JP6880785B2 - Inkjet printing ink, inkjet recording device, and inkjet recording method - Google Patents

Description

The present invention relates to an inkjet printing ink, an inkjet recording device, and an inkjet recording method.

In recent years, the diversification of inkjet ink technology has progressed, and studies on inkjet printing ink for printing on fabrics have been active.

The inkjet printing ink is required to have comfort, friction fastness, washing fastness, and the like, in addition to the characteristics required for the inkjet ink for paper and film.

Therefore, 400% to 1,000% of film elongation, inkjet printing inks have been proposed using a water-dispersible resin having a tensile strength ^{20N / mm 2 ~50N / mm 2} ( e.g., see Patent Document 1) ..
Also, film elongation of 650% to 1,200%, using a water-dispersible resin having a tensile strength ^{15N / mm 2 ~55N / mm 2} , has been proposed for inkjet textile printing inks used blocked isocyanate compound as a crosslinking agent (See, for example, Patent Document 2).
Further, for printing inkjet using a polyurethane resin having a glass transition point of −35 ° C. to 10 ° C. and ^{a polyol having an SP value of 10 (cal / cm 3} ) ^{1/2 to} 15.5 (cal / cm ³ ) ^1/2. Inks have been proposed (see, for example, Patent Document 3).
Furthermore, a 400% to 1,000% of film elongation, and the film strength of the resin is 100% to 400% water-dispersible resin and film elongation is ^20N / mm ^{2 ~50N} / mm 2 An ink set for printing inkjet, which is a combination with an overcoating agent containing the ink jet, has been proposed (see, for example, Patent Document 4).
Further, an ink for inkjet printing containing a 2-pyrrolidone-based solvent has been proposed (see, for example, Patent Document 5).

However, the above-mentioned prior art has not yet solved the above-mentioned problems.
Therefore, the present invention provides an inkjet printing ink which has good ejection stability, can obtain high friction fastness and washing fastness in the obtained printed matter, and can prevent cracks at the time of pulling. The purpose is.

The printing ink for inkjet of the present invention as a means for solving the above-mentioned problems is a printing ink for inkjet containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles, and the organic solvent contains glycerin. The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet, and the polycarbonate urethane resin particles have a glass transition temperature. Is -25 ° C or higher and 5 ° C or lower, the film elongation is 400% or higher and 600% or lower, the film strength is 52 MPa or higher and 58 MPa or lower, and the content is 8% by mass or more with respect to the total amount of the printing ink for inkjet. Further, the mass ratio (glycerin / polycarbonate urethane resin particles) of the glycerin content (mass%) and the content (mass%) of the polycarbonate urethane resin particles is 0.8 or more and 1.2 or less. der is, the pigment is being covered with a resin, further, for the ink jet characterized by containing 3-methyl-1,3-butanediol or 2-amino-2-ethyl-1,3-propanediol Printing ink.

According to the present invention, there is provided an inkjet printing ink which has good ejection stability, can obtain high friction fastness and washing fastness in the obtained printed matter, and can prevent cracks at the time of pulling. Can be done.

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

(Inkjet printing ink)
The inkjet printing ink of the present invention (hereinafter, also referred to as “ink”) is an inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles, and the organic solvent is glycerin. The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet, and the polycarbonate urethane resin particles are glass. The transfer temperature is -25 ° C or higher and 5 ° C or lower, the film elongation is 400% or higher and 600% or lower, the film strength is greater than 50 MPa, and the content is 8% by mass or more with respect to the total amount of the printing ink for inkjet. Yes, and further include other ingredients as needed.
The inkjet printing ink of the present invention, conventional film elongation of 400% to 1,000%, in textile printing ink jet ink using a water-dispersible resin having a tensile strength ^{20N / mm 2 ~50N / mm 2} , pretreatment There is a problem that robustness if not performed is insufficient 650% to 1,200% of film elongation, using a water-dispersible resin having a tensile strength ^{15N / mm 2 ~55N / mm 2} , block Inkjet ink for printing, which uses an isocyanate-based compound as a cross-linking agent, requires careful temperature control during storage and transportation because a cross-linking agent is added, and there is a problem that the ejection stability of the ink during printing is insufficient. It is based on the finding that there is.
The inkjet printing ink of the present invention is a conventional polyurethane resin having a glass transition point of −35 ° C. to 10 ° C. and an SP value of 10 (cal / cm ³ ) ^{1/2 to} 15.5 (cal / cm ^3). ) The ^{printing inkjet ink using 1/2} polyol has a problem that the fastness is insufficient when the pretreatment is not performed, the film elongation is 400% to 1,000%, and the film is formed. strength in ^20N / mm 2 ^~50N / mm combined in a printing ink-jet ink set of an overcoat agent containing ² water-dispersible resin and film elongation is that the resin is 100% to 400%, of the overcoat It is based on the finding that there is a problem that coating is required, the size of the device is increased, and the operation procedure is increased.
Further, the ink jet printing ink of the present invention is based on the finding that the conventional ink jet printing ink containing a 2-pyrrolidone solvent has a problem that the washing fastness and the friction fastness are insufficient. ..

Hereinafter, the organic solvent, water, coloring material, resin, additive, etc. used for the ink will be described.

<Organic solvent>
The organic solvent contains glycerin and, if necessary, other organic solvent.

Among the water-soluble organic solvents, the glycerin has a relatively high affinity with water and has a high effect of suppressing the evaporation of water. In addition, since it has a relatively high viscosity, it is also useful for adjusting the viscosity.

The content of glycerin with respect to the total amount of the organic solvent is 30% by mass or more, and is preferably 40% by mass or more from the viewpoint of suppressing the viscosity of the entire inkjet printing ink and suppressing the increase in viscosity during drying in the vicinity of the nozzle. In order to improve the drying property after permeating into the fabric, 95% by mass or less is preferable.
The content of glycerin with respect to the total amount of the inkjet printing ink is 5% by mass or more, preferably 6% by mass or more, and suppresses the viscosity of the entire inkjet printing ink and suppresses the increase in viscosity during drying in the vicinity of the nozzle. Therefore, it is preferably 30% by mass or less. When the content with respect to the total amount of the printing ink for inkjet is 5% by mass or more, drying suppression in the vicinity of the nozzle can be improved.

The other organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines and sulfur-containing compounds.
Specific examples of other water-soluble organic solvents include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4. -Butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4- Pentandiol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexane Diol, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone. , 1,3-Dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N- Amidos such as dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. And so on.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because it not only functions as a wetting agent but also has good drying properties.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers: Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether can be mentioned.

The content of the organic solvent in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 60% by mass or less from the viewpoint of ink drying property and ejection reliability. More preferably, it is 20% by mass or more and 60% by mass or less.

<Resin particles>
The resin particles include polycarbonate urethane resin particles, and if necessary, other resin particles include a second resin particle.

<< Polycarbonate urethane resin particles >>
The polycarbonate urethane resin particles can improve wear resistance.
When resin particles other than the polycarbonate urethane resin particles are used, the frictional fastness of the printed material tends to be low, and the effect of the present invention cannot be obtained.

The glass transition temperature of the polycarbonate urethane resin particles is −25 ° C. or higher and 5 ° C. or lower, preferably −20 ° C. or higher and 5 ° C. or lower, and more preferably −20 ° C. or higher and 0 ° C. or lower. When the glass transition temperature is -25 ° C or higher, the permeability to the fiber is suppressed and bleeding can be suppressed, and when the glass transition temperature is 5 ° C or lower, the fiber is easily adapted to the fiber and the coverage of the fiber is high. can do. The glass transition temperature can be measured using, for example, a differential scanning calorimetry device (DSC-60A, manufactured by Shimadzu Corporation).

The film elongation of the polycarbonate urethane resin particles is 400% or more and 600% or less, preferably 450% or more and 600% or less, and more preferably 450% or more and 580% or less. When the film elongation is 400% or more, it is easy to cope with the expansion and contraction of the fabric, especially when it is used for clothing such as T-shirts, and the toughness can be increased. When it is 600% or less, the printing ink It is possible to suppress excessive elongation and sagging of the ink and maintain a natural texture.

The film strength of the polycarbonate urethane resin particles is more than 50 MPa, more preferably 52 MPa or more and 58 MPa or less. When the film strength is larger than 50 MPa, friction fastness and washing fastness can be improved.

The film elongation and the film elongation can be measured as follows.
Polycarbonate urethane resin particles are coated on a polytetrafluoroethylene sheet so that the average film thickness after drying is 500 μm, dried at room temperature (25 ° C.) for 15 hours, further dried at 80 ° C. for 6 hours, and then 120 ° C. After drying for 20 minutes in the above, the film is peeled off from the polytetrafluoroethylene sheet to obtain a water-dispersible resin film.
The film elongation of the water-dispersible resin film obtained at a measurement temperature of 20 ° C. and a measurement speed of 200 mm / min using a Tencilon universal testing machine (device name: RTC-1225A, manufactured by Orientec Co., Ltd.). And measure the film strength.
The length of the resin film that elongates before breaking is measured, and the value obtained by expressing the ratio to the original length as a percentage is defined as the film elongation. The film strength is the strength at break.

The polycarbonate urethane resin particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, a commercially available product can be used. Examples of the commercially available product include trade name: Takelac W-6110 (manufactured by Mitsui Chemicals, Inc., glass transition temperature: -20 ° C., film elongation: 550, film strength: 55 MPa, solid content concentration: 31% by mass) and the like. Can be mentioned.

The content of the polycarbonate urethane resin particles is 8% by mass or more, preferably 9% by mass or more, and more preferably 20% by mass or less with respect to the total amount of the printing ink for inkjet. When the content is 8% by mass or more, a sufficient thickness can be obtained for the fiber, so that the toughness can be improved. The texture and fastness can be improved by appropriately permeating and coating the fibers with polycarbonate urethane resin particles.

<< Second resin particles >>
As the type of resin particles contained in the ink, in addition to the polycarbonate urethane resin particles of the present invention, a second resin particle can be appropriately selected depending on the intended purpose. For example, urethane resin, polyester resin, acrylic. Examples thereof include based resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.
Resin particles made of these resins may be used. It is possible to obtain ink by mixing resin particles with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is dispersed as a dispersion medium. As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used. Further, these may be used alone or in combination of two or more kinds of resin particles.

The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

The content of the resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of fixability and storage stability of the ink, 1% by mass or more and 30% by mass or less with respect to the total amount of the ink. Is preferable, and 5% by mass or more and 20% by mass or less is more preferable.

The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose, but from the viewpoint of improving image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number of inks. Is preferably 20 nm or more and 1000 nm or less, and more preferably 20 nm or more and 150 nm or less. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

[Mass ratio (glycerin / polycarbonate urethane resin particles)]
The mass ratio (glycerin / polycarbonate urethane resin particles) of the glycerin content (mass%) and the polycarbonate urethane resin particles content (mass%) is preferably 0.8 or more and 2.5 or less. It is more preferably 0.0 or more and 2.5 or less, and particularly preferably 1.0 or more and 1.5 or less. When the mass ratio (glycerin / polycarbonate urethane resin particles) is 0.8 or more and 2.5 or less, the robustness can be improved. In addition, it is considered that the balance between permeability to fibers and adhesiveness can be improved.

<Water>
The content of water in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of ink drying property and ejection reliability, it is preferably 10% by mass or more and 90% by mass or less, and 20% by mass. % To 60% by mass is more preferable.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Moreover, you may use a mixed crystal.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by known methods such as contact method, furnace method, and thermal method. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, 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, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmin 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Magenta), 104, 105, 106, 108 ( Cadmium Red), 112, 114, 122 (Quinacridone Magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As the dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52,80,82,249,254,289, C.I. I. Acid Blue 9,45,249, C.I. I. Acid Black 1,2,24,94, C.I. I. Hood Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1,2,15,71,86,87,98,165,199,202, C.I. I. Dilekdo Black 19,38,51,71,154,168,171,195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3, 4, 35 can be mentioned.

The pigment is preferably coated with a resin. Since the pigment is coated with a resin, friction fastness and washing fastness can be improved, which is particularly effective for selective fastness. Further, by coating the pigment with a resin, the affinity with the polycarbonate urethane resin particles is increased, and the retention on the fiber can be enhanced.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass, from the viewpoint of improving image density, good fixability and ejection stability. It is as follows.

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin coating pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effects of the present invention are not impaired. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low molecular weight dispersant and a high molecular weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonate Na formalin condensate can also be suitably used as a dispersant.
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 mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. It is preferable to use a disperser for dispersion.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1 mass is used. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
If necessary, the pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifuge, or the like.

<Additives>
If necessary, a surfactant, a defoaming agent, an antiseptic / antifungal agent, a rust preventive, a pH adjuster, or the like may be added to the ink.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, and side chain double-ended modified polydimethylsiloxane. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. A polyoxyalkylene ether polymer compound is particularly preferable because it has a low foaming property. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counterions of the salts in these fluorine-based surfactants are Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside agent include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, salt of polyoxyethylene alkyl ether sulfate, and the like.
These may be used alone or in combination of two or more.

一般式（Ｓ−１）
（但し、一般式（Ｓ−１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ−６１８、ＫＦ−６４２、ＫＦ−６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ−ＳＳ−５６０２、ＳＳ−１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ−２１０５、ＦＺ−２１１８、ＦＺ−２１５４、ＦＺ−２１６１、ＦＺ−２１６２、ＦＺ−２１６３、ＦＺ−２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ−３３、ＢＹＫ−３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as modifying groups exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the general formula (S-1) is dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

General formula (S-1)
(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)
Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

一般式（Ｆ−１）
上記一般式（Ｆ−１）で表される化合物において、水溶性を付与するためにｍは０〜１０の整数が好ましく、ｎは０〜４０の整数が好ましい。
一般式（Ｆ−２）
Ｃ_ｎＦ_{２ｎ＋１−}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ａ−Ｙ
上記一般式（Ｆ−２）で表される化合物において、ＹはＨ、又はＣｎＦ_２ｎ＋１でｎは１〜６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−ＣｎＦ_２ｎ＋１でｎは４〜６の整数、又はＣｐＨ_２ｐ＋１でｐは１〜１９の整数である。ａは４〜１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ−１１１、Ｓ−１１２、Ｓ−１１３、Ｓ−１２１、Ｓ−１３１、Ｓ−１３２、Ｓ−１４１、Ｓ−１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ−９３、ＦＣ−９５、ＦＣ−９８、ＦＣ−１２９、ＦＣ−１３５、ＦＣ−１７０Ｃ、ＦＣ−４３０、ＦＣ−４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ−４７０、Ｆ−１４０５、Ｆ−４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ−１００、ＦＳＮ、ＦＳＯ−１００、ＦＳＯ、ＦＳ−３００、ＵＲ、キャプストーンＦＳ−３０、ＦＳ−３１、ＦＳ−３１００、ＦＳ−３４、ＦＳ−３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ−１３６Ａ，ＰＦ−１５６Ａ、ＰＦ−１５１Ｎ、ＰＦ−１５４、ＰＦ−１５９（オムノバ社製）、ユニダインＤＳＮ−４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ−３１００、ＦＳ−３４、ＦＳ−３００、株式会社ネオス製のＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ、オムノバ社製のポリフォックスＰＦ−１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ−４０３Ｎが特に好ましい。 As the fluorine-based surfactant, a compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine is more preferable.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain. Among these, polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain are preferable because they have low foaming property, and are particularly fluorine-based compounds represented by the general formulas (F-1) and (F-2). Surfactants are preferred.

General formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10, and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
C _n F _{2n + 1-} CH ₂ CH (OH) CH _2- O- (CH ₂ CH ₂ O) _a- Y
In the compound represented by the above general formula (F-2), Y is H or CnF _{2n + 1} and n is an integer of 1 to 6, or CH ₂ CH (OH) CH _2- CnF _{2n + 1} and n is 4 to 6. It is an integer, or CpH _{2p + 1} and p is an integer of 1-19. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant. Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by The Chemours Company); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omniova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) Among these, FS-3100, FS-34, FS- of The Chemours Co., Ltd., from the viewpoint of remarkably improving good print quality, particularly color development, penetrability to paper, wettability, and leveling property. 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omninova, and Unidyne DSN-manufactured by Daikin Industries, Ltd. 403N is particularly preferable.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of excellent wettability and ejection stability and improvement in image quality, 0.001 mass is used. % Or more and 5% by mass or less are preferable, and 0.05% by mass or more and 5% by mass or less are more preferable.

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

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

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

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

The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, more preferably 8 to 11, from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

<Pretreatment liquid>
The pretreatment liquid contains a coagulant, an organic solvent, and water, and may contain a surfactant, an antifoaming agent, a pH adjuster, an antiseptic / antifungal agent, an anticorrosive agent, and the like, if necessary.
As the organic solvent, surfactant, defoaming agent, pH adjuster, antiseptic / antifungal agent, and rust preventive, the same materials as those used for ink can be used, and other materials used for known treatment liquids can be used. ..
The type of coagulant is not particularly limited, and examples thereof include water-soluble cationic polymers, acids, and polyvalent metal salts.

<Post-treatment liquid>
The post-treatment liquid is not particularly limited as long as it is possible to form a transparent layer. The post-treatment liquid is obtained by selecting and mixing organic solvents, water, resins, surfactants, antifoaming agents, pH adjusters, antiseptic and antifungal agents, rust preventives and the like, if necessary. Further, the post-treatment liquid may be applied to the entire area of the recording area formed on the recording medium, or may be applied only to the area where the ink image is formed.

<Recording medium>
The recording medium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cloth.
Examples of the cloth include cotton, polyester, a blend of cotton and chemical fibers, nylon, polyamide fibers, silk, and woven fabrics made of wool, nets, and non-woven fabrics.

(Inkjet recording device and inkjet recording method)
The inkjet recording apparatus of the present invention is an inkjet recording apparatus having an inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles, and an ink ejection unit for ejecting the inkjet printing ink. The organic solvent contains glycerin, and the content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet, and the polycarbonate. The urethane resin particles have a glass transition temperature of -25 ° C or higher and 5 ° C or lower, a film elongation of 400% or higher and 600% or lower, a film strength of more than 50 MPa, and a content of the total amount of the ink jet printing ink. It is 8% by mass or more, and further has other means as needed.

The inkjet recording method of the present invention is an inkjet recording method including an ejection step of ejecting an inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles from an ink ejection unit, wherein the organic solvent is used. The polycarbonate urethane resin particles contain glycerin, and the content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet. The glass transition temperature is -25 ° C or higher and 5 ° C or lower, the film elongation is 400% or higher and 600% or lower, the film strength is greater than 50 MPa, and the content is 8% by mass or more with respect to the total amount of the inkjet printing ink. And further includes other steps as needed.
As the inkjet printing ink, the same ink as the inkjet printing ink of the present invention can be used.

The inkjet recording method can be preferably carried out by the inkjet recording apparatus.

The inkjet recording device preferably does not have a pretreatment device.
The inkjet recording method preferably does not include a pretreatment step.

<< Ink ejection part and ink ejection process >>
The ink ejection unit is a member that ejects ink jet printing ink.
The ink ejection process is a step of ejecting printing ink for inkjet.
The ink ejection step can be more preferably carried out by the ink ejection portion.

It is preferable that the ink ejection unit applies a stimulus to the ink to eject the ink.
In the ink ejection step, it is preferable to apply a stimulus to the ink to eject the ink.

The stimulus is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include heat (temperature), pressure, vibration, and light. These may be used alone or in combination of two or more. Among these, heat and pressure are preferably mentioned.

As an aspect of ejecting the ink, for example, a piezoelectric element is used as a pressure generating means for pressurizing the ink in the ink flow path to deform a vibrating plate forming a wall surface of the ink flow path to increase the internal volume of the ink flow path. A so-called piezo method in which ink droplets are ejected by changing the ink (see, for example, Japanese Patent Publication No. 2-51734); a so-called thermal method in which ink is heated in an ink flow path using a heat generating resistor to generate bubbles (see, for example, Japanese Patent Publication No. 2-51734). (For example, see Japanese Patent Publication No. 61-59911); The vibrating plate and the electrode forming the wall surface of the ink flow path are arranged to face each other, and the vibrating plate is deformed by the electrostatic force generated between the vibrating plate and the electrode. Examples thereof include an electrostatic method in which the volume inside the ink flow path is changed to eject ink droplets (see, for example, Japanese Patent Application Laid-Open No. 6-71882).

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

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording devices by the inkjet recording method, for example, an inkjet recording device (inkjet stamping device).
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method of recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, and other devices called pretreatment devices and posttreatment devices. ..
The recording device and recording method may include a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the print surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form a three-dimensional image are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous line printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanical unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage section 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided behind the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

This recording device can include not only a portion for ejecting ink but also a device called a pretreatment device, a posttreatment device, and the like. However, if the ink of the present invention is used, friction is performed even without the pretreatment device. Robustness and selective robustness can be obtained.
As one aspect of the pretreatment apparatus and the posttreatment apparatus, it has a pretreatment liquid and a posttreatment liquid as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is an embodiment in which a liquid accommodating portion and a liquid discharge head are added, and a pretreatment liquid or a posttreatment liquid is discharged by an inkjet recording method.
As another aspect of the pretreatment device and the posttreatment device, there is a mode in which a pretreatment device and a posttreatment device by, for example, a blade coating method, a roll coating method, and a spray coating method are provided other than the inkjet recording method.

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

The glass transition temperature, film elongation, and film strength of the resin particles were measured as follows.

(Glass-transition temperature)
The glass transition temperature was measured using a differential scanning calorimetry device (DSC-60A, manufactured by Shimadzu Corporation).

(Film elongation and film strength)
Water-dispersible resin particles (resin particles) are coated on a polytetrafluoroethylene sheet so that the average film thickness after drying is 500 μm, dried at room temperature (25 ° C.) for 15 hours, and further dried at 80 ° C. for 6 hours. After drying, it was dried at 120 ° C. for 20 minutes and then peeled off from the polytetrafluoroethylene sheet to obtain a water-dispersible resin film.
The film elongation of the water-dispersible resin film obtained at a measurement temperature of 20 ° C. and a measurement speed of 200 mm / min using a Tencilon universal testing machine (device name: RTC-1225A, manufactured by Orientec Co., Ltd.). And the film strength was measured.
The length of the resin film extending until it broke was measured, and the value expressed as a percentage of the original length was taken as the film elongation. The film strength was the strength at break.

(Example of preparation of pigment dispersion)
<Preparation of surfactant-dispersed pigment dispersion>
15 parts by mass of carbon black pigment (trade name: Monarch800, manufactured by Cabot), 2 parts by mass of anionic surfactant (trade name: Pionin A-51-B, manufactured by Takemoto Oil & Fat Co., Ltd.), and 83 parts by mass of ion-exchanged water. After premixing, a black pigment dispersion having a solid content concentration of 15% by mass was circulated and dispersed for 7 hours in a disc-type bead mill (KDL type of Simmal Surfactant, media: using zirconia balls having a diameter of 0.3 mm). Obtained.

(Example of Preparation of Resin Part-Coated Pigment Dispersion)
<Preparation of resin partially coated pigment dispersion>
First, as a preparation of the polymer solution, the inside of a 1 L flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas introduction tube, a reflux tube, and a dropping funnel was sufficiently replaced with nitrogen gas, and then 11.2 g of styrene and acrylic acid were prepared. Add 2.8 g, lauryl methacrylate 12.0 g, polyethylene glycol methacrylate 4.0 g, styrene macromer (manufactured by Toa Synthetic Co., Ltd., trade name: AS-6) 4.0 g, and mercaptoethanol 0.4 g, and raise to 65 ° C. It was warm. Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyethyl methacrylate 60.0 g, styrene macromer 36.0 g, mercaptoethanol 3.6 g, azobisdimethylvaleronitrile A mixed solution of 2.4 g and 18 g of methyl ethyl ketone was added dropwise into the flask over 2.5 hours.

After completion of the dropwise addition, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was added dropwise to the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobisdimethylvaleronitrile was added, and the mixture was further aged for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added into the flask to obtain 800 g of a polymer solution having a concentration of 50% by mass. Next, a part of the polymer solution was dried and measured by gel permeation chromatography (standard: polystyrene, solvent: tetrahydrofuran), and the mass average molecular weight was 15,000.

The obtained polymer solution (28 g), carbon black (trade name: Monarch800, manufactured by Cabot Corporation) (26 g), 1 mol / L potassium hydroxide solution (13.6 g), methyl ethyl ketone (20 g), and ion-exchanged water (30 g) were sufficiently stirred. Then, it was kneaded 20 times using a 3-roll mill (manufactured by Noritake Company, Inc., trade name: NR-84A). The obtained paste was put into 200 g of ion-exchanged water and sufficiently stirred, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain 160 g of a black resin partially coated pigment dispersion. Finally, the resin partially coated pigment dispersion is filtered using a membrane filter having an average pore size of 0.8 μm, filtered through the filter, and then the water content of the resin partially coated pigment dispersion is evaporated at 40 ° C. The pigment concentration was adjusted to 18.0% by mass to obtain a resin partially coated pigment dispersion. When the number of coarse particles present in 5 μL of the obtained resin partially coated pigment dispersion was measured by AccuSizer780 (manufactured by Particle Sizeing Systems), the number of coarse particles having a particle size of 0.5 μm or more was 1.3 × 10 ^6. The number of coarse particles of 1.0 μm or more was 8.9 × 10 ³ . The resin content in the carbon black partially coated with the resin was 35% by mass.

(Example 1)
Surface active agent dispersion type pigment dispersion 7.00% by mass, polycarbonate urethane resin particles (trade name: Takelac W-6110, manufactured by Mitsui Chemicals, Inc., glass transition temperature: -20 ° C, film elongation: 550%, film strength : 55 MPa, solid content concentration: 31% by mass) 8.00% by mass, glycerin (manufactured by Nichiyu Co., Ltd.) 7.00% by mass, 3-methyl-1,3-butanediol (manufactured by Kuraray Co., Ltd.) 14.00 Mass%, Proxcel GXL (manufactured by Ronza Japan Co., Ltd.) 0.05 mass% as a preservative, 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 2.00 mass%, interface As an activator, trade name: Zonil FS-300 (manufactured by DuPont) 0.50% by mass and pure water are added and mixed so that the total becomes 100% by mass, and the mixture is stirred for 30 minutes and printed for inkjet. Got ink.

(Examples 2 to 5 and Comparative Examples 1 to 9)
Inkjet printing ink was obtained in the same manner as in Example 1 except that the composition was changed as shown in Tables 1 to 3 below in Example 1.

Next, "washing fastness", "friction fastness", "cracking during tension", and "discharge stability" were evaluated as follows. The results are shown in Tables 1 to 3 below.

[Making printed matter]
Using a 100% cotton white T-shirt (trade name: heavy weight plain T-shirt 5.6oz, manufactured by Toms Co., Ltd.) as a cloth, ink is introduced into a textile printer (device name: MMP813BT, manufactured by Mastermind Co., Ltd.) and inkjet. Printing was performed with printing ink. The printing conditions were 1,440 dpi × 720 dpi, and solid printing of 80 mm × 80 mm. The printed fabric was heat-treated at 160 ° C. for 1 minute and dried to obtain a printed fabric.

(Washing fastness)
Based on JIS L0844, each textile is washed 10 times using a fully automatic washing machine (device name: ASW-45A1, manufactured by Sanyo Electric Co., Ltd.), and the degree of fading is determined using a discoloration gray scale. It was visually confirmed and "washing fastness" was evaluated based on the following evaluation criteria.
-Evaluation criteria-
A: 5th grade B: 4th grade or more and less than 5th grade C: 3rd grade or more and less than 4th grade D: less than 3rd grade

(Friction fastness)
The test was carried out using a type I testing machine according to the method specified in JIS L0849. Dry friction is tested according to the dry test specified in JIS L0849, wet friction is tested according to the wet test specified in JIS L0849, the degree of contamination is visually confirmed using a contamination gray scale, and based on the following evaluation criteria. The "friction fastness" was evaluated.
A: 4th grade or higher and 5th grade or lower B: 3rd grade or higher and lower than 4th grade C: 2nd grade or higher and lower than 3rd grade D: 2nd grade or lower

(Cracks when pulled)
The presence or absence of cracks when the printed material was pulled up, down, left and right by hand was visually confirmed, and "cracks during pulling" were evaluated based on the following evaluation criteria.
-Evaluation criteria-
A: No cracks occur B: Some cracks occur C: Clearly cracks occur.

(Discharge stability)
In the production of the printed matter, 10 T-shirts (printed matter) were printed continuously under 50% gray solid printing with printing conditions of 1,440 dpi × 720 dpi and 180 mm × 200 mm. The number of nozzle clogging that occurred while printing 10 sheets was counted.

In Tables 1 to 3 above, the trade names of the ingredients and the names of the manufacturing companies are as follows. The content of the resin particles in Tables 1 to 3 is a solid content conversion value.
-Takelac W-6110: manufactured by Mitsui Chemicals, Inc., glass transition temperature: -20 ° C, film elongation: 550%, film strength: 55 MPa, solid content concentration: 31% by mass.
-Takelac WS-6021: Mitsui Chemicals, Inc., glass transition temperature: -60 ° C, film elongation: 750%, film strength: 50 MPa, solid content concentration: 30% by mass
-Superflex 460: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., glass transition temperature: -21 ° C, film elongation: 750%, film strength: 25 MPa, solid content concentration: 38% by mass.
-Superflex 460S: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., glass transition temperature: -25 ° C, film elongation: 900%, film strength: 30 MPa, solid content concentration: 38% by mass
-Superflex 470: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., glass transition temperature: -31 ° C, film elongation: 640%, film strength: 40 MPa, solid content concentration: 38% by mass.
-Superflex 150: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., glass transition temperature: 40 ° C., film elongation: 330%, film strength: 45 MPa, solid content concentration: 30% by mass.
-Superflex 840: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., glass transition temperature: 5 ° C., film elongation: 690%, film strength: 40 MPa, solid content concentration: 27% by mass
-Bontiter HUX-380: manufactured by ADEKA Corporation, glass transition temperature: -5 ° C to -35 ° C, film elongation: 500%, film strength 38 MPa, solid content concentration: 38 mass%
・ Glycerin: manufactured by Nichiyu Co., Ltd. ・ 3-Methyl-1,3-butanediol: manufactured by Kuraray Co., Ltd. ・ Proxcel GXL: manufactured by Lonza Japan Co., Ltd. ・ 2-Amino-2-ethyl-1,3-propanediol: Tokyo Made by Kasei Kogyo Co., Ltd. ・ Zonir FS-300: Made by DuPont

Examples of aspects of the present invention are as follows.
<1> An inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles.
The organic solvent contains glycerin and
The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet.
The polycarbonate urethane resin particles have a glass transition temperature of −25 ° C. or higher and 5 ° C. or lower, a film elongation of 400% or higher and 600% or lower, a film strength of more than 50 MPa, and a total content of the ink jet printing ink. It is an inkjet printing ink characterized by having a relative content of 8% by mass or more.
<2> The inkjet printing ink according to <1>, wherein the pigment is coated with a resin.
<3> The ink jet printing ink according to any one of <1> to <2>, wherein the coating strength of the polycarbonate urethane resin particles is 52 MPa or more and 58 MPa or less.
<4> The mass ratio (glycerin / polycarbonate urethane resin particles) of the glycerin content (mass%) and the polycarbonate urethane resin particles content (mass%) is 1.0 or more and 2.5 or less. The printing ink for inkjet according to any one of <1> to <3>.
<5> The ink jet printing ink according to <4>, wherein the mass ratio (glycerin / polycarbonate urethane resin particles) is 1.0 or more and 1.5 or less.
<6> The ink jet printing ink according to any one of <1> to <5>, wherein the content of the glycerin is 95% by mass or less based on the total amount of the organic solvent.
<7> The ink jet printing ink according to any one of <1> to <6>, wherein the content of the glycerin is 40% by mass or more with respect to the total amount of the organic solvent.
<8> The inkjet printing ink according to any one of <1> to <7>, wherein the content of the glycerin is 6% by mass or more with respect to the total amount of the inkjet printing ink.
<9> The inkjet printing ink according to any one of <1> to <8>, wherein the content of the glycerin is 30% by mass or less based on the total amount of the inkjet printing ink.
<10> The inkjet printing ink according to any one of <1> to <9>, wherein the content of the polycarbonate urethane resin particles is 9% by mass or more with respect to the total amount of the inkjet printing ink.
<11> The inkjet printing ink according to any one of <1> to <10>, wherein the content of the polycarbonate urethane resin particles is 20% by mass or less with respect to the total amount of the inkjet printing ink.
<12> An inkjet recording apparatus including an inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles, and an ink ejection unit for ejecting the inkjet printing ink.
The organic solvent contains glycerin and
The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet.
The polycarbonate urethane resin particles have a glass transition temperature of −25 ° C. or higher and 5 ° C. or lower, a film elongation of 400% or higher and 600% or lower, a film strength of more than 50 MPa, and a total content of the ink jet printing ink. It is an inkjet recording apparatus characterized by having a relative mass of 8% by mass or more.
<13> The inkjet recording device according to <12>, which does not have a pretreatment device.
<14> The inkjet recording apparatus according to any one of <12> to <13>, wherein the pigment is coated with a resin.
<15> The inkjet recording apparatus according to any one of <12> to <14>, wherein the film strength of the polycarbonate urethane resin particles is 52 MPa or more and 58 MPa or less.
<16> The mass ratio (glycerin / polycarbonate urethane resin particles) of the glycerin content (mass%) and the polycarbonate urethane resin particles content (mass%) is 1.0 or more and 2.5 or less. The inkjet recording apparatus according to any one of <12> to <15>.
<17> An inkjet recording method including an ejection step of ejecting an inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles from an ink ejection unit.
The organic solvent contains glycerin and
The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet.
The polycarbonate urethane resin particles have a glass transition temperature of −25 ° C. or higher and 5 ° C. or lower, a film elongation of 400% or higher and 600% or lower, a film strength of more than 50 MPa, and a total content of the ink jet printing ink. This is an inkjet recording method characterized by having a relative content of 8% by mass or more.
<18> The inkjet recording method according to <17>, which does not include a pretreatment step.
<19> The inkjet recording method according to any one of <17> to <18>, wherein the pigment is coated with a resin.
<20> The inkjet recording method according to any one of <17> to <19>, wherein the film strength of the polycarbonate urethane resin particles is 52 MPa or more and 58 MPa or less.
<21> The mass ratio (glycerin / polycarbonate urethane resin particles) of the glycerin content (mass%) and the polycarbonate urethane resin particles content (mass%) is 1.0 or more and 2.5 or less. The inkjet recording method according to any one of <17> to <20>.

The inkjet printing ink according to any one of <1> to <11>, the inkjet recording apparatus according to any one of <12> to <16>, and any of the above <17> to <21>. The described inkjet recording method can solve the conventional problems and achieve the object of the present invention.

Japanese Unexamined Patent Publication No. 2009-30014 Japanese Unexamined Patent Publication No. 2009-215506 JP-A-2009-96914 Japanese Unexamined Patent Publication No. 2010-150453 Japanese Unexamined Patent Publication No. 2014-148564

400 Image forming device (inkjet recording device)

Claims (4)

An inkjet printing ink containing water, pigments, organic solvents, and polycarbonate urethane resin particles.
The organic solvent contains glycerin and
The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet.
The polycarbonate urethane resin particles have a glass transition temperature of −25 ° C. or higher and 5 ° C. or lower, a film elongation of 400% or higher and 600% or lower, a film strength of 52 MPa or higher and 58 MPa or lower, and a content for the inkjet. It is 8% by mass or more with respect to the total amount of the printing ink, and further, the mass ratio of the content of the glycerin (mass%) to the content of the polycarbonate urethane resin particles (mass%) (glycerin / polycarbonate urethane resin particles). but state, and are 0.8 or more and 1.2 or less,
The pigment is coated with a resin and
Further, an inkjet printing ink containing 3-methyl-1,3-butanediol or 2-amino-2-ethyl-1,3-propanediol. An inkjet recording apparatus having an inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles, and an ink ejection unit for ejecting the inkjet printing ink.
The organic solvent contains glycerin and
The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet.
The polycarbonate urethane resin particles have a glass transition temperature of −25 ° C. or higher and 5 ° C. or lower, a film elongation of 400% or higher and 600% or lower, a film strength of 52 MPa or higher and 58 MPa or lower, and a content for the inkjet. It is 8% by mass or more with respect to the total amount of the printing ink, and further, the mass ratio of the content of the glycerin (mass%) to the content of the polycarbonate urethane resin particles (mass%) (glycerin / polycarbonate urethane resin particles). However, it is 0.8 or more and 1.2 or less.
The pigment is coated with a resin and
An inkjet recording apparatus, wherein the ink jet printing ink further contains 3-methyl-1,3-butanediol or 2-amino-2-ethyl-1,3-propanediol. The inkjet recording apparatus according to claim 2, which does not have a pretreatment apparatus. An inkjet recording method including an ejection step of ejecting an inkjet printing ink containing water, a pigment, an organic solvent, and polycarbonate urethane resin particles from an ink ejection unit.
The organic solvent contains glycerin and
The content of the glycerin is 30% by mass or more with respect to the total amount of the organic solvent and 5% by mass or more with respect to the total amount of the printing ink for inkjet.
The polycarbonate urethane resin particles have a glass transition temperature of −25 ° C. or higher and 5 ° C. or lower, a film elongation of 400% or higher and 600% or lower, a film strength of 52 MPa or higher and 58 MPa or lower, and a content for the inkjet. It is 8% by mass or more with respect to the total amount of the printing ink, and further, the mass ratio of the content of the glycerin (mass%) to the content of the polycarbonate urethane resin particles (mass%) (glycerin / polycarbonate urethane resin particles). However, it is 0.8 or more and 1.2 or less.
The pigment is coated with a resin and
An inkjet recording method, wherein the ink jet printing ink further contains 3-methyl-1,3-butanediol or 2-amino-2-ethyl-1,3-propanediol.

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