid discharge unit, there is a liquid discharge head in which the liquid discharge head and the scanning movement mechanism are integrated by holding the liquid discharge head movably by a guide member forming a part of the scanning movement mechanism.

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

Further, as a liquid discharge unit, there is a liquid discharge unit in which a tube is connected to a liquid discharge head to which a supply / circulation mechanism or a flow path component is attached, and the liquid discharge head and the supply mechanism are integrated. Through this tube, the liquid of the liquid storage source is supplied to the liquid discharge head.
The main scanning movement mechanism shall also include a single guide member. Further, the supply mechanism includes a single tube and a single loading unit.

In the present invention, the "device for discharging a liquid" is a device provided with a liquid discharge head or a liquid discharge unit and driving the liquid discharge head to discharge the liquid. The device for discharging the liquid includes not only a device capable of discharging the liquid to a device to which the liquid can adhere, but also a device for discharging the liquid toward the air or the liquid.

The "device for discharging the liquid" can also include means for feeding, transporting, and discharging paper to which the liquid can adhere, as well as a pretreatment device, a posttreatment device, and the like.

Further, the "device for discharging a liquid" is not limited to a device in which a significant image such as characters and figures is visualized by the discharged liquid. For example, those that form patterns that have no meaning in themselves and those that form a three-dimensional image are also included.
The above-mentioned "material to which a liquid can adhere" means a material to which a liquid can adhere at least temporarily, such as one that adheres and adheres, and one that adheres and permeates. Specific examples include media such as paper, recording paper, recording paper, film, cloth, and other recording media, electronic substrates, electronic components such as piezoelectric elements, powder layers (powder layers), organ models, and inspection cells. Yes, including anything to which the liquid adheres, unless otherwise specified.

The material of the above-mentioned "material to which liquid can be attached" may be paper, thread, fiber, cloth, leather, metal, plastic, glass, wood, ceramics or the like as long as the liquid can be attached even temporarily.

Further, the "device for discharging the liquid" includes, but is not limited to, a device in which the liquid discharge head and the device to which the liquid can adhere move relatively. Specific examples include a serial type device that moves the liquid discharge head, a line type device that does not move the liquid discharge head, and the like.

In the present invention, the "liquid discharge head" is a functional component that discharges and ejects a liquid from a nozzle.
The liquid to be discharged may have a viscosity and surface tension that can be discharged from the head, and is not particularly limited, but has a viscosity of 30 mPa · s or less at room temperature, under normal pressure, or by heating or cooling. Is preferable. More specifically, solvents such as water and organic solvents, colorants such as dyes and pigments, polymerizable compounds, resins, functionalizing materials such as surfactants, biocompatible materials such as DNA, amino acids and proteins, and calcium. , Solvents, suspensions, emulsions, etc. containing edible materials such as natural pigments, etc., which are, for example, inks for inkjets, surface treatment liquids, components of electronic elements and light emitting elements, and electronic circuit resist patterns. It can be used in applications such as a forming liquid and a material liquid for three-dimensional modeling.

In addition, image formation, recording, printing, printing, printing, modeling, etc. in the terms of the present application are all synonymous.

<< Heating process and heating means >>
The heating step is a step of heating a recording medium on which an image is recorded, and can be carried out by a heating means.
As the inkjet printing method, high image quality recording can be performed on a non-penetrating recording medium as the recording medium, but an image having higher image quality, scratch resistance, and high adhesion to the recording medium can be formed. It is preferable to heat the impermeable recording medium after recording so that it can cope with high-speed recording conditions. When the heating step is included after recording, the 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, more preferably 40 ° C. or higher and 100 ° C. or lower, and particularly preferably 50 ° C. or higher and 90 ° C. or lower, from the viewpoint of drying property and film formation temperature. When the heating temperature is 40 ° C. or higher and 120 ° C. or lower, damage due to heat of the impermeable recording medium can be prevented, and 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, by driving the recording head in response to the image signal while moving the carriage 133, ink droplets are ejected to the stopped recording medium 142 to record an image. The image formed on the recording medium 142, which is on the guide member 153 that holds the recording medium down and is conveyed on the transfer belt 151 that is stretched between the transfer roller 157 and the tension roller 158, is warm air. Warm air 202 is blown by a heating fan 201 as a generating part to dry it.
A heater group 203 is provided on the opposite side of the transport belt 151 from the recording medium 142, and the image-formed recording medium 142 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 a stimulus generating means, a controlling means, and the like.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generator, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element and a heat generating resistor. Examples thereof include a thermal actuator that utilizes a phase change due to a film boiling of a liquid using an electrothermal conversion element such as, a shape memory alloy actuator that uses a metal phase change due to 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 of the means can be controlled, and can be appropriately selected depending on the intended purpose. Examples thereof include devices such as sequencers and computers.

As an example of the inkjet printing method of the present invention, there is a step of applying a pigment-free clear ink or an ink containing a white pigment as a coloring material (white ink) to a recording medium, and a color coloring material. It is also possible to use a recording method including 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 applied to a part of the recording medium, for example, it may be applied to the same place as the place where recording is performed, or may be applied to a part common to the place 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 ink of a color other than white is used on the recording medium for recording. According to this method, for example, even when a transparent film is used, the white ink adheres to the surface of the recording medium, so that the visibility of recording can be ensured. Since the ink of the present invention has good drying property, high gloss, scratch resistance, etc. even for a non-penetrating recording medium, white ink is used for a non-penetrating recording medium such as a transparent film in order to improve visibility. Can be applied.

Further, by applying white ink after recording on a transparent film, it is possible to obtain an image having the same excellent visibility. 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 inkjet printing method and can be widely used. In addition to the inkjet printing method, for example, the blade coating method, the gravure coating method, the gravure offset coating method, the bar coating method, the roll coating method, the knife coating method, the air knife coating method, the comma coating method, the U comma coating method, and the AKKU coating method. , Smoothing coat method, micro gravure coat method, reverse roll coat method, 4 to 5 roll coat method, dip coat method, curtain coat method, slide coat method, die coat method, spray coat method and the like.
As an example of the embodiment, when the white ink is applied to the entire surface of the recording medium, it is applied by a coating method other than the inkjet printing method, and when recording with an ink of a color other than white, it is recorded by the inkjet printing method. It is possible to do so.
As another embodiment, both recording using white ink and recording using ink of a color other than white can be recorded 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. And has other members as needed.
The printed matter can be preferably obtained by an inkjet printing apparatus and an inkjet printing method.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Preparation Example 1 of Pigment Dispersion)
<Preparation of self-dispersing black pigment dispersion>
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using 0.3 mm diameter zirconia balls) to self-disperse black pigment dispersion (Pigment solid content concentration: 15% by mass) was obtained.
・ Carbon black pigment (trade name: Monarch800, manufactured by Cabot Corporation) ・ ・ ・ 15 parts by mass ・ Anionic surfactant (trade name: Pionin A-51-B, manufactured by Takemoto Oil & Fat Co., Ltd.) ・ ・ ・ 2 parts by mass ・Ion-exchanged water: 83 parts by mass

(Preparation Example 2 of Pigment Dispersion)
<Preparation of self-dispersing cyan pigment dispersion>
Similar to Preparation Example 1 of Pigment Dispersion, 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.) in Preparation Example 1 of the pigment dispersion. 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 Preparation Example 1 of the pigment dispersion, the carbon black pigment was changed to Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.) in the same manner as in Preparation Example 1 of the pigment dispersion. A dispersed 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 the pigment dispersion, the carbon black pigment was changed to Pigment Yellow 74 (trade name: First Yellow 531; manufactured by Dainichi Seika Kogyo Co., Ltd.) in the same manner as in Preparation Example 1 of the pigment dispersion. , A self-dispersing yellow pigment dispersion (pigment solid content concentration: 15% by mass) was obtained.

(Preparation Example 5 of Pigment Dispersion)
<Preparation of resin-dispersed black pigment dispersion>
-Preparation of polymer solution A-
After sufficient nitrogen gas substitution in a 1 L flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas introduction tube, a reflux tube, and a dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, and lauryl methacrylate 12. 0 g, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (trade name: AS-6, manufactured by Toa Synthetic Co., Ltd.), and 0.4 g of mercaptoethanol were mixed and heated to 65 ° C. Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyl ethyl methacrylate 60.0 g, styrene macromer 36.0 g, mercaptoethanol 3.6 g, azobismethyl A mixed solution of 2.4 g of valeronitrile and 18.0 g of methyl ethyl ketone was added dropwise into the flask over 2.5 hours. After the dropping, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18.0 g of methyl ethyl ketone was added dropwise to the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added, and the mixture was further aged for 1 hour. After completion of the reaction, 364.0 g of methyl ethyl ketone was added into the flask to obtain 800 g of 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. Kneaded using. The obtained paste was put into 200 g of pure water, stirred sufficiently, and then methyl ethyl ketone and water were distilled off with an evaporator, and in order to further remove coarse particles, the obtained dispersion was made of a poly having an average pore size of 5.0 μm. 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 was obtained by pressure filtration with a vinylidene floride membrane filter (trade name: Durapore SVLP04700, manufactured by Merck). ..

(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 containing a stirrer, a reflux cooling tube, and a thermometer. Parts, 220 parts by mass of 2,2-dimethylolpropionic acid (hereinafter, also referred to as "DMPA"), and 1,347 parts by mass of N-methylpyrrolidone (hereinafter, also referred to as "NMP") are nitrogen. It 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 dilaurylate (catalyst) were added and heated to 90 ° C., and a urethanization reaction was carried out over 5 hours. 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, and 5,400 parts by mass of water and 15 parts by mass of triethylamine were extracted under strong stirring. Was added to the mixed solution of.
Next, 1,500 parts by mass of ice was added, and 626 parts by mass of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction so that the solid content concentration became 30% by mass. The solvent was distilled off from the mixture to obtain a polycarbonate-based polyurethane resin emulsion.
The obtained polycarbonate-based polyurethane resin emulsion was measured with a "film-forming temperature tester" (manufactured by Imoto Seisakusho Co., Ltd.), and the minimum film-forming temperature was 55 ° C.

(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 a polyether polyol (“PTMG1000”, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 1,000), 2,2-Dimethylol propionic acid 15.7 parts by mass, isophorone diisocyanate 48.0 parts by mass, and methyl ethyl ketone 77.1 parts by mass as an organic solvent, and dibutyltin dilaurate as a catalyst (hereinafter, also referred to as "DMTDL"). 0.06 parts by mass was used and reacted.
After continuing the reaction for 4 hours, 30.7 parts by mass of methyl ethyl ketone was supplied as a diluting solvent, and the reaction was further continued.
When the weight average molecular weight of the reaction product reaches the range of 20,000 or more and 60,000 or less, 1.4 parts by mass of methanol is added and the reaction is terminated to obtain an organic solvent solution of urethane resin. It was.
The carboxyl group of the urethane resin was neutralized by adding 13.4 parts by mass of a 48 mass% potassium hydroxide aqueous solution to the organic solvent solution of the urethane resin. Then, 715.3 parts by mass of water was added, and the mixture was sufficiently stirred, followed by aging and desolvation to obtain a polyether polyurethane resin emulsion having a solid content concentration of 30% by mass.
With respect to the obtained polyether polyurethane resin emulsion, the minimum film forming temperature was measured in the same manner as in Preparation Example 1 of the polycarbonate 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, a polyether polyol (“PTMG1000”, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 1,000) is used as a polyester polyol (“Polylite OD-X-2251”, manufactured by DIC Co., Ltd.). , Weight average molecular weight: 2,000), a polyester-based 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.
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 of the polycarbonate-based polyurethane resin emulsion. As a result, the minimum film forming temperature was 74 ° C.

(Example A1)
Self-dispersion type black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Industry Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-Silicone Resin Emulsion 4 (trade name: AE980, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): -14 ° C.) 2.0% by mass, polycarbonate-based 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, dipropylene glycol monomethyl ether 4.0 Mass%, as an antiseptic, trade name: Proxel LV (manufactured by Abyssia) 0.1% by mass, and high pure water are added so as to be the remaining amount, mixed and stirred, and a polypropylene filter having an average pore size of 0.2 μm (product). Name: Ink A1 was produced by filtering with a Betafine polypropylene pleated filter PPG series (manufactured by 3M).

(Examples A2 to A12 and Comparative Examples A1 to A2)
In Example A1, Examples A2 to A12 and Comparative Examples A1 to A2 are the same as in Example A1 except that the composition and the content are changed to those shown in Tables A-1 to A-3 below. Inks A2 to A14 of the above were prepared.

In Tables A-1 to A-3, the product names of the ingredients 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: Made by Shin-Etsu Chemical Co., Ltd., Product name: KF-945, HLB value: 4.0
-Polyether-modified silicone 2: Made by Shin-Etsu Chemical Co., Ltd., Product name: KF-6017, HLB value: 4.5
• Polyether-modified Silicone 3: Ultra Adives Inc. Made by the company, 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: Made by Toray Dow Co., Ltd., Product name: SH-3772M, HLB value: 6.0
-Polyether-modified silicone 5: Manufactured by Nissin Chemical Industry Co., Ltd., Product name: Silface SAG005, HLB value: 7.0
-Polyether-modified silicone 6: Made by Toray Dow Co., Ltd., Product 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: Made by Shin-Etsu Chemical Co., Ltd., Product name: KF-353, HLB value: 10.0
-Acrylic-silicone resin emulsion 1: manufactured by Daicel FineChem Co., Ltd., 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: Made by Toa Synthetic Co., Ltd., Product name: Cymac 480, Solid content concentration: 30% by mass, Tg: 0 ° C.
-Acrylic-silicone resin emulsion 4: Product name: AE980, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, Tg: -14 ° C.
-Acrylic-silicone resin emulsion 5: Product name: AE981A, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, Tg: -15 ° C.
-Acrylic-silicone resin emulsion 6: Product name: AE982, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, Tg: 0 ° C.
-Preservative: Made by Abyssia Co., Ltd., Product 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 property (beading)" and "scratch resistance" is considerably stricter than that of recording on ordinary paper.

<Storage stability (appearance evaluation)>
30 mL capacity container (trade name: Glass Bayer SV-30, manufactured by Nichiden Rika Glass Co., Ltd.), 50 ° C., 60 ° C., and the obtained inks A1 to A14 of Examples A1 to A12 and Comparative Examples A1 to A2. 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 actual use that the evaluation is B or higher.
[Evaluation criteria]
A: No phase separation in 70 ° C storage B: No phase separation in 60 ° C storage but phase separation in 70 ° C storage C: No phase separation in 50 ° C storage but in 60 ° C storage Phase-separated D: Phase-separated when stored at 50 ° C.

[Formation of solid image]
Next, the obtained inks A1 to A12 of Examples A1 to A12 and inks A1 to A14 of Comparative Examples A1 to A2 were filled in an inkjet printer (device name: IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.), and a polyvinyl chloride film (CPPVWP1300) was filled. , Made by Sakurai Co., Ltd., hereinafter also referred to as "PVC film"), a solid image was recorded with 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 AS ONE Corporation) set at 80 ° C. for 1 hour.
The IPSiO GXe5500 remodeling machine is a remodeling of the IPSiO GXe5500 machine so that ^{a recording equivalent to a recording speed of 30 m 2} / hr with a printing width of 150 cm can be reproduced in A4 size, and the pot plate is installed and recorded. It was modified so that the later heating conditions (heating temperature, heating time) could be changed.

<Fixability (beading)>
The recording unevenness of the solid image formed on the PVC film recording medium was visually observed, and the "fixability (beading)" was evaluated based on the following evaluation criteria. It is desirable in actual use that the evaluation is B or higher.
[Evaluation criteria]
A: Very good (no beading at all)
B: Good (slight beading was observed)
C: Normal (there was beading)
D: Bad (there was significant beading)

<Scratch resistance>
A solid image formed on a 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 obtained based on the following evaluation criteria. Was evaluated. It is desirable in actual use that the evaluation is B or higher.
[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 times or more and 49 times or less No C: The image did not change even after rubbing 30 times or less.

<Solvent resistance>
A solid image formed on a PVC film recording medium is immersed in a 60 mass% ethanol aqueous solution at room temperature (25 ° C.) for 24 hours, then naturally dried at room temperature (25 ° C.) for 24 hours, and then X-Rite938 (X). -Measure the image density using (manufactured by Rite), calculate 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, and based on the following evaluation criteria, "solvent resistance""Gender" was evaluated. It is desirable in actual use that the evaluation is B or higher.
〔Evaluation criteria〕
AA: Decrease in image density value is less than 10% A: Decrease in image density value is 10% or more and less than 20% B: Decrease in image density value is 20% or more and less than 30% C: 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 glossiness meter (manufactured by BYK Gardener, 4501), the average value of the gloss values was calculated, and based on the following evaluation criteria, ""Imageglossiness" was evaluated. It is desirable in actual use that the evaluation is B or higher.
〔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 a solid image formed on a PVC film recording medium, the number of remaining cells of 100 test cells was counted by a grid peeling test using a cloth adhesive tape (Nichiban Co., Ltd., 123LW-50), and the following evaluation was performed. Based on the criteria, the "adhesion" to the recording medium was evaluated. It is desirable in actual use that the evaluation is B or higher.
〔Evaluation criteria〕
AA: Number of remaining cells is 98 or more A: Number of remaining cells is 90 or more and less than 98 B: Number of remaining cells is 70 or more and less than 90 C: Number of remaining cells is less than 70

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

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

From the results in 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 the effect of different printing devices)
<Test Example 1>
The ink A6 of Example A6 was filled in a printing recording device (IPSiO GXe5500 (manufactured by Ricoh Corporation) remodeling machine) and left for 24 hours in an environment of temperature: 35 ° C. and humidity: 30% RH. During leaving, the circulation mechanism was operated once an hour for 2 minutes. In addition, the circulation mechanism was operated for 1 minute before printing.
Next, after being left to stand, in an environment of temperature: 35 ° C. and humidity: 30% RH, a polyvinyl chloride film (CPPVWP1300, manufactured by Sakurai Co., Ltd., hereinafter also referred to as "PVC film") recording medium. A solid image was obtained when the amount of ink adhered was 0.6 g / cm ^2. After recording, the solid image was dried on a hot plate (device name: NINOS ND-1, manufactured by AS ONE Corporation) set at 80 ° C. for 1 hour. 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. 4 to 15.

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 the device name: X-Rite938 (manufactured by X-Rite), and the average value, maximum value (Max) and minimum value of the measured values were measured. The difference value (Max-Min) of the value (Min) was calculated.

(Density uniformity of solid image)
Using the obtained solid image, "density uniformity of the solid image" was evaluated based on the following evaluation criteria. In addition, B or higher is a level at which there is no problem in actual use.
〔Evaluation criteria〕
A: Solid image is uniform B: There is some density unevenness when looking closely at the solid image C: There is large unevenness in the density of the solid image D: There is large unevenness in the density of the solid image, and some recording media You can see the white background of

(Isolated dot diameter)
Using the ink A6 of Example A6, a nozzle check pattern is printed under the same equipment and conditions, and an observation image of isolated dots at a magnification of 450 times is taken with a digital microscope to measure the diameter of the isolation dots. Got Next, the obtained image was binarized with image processing software, and the diameters of the isolated dots were calculated. The number of observation images of isolated dots is 28 dots.

<Test Example 2>
In Test Example 1, a solid image was obtained in the same manner as in Test Example 1 except that the print recording device (IPSiO GXe5500 (manufactured by Ricoh Co., Ltd.) modified machine) was changed to IPSiO GXe5500 (manufactured by Ricoh Co., Ltd.). Since the IPSiO GXe5500 does not have a mechanism for circulating ink, the ink does not circulate.

Using the obtained solid image, "image density", "solid image density uniformity", 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 in Table A-5, Test Example 1 using a printing device having a mechanism for circulating ink in the head was compared with Test Example 2 using a printing device 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 ink A6 used in Test Example 1 is circulated and stirred, so that even if the ink using the surfactant having a low HLB value is left at a high temperature, the phase separation of the surfactant is suppressed. it is conceivable that.

(Example B1)
Self-dispersion type black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Industry Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-Silicone Resin Emulsion 4 (Product Name: AE980, manufactured by E-Tech Co., Ltd., Solid Content Concentration: 50% by Mass, Glass Transition Temperature (Tg): -14 ° C) 2.0% by Mass, Fluororesin Emulsion 1 (Mitsui) -Manufactured by 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-methylbutanol 3.0% by mass, 2 -Methyl-2,4-pentandiol 3.0% by mass, dipropylene glycol monomethyl ether 4.0% by mass, trade name as a preservative: Proxel LV (manufactured by Abyssia) 0.1% by mass, and high pure water remaining Ink B1 was prepared by adding the mixture so as to be the same, 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, manufactured by 3M Co., Ltd.).

(Examples B2 to B12 and Comparative Examples B1 to B2)
In Example B1, Examples B2 to B12 and Comparative Examples B1 to B2 are the same as in Example B1, except that the composition and the content are changed to those shown in Tables B-1 to B-3 below. Inks B2 to B14 of the above were prepared.

In Tables B-1 to B-3, the product names of the ingredients and the names of the manufacturing companies are as follows.
-Fluororesin emulsion 1: Mitsui-DuPont Fluorochemical Co., Ltd., trade name: Teflon (registered trademark) AF160, solid content concentration: 30% by mass, Tg: 160 ° C.
-Fluororesin emulsion 2: Mitsui-DuPont Fluorochemical Co., Ltd., trade name: Teflon (registered trademark) AF2400, solid content concentration: 30% by mass, Tg: 240 ° C.
-Fluororesin emulsion 3: Made by Asahi Glass Co., Ltd., Product name: Lumiflon FE4400, Solid content concentration: 30% by mass, Tg: 48 ° C.
The colorants in Tables B-1 to B-3, polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives are the colorants in Tables A-1 to A-3. Similar to polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives were used.

Next, "storage stability", "fixing property (beading)", "scratch resistance", "solvent resistance", "image glossiness", "adhesion", and "weather resistance" are as follows. "Gender" was evaluated. The results are shown in Table B-4. The evaluation of "storage stability", "fixing property (beading)", "scratch resistance", "solvent resistance", "image glossiness", and "adhesion" is the same as in Example A1. Evaluated.

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

<Weather resistance>
Weather resistance (xenon lamp method) was carried out by a fading test based on JIS K5600-7-7: 2008. Using a high-acceleration weather resistance tester (device name: Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.), a xenon lamp was used to cover the solid part of a solid image, and the irradiance was 180 W. The ultraviolet rays were exposed at / m ² , the image density after exposure was measured, the color difference ΔE of the image density after exposure with respect to the image density before exposure was calculated, and the “weather resistance” was evaluated based on the following evaluation criteria. .. It is desirable in actual use that the evaluation is B or higher.
[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

Examples B1 and B2 are preferable examples of the present invention, which have excellent adhesion to a PVC film recording medium, obtain high image glossiness even when printed on a non-penetrating recording medium, and have resistance to resistance. It can be seen that an image having scratch resistance, solvent resistance, and weather resistance can be obtained.
Examples B3 and B4 were examples in which the HLB value of the polysiloxane surfactant was slightly high, and the fixability was inferior to that of Example B1.
Examples B5 and B6 are examples in which the HLB value of the polysiloxane surfactant is slightly low, and the storage stability is inferior to that of Example B1.
Example B7 is an example in which the amount of the polysiloxane surfactant added is slightly small, and the result is that the fixability and solvent resistance are inferior to those of Example B1.
Example B8 is an example in which the amount of the polysiloxane surfactant added is slightly large, and the storage stability is inferior to that of Example B1.
In Examples B9 and B10, the Tg of the acrylic-silicone resin emulsion was higher than 0 ° C., and the results showed that the adhesion and weather resistance were inferior to those of Example B1.
In Example B11, the content of the acrylic-silicone resin particles was slightly insufficient as compared with the polysiloxane surfactant, and the storage stability was inferior as compared with 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, and the result is that the image glossiness and weather resistance are inferior to those of Example B1.

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

From the results 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-dispersion type black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Industry Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-Silicone Resin Emulsion 4 (trade name: AE980, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): -14 ° C.) 2.0% by mass, both vinyl chloride-ethylene type Polymer resin emulsion (manufactured by Sumika Chemtex Co., Ltd., trade name: Sumi Elite 1210, solid content concentration: 50% by mass) 14.0% by mass, 1,2-propanediol 12.0% by mass, 1,3-propane 10.0% by mass of diol, 3.0% by mass of 1,2-butanediol, 3.0% by mass of 2,3-butanediol, 3.0% by mass of 3-methoxy-3-methylbutanol, 2-methyl-2 , 4-Pentanediol 3.0% by mass, Dipropylene glycol monomethyl ether 4.0% by mass, as a preservative Trade name: Proxel LV (manufactured by Abyssia) 0.1% by mass, and high pure water as the remaining amount Ink C1 was prepared by adding, 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, manufactured by 3M).

(Examples C2 to C12 and Comparative Examples C1 to C2)
In Example C1, Examples C2 to C12 and Comparative Examples C1 to C2 are the same as in Example C1, except that the composition and the content are changed to those shown in Tables C-1 to C-3 below. Inks C2 to C14 of the above were prepared.

In Tables C-1 to C-3, the product names of the ingredients and the names of the manufacturing companies are as follows.
-Vinyl chloride-ethylene copolymer resin emulsion: manufactured by Sumika Chemtex Co., Ltd., trade name: Sumi Elite 1210, solid content concentration: 50% by mass
-Vinyl chloride-acrylic copolymer resin emulsion: manufactured by Nisshin Kagaku Kogyo Co., Ltd., trade name: Viniblanc 711, solid content concentration: 30% by mass
-Vinyl chloride resin emulsion: Wacker Chemie AG, trade name: VINNOL E15 / 48A, solid content concentration: 50% by mass
The coloring materials in Tables C-1 to C-3, polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives are the coloring materials in Tables A-1 to A-3. Similar to polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives were used.

Next, "storage stability", "viscosity stability over time", "fixability (beading)", "scratch resistance", "image glossiness", and "adhesion" are evaluated as follows. did. The results are shown in Table C-4. The "storage stability", "fixability (beading)", "scratch resistance", "image glossiness", 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 Nichiden 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 rate of change in viscosity of the ink after storage with respect to the viscosity of the ink before storage was calculated, and "viscosity stability over time" was evaluated based on the following evaluation criteria. It is desirable in actual use that the evaluation is B or higher.
[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 preferable examples of the present invention, and are excellent in adhesion to a PVC film recording medium, high image glossiness can be obtained even when printed on a non-permeable recording medium, and resistance to resistance. It can be seen that an image having scratch resistance, solvent resistance, and viscosity stability over time can be obtained.
Examples C3 and C4 were examples in which the HLB value of the polysiloxane surfactant was slightly high, and the fixability was inferior to that of Example C1.
Examples C5 and C6 were examples in which the HLB value of the polysiloxane surfactant was slightly low, and the storage stability was inferior to that of Example C1.
Example C7 is an example in which the amount of the polysiloxane surfactant added is slightly small, resulting in inferior fixability and solvent resistance as compared with Example C1.
Example C8 is an example in which the amount of the polysiloxane surfactant added is slightly large, and the result is that the storage stability and the viscosity stability over time are inferior to those of Example C1.
In Examples C9 and C10, the Tg of the acrylic-silicone resin emulsion was higher than 0 ° C., and the adhesion was inferior to that of Example C1.
Example C11 is an example in which the content of the acrylic-silicone resin particles is slightly insufficient as compared with the polysiloxane surfactant, and the result is that the storage stability and the viscosity stability over time are inferior to those of Example C1. became.
Example C12 is an example in which the content of the acrylic-silicone resin particles is slightly higher than that of the polysiloxane surfactant, and the result is that the image glossiness is inferior to that of Example C1.

On the other hand, Comparative Examples C1 to C2 are examples in which the ink does not contain all of the polysiloxane surfactant and the acrylic-silicone resin particles having an HLB value of 8 or less, and Comparative Example C1 is described in 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 to Example C1.

From the results in 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 over time, image glossiness, and adhesion.

(Example D1)
Self-dispersion type black pigment dispersion 20.0% by mass, polyester-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Industry Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-Silicone Resin Emulsion 4 (Product Name: AE980, manufactured by E-Tech Co., Ltd., Solid Content Concentration: 50% by Mass, Glass Transition Temperature (Tg): -14 ° C) 2.0% by Mass, Polyester Resin Emulsion 1 (Unitica) Made by Co., Ltd., trade name: KZA-1449, 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-Butandiol 3.0% by mass, 2,3-Butandiol 3.0% by mass, 3-methoxy-3-methylbutanol 3.0% by mass, 2-Methyl-2,4-Pentanediol 3.0 Add mass%, dipropylene glycol monomethyl ether 4.0 mass%, trade name: Proxel LV (manufactured by Abyssia) 0.1 mass% as an antiseptic, and high pure water to the remaining amount, mix and stir. Ink D1 was produced by filtering with a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M).

(Examples D2 to D12 and Comparative Examples D1 to D2)
In Example D1, Examples D2 to D12 and Comparative Examples D1 to D2 are the same as in Example D1, except that the composition and the content are changed to those shown in Tables D-1 to D-3 below. Inks D2 to D14 of the above were prepared.

In Tables D-1 to D-3, the product names of the ingredients and the names of the manufacturing companies are as follows.
-Polyester resin emulsion 1: Made by Unitika Co., Ltd., trade name: KZA-1449, solid content concentration: 30% by mass
-Polyester resin emulsion 2: Made by Takamatsu Oil & Fat Co., Ltd., Product name: A-125S, Solid content concentration: 30% by mass
-Polyester resin emulsion 3: Made by Takamatsu Oil & Fat Co., Ltd., Product name: A-160P, Solid content concentration: 25% by mass
The coloring materials in Tables D-1 to D-3, polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives are the coloring materials in Tables A-1 to A-3. Similar to polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives were used.

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

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

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

From the results in 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-dispersion type black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Industry Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-Silicone Resin Emulsion 4 (trade name: AE980, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): -14 ° C.) 2.0% by mass, acrylic-styrene resin emulsion 1 (Manufactured by 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 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 a preservative: Proxel LV (manufactured by Abyssia) 0.1% by mass, and high pure water are added so as to be the remaining amount. Then, the mixture was mixed and stirred, and filtered through a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M) to prepare ink E1.

(Examples E2 to E12 and Comparative Examples E1 to E2)
In Example E1, Examples E2 to E12 and Comparative Examples E1 to E2 are the same as in Example E1 except that the composition and the content are changed to those shown in Tables E-1 to E-3 below. Inks E2 to E14 of the above were prepared.

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

Next, "storage stability", "fixing property (beading)", "scratch resistance", "discharge reliability", "image glossiness", and "adhesion" were evaluated as follows. .. The results are shown in Table E-4. The "storage stability", "fixability (beading)", "scratch resistance", "image glossiness", and "adhesion" were evaluated in the same manner as in Example A1.

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

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

On the other hand, Comparative Examples E1 to E2 are examples in which the ink does not contain all of the polysiloxane surfactant and the acrylic-silicone resin particles having an HLB value of 8 or less, and Comparative Example E1 is described in Example E1. In comparison, the fixability and the discharge reliability were particularly inferior. Comparative Example E2 was particularly inferior in storage stability and adhesion to Example E1.

From the results 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-dispersion type black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Industry Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-Silicone Resin Emulsion 4 (trade name: AE980, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): -14 ° C.) 2.0% by mass, polyvinyl alcohol resin emulsion 1 ( Made by Japan Vam & 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% 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 a preservative: Proxel LV (manufactured by Abyssia) 0.1% by mass, and high pure water were added so as to be the remaining amount. The ink F1 was prepared by mixing and stirring with a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M).

(Examples F2 to F12 and Comparative Examples F1 to F2)
In Example F1, Examples F2 to F12 and Comparative Examples F1 to F2 are the same as in Example F1 except that the composition and the content are changed to those shown in Tables F-1 to F-3 below. Inks F2 to F14 of the above were prepared.

In Tables F-1 to F-3, the product names of the ingredients and the names of the manufacturing companies are as follows.
-Polyvinyl alcohol resin emulsion 1: Made by Japan Vam & Poval Co., Ltd., Product name: Poval JF-17, Solid content concentration: 30% by mass
-Polyvinyl alcohol resin emulsion 2: Made by Japan Vam & Poval Co., Ltd., Product name: Poval JF-04, Solid content concentration: 30% by mass
-Polyvinyl alcohol resin emulsion 3: Made by Japan Vam & Poval Co., Ltd., Product name: Poval JF-05, Solid content concentration: 30% by mass
The colorants in Tables F-1 to F-3, polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives are the colorants in Tables A-1 to A-3. Similar to polysiloxane surfactants, styrene-acrylic resin particles, organic solvents, and preservatives were used.

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

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

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

From the results in Table F-4, it can be seen that the ink of the present invention is suitable for outdoor use. Further, the 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-dispersion type black pigment dispersion 20.0% by mass, polyether-modified silicone 2 (polysiloxane surfactant, trade name: KF-6017, manufactured by Shin-Etsu Chemical Industry Co., Ltd., HLB value: 4.5) 1.0 mass %, Acrylic-Silicone Resin Emulsion 4 (trade name: AE980, manufactured by E-Tech Co., Ltd., solid content concentration: 50% by mass, glass transition temperature (Tg): -14 ° C.) 2.0% by mass, polycarbonate-based polyurethane resin emulsion ( Solid content concentration: 30% by mass) 23.3% by mass, N, N-dimethyl-β-butoxypropionamide 22.0 parts 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, commercial as an antiseptic Name: Proxel LV (manufactured by Abyssia) 0.1% by mass and high pure water are added so as to be the remaining amount, mixed and stirred, and a polypropylene filter having an average pore diameter of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG) Ink G1 was produced by filtering with a series (manufactured by 3M Co., Ltd.).

(Examples G2 to G12 and Comparative Examples G1 to G2)
In Example G1, Examples G2 to G12 and Comparative Examples G1 to G2 are the same as in Example G1 except that the composition and the content are changed to those shown in Tables G-1 to G-3 below. Inks G2 to G14 of the above were prepared.

In Tables G-1 to G-3, the product names of the ingredients and the names of the manufacturing companies are as follows.
・ N, N-dimethyl-β-butoxypropionamide: manufactured by Idemitsu Kosan Co., Ltd. ・ N, N-dimethyl-β-heptoxypropionamide: manufactured by Idemitsu Kosan Co., Ltd. ・ N, N-diethyl-β-butoxypropionamide: N, N-diethyl-β-butoxypropionamide manufactured by Idemitsu Kosan Co., Ltd .: Manufactured by Idemitsu Kosan Co., Ltd. Coloring materials, polysiloxane surfactants, styrene-acrylic resin particles in Tables G-1 to G-3. , Polyurethane resin particles, organic solvents, and preservatives include the coloring materials, polysiloxane surfactants, styrene-acrylic resin particles, polyurethane resin particles, organic solvents, and preservatives in Tables A-1 to A-3. A similar one was used.

Next, "storage stability", "fixing property (beading)", "scratch resistance", "solvent resistance", "image glossiness", "adhesion", and "drying" are as follows. "Sex" was evaluated. The results are shown in Table G-4. The evaluation of "storage stability", "fixing property (beading)", "scratch resistance", "solvent resistance", "image glossiness", and "adhesion" is the same as in Example A1. Evaluated.

<Dryness>
The obtained ink jet printers (device name: IPSiO GXe5500 remodeling machine, manufactured by Ricoh Co., Ltd.) were filled with the obtained inks G1 to G12 and inks G1 to G14 of Comparative Examples G1 to G2, and a polyvinyl chloride film (CPPVWP1300, Sakurai) was filled. A solid image was recorded on a recording medium manufactured by Co., Ltd. (hereinafter, also referred to as "PVC film") with 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 AS ONE Corporation) set at 50 ° C. The filter paper was pressed against the solid portion of the solid image after drying, the transfer of ink to the filter paper was visually observed, and the "dryness" was evaluated based on the following evaluation criteria.
[Evaluation criteria]
A: No transfer to filter paper under drying conditions of 50 ° C for 5 minutes or less B: No transfer to filter paper under drying conditions of 50 ° C for more than 5 minutes for 8 minutes or less C: Drying conditions for more than 8 minutes at 50 ° C for 10 minutes or less D: Transfer to filter paper does not disappear even under drying conditions of 50 ° C for more than 10 minutes.

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

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

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

(Test Examples A to G)
<Evaluation of the effect on heat drying>
In the ink A1 of Example A1, the ink B1 of Example B1, the ink C1 of Example C1, the ink D1 of Example D1, the ink E1 of Example E1, the ink F1 of Example F1, and the ink G1 of Example G1. , Fixability (beading) and resistance in the same manner as in Example A1 except that the heating conditions (heating temperature, heating time) after recording were changed as shown in Tables H-1 to H-7 below. The scratchability was evaluated, and the dryness was evaluated in the same manner as in Example G1. The results are shown in Tables H-1 to H-7.
In addition, in Test Examples A1-8, B1-8, C1-8, D1-8, E1-8, F1-8, and G1-8, ink A1, ink B1, ink C1, ink D1, ink E1, ink A solid image was recorded using F1 and ink G1 in the same manner as in Example A1, and the image was dried by leaving it at 25 ° C. for 24 hours without heating after recording.

（ただし、前記一般式（１）中、Ｒ_１、Ｒ_２、及びＲ_３は、それぞれ独立に、エーテル結合を有していてもよい炭素数１以上８以下の炭化水素基を表す。）
＜４＞ 前記ポリシロキサン界面活性剤のＨＬＢ値が、４．５以上７．０以下である前記＜１＞から＜３＞のいずれかに記載のインクである。
＜５＞ 前記ポリシロキサン界面活性剤の含有量が、１．０質量％以上２．０質量％以下である前記＜１＞から＜４＞のいずれかに記載のインクである。
＜６＞ 前記アクリル−シリコーン樹脂粒子のガラス転移温度が、０℃以下である前記＜１＞から＜５＞のいずれかに記載のインクである。
＜７＞ 前記ポリシロキサン界面活性剤の含有量Ａ（質量％）と、前記アクリル−シリコーン樹脂粒子の含有量Ｂ（質量％）との質量比（Ｂ／Ａ）が、０．８以上１．５以下である前記＜１＞から＜６＞のいずれかに記載のインクである。
＜８＞ 前記アクリル−シリコーン樹脂粒子に由来するシリコーンの含有量が、０．０１質量％以上０．０４質量％以下である前記＜１＞から＜７＞のいずれかに記載のインクである。
＜９＞ 前記アクリル−シリコーン樹脂粒子の最低造膜温度が、２０℃以下である前記＜１＞から＜８＞のいずれかに記載のインクである。
＜１０＞ 前記アクリル−シリコーン樹脂粒子の含有量が、０．５質量％以上５質量％以下である前記＜１＞から＜９＞のいずれかに記載のインクである。
＜１１＞ 前記フッ素樹脂粒子のガラス転移温度が、１００℃以上３００℃以下である前記＜１＞から＜１０＞のいずれかに記載のインクである。
＜１２＞ 前記有機溶剤の含有量が、１０質量％以上６０質量％以下である前記＜１＞から＜１１＞のいずれかに記載のインクである。
＜１３＞ 前記一般式（１）で表される化合物の含有量が、５質量％以上３０質量％以下である前記＜３＞から＜１２＞のいずれかに記載のインクである。
＜１４＞ 色材をさらに含有する前記＜１＞から＜１３＞のいずれかに記載のインクである。
＜１５＞ 前記色材が、顔料である前記＜１４＞に記載のインクである。
＜１６＞ 前記＜１＞から＜１５＞のいずれかに記載のインクを収容するインク収容部と、
前記インクに刺激を印加し、前記インクを吐出させる吐出ヘッドと、を有することを特徴とするインクジェット印刷装置である。
＜１７＞ 前記吐出ヘッドが、個別液室と、前記個別液室にインクを流入させるための流入流路と、インクを前記個別液室から流出させるための流出流路と、を有するインク吐出ヘッドである前記＜１６＞に記載のインクジェット印刷装置である。
＜１８＞ 前記インクを前記流入流路から前記流出流路に向かって循環させる循環手段をさらに有する前記＜１７＞に記載のインクジェット印刷装置である。
＜１９＞ 前記＜１＞から＜１５＞のいずれかに記載のインクに刺激を印加し、前記インクを吐出させて記録媒体に印刷するインク吐出工程を含むことを特徴とするインクジェット印刷方法である。
＜２０＞ インクを個別液室に流入させるための流入流路と、インクを前記個別液室から流出させるための流出流路と、を有するインク吐出ヘッドを用い、熱エネルギー及び力学的エネルギーのいずれかをインクに作用させて前記インクを吐出して印刷する印刷工程をさらに含み、
前記インクとして、前記＜１＞から＜１５＞のいずれかに記載のインクを用いる前記＜１９＞に記載のインクジェット印刷方法である。
＜２１＞ 非印刷中に、インクを前記流入流路から前記流出流路に向かって循環させる循環工程を含む前記＜２０＞に記載のインクジェット印刷方法である。
＜２２＞ 前記記録媒体を加熱する加熱工程を含む前記＜１９＞から＜２１＞のいずれかに記載のインクジェット印刷方法である。
＜２３＞ 前記加熱工程における加熱温度が、４０℃以上１００℃以下である前記＜２２＞に記載のインクジェット印刷方法である。
＜２４＞ 記録媒体と、前記記録媒体上に、ポリシロキサン界面活性剤、及びアクリル−シリコーン樹脂粒子を含有する画像と、を有し、
前記ポリシロキサン界面活性剤のＨＬＢ値が、８以下であることを特徴とする印刷物である。 Examples of aspects of the present invention are as follows.
<1> Contains water, an organic solvent, a polysiloxane surfactant, and acrylic-silicone resin particles.
The ink is characterized in that the HLB value of the polysiloxane surfactant is 8 or less.
<2> 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).

(However, in the general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrocarbon group having 1 to 8 carbon atoms which may have an ether bond.)
<4> The ink according to any one of <1> to <3>, wherein the HLB value of the polysiloxane surfactant is 4.5 or more and 7.0 or less.
<5> The ink according to any one of <1> to <4>, wherein the 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 the acrylic-silicone resin particles have a glass transition temperature of 0 ° C. or lower.
<7> The mass ratio (B / A) of 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 the 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 the 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 the fluororesin particles have a glass transition temperature of 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>, which further contains a coloring material.
<15> The ink according to <14>, wherein the coloring material is a pigment.
<16> An ink accommodating portion for accommodating the ink according to any one of <1> to <15>, and an ink accommodating portion.
The inkjet printing apparatus is characterized by having an ejection head that applies a stimulus to the ink and ejects the ink.
<17> The ink ejection head has an individual liquid chamber, an inflow flow path for allowing ink to flow into the individual liquid chamber, and an outflow flow path for causing ink to flow out of the individual liquid chamber. The inkjet printing apparatus according to <16>.
<18> The inkjet printing apparatus according to <17>, further comprising a circulation means for circulating the ink from the inflow channel to 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>, ejecting the ink, and printing on a recording medium. ..
<20> Using an ink ejection head having an inflow flow path for flowing ink into the individual liquid chambers and an outflow flow path for flowing out ink from the individual liquid chambers, either thermal energy or mechanical energy can be used. Further includes a printing step of causing the ink to act on the ink to eject the ink and printing.
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>, which comprises a circulation step of circulating ink from the inflow channel to the outflow channel during non-printing.
<22> The inkjet printing method according to any one of <19> to <21>, which includes a heating step of heating the recording medium.
<23> The inkjet printing method according to <22>, wherein the 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 are provided.
It is a printed matter characterized in that the HLB value of the polysiloxane surfactant is 8 or less.

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

Japanese Unexamined Patent Publication No. 2005-220352 Japanese Unexamined Patent Publication No. 2011-094082

142: Recording medium 6: Individual liquid chamber

Claims (14)

Contains water, organic solvent, polysiloxane surfactant, and acrylic-silicone resin particles,
HLB value of the polysiloxane surface active agent state, and are 8 or less,
The organic solvent is, ink which is characterized that you containing a compound represented by the following general formula (1).

(However, in the general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrocarbon group having 1 or more and 8 or less carbon atoms which may have an ether bond.) The ink according to claim 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 according to any one of claims 1 to 2 , 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 3 , wherein the 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 4 , wherein the acrylic-silicone resin particles have a glass transition temperature of 0 ° C. or lower. When the mass ratio (B / A) of the content A (mass%) of the polysiloxane surfactant and the content B (mass%) of the acrylic-silicone resin particles is 0.8 or more and 1.5 or less. The ink according to any one of claims 1 to 5. An inkjet printing apparatus comprising an ink accommodating portion for accommodating the ink according to any one of claims 1 to 6 and an ejection head for applying a stimulus to the ink to eject the ink. A claim that the ejection head is an ink ejection head having an individual liquid chamber, an inflow flow path for inflowing ink into the individual liquid chamber, and an outflow flow path for discharging ink from the individual liquid chamber. Item 7. The inkjet printing apparatus according to item 7. The inkjet printing apparatus according to claim 8 , further comprising a circulation means for circulating the ink from the inflow channel to the outflow channel. An inkjet printing method comprising an ink ejection step of applying a stimulus to the ink according to any one of claims 1 to 6 to eject the ink and printing on a recording medium. Using an ink ejection head having an inflow flow path for allowing ink to flow into the individual liquid chambers and an outflow flow path for causing ink to flow out of the individual liquid chambers, either thermal energy or mechanical energy is applied to the ink. Further includes a printing step of ejecting and printing the ink by acting on the ink.
The inkjet printing method according to claim 10 , wherein the ink according to any one of claims 1 to 6 is used as the ink. The inkjet printing method according to claim 11 , further comprising a circulation step of circulating ink from the inflow channel to the outflow channel during non-printing. The inkjet printing method according to any one of claims 10 to 12 , further comprising a heating step of heating the recording medium. The inkjet printing method according to claim 13 , wherein the heating temperature in the heating step is 40 ° C. or higher and 100 ° C. or lower.

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