JP6651993B2 - Ink, inkjet recording method, and recorded matter - Google Patents

Description

  The present invention relates to an ink, an inkjet recording method, and a recorded matter.

  In industrial applications such as advertising 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-permeable recording medium is used. Various inks have been developed.

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

  The present invention provides an ink having good storage stability, high image glossiness, and an image having excellent fixability, abrasion resistance, solvent resistance, and adhesion to a non-permeable recording medium. With the goal.

  The ink of the present invention as a means for solving the above-mentioned problem includes water, an organic solvent, a polysiloxane surfactant, a modified polyvinyl alcohol, vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester. And at least one selected from resin particles, and the polysiloxane surfactant has an HLB value of 8 or less.

  According to the present invention, there is provided an ink having good storage stability, high image glossiness, and an image having excellent fixability, abrasion resistance, solvent resistance, and adhesion to a non-permeable recording medium. be able to.

FIG. 1 is a perspective explanatory view showing an example of a serial type image forming apparatus. FIG. 2 is a perspective explanatory view showing an example of a main tank of the apparatus of FIG. FIG. 3 is a schematic diagram showing an example of the heating means of the apparatus of FIG.

(ink)
The ink of the present invention comprises water, an organic solvent, a polysiloxane surfactant, a modified polyvinyl alcohol, and at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles. The polysiloxane surfactant has an HLB value of 8 or less, and further contains other components as necessary.
The ink of the present invention is excellent in fixability to a non-permeable recording medium because the conventional solvent-based ink is fixed while swelling the non-permeable recording medium with an organic solvent in the ink. Based on the finding that the recorded matter has a structure in which the ink coating is merely applied on the recording medium, so the fixability of the ink coating to the recording medium is insufficient, and the high-speed recording performance is poor. Things. In addition, assuming that the recording medium is used outdoors, the recorded article is required to have properties such as tough scratch resistance, solvent resistance, and image hardness which are inferior to those for indoor use. However, it is based on the knowledge that there is a problem that the conventional aqueous ink does not have sufficient properties comparable to those of the solvent-based ink.

The present inventors have also found the following.
Of the components contained in the ink, the selection of a surfactant determines the fixability of the ink to a non-permeable recording medium on which recording is performed, and thus plays a very important role. The present inventors have found that by adding a compound having an HLB value of 8 or less to the ink among the polysiloxane surfactants, the fixing property of the ink is significantly improved. The reason for this is not clear, but it is presumed that if the HLB value is 8 or less, the hydrophobicity increases, and the affinity with various non-permeable recording media is improved.
In addition, by improving the fixability of the ink to the non-permeable recording medium, it is possible to suppress a phenomenon (adhesion) in which adjacent ink droplets unite and contract after landing, even during high-speed recording. It has been found that a high quality image can be obtained. In addition, it has been found that the improvement in the fixing speed can also improve the drying property and improve the adhesion, so that the transfer to the backing paper at the time of winding the recording medium after recording can be suppressed.

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

  Then, the inventors have found that when a predetermined amount of modified polyvinyl alcohol 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.

  Further, by including at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles in the ink, the resulting image has high image glossiness and abrasion resistance. It has been found that it can be provided. Furthermore, surprisingly, by using the polysiloxane surfactant together with the modified polyvinyl alcohol and at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles, It has been found that not only the scratch resistance of the coating film formed after recording but also the solvent resistance can be greatly improved.

<Polysiloxane surfactant>
Examples of the polysiloxane surfactant include a compound having a hydrophilic group or a hydrophilic polymer chain in a side chain of a compound having a polysiloxane structure (silicone compound) such as polydimethylsiloxane, and a polydimethylsiloxane or the like. A compound having a hydrophilic group or a hydrophilic polymer chain at a terminal of a compound having a siloxane structure (silicone compound) is exemplified. The polysiloxane surfactant only has to have a polysiloxane structure in its structure, and is meant to include a polysiloxane surfactant.

The hydrophilic groups and the hydrophilic polymer chains, for example, a polyether group (polyethylene oxide, polypropylene Oki command and copolymers thereof), polyglycerol _{(C 3 Η 6 O (CH} 2 CH (OH) CH _{2 O)} n -H, etc.), pyrrolidones, betaines ^{_{(C 3 Η 6 n + (}} C 2 H 4) 2 -CH 2 COO - , etc.), sulfate _{(C 3 H 6 O (C} 2 H 4 O) _n -SO ₃ Na, etc.), phosphate _{(C 3 Η 6 O (C} 2 H 4 O) n -P (= O) OHONa etc.), quaternary salt ^{_{(C 3 H 6 n + (}} C 2 H 4 ) ₃ Cl— ^{and the} like). Here, in the above chemical formula, n represents an integer of 1 or more. Among these, it is preferable to have a polyether group.
In addition, polydimethylsiloxane having a polymerizable vinyl group at a terminal and other copolymerizable monomers (a hydrophilic monomer such as (meth) acrylic acid or a salt thereof may be used for at least a part of the monomers. (Preferably) and a vinyl copolymer having a silicone-based compound chain such as polydimethylsiloxane in the side chain obtained by copolymerization thereof.
Among these, a compound having a polysiloxane structure and a compound having a hydrophilic polymer chain are preferable, and a polyether group is more preferably contained as the hydrophilic polymer chain, and a polysiloxane surfactant is used as a hydrophobic group. It is particularly preferable that the nonionic surfactant has methylpolysiloxane and has a structure of polyoxyethylene as a hydrophilic group.

  The HLB of the polysiloxane surfactant is 8 or less, preferably 4.5 or more and 7.0 or less. When the HLB is 8 or less, excellent ink fixability can be ensured even when inkjet recording is performed on various non-permeable recording media, and is 4.5 or more and 7.0 or less. Temperature at which no phase separation occurs between the ink and the ink.

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

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

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

  The content of the polysiloxane surfactant is preferably from 0.1% by mass to 4.0% by mass, more preferably from 1.0% by mass to 2.0% by mass, 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, fixability of the ink to various non-permeable recording media can be improved, and image quality such as gloss can be improved.

<Modified polyvinyl alcohol>
The modified polyvinyl alcohol can suppress the occurrence of separation of the polysiloxane surfactant in the ink, and can improve storage stability.

  Examples of the modified polyvinyl alcohol include silanol-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, and acetoacetyl-modified polyvinyl alcohol. These may be used alone or in combination of two or more. Among these, silanol-modified polyvinyl alcohol is preferred. By using a silanol-modified polyvinyl alcohol, it is possible to ensure good adhesion of an image formed by inkjet recording to a recording medium without impairing the storage stability of the ink.

  From the viewpoint of strong hydrophilicity, the modified polyvinyl alcohol is preferably used as an aqueous solution dissolved under warm water of about 90 ° C. From the viewpoint of solubility in water and storage stability when formed into an ink, More preferably, it is used as a 10% by mass aqueous solution under about 90 ° C. warm water.

  As the modified polyvinyl alcohol, a commercial product may be used. As the commercial product, a trade name: T330H (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration: 10% by mass), a trade name: R2105 (solid Partial concentration: 10% by mass), trade name: R1130 (solid content concentration: 10% by mass), (all manufactured by Kuraray Co., Ltd.) and the like.

  The content of the modified polyvinyl alcohol is preferably from 0.5% by mass to 5% by mass, more preferably from 0.8% by mass to 2.5% by mass, based on the total amount of the ink.

[Mass ratio (B / A)]
The mass ratio (B / A) of the content A (% by mass) of the polysiloxane surfactant to the content B (% by mass) of the modified polyvinyl alcohol is preferably 0.6 or more and 1.8 or less. , 0.8 or more and 1.5 or less. When the mass ratio (B / A) is 0.6 or more and 1.8 or less, the temperature at which the separation of the polysiloxane surfactant occurs in the ink can be increased, and the image quality such as gloss can be improved. Can be improved.

<Resin particles>
The resin particles contain at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles, and further contain other resins as necessary.

<<< vinyl chloride resin particles >>>
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 miscibility with the pigment and other resin particles contained in the ink. From the viewpoint of excellent adhesion to a non-polar recording medium, vinyl chloride-ethylene copolymer resin particles are more preferable.

  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 And resin particles. These may be used alone or in combination of two or more.

Examples of the commercially available vinyl chloride resin particles include, for example, Part No. 985 (solid content concentration: 40% by mass, anionic) in the Vinibran (registered trademark) series manufactured by Nissin Chemical Industry Co., Ltd.
Examples of the commercially available vinyl chloride-acrylic copolymer resin particles include, for example, part number 278 (solid content concentration: 43% by mass, anionic) and 700 (from Nisshin Chemical Industry Co., Ltd.) Solids concentration: 30% by mass, anionic), 701 (solids concentration: 30% by mass, anionic), 711 (solids concentration: 30% by mass, anionic), 721 (solids concentration: 30% by mass, Anionic), 700 FS (solid content: 30% by mass, anionic), 701RL35 (solid content: 30% by mass, anionic), 701RL (solid content: 30% by mass, anionic), 701RL65 (solid content) Concentration: 30% by mass, anionic). 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: 50% by mass ± 1% by mass, anionic ), 1210 (solids concentration: 50% by mass ± 1% by mass, anionic), 1320 (solids concentration: 50% by mass ± 1% by mass, anionic) and the like. These may be used alone or in combination of two or more.
As other commercially available products, a vinyl chloride copolymer resin particle obtained by introducing a hydroxyl component into a vinyl chloride resin, a part number E15 / 48A of a VINNOL series manufactured by Wacker Chemie AG (solid content concentration: 50% by mass, anion ), E22 / 48A (solid content: 30% by mass, anionic). These may be used alone or in combination of two or more.

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

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

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

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

  Examples of the compound having two or more active hydrogen atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane. 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, polyoxytetramethylene glycol, polyoxytetramethylene glycol, 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 in the production of the polyurethane resin particles include those obtained by reacting a carbonate ester and 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 carbonate 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, 2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol , Bisphenol-A, bisphe -F, relatively low molecular weight dihydroxy compounds such as 4,4'-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene succinate, poly And polyester polyols such as caprolactone. These may be used alone or in combination of two or more.

--- Polyester polyol ---
Examples of the polyester polyol include, for example, those obtained by an esterification reaction of a low-molecular-weight polyol and a polycarboxylic acid, polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymers thereof. Polyester and the like. 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, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and 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 phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene isocyanate. Examples thereof include aliphatic or alicyclic diisocyanates such as diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate. These may be used alone or in combination of two or more. Among them, the ink of the present invention is used also for outdoor applications such as posters and signboards, and thus requires a coating film having extremely high long-term weather resistance. Formula diisocyanates are preferred.

Furthermore, 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 based on the total amount of the isocyanate compound.

[Production method of polyurethane resin particles]
The polyurethane resin particles can be obtained by a manufacturing method generally used conventionally, and examples thereof include the following method.
First, an isocyanate-terminated urethane prepolymer is produced by reacting the polyol and the polyisocyanate in the absence of a solvent or in the presence of an organic solvent at an equivalent ratio at which an isocyanate group becomes excessive.
Next, 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; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; Examples include amides such as formamide, N-methylpyrrolidone, and N-ethylpyrrolidone. These may be used alone or in combination of two or more.
Examples of the chain extender include polyamine and other active hydrogen group-containing compounds.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 1,4-cyclohexane Diamines such as diamines; polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; hydrazines such as hydrazine, N, N'-dimethylhydrazine and 1,6-hexamethylenebishydrazine; succinic dihydrazide, adipic dihydrazide And dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide and isophthalic acid dihydrazide. These may be used alone or in combination of two or more.

  Examples of the other active hydrogen group-containing compounds include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin and sorbitol; phenols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A and hydroquinone And water. These may be used alone or in combination of two or more as long as the storage stability of the ink is not reduced.

  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 image scratch resistance due to the high cohesive force of the carbonate group. When the polycarbonate-based polyurethane resin particles are used, an ink suitable for a recorded matter used in a severe environment such as an outdoor use can be obtained.

  As the polyurethane resin particles, commercially available products may be used. For example, U-coat UX-485 (polycarbonate-based polyurethane resin particles), U-coat UWS-145 (polyester-based polyurethane resin particles), Permarine UA-368T (polycarbonate-based polyurethane resin) Resin particles) and Permarin UA-200 (polyether-based polyurethane resin particles) (all manufactured by Sanyo Chemical Industries, Ltd.). These may be used alone or in combination of two or more.

<< Fluororesin particles >>
The fluororesin particles can improve high image gloss and abrasion resistance. Furthermore, surprisingly, when the polysiloxane surfactant, the modified polyvinyl alcohol, and the fluororesin particles are used in combination, the fluctuation of the ink characteristics during long-term storage is greatly suppressed, and the fluctuation of the viscosity over time is stabilized, and the recording is performed. Not only scratch resistance but also solvent resistance of a coating film formed later can be greatly improved.
The fluororesin particles only need to have fluorine in the structure, and are meant to include fluororesin particles.

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

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

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

  The glass transition temperature (Tg) of the fluororesin particles is preferably from 100 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. When the glass transition temperature is 100 ° C. or more and 300 ° C. or less, an image formed on a non-permeable recording medium with an ink containing fluororesin particles and at least one type of resin particles other than fluororesin particles is generally used. When dried in the range of 50 ° C. or more and 150 ° C. or less, which is a proper drying temperature, the fluororesin particles can maintain their shape as particles, so that the uniformity due to one or more types of resin particles other than the fluororesin particles is obtained. The strength of the resin formed by resin particles other than one or more kinds of fluororesin particles can be improved by preventing the formation of the film from being hindered, but rather by the fluororesin particles behaving like a filler. From such a viewpoint, the glass transition temperature of the fluororesin particles used is preferably higher than the drying temperature of the recorded matter, more preferably higher by 20 ° C. or higher, and particularly preferably higher by 50 ° C. or higher.

As the fluororesin particles, an appropriately synthesized one may be used, or a commercially available product may be used.
Examples of the commercially available products include, among the Teflon AF series, trade name: AF1600 (Tg: 160 ° C.), trade name: AF2400 (Tg: 240 ° C.) (all made by Mitsui / Dupont Fluorochemical Co., Ltd.), trade names : Lumiflon FE4400 (manufactured by Asahi Glass Co., Ltd., Tg: 48 ° C.).

  The mass ratio of the content (% by mass) of the fluororesin particles to the total content (% by mass) of the resin particles other than the fluororesin particles (fluororesin particles / resin particles other than the fluororesin particles) is 0.05 It is preferably from 4.0 to 4.0, more preferably from 0.1 to 2.0, and particularly preferably from 0.2 to 1.5. When the mass ratio (fluororesin particles / resin particles other than fluororesin particles) is 0.05 or more and 4.0 or less, the fluororesin can be formed without deteriorating the characteristics of a 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 emulsification of polytetrafluoroethylene (PTFE), or the like.

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

In a fluororesin particle solution obtained by dissolving the fluororesin particles in an organic solvent such as tetrafluoroethylene (TFE), the content of the fluororesin particles is 10% by mass to 70% by mass based on the total amount of the fluororesin particle solution. % Or less, more preferably 20% by mass or more and 60% by mass or less, particularly preferably 30% by mass or more and 50% by mass or less. When the content is 70% by mass or less, in the next dispersion step, an increase in viscosity when mixed with water can be suppressed, the volume average particle size of the obtained aqueous dispersion can be reduced, and storage stability can be reduced. Can be improved. Further, when the content is 10% by mass or more, the concentration of the fluororesin can be prevented from further lowering in the next dispersion step, and it is not necessary to remove a large amount of the organic solvent in the solvent removal step.
The apparatus for dissolving the fluororesin particles in the organic solvent is not particularly limited as long as it has a tank into which a liquid can be charged and can appropriately stir, and can be appropriately selected depending on the purpose.
When the fluororesin particles are hardly dissolved, heating may be performed.

  The temperature in the dispersion step is preferably 40 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 20 ° C. or lower, and particularly preferably 15 ° C. or lower. When the temperature is 40 ° C. or less, the average particle size of the obtained aqueous dispersion can be 500 nm or less even when the content of the surfactant and the like is small. The temperature of the dispersion step is preferably maintained at 40 ° C. or lower throughout this step, but the temperature of the system may be difficult to maintain because the liquid temperature tends to rise due to shear heat 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 the addition of 0.8 times the amount of water of the organic solvent contained in the fluororesin particle solution is completed. It is more preferable to control the temperature to 40 ° C. or lower until the addition of the amount of water 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.

<< polyester resin particles >>
The polyester resin particles can improve high image gloss and abrasion resistance. Furthermore, surprisingly, by using the polysiloxane surfactant, the modified polyvinyl alcohol, and the polyester resin particles in combination, fluctuations in ink characteristics during long-term storage are greatly suppressed, and fluctuations in viscosity over time are stabilized. In addition, not only the scratch resistance of the coating film formed after recording but also the solvent resistance can be greatly improved.

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

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

It is preferable that the resin particles are mixed with a material such as a coloring material or an organic solvent in a state of a resin emulsion in which water is dispersed as a dispersion medium to obtain an ink.
Considering the easiness of the operation of preparing an aqueous ink by blending with an organic solvent, a coloring material, and water, and dispersing as uniformly as possible in the ink, the resin particles are stably dispersed using water as a dispersion medium. It is preferable to add it to the ink in the state of a resin emulsion, which is in a state of being prepared.

  The resin particles are easily formed into a film by being dissolved in an organic solvent to be added to the ink, so that a film-like recording layer is formed. The film formation of the resin particles is promoted with the evaporation of the organic solvent and water. Therefore, when the ink of the present invention is used, it is possible to perform recording without a heating step.

  In dispersing the resin particles, using water as a dispersion medium, the resin particles include forced emulsification type resin particles using a dispersant, a so-called self-emulsification type resin particle having an anionic group in a molecular structure. No. Of these, self-emulsifying resin particles having an anionic group in the molecular structure are preferred from the viewpoint of increasing the strength of the recorded matter.

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

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

Examples of a method for producing an aqueous dispersion of the 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.
As a method of producing an aqueous dispersion using the forced emulsification type resin particles, for example, a surfactant such as a nonionic surfactant or an anionic surfactant is used. These may be used alone or in combination of two or more. Among these, it is preferable to use a nonionic surfactant from the viewpoint of water resistance.

  Examples of the nonionic surfactant include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hardened castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkyl alkanolamide, polyalkylene glycol (meth) acrylate, and the like. Among them, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine 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 taurates, sulfosuccinates, ether sulfonates, ethers Examples include carboxylate, fatty acid salt, naphthalenesulfonic acid formalin condensate, alkylamine salt, quaternary ammonium salt, alkylbetaine, alkylamine oxide and the like. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferred.

  When producing an aqueous dispersion using the forced emulsification type resin particles, the content of the surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. It is preferably from 0.1% by mass to 30% by mass, more preferably from 5% by mass to 20% by mass, based on the total amount of the 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 suitably formed into a film, an ink having excellent adhesion and water resistance is obtained, and the recorded matter is blocked. It is preferably used.

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

  Examples of the qualitative and quantitative amounts of the resin particles include, for example, “Test Methods and Evaluation Results of Each Dynamic Property of Plastic Materials (22); Takeo Yasuda, Plastics: Japan Plastics Industry Federation /“ Plastics ”Editing Committee Can be confirmed by the procedure described in detail in "1. Specifically, it can be confirmed by analyzing by infrared spectroscopy (IR), thermal analysis (DSC, TG / DTA), pyrolysis gas chromatography (PyGC), nuclear magnetic resonance (NMR), or the like.

  When the ink of the present invention is heated, the residual solvent is 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., it is preferable to perform heating from the viewpoint that the film formation of the resin is not defective and the image fastness can be improved. . Further, it is preferable to perform the heating after applying the ink 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, the adjustment is performed by controlling the glass transition temperature (hereinafter, also referred to as “Tg”) of the resin particles. When the resin particles are a copolymer, it can be adjusted by changing the ratio of the monomers forming the copolymer. In addition, the minimum film-forming temperature refers to a 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 increased. In a temperature range lower than 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) 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 to a target value by a control factor of the volume average particle size of the resin particles.

The Tg of the resin particles refers to a value measured using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.). Specifically, the measurement is performed under the following continuous temperature programs 1 to 4, and the value measured by the temperature program 3 can be used as Tg. The reason why the measurement is performed in the above-mentioned temperature program of heating and cooling and the measured value of the temperature program 3 is used is to ensure reproducibility of the measured value.
Temperature program:
1. 30 ° C to 250 ° C: heating rate 30 ° C / min, holding time 1 min
2. 250 ° C to -100 ° C: cooling rate 30 ° C / min, holding time 30min
3. -100 ° C to 250 ° C: heating rate 5 ° C / min, holding time 1min
4. 250 ° C to 30 ° C: cooling rate 30 ° C / min, holding time 2min

  The content of the resin particles is preferably from 3% by mass to 10% by mass, more preferably from 4% by mass to 8% by mass, based on the total amount of the ink.

<< Other resin particles >>
As the other resin particles, for example, epoxy resin particles, polyamide resin particles, polyether resin particles, acrylic resin particles such as acrylic-silicone resin particles, polyolefin resin particles, polystyrene resin particles, polyvinyl ester resin particles, polyacrylic Examples include acid resin particles, addition-type synthetic resin particles such as unsaturated carboxylic acid-based resins, and natural polymers such as celluloses, rosins, and natural rubber. These may be used alone or in combination of two or more.
As the resin particles, appropriately synthesized ones or commercially available ones may be used.

<Organic solvent>
The organic solvent is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a water-soluble organic solvent. In addition, the water solubility means that 5 g or more is dissolved in 100 g of water at 25 ° C., for example.

  Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 3-methoxy-3-methylbutanol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, 6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, etc. Polyhydric alcohols, ethylene glycol monoethyl ether, ethylene Polyhydric alcohol alkyl ethers such as 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, ethylene glycol monophenyl ether, ethylene Polyhydric alcohol aryl ethers such as glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone Such as nitrogen-containing heterocyclic compounds, formamide, N-methylformamide, N, N-dimethylforma Amides such as de, monoethanolamine, diethanolamine, amines such as triethylamine, dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, and the like ethylene carbonate. These may be used 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 with respect to the total amount of the ink, from the viewpoint of the drying property of the ink and the ejection reliability. .

<Water>
The water is not particularly limited and may be appropriately selected depending on the 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 from 15% by mass to 60% by mass, more preferably from 20% by mass to 40% by mass, based on the total amount of the ink. When the content is 15% by mass or more, high viscosity can be prevented and ejection stability can be improved. When the content is 60% by mass or less, wettability to a non-permeable recording medium becomes suitable, Image quality can be improved.

<Other ingredients>
Other components include coloring materials, surfactants other than polysiloxane surfactants, preservatives and fungicides, rust inhibitors, pH adjusters, rubbers and plastics such as hindered phenol and hindered phenol amine. And colorless anti-aging agents.

<Color material>
The coloring material is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include pigments and dyes. Among these, pigments are preferred.
Examples of the pigment include an inorganic pigment and an organic pigment.

  As the inorganic pigment, for example, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, contact method, furnace method, manufactured by known methods such as thermal method Carbon black. These may be used alone or in combination of two or more.

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

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

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

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

To disperse the pigment in the ink, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of coating and dispersing the surface of the pigment with a resin, a method of dispersing using a dispersant, And the like.
As a method of introducing a hydrophilic functional group into a pigment to form a self-dispersing pigment, for example, a self-dispersing pigment which is capable of dispersing in water by adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon). Can be used.
As a method of coating and dispersing the surface of the pigment with a resin, a method in which the pigment is included in microcapsules and dispersible in water can be used. This can be rephrased as a resin-coated pigment. In this case, it is not necessary that all the pigments to be incorporated into the ink be coated on the resin. It may be.
Examples of a method of dispersing using a dispersant include a method of dispersing using a known low-molecular type dispersant and a high-molecular type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and Na-formalin condensate of naphthalenesulfonic acid can also be suitably used as the dispersant.
One type of dispersant may be used alone, or two or more types may be used in combination.

<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 dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. For dispersion, a disperser is preferably used.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the dispersion frequency of the pigment is good, and the image quality such as ejection stability and image density is also high. 500 nm or less is preferable, and 20 nm or more and 150 nm or less are more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by 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 that good ejection stability is obtained and that the image density is increased, 0.1 mass % To 50% by mass, more preferably 0.1% to 30% by mass.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifuge, or the like, if necessary.

The number average particle size of the pigment is not particularly limited and may be appropriately selected depending on the intended purpose. When the number average particle size is 20 nm or more, the dispersion operation and the classification operation are facilitated, and when the number average particle size is 150 nm or less, not only the pigment dispersion stability as the 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, for example, using a particle size analyzer (Microtrac 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 more preferably 1% by mass or more and 10% by mass or less based on the total amount of the ink, from the viewpoints of image density, fixing property, and ejection stability. Is more preferred. 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 chroma can be obtained.

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

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

The surfactant other than the polysiloxane surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the surfactant include an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant. No. These may be used alone or in combination of two or more. Among these, a nonionic surfactant is preferable from the viewpoint of dispersion stability and image quality.
Further, depending on the composition, a fluorine-based surfactant or a silicone-based surfactant can be used in combination or alone.

  Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include sorbitan fatty acid esters and ethylene oxide adducts 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 from 0.1% by mass to 5% by mass. When the content is 0.1% by mass or more, the wettability to a non-permeable recording medium can be ensured, so that the image quality can be improved. When the content is 5% by mass or less, the ink hardly foams. Excellent ejection stability is obtained.

<Defoaming agent>
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, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

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

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

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

[Ink production method]
As a method for producing the ink, for example, the water, the organic solvent, the polysiloxane surfactant, the modified polyvinyl alcohol, at least one of the vinyl chloride resin particles and the polyurethane resin particles, and if necessary, the Other components can be manufactured by stirring and mixing. 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 usual stirring blade, a magnetic stirrer, a high-speed disperser, and the like can be used.

The physical properties of the ink are not particularly limited and may be appropriately selected depending on the 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, and more preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving 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 measurement conditions, measurement can be performed at 25 ° C. using a standard cone rotor (1 ° 34 ′ × R24), a sample liquid amount 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 suitably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably from 7 to 12, and more preferably from 8 to 11, from the viewpoint of preventing corrosion of the metal member that comes into contact with the ink.

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

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used, but good image formation can be performed even by using a non-permeable base material.
The non-permeable substrate is a substrate having a surface having low water permeability and low absorptivity. And 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 substrate, for example, a plastic film such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, a polypropylene, a polyethylene, and a polycarbonate film can be suitably used.

Further, even when the recording medium is colored (colored recording medium) by applying white ink before the color ink at the time of color recording, the color of the recording medium can be made uniform to white. Can be improved.
Representative examples of the colored recording medium include colored paper, the film, fabric, clothing, and ceramics.

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

  The container is not particularly limited and, depending on the purpose, its shape, structure, size, material, and the like can be appropriately selected.For example, an aluminum laminated film, an ink bag formed of a resin film, or the like can be used. Those having at least are mentioned.

(Inkjet recording method and inkjet recording apparatus)
The ink jet recording method of the present invention preferably includes an ink flying step and a heating step, and further includes other steps as necessary.
The inkjet recording apparatus preferably has an ink flying unit and a heating unit, and further includes other units as necessary.
The inkjet recording method of the present invention can be suitably performed by the inkjet recording apparatus, and the ink flying step can be suitably performed by the ink flying means. The heating step can be suitably performed by the heating means. Further, the other steps can be suitably performed by the other means.

<Ink flying process and ink flying means>
The ink flying step is a step of applying a stimulus to the ink of the present invention to form an image by flying the ink, and can be performed by an ink flying means.
The ink flying means is not particularly limited, and includes, for example, an ink jet head.

  As the ink-jet head, a piezoelectric element is used as a pressure generating means for pressurizing the ink in the ink flow path, and the diaphragm forming the wall of the ink flow path is deformed to change the volume in the ink flow path and eject ink droplets. A so-called piezo type (see Japanese Patent Application Laid-Open No. 2-51734), and a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Application Laid-Open No. 61-59911) Japanese Patent Application Laid-Open Publication No. HEI 9-131, the diaphragm forming the wall surface of the ink flow path and the electrode are arranged to face each other, and the vibration plate is deformed by the electrostatic force generated between the vibration plate and the electrode, thereby changing the volume in the ink flow path. Any case, such as an electrostatic type in which ink droplets are ejected by discharging (see JP-A-6-71882), is included.

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

  The mode of the ink flight is not particularly limited, and varies depending on the type of the stimulus. For example, when the stimulus is “heat”, the ink in the print head is subjected to heat corresponding to a print signal. Energy is applied using, for example, a thermal head or the like, a bubble is generated in the ink by the thermal energy, and the ink is ejected as a droplet from a nozzle hole of the recording head by a pressure of the bubble. Is mentioned. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element adhered to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends, There is a method in which the volume is reduced and the ink is ejected and ejected from the nozzle holes of the recording head as droplets.

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

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

As the heating unit, many known devices can be used, for example, devices such as forced air heating using a hot air generating unit, radiant heating, conduction heating, high frequency drying, and microwave drying. . These may be used alone or in combination of two or more.
The heating temperature can be changed according to the type and amount of the organic solvent contained in the ink, and the minimum film forming temperature of the resin particles to be added, and further changed according to the type of the recording medium to be printed. be able to.

  The heating temperature is preferably high from the viewpoints of drying properties and film forming temperature, more preferably from 40 ° C to 100 ° C, and particularly preferably from 50 ° C to 90 ° C. When the heating temperature is 40 ° C. or more and 120 ° C. or less, damage to the non-permeable recording medium due to heat can be prevented, and non-ejection due to warming of the ink head can be suppressed.

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

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

  When using the white ink, it is also effective to use the following recording method. White ink is applied to a recording medium, and recording is performed thereon with ink of a color other than white. According to this method, for example, even when a transparent film is used, the white ink is attached 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 properties, high gloss, and abrasion resistance even for a non-permeable recording medium, the white ink is applied to a non-permeable recording medium such as a transparent film in order to improve visibility. Can be applied.

  Also, by recording on a transparent film and then applying a white ink, it is possible to obtain an image having the same excellent visibility. If a clear ink is used instead of the white ink, it can function as a protective layer.

The ink of the present invention is not limited to the ink jet recording method and can be widely used. In addition to the ink jet recording method, for example, a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, a U comma coating method, an AKKU coating method Smoothing coat method, microgravure coat method, reverse roll coat method, four to five 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 ink jet recording method, and when recording with an ink of a color other than white, the recording is performed by the ink jet recording method. It is possible to perform the following.
As another embodiment, it is possible to use an ink jet recording method for recording using a white ink or recording using an ink of a color other than white.
The same is true when clear ink is used instead of white ink.

<Recording device and recording method>
The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording system, for example, a printer, a facsimile apparatus, a copying apparatus, a combined printer / fax / copier machine, and a three-dimensional printing apparatus.
In the present invention, a recording device and a recording method are a device capable of discharging ink, various processing liquids, and the like to a recording medium, and a method of performing recording using the device. The recording medium means a medium to which ink and various processing liquids can be temporarily attached.
This recording apparatus can include not only a head portion for discharging ink, but also means for feeding, transporting, and discharging a recording medium, and other devices referred to as a pre-processing device and a post-processing device. .
The recording device and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printing surface or the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a warm air heater or an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording apparatus and the recording method are not limited to those in which a significant image such as a character or a graphic is visualized by ink. For example, those that form a pattern such as a geometric pattern and the like that form a three-dimensional image are also included.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise limited.
Furthermore, this recording apparatus can use not only a desktop type but also a wide recording apparatus that can print on an A0 size recording medium, or a continuous paper wound in a roll shape as a recording medium. Also includes a continuous form printer.
An example of the recording apparatus will be described with reference to FIGS. FIG. 1 is a perspective explanatory view of the same 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 mechanism section 420 is provided inside an 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 packaged with, for example, an aluminum laminate film. It is formed by a member. The ink storage unit 411 is stored in a storage container case 414 made of, for example, plastics. Thus, 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. The main tank 410 is detachably mounted on the cartridge holder 404. Thus, the ink discharge ports 413 of the main tank 410 and the discharge heads 434 for the respective colors communicate with each other via the supply tubes 436 for the respective colors, and the ink can be discharged from the discharge heads 434 to the recording medium.

FIG. 3 is a schematic diagram showing an example of the heating means of the apparatus of FIG. As shown in FIG. 3, by driving the recording head in accordance with an image signal while moving the carriage 133, an ink droplet is ejected onto the recording medium 142 that has stopped, thereby recording an image. The image formed on the recording medium 142 conveyed on the conveyance belt 151 stretched between the conveyance roller 157 and the tension roller 158 on the guide member 153 for lowering the recording medium is added with hot air. Drying is performed by blowing warm air 202 from a heating fan 201 as a generating unit.
Note that a heater group 203 is provided on the side of the conveyor belt 151 opposite to the recording medium 142, and can heat the recording medium 142 on which an image is formed.

(Recorded)
The recorded matter of the present invention has an image formed on a recording medium using the ink of the present invention.
A recorded matter can be obtained by recording using an inkjet recording apparatus and an inkjet recording method.
Further, the recorded matter of the present invention is a recording medium, on the recording medium, a polysiloxane surfactant, a modified polyvinyl alcohol, and selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles. And a recording layer containing at least one of the polysiloxane surfactants described above, wherein the polysiloxane surfactant has an HLB value of 8 or less.

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

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

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

(Preparation example 3 of pigment dispersion)
<Preparation of self-dispersion type magenta pigment dispersion>
Except that the carbon black pigment was changed to Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan KK) in Preparation Example 1 of the pigment dispersion, the same procedure as in Preparation Example 1 of the pigment dispersion was performed. A dispersed magenta pigment dispersion (pigment solids concentration: 15% by mass) was obtained.

(Preparation example 4 of pigment dispersion)
<Preparation of self-dispersion type yellow pigment dispersion>
Except that the carbon black pigment was changed to Pigment Yellow 74 (trade name: First Yellow 531, manufactured by Dainichi Seika Kogyo Co., Ltd.) in Preparation Example 1 of the pigment dispersion, the same procedure as in Preparation Example 1 of the pigment dispersion was performed. Thus, a self-dispersion type yellow pigment dispersion (pigment solid content concentration: 15% by mass) was obtained.

(Preparation Example 5 of Pigment Dispersion)
<Preparation of resin dispersion type black pigment dispersion>
-Preparation of polymer solution A-
After sufficiently replacing the inside of a 1 L flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas inlet tube, a reflux tube, and a dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, and lauryl methacrylate12. 0 g, polyethylene glycol methacrylate 4.0 g, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) 4.0 g, and mercaptoethanol 0.4 g were mixed and heated to 65 ° C. Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxylethyl methacrylate, 36.0 g of the styrene macromer, 3.6 g of mercaptoethanol, and azobismethyl A mixed solution of 2.4 g of valeronitrile and 18.0 g of methyl ethyl ketone was dropped into the flask over 2.5 hours. After the dropwise addition, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18.0 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added, and the mixture was further aged for 1 hour. After the completion of the reaction, 364.0 g of methyl ethyl ketone was added into the flask to obtain 800 g of a polymer solution A having a concentration of 50% by mass.

-Preparation of resin dispersion type black pigment dispersion-
After sufficiently stirring 28 g of the polymer solution A, 42 g of carbon black (trade name: FW100, manufactured by Degussa), 13.6 g of a 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of water, a roll mill was used. And kneaded. The obtained paste was poured into 200 g of pure water, and after sufficiently stirring, methyl ethyl ketone and water were distilled off with an evaporator. In order to further remove coarse particles, the obtained dispersion was mixed with a polystyrene having an average pore size of 5.0 μm. Pressure-filtered with a vinylidene fluoride membrane filter (trade name: PODMF-500, manufactured by Wintech Co., Ltd.), and a resin-dispersed black pigment dispersion having a pigment solids concentration of 15% by mass and a solids concentration of 20% by mass I got

(Example of preparation of acrylic resin emulsion)
900 g of ion-exchanged water and 1 g of sodium lauryl sulfate were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature was raised to 70 ° C. while stirring and replacing with nitrogen. The internal temperature was maintained at 70 ° C., and 4 g of potassium persulfate was added as a polymerization initiator. After dissolution, 20 g of acrylamide, 615 g of styrene, 30 g of butyl acrylate, and 350 g of methacrylic acid were previously added to 450 g of ion-exchanged water and 3 g of sodium lauryl sulfate. The emulsified product added under stirring was dropped into the reaction solution continuously over 4 hours. After completion of the dropwise addition, the mixture was aged for 3 hours. After cooling the obtained aqueous emulsion to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content concentration to 30% by mass and the pH to 8.
With respect to this acrylic resin emulsion, the minimum film forming temperature measured by a film forming temperature test apparatus (manufactured by Imoto Machinery Co., Ltd.) was 53 ° C.

(Example 1)
20.0% by mass of a self-dispersible black pigment dispersion (pigment solid content: 15% by mass), polyether-modified silicone 2 (trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB: 4.5) 1 0.0% by mass, silanol-modified polyvinyl alcohol 2 aqueous solution (trade name: R-1130, manufactured by Kuraray Co., Ltd., solid content concentration: 10% by mass) 10.0% by mass, vinyl chloride-ethylene copolymer resin emulsion (product) Name: Sumilite 1210, manufactured by Sumika Chemtex Co., Ltd., solid content concentration: 50% by mass) 14.0% by mass, 12.0% by mass of 1,2-propanediol, 10.0% by mass of 1,3-propanediol , 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 3.0% by mass of 4-pentanediol, 4.0% by mass of dipropylene glycol monomethyl ether, 0.1% by mass of Proxel LV (manufactured by Arch Chemicals Japan KK) as a preservative, and 100% by mass of highly pure water %, The mixture was stirred, and filtered through a polypropylene filter having an average pore diameter of 0.2 μm (trade name: Betafine BTJ, manufactured by 3M) to prepare Ink 1.

(Examples 2 to 12, and Comparative Examples 1 to 3)
In Example 1, the inks of Examples 2 to 12 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the compositions and the contents described in Tables 1 to 3 below were changed. Was prepared.

In addition, in said Tables 1-3, the brand name of a component and the name of a manufacturer are as follows.
-Polyoxyalkylene group-containing silicone compound 1: manufactured by Toray Dow, trade name: FZ2110, HLB: 1.0
-Polyether-modified silicone 1: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-945, HLB: 4.0
-Polyether-modified silicone 2: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6017, HLB: 4.5
-Polyether-modified silicone 3: Ultra Additives Inc. Product name: FormBan MS-575, HLB: 5.0
-Polyoxyalkylene group-containing silicone compound 2: Toray Dow Co., Ltd., trade name: FZ2166, HLB: 5.8
-Polyether-modified silicone 4: manufactured by Toray Dow Co., Ltd., trade name: SH-3772M, HLB: 6.0
-Polyether-modified silicone 5: manufactured by Nissin Chemical Industry Co., Ltd., trade name: Sylface SAG005, HLB: 7.0
-Polyether-modified silicone 6: manufactured by Toray Dow Co., Ltd., trade name: L7001, HLB: 7.4
-Polyether-modified silicone 7: manufactured by Toray Dow Co., Ltd., trade name: SH-3773M, HLB: 8.0
-Polyether-modified silicone 8: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353, HLB: 10.0
・ Carboxyl-modified polyvinyl alcohol aqueous solution: manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: T330H, solid content: 10% by mass
-Silanol-modified polyvinyl alcohol 1 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R2105, solid content concentration: 10% by mass
-Silanol-modified polyvinyl alcohol 2 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R1130, solid content concentration: 10% by mass
-Vinyl chloride-ethylene copolymer resin emulsion: manufactured by Sumika Chemtex Co., Ltd., trade name: Sumilite 1210, solid content concentration: 50% by mass
・ Vinyl chloride-acrylic copolymer resin emulsion: manufactured by Nissin Chemical Industry Co., Ltd., trade name: VINIBLAN 711, solid content concentration: 30% by mass
-Vinyl chloride copolymer resin emulsion: manufactured by Wacker Chemie AG, trade name: VINNOL E15 / 48A, solid content concentration: 84% by mass
-Preservatives: Arch Chemicals Japan Co., Ltd., trade name: Proxel LV

  Next, "storage stability", "fixing property (beading)", "scratch resistance", "solvent resistance", "image glossiness", and "adhesion" were evaluated as follows. The results are shown in Table 4 below.

  In consideration of the use for outdoor applications, the evaluation of "fixing property (beading)" and "scratch resistance" adopted a considerably stricter evaluation criterion than that of recording on ordinary paper.

<Storage stability (appearance evaluation)>
The obtained inks 1 to 15 of Examples 1 to 12 and Comparative Examples 1 to 3 were stored at 50 ° C., 60 ° C., and 70 ° C. for 7 days, respectively, and visually checked based on the following criteria. Sex "was evaluated. It is practically desirable that the evaluation is B or higher.
[Evaluation criteria]
A: No phase separation at 70 ° C storage
B: No phase separation at 60 ° C. storage, but phase separation at 70 ° C. storage
C: No phase separation at 50 ° C. storage, but phase separation at 60 ° C. storage
D: Phase separation occurs at 50 ° C storage

[Formation of solid image]
Next, the obtained inks 1 to 15 of Examples 1 to 12 and Comparative Examples 1 to 3 were filled in an ink jet printer (device name: IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.), and a polyvinyl chloride film (CPPVWP1300). A solid image was recorded on a recording medium. After recording, the solid image was dried for 1 hour on a hot plate (NINOS ND-1, manufactured by AS ONE Corporation) set at 80 ° C.
Note that the IPSiO GXe5500 remodeling machine is a remodeling of the IPSiO GXe5500 machine so that a print corresponding to a recording speed of 30 m ² / hr can be reproduced in A4 size with a print width of 150 cm, and the pot plate is installed and recorded. It was modified so that the subsequent heating conditions (heating temperature, heating time) could be changed.

<Fixing property (beading)>
The recording unevenness of the solid image formed on the PVC film recording medium was visually observed, and “fixing property (beading)” was evaluated based on the following evaluation criteria. It is practically desirable that the evaluation is B or higher.
[Evaluation criteria]
A: Very good (no beading)
B: Good (slight beading was observed)
C: Normal (beading occurred)
D: Bad (significant beading occurred)

<Scratch resistance>
The solid image formed on the PVC film recording medium was rubbed with a dry cotton (Kanakin No. 3) under a load of 400 g, the state of the image was visually observed, and the "scratch resistance" was evaluated based on the following evaluation criteria. Was evaluated. It is practically desirable 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 at the stage of rubbing 50 times but did not affect the image B: The image changed even after rubbing from 31 to 49 times No C: The image did not change even if it was rubbed 30 times or less.

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

<Image gloss>
The 60 ° gloss level of the solid image formed on the PVC film recording medium was measured four times with a gloss meter (4501 manufactured by BYK Gardener), and the average value of the gloss values was determined. Image glossiness "was evaluated. It is practically desirable 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 the solid image formed on the PVC film recording medium, the number of remaining squares of 100 test squares was counted by a grid-cut peeling test using a cloth adhesive tape (manufactured by Nichiban Co., Ltd., 123LW-50), and the following evaluation was performed. "Adhesion" to the recording medium was evaluated based on the standard. It is practically desirable 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

Example 1 and Example 2 are preferred examples of the present invention, and have excellent adhesion to a PVC film recording medium, provide a high image gloss even when printed on a non-permeable recording medium, and have a high image resistance. It can be seen that an image having abrasion resistance and solvent resistance can be obtained.
Examples 3 and 4 are examples in which the HLB of the polysiloxane surfactant was slightly higher, and resulted in inferior fixability as compared with Example 1.
Examples 5 and 6 are examples in which the HLB of the polysiloxane surfactant was slightly lower, and resulted in inferior storage stability as compared with Example 1.
Example 7 is an example in which the addition amount of the polysiloxane surfactant was slightly small, and resulted in inferior fixability and solvent resistance as compared with Example 1.
Example 8 is an example in which the addition amount of the polysiloxane surfactant was slightly large, and resulted in inferior storage stability as compared with Example 1.
Example 11 is an example in which the amount of the modified polyvinyl alcohol added was slightly smaller than that of the polysiloxane surfactant, and resulted in inferior storage stability as compared with Example 1.
Example 12 is an example in which the amount of the modified polyvinyl alcohol added was slightly larger than that of the polysiloxane surfactant, and the image gloss was inferior to that of Example 1.

  On the other hand, in Comparative Examples 1 to 3, a polysiloxane surfactant having an HLB value of 8 or less, a modified polyvinyl alcohol, and at least one kind selected from polyurethane resin particles, fluororesin particles, and polyester resin particles. This is an example in which the ink is not an all-inclusive ink. Comparative Example 2 was particularly inferior in storage stability and adhesion as compared with Example 1. Comparative Example 3 was particularly inferior to Example 1 in abrasion resistance and solvent resistance.

  From the results shown in Table 4, it can be seen that the ink of the present invention is suitable for outdoor use. In addition, the inks of Examples 1 to 12 were excellent in fixability, scratch resistance, solvent resistance, image gloss, and adhesion to a recording medium.

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

(Preparation example 2 of polyurethane resin particles)
<Preparation of polyether-based polyurethane resin emulsion>
In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 100.2 parts by mass of polyether polyol (“PTMG1000”, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 1,000), 15.7 parts by mass of 2,2-dimethylolpropionic acid, 48.0 parts by mass of isophorone diisocyanate, 77.1 parts by mass of methyl ethyl ketone as an organic solvent, and dibutyltin dilaurate as a catalyst (hereinafter, also referred to as “DMTDL”) The reaction was carried out using 0.06 parts by mass.
After continuing the 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 reactant reaches a 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 a solution of a urethane resin in an organic solvent. Was.
The carboxyl group of the urethane resin was neutralized by adding 13.4 parts by mass of a 48% by mass aqueous solution of potassium hydroxide to the organic solvent solution of the urethane resin. Next, 715.3 parts by mass of water was added and the mixture was sufficiently stirred, and then subjected to aging and solvent removal to obtain a polyether-based polyurethane resin emulsion having a solid content concentration of 30% by mass.
The minimum film forming temperature of the obtained polyether-based polyurethane resin emulsion 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 43 ° C.

(Preparation example 3 of polyurethane resin particles)
<Preparation of polyester-based 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) was replaced with a polyester polyol (“Polylite OD-X-2251”, manufactured by DIC Corporation). , Weight average molecular weight: 2,000) to obtain a polyester-based polyurethane resin emulsion having a solid content of 30% by mass in the same manner as in Preparation Example 2 of the polyurethane resin particles.
The minimum film forming temperature of the obtained polyester-based polyurethane resin emulsion 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 13)
20.0% by mass of the self-dispersion type black pigment dispersion (pigment solids concentration: 15% by mass) of the pigment dispersion preparation example 1 and polyether-modified silicone 2 (trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd.) , HLB: 4.5) 1.0% by mass, 23.3% by mass of the polycarbonate-based polyurethane resin emulsion of Preparation Example 1 of the polyurethane resin particles (solid content concentration: 30% by mass), and an aqueous solution of silanol-modified polyvinyl alcohol 2 (commercially available) Name: R-1130, Kuraray Co., Ltd. solid content concentration: 10% by mass) 10.0% by mass, 12.0% by mass of 1,2-propanediol, 10.0% by mass of 1,3-propanediol, 1, 3.0 mass% of 2-butanediol, 3.0 mass% of 2,3-butanediol, 3.0 mass% of 3-methoxy-3-methylbutanol, 2-methyl-2, -3.0% by mass of pentanediol, 4.0% by mass of dipropylene glycol monomethyl ether, 0.1% by mass of Proxel LV (manufactured by Arch Chemicals Japan KK) as a preservative, and 100% by mass of high pure water %, The mixture was stirred, and the mixture was filtered through a polypropylene filter having an average pore size of 0.2 μm to prepare Ink 16.

(Examples 14 to 24 and Comparative Examples 4 to 5)
In Example 13, the inks 17 to 29 of Examples 14 to 24 and Comparative Examples 4 to 5 were prepared in the same manner as in Example 13 except that the compositions and the contents described in Tables 5 to 7 below were changed. Was prepared.

In Tables 5 to 7, the trade names of the components and the names of the manufacturers are as follows.
-Polyoxyalkylene group-containing silicone compound 1: manufactured by Toray Dow, trade name: FZ2110, HLB: 1.0
-Polyether-modified silicone 1: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-945, HLB: 4.0
-Polyether-modified silicone 2: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6017, HLB: 4.5
-Polyether-modified silicone 3: Ultra Additives Inc. Product name: FormBan MS-575, HLB: 5.0
-Polyoxyalkylene group-containing silicone compound 2: Toray Dow Co., Ltd., trade name: FZ2166, HLB: 5.8
-Polyether-modified silicone 4: manufactured by Toray Dow Co., Ltd., trade name: SH-3772M, HLB: 6.0
-Polyether-modified silicone 5: manufactured by Nissin Chemical Industry Co., Ltd., trade name: Sylface SAG005, HLB: 7.0
-Polyether-modified silicone 6: manufactured by Toray Dow Co., Ltd., trade name: L7001, HLB: 7.4
-Polyether-modified silicone 7: manufactured by Toray Dow Co., Ltd., trade name: SH-3773M, HLB: 8.0
-Polyether-modified silicone 8: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353, HLB: 10.0
・ Carboxyl-modified polyvinyl alcohol aqueous solution: manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: T330H, solid content concentration: 10% by mass
-Silanol-modified polyvinyl alcohol 1 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R2105, solid content concentration: 10% by mass
-Silanol-modified polyvinyl alcohol 2 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R1130, solid content concentration: 10% by mass
-Preservatives: Arch Chemicals Japan Co., Ltd., trade name: Proxel LV

  Using the obtained inks 16 to 29 of Examples 13 to 24 and Comparative Examples 4 to 5, in the same manner as in Examples 1 to 12 and Comparative Examples 1 to 3, "fixing property (beading)", " "Storage stability", "scratch resistance", "solvent resistance", "image gloss", and "adhesion" were evaluated. The results are shown in Table 8 below.

Examples 13 and 14 are preferred examples of the present invention, and have excellent adhesiveness to a PVC film recording medium, provide high image glossiness even when printed on a non-penetrable recording medium, and have a high image resistance. It can be seen that an image having abrasion resistance and solvent resistance can be obtained.
Examples 15 and 16 are examples in which the HLB of the polysiloxane surfactant was slightly higher, and resulted in inferior fixability as compared with Example 13.
Examples 17 and 18 are examples in which the HLB of the polysiloxane surfactant was slightly lower, and resulted in inferior storage stability as compared with Example 13.
Example 19 is an example in which the addition amount of the polysiloxane surfactant was slightly small, and resulted in inferior fixability and solvent resistance as compared with Example 13.
Example 20 is an example in which the addition amount of the polysiloxane surfactant was slightly large, and resulted in inferior storage stability as compared with Example 13.
Example 23 is an example in which the amount of the modified polyvinyl alcohol added was slightly smaller than that of the polysiloxane surfactant, and resulted in inferior storage stability as compared with Example 13.
Example 24 is an example in which the amount of the modified polyvinyl alcohol added was slightly larger than that of the polysiloxane surfactant, and the image gloss was inferior to that of Example 13.

  In contrast, Comparative Examples 4 and 5 were selected from polysiloxane surfactants having an HLB value of 8 or less, modified polyvinyl alcohol, and vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles. Comparative Example 4 was particularly inferior in fixability and solvent resistance as compared with Example 13 in this example. Comparative Example 5 was particularly inferior in storage stability and adhesion as compared with Example 13.

(Preparation example 1 of fluororesin emulsion)
<Preparation of fluororesin emulsion 1>
200 parts by mass of a resin solution (solid content concentration: 15% by mass) in which Teflon AF1600 (Tg: 160 ° C., manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.) is dissolved in perfluoro (2-butyltetrahydrofuran), and a glass container with a jacket Volume: 2 L), and the mixture was stirred with a stirrer (MAZELA1000, manufactured by Tokyo Rika Co., Ltd.) while maintaining the system temperature at 13 ° C. by passing cold water through the jacket (rotational speed: 600 rpm). Thereafter, while stirring, 10 parts by mass of a 10% by mass aqueous solution of a surfactant (trade name: Unidyne DSN-403N, manufactured by Daikin Industries, Ltd.) previously dissolved in water is added, followed by 100 g / min. At a rate, 190 parts by mass of distilled water at 13 ° C. was added. During the addition of distilled water, the temperature in the system was always 15 ° C. or less. After the addition of distilled water was completed, the mixture was stirred for 30 minutes to obtain a fluororesin emulsion having a solid content of 8% by mass. Further, 400 parts by mass of this aqueous dispersion was placed in a 1 L flask, heated in an oil bath heated to about 50 ° C., and concentrated under reduced pressure. Concentration was terminated once when the mass of (flask + aqueous dispersion) was reduced by about 260 parts by mass, and after cooling to room temperature, 200 parts by mass of distilled water was added. 340 parts by mass of this aqueous dispersion was placed again in a 1 L flask, heated in an oil bath heated to about 50 ° C., and concentrated under reduced pressure. Concentration was completed when the weight of (flask + aqueous dispersion) was reduced by about 240 g, and cooled to room temperature. Through the above operation, a fluororesin emulsion 1 having a solid content of 30% by mass was obtained.

(Preparation example 2 of fluororesin emulsion)
<Preparation of fluororesin emulsion 2>
The solid content concentration was changed in the same manner as in Preparation Example 1 of the fluororesin emulsion, except that Teflon AF1600 was changed to Teflon AF2400 (Tg: 240 ° C., manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.). Was 30% by mass to obtain a fluororesin emulsion 2.

(Preparation example 3 of fluororesin emulsion)
<Preparation of fluororesin emulsion 3>
In the preparation of the fluororesin emulsion 1, except that the Teflon AF1600 was changed to Lumiflon FE4400 (Tg: 48 ° C., manufactured by Asahi Glass Co., Ltd.), the fluorine concentration of the solid was 30% by mass. Resin emulsion 3 was obtained.

(Example 25)
20.0% by mass of a self-dispersible black pigment dispersion (pigment solid content: 15% by mass), polyether-modified silicone 2 (trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB: 4.5) 1 0.0% by mass, silanol-modified polyvinyl alcohol 2 aqueous solution (trade name: R-1130, manufactured by Kuraray Co., Ltd., solid content concentration: 10% by mass) 10.0% by mass, fluororesin emulsion 1 (Solid content concentration: 30% by mass) ) 6.0% by mass, 12.0% by mass of 1,2-propanediol, 10.0% by mass of 1,3-propanediol, 3.0% by mass of 1,2-butanediol, 2,3-butanediol 3 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 %, Proxel LV (manufactured by Arch Chemicals Japan KK) 0.1% by mass as a preservative, and high-purity water to a total of 100% by mass. Was filtered through a 0.2 μm polypropylene filter (trade name: Betafine BTJ, manufactured by 3M) to produce Ink 30.

(Examples 26 to 36 and Comparative Examples 6 to 8)
In Example 25, inks 31 to 44 of Examples 26 to 36 and Comparative Examples 6 to 8 were prepared in the same manner as in Example 25, except that the compositions and the contents described in Tables 9 to 11 below were changed. Was prepared.

In Tables 9 to 11, the trade names of the components and the names of the manufacturers are as follows.
-Polyoxyalkylene group-containing silicone compound 1: manufactured by Toray Dow, trade name: FZ2110, HLB: 1.0
-Polyether-modified silicone 1: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-945, HLB: 4.0
-Polyether-modified silicone 2: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6017, HLB: 4.5
-Polyether-modified silicone 3: Ultra Additives Inc. Product name: FormBan MS-575, HLB: 5.0
-Polyoxyalkylene group-containing silicone compound 2: Toray Dow Co., Ltd., trade name: FZ2166, HLB: 5.8
-Polyether-modified silicone 4: manufactured by Toray Dow Co., Ltd., trade name: SH-3772M, HLB: 6.0
-Polyether-modified silicone 5: manufactured by Nissin Chemical Industry Co., Ltd., trade name: Sylface SAG005, HLB: 7.0
-Polyether-modified silicone 6: manufactured by Toray Dow Co., Ltd., trade name: L7001, HLB: 7.4
-Polyether-modified silicone 7: manufactured by Toray Dow Co., Ltd., trade name: SH-3773M, HLB: 8.0
-Polyether-modified silicone 8: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353, HLB: 10.0
・ Carboxyl-modified polyvinyl alcohol aqueous solution: manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: T330H, solid content concentration: 10% by mass
-Silanol-modified polyvinyl alcohol 1 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R2105, solid content concentration: 10% by mass
-Silanol-modified polyvinyl alcohol 2 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R1130, solid content concentration: 10% by mass
-Preservatives: Arch Chemicals Japan Co., Ltd., trade name: Proxel LV

  Using the obtained inks 30 to 44 of Examples 25 to 36 and Comparative Examples 6 to 8, in the same manner as in Examples 1 to 12 and Comparative Examples 1 to 3, “fixing property (beading)”, "Storage stability", "scratch resistance", "solvent resistance", "image gloss", and "adhesion" were evaluated.

Examples 25 and 26 are preferred examples of the present invention, and have excellent adhesiveness to a PVC film recording medium, provide a high image glossiness even when printed on a non-permeable recording medium, and have a high image resistance. It can be seen that an image having abrasion resistance and solvent resistance can be obtained.
Example 27 and Example 28 are examples in which the HLB of the polysiloxane surfactant was slightly higher, and resulted in inferior fixability as compared with Example 25.
Examples 29 and 30 are examples in which the HLB of the polysiloxane surfactant was slightly lower, and resulted in inferior storage stability as compared with Example 25.
Example 31 is an example in which the addition amount of the polysiloxane surfactant was slightly small, and resulted in inferior fixability and solvent resistance as compared with Example 25.
Example 32 is an example in which the addition amount of the polysiloxane surfactant was slightly large, and resulted in inferior storage stability as compared with Example 25.
Example 35 is an example in which the amount of the modified polyvinyl alcohol added was slightly smaller than that of the polysiloxane surfactant, and resulted in inferior storage stability as compared with Example 25.
In Example 36, the amount of the modified polyvinyl alcohol added was slightly larger than that of the polysiloxane surfactant, and the result was that the image gloss was inferior to Example 25.

  In contrast, Comparative Examples 6 to 8 were selected from polysiloxane surfactants having an HLB value of 8 or less, modified polyvinyl alcohol, and vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles. In Comparative Example 6, the fixability and the solvent resistance were particularly inferior to those of Example 25. Comparative Example 7 was particularly inferior in storage stability and adhesion to Example 25. Comparative Example 8 was particularly inferior in scratch resistance and solvent resistance as compared with Example 25.

(Example 37)
20.0% by mass of a self-dispersible black pigment dispersion (pigment solid content: 15% by mass), polyether-modified silicone 2 (trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., HLB: 4.5) 1 0.0% by mass, 10.0% by mass of a silanol-modified polyvinyl alcohol 2 aqueous solution (trade name: R-1130, manufactured by Kuraray Co., Ltd., solid content concentration: 10% by mass), polyester resin emulsion 1 (trade name: KZA1449, Unitika Ltd.) 6.0% by mass, 12.0% by mass of 1,2-propanediol, 10.0% by mass of 1,3-propanediol, 3.0% by mass of 1,2-butanediol. % By mass, 3.0% by mass of 2,3-butanediol, 3.0% by mass of 3-methoxy-3-methylbutanol, 3.0% by mass of 2-methyl-2,4-pentanediol , 4.0% by mass of dipropylene glycol monomethyl ether, 0.1% by mass of Proxel LV (manufactured by Arch Chemicals Japan Co., Ltd.) as a preservative, and 100% by mass of high-purity water to make a total amount of 100% by mass. The resulting mixture was added, mixed and stirred, and filtered through a polypropylene filter having an average pore diameter of 0.2 μm (trade name: Betafine BTJ, manufactured by 3M) to prepare Ink 45.

(Examples 38 to 48 and Comparative Examples 9 to 10)
In Example 37, inks 45 to 58 of Examples 38 to 48 and Comparative Examples 9 to 10 were prepared in the same manner as in Example 37, except that the compositions and contents were changed as shown in Tables 13 to 15 below. Was prepared.

In addition, in said Tables 13-15, the brand name of a component and the manufacturer name are as follows.
-Polyoxyalkylene group-containing silicone compound 1: manufactured by Toray Dow, trade name: FZ2110, HLB: 1.0
-Polyether-modified silicone 1: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-945, HLB: 4.0
-Polyether-modified silicone 2: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6017, HLB: 4.5
-Polyether-modified silicone 3: Ultra Additives Inc. Product name: FormBan MS-575, HLB: 5.0
-Polyoxyalkylene group-containing silicone compound 2: Toray Dow Co., Ltd., trade name: FZ2166, HLB: 5.8
-Polyether-modified silicone 4: manufactured by Toray Dow Co., Ltd., trade name: SH-3772M, HLB: 6.0
-Polyether-modified silicone 5: manufactured by Nissin Chemical Industry Co., Ltd., trade name: Sylface SAG005, HLB: 7.0
-Polyether-modified silicone 6: manufactured by Toray Dow Co., Ltd., trade name: L7001, HLB: 7.4
-Polyether-modified silicone 7: manufactured by Toray Dow Co., Ltd., trade name: SH-3773M, HLB: 8.0
-Polyether-modified silicone 8: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353, HLB: 10.0
・ Carboxyl-modified polyvinyl alcohol aqueous solution: manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: T330H, solid content concentration: 10% by mass
-Silanol-modified polyvinyl alcohol 1 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R2105, solid content concentration: 10% by mass
-Silanol-modified polyvinyl alcohol 2 aqueous solution: manufactured by Kuraray Co., Ltd., trade name: R1130, solid content concentration: 10% by mass
-Polyester resin emulsion 1: manufactured by Unitika Ltd., trade name: KZA1449, solid content concentration 30% by mass
-Polyester resin emulsion 2: manufactured by Takamatsu Yushi Co., Ltd., trade name: A-125S, solid content concentration 30% by mass
-Polyester resin emulsion 3: manufactured by Takamatsu Yushi Co., Ltd., trade name: A-160P, solid content concentration 25% by mass
-Preservatives: Arch Chemicals Japan Co., Ltd., trade name: Proxel LV

  Using the obtained inks 45 to 58 of Examples 37 to 48 and Comparative Examples 9 to 10, in the same manner as in Examples 1 to 12 and Comparative Examples 1 to 3, "fixing property (beading)", " "Storage stability", "scratch resistance", "solvent resistance", "image gloss", and "adhesion" were evaluated. The results are shown in Table 16 below.

Example 37 and Example 38 are preferred examples of the present invention, and have excellent adhesion to a PVC film recording medium, can achieve high image glossiness even when printed on a non-permeable recording medium, and have high image gloss resistance. It can be seen that an image having abrasion resistance and solvent resistance can be obtained.
Example 39 and Example 40 are examples in which the HLB of the polysiloxane surfactant was slightly higher, and resulted in inferior fixability and adhesion as compared with Example 37.
Example 41 and Example 42 are examples in which the HLB of the polysiloxane surfactant was slightly lower, and resulted in poorer storage stability than Example 37.
Example 43 is an example in which the addition amount of the polysiloxane surfactant was slightly smaller, and resulted in inferior fixability and solvent resistance as compared with Example 37.
Example 44 is an example in which the addition amount of the polysiloxane surfactant was slightly large, and resulted in inferior fixability, storage stability, and adhesion as compared with Example 37.
Example 47 is an example in which the amount of the modified polyvinyl alcohol added was slightly smaller than that of the polysiloxane surfactant, and resulted in inferior fixability, storage stability, and adhesion as compared with Example 37.
Example 38 is an example in which the amount of the modified polyvinyl alcohol added was slightly larger than that of the polysiloxane surfactant, and resulted in inferior fixability, image glossiness, and adhesion as compared with Example 37.

  In contrast, Comparative Examples 9 to 10 were selected from polysiloxane surfactants having an HLB value of 8 or less, modified polyvinyl alcohol, and vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles. In Comparative Example 10, the fixing property and the solvent resistance were particularly inferior to those of Example 37. Comparative Example 11 was particularly inferior in storage stability and adhesion as compared with Example 37.

(Test Examples 1 to 32)
<Evaluation of the effect of heating and drying>
In the ink 1 of Example 1, the ink 16 of Example 13, the ink 30 of Example 25, and the ink 45 of Example 37, as shown in Tables 17 and 18, the heating conditions after recording (heating temperature, heating temperature) The fixing property (beading), the adhesion and the abrasion resistance were evaluated in the same manner as in Example 1 except that the time was changed to (time). The results are shown in Tables 17 and 18 below.
It should be noted that, in Test Examples 8, 16, 16, and 32, recording of a solid image was performed in the same manner as in Example 1 using Ink 1, Ink 16, Ink 30, and Ink 45, respectively. And dried without heating after recording (leaving at 25 ° C. for 24 hours).

Aspects of the present invention are, for example, as follows.
<1> Contains water, an organic solvent, a polysiloxane surfactant, a modified polyvinyl alcohol, and at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles. And
An ink characterized in that the polysiloxane surfactant has an HLB value of 8 or less.
<2> The ink according to <1>, wherein the polysiloxane surfactant has an HLB value of 4.5 or more and 7.0 or less.
<3> The ink according to any one of <1> to <2>, wherein the content of the polysiloxane surfactant is 1.0% by mass or more and 2.0% by mass or less.
<4> The ink according to any one of <1> to <3>, wherein the modified polyvinyl alcohol is a silanol-modified polyvinyl alcohol.
<5> The mass ratio (B / A) of the content A (% by mass) of the polysiloxane surfactant to the content B (% by mass) of the modified polyvinyl alcohol is 0.8 or more and 1.5 or less. The ink according to any one of <1> to <4> above.
<6> The ink according to any one of <1> to <5>, further including a coloring material.
<7> The ink according to any one of <1> to <6>, wherein the content of the modified polyvinyl alcohol is 0.5% by mass or more and 5% by mass or less.
<8> The ink according to any one of <1> to <7>, wherein the content of the modified polyvinyl alcohol is 0.8% by mass or more and 2.5% by mass or less.
<9> The polyurethane resin particles according to any one of <1> to <8>, wherein the polyurethane resin particles are at least one selected from polyether-based polyurethane resin particles, polycarbonate-based polyurethane resin particles, and polyester-based polyurethane resin particles. Of ink.
<10> The vinyl chloride resin particles are at least one selected from acryl-vinyl chloride copolymer resin particles, ethylene-vinyl chloride copolymer resin particles, and vinyl chloride-based copolymer resin particles. An ink according to any one of <1> to <9>.
<11> The ink according to any one of <1> to <10>, wherein the polyurethane resin particles have a volume average particle diameter of 10 nm or more and 1,000 nm or less.
<12> The ink according to any one of <1> to <11>, wherein the vinyl chloride resin particles have a volume average particle diameter of 10 nm or more and 1,000 nm or less.
<13> The ink according to any one of <1> to <12>, wherein the content of the polyurethane resin particles is 3% by mass or more and 10% by mass or less.
<14> The ink according to any one of <1> to <13>, wherein the content of the vinyl chloride resin particles is 3% by mass or more and 10% by mass or less.
<15> The ink according to any one of <1> to <14>, wherein the content of the organic solvent is 10% by mass or more and 60% by mass or less.
<16> The ink according to any one of <6> to <15>, wherein the coloring material is a pigment.
<17> The ink according to any one of <6> to <16>, wherein the content of the coloring material is 0.1% by mass or more and 15% by mass or less.
<18> An ink jet recording method including an ink flying step of applying a stimulus to the ink according to any one of <1> to <17> to fly the ink and record an image on a recording medium. It is.
<19> The inkjet recording method according to <18>, further including a heating step of heating the recording medium.
<20> The inkjet recording method according to <19>, wherein a heating temperature in the heating step is 40 ° C or more and 100 ° C or less.
<21> a recording medium;
On the recording medium, a polysiloxane surfactant, modified polyvinyl alcohol, and at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles are included. And a recording layer,
A recorded matter, wherein the HLB value of the polysiloxane surfactant is 8 or less.

  The ink according to any one of <1> to <17>, the inkjet recording method according to any one of <18> to <20>, and the recorded matter according to <21>, The problem can be solved and the object of the present invention can be achieved.

JP 2005-220352 A JP 2011094082 A

  142: Recording medium

Claims (10)

Water, an organic solvent, a polysiloxane surfactant, a modified polyvinyl alcohol, and at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles,
An ink, wherein the polysiloxane surfactant has an HLB value of 8 or less.   The ink according to claim 1, wherein the HLB value of the polysiloxane surfactant is from 4.5 to 7.0.   The ink according to claim 1, 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 3, wherein the modified polyvinyl alcohol is a silanol-modified polyvinyl alcohol.   The mass ratio (B / A) of the content A (% by mass) of the polysiloxane surfactant and the content B (% by mass) of the modified polyvinyl alcohol is 0.8 to 1.5. Item 5. The ink according to any one of Items 1 to 4.   The ink according to any one of claims 1 to 5, further comprising a coloring material.   An ink jet recording method, comprising: a step of applying a stimulus to the ink according to any one of claims 1 to 6, causing the ink to fly, and recording an image on a recording medium.   The inkjet recording method according to claim 7, further comprising a heating step of heating the recording medium.   The inkjet recording method according to claim 8, wherein a heating temperature in the heating step is 40C or more and 100C or less. A recording medium;
A recording layer containing, on the recording medium, a polysiloxane surfactant, a modified polyvinyl alcohol, and at least one selected from vinyl chloride resin particles, polyurethane resin particles, fluororesin particles, and polyester resin particles. , And
A recorded matter, wherein the HLB value of the polysiloxane surfactant is 8 or less.