inkjet engraving medium and ink set, and inkjet engraving method

专利摘要:
RECORDING MEDIA WITH INK JET AND INK SET, AND METHOD OF RECORDING WITH INK JET. An inkjet recording medium and ink set including water-containing ink, a water-soluble organic solvent comprising an amide compound represented by the following chemical structure 1, a surface active agent; and a coloring agent, and a recording medium containing a substrate; and a coated layer on at least one side of the substrate, in which the amount of pure water transfer to the recording medium that the coated layer has is 2 ml / m2 to 35 ml / m2 during a contact time of 100 ms and 3 ml / m2 to 40 ml / m2 for a contact time of 400 ms when measured by a dynamic liquid absorption test device at 23 ° C and 50% RH: Chemical structure 1.
公开号:BR102012019076B1
申请号:R102012019076-1
申请日:2012-06-28
公开日:2021-01-26
发明作者:Hidefumi Nagashima；Hiroshi Gotou
申请人:Ricoh Company, Ltd.；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED REQUEST
This patent application is based on and claims priority under 35 USC §119 for JP Patent Applications No. 2011-142598 and 2011-240933, filed on June 28, 2011 and November 2, 2011, respectively, whose total disclosures are incorporated by reference into this document. BACKGROUND OF THE INVENTION Field of the Invention
The present invention relates to an inkjet engraving medium and ink set, and an inkjet engraving method. BACKGROUND DESCRIPTION
Inkjet engraving is known as an excellent engraving method capable of accommodating a comparatively wide selection of engraving media. Consequently, research and development of new types of recording devices, recording methods, recording materials, etc. continues to be widely conducted.
In particular, pigment ink that uses a pigment as a coloring agent is proposed for ink for inkjet engraving. Pigment ink is superior to ink that uses a dye as a coloring agent when it comes to less blurred images on flat paper because the pigment ink has excellent image density, water resistance and weathering properties.
However, for recording media that have coated layers and, in particular, media with poor ink absorption, images produced with pigment ink have a lower color and gloss.
In addition, the drying of the ink takes time, thus causing problems when fixing the images, etc.
To solve these problems, JP Patent Application Publication n- 2008-101192 (JP-2008-101192-A) describes a recording ink with which vivid images, which have a quality close to those for commercial printing and published printed material, they are formed on coated paper for printing which has poor liquid absorption capacity without having a problem with the drying speed.
However, the inkjet images produced, printed on this coated paper, have problems with respect to the fixation, curl, etc. properties.
JP-2001-096902-A describes an aqueous ink set for inkjet engraving and an inkjet recording medium formed from a film substrate on which quality images are formed with the aqueous ink.
However, useful media is limited to film that has high air permeability, that is, high ink absorption, and furthermore requires processing to give the film a solvent-absorbing layer on one side and a layer for receiving paint on the opposite side.
Therefore, it is difficult to obtain recorded materials that have a high image density in the recording media described above and free from the problems described above such as fixation and timing properties. SUMMARY OF THE INVENTION
In view of the above, the present invention provides an inkjet recording medium and ink set, which includes a water-containing ink; a water-soluble organic solvent containing an amide compound represented by the following chemical structure 1; a surface active agent; and a coloring agent; and the recording medium including a substrate; and a coated layer on at least one side of the substrate, in which a quantity of pure water transfer to the recording medium that has the coated layer is 2 ml / m2 to 35 ml / m2 during a contact time of 100 ms and 3 ml / m2 to 40 ml / m2 during a 400 ms contact time as measured by a dynamic liquid absorption test device at 23 ° C and 50% RH (relative humidity) (relative humidity).
Chemical structure 1
As another aspect of the present invention, an inkjet engraving method including discharging ink for inkjet engraving onto a recording medium having the layer coated on at least one side thereof, wherein a quantity of pure water transfer to the recording medium is 2 ml / m2 to 35 ml / m2 during a contact time of 100 ms and 3 ml / m2 to 40 ml / m2 during a contact time of 400 ms when measured by an absorption test device liquid dynamics at 23 ° C and 50% RH (relative humidity) and where the inkjet ink comprises water, a water-soluble organic solvent comprising an amide compound represented by the following chemical structure 1, an active surface agent , and a coloring agent.
Chemical structure 1 BRIEF DESCRIPTION OF THE DRAWINGS
Various other objects, aspects and advantages of the operator of the present invention will be more fully appreciated as it becomes better understood from the detailed description when considered in connection with the accompanying drawings in which similar reference characters designate corresponding parts completely and in full. that: figure 1 is a schematic diagram illustrating an ink cartridge; figure 2 is a schematic diagram illustrating an example of variation of the ink cartridge illustrated in figure 1; figure 3 is a perspective view illustrating an inkjet engraving device in which the cover of the ink cartridge installation unit; figure 4 is a cross section illustrating the entire configuration of the ink jet recording device of figure 3; figure 5 is an enlarged schematic diagram illustrating an inkjet head; figure 6 is a plan view showing the main part of a subsystem that contains an ink discharge device maintenance device; figure 7 is a schematic diagram illustrating the structure of the system in figure 6; figure 8 is a diagram illustrating the right side part of the system of figure 6; figure 9 is a front cross section showing a simulated discharge receiving unit on the recording device; and figure 10 is a diagram showing a latent part of the unit shown in figure 9. DETAILED DESCRIPTION OF THIS DISCLOSURE
The inkjet engraving ink for use in the present disclosure contains at least water, a water-soluble organic solvent, a surface active agent, and a coloring agent. Other optional materials may also be contained. WATER-SOLUBLE ORGANIC SOLVENT (MOISTURING AGENT)
The inkjet engraving ink for use in the present disclosure contains at least one amide compound represented by the following chemical structure 1 as the water-soluble organic solvent. Other optional water-soluble organic solvents mentioned below can be mixed for use.
Chemical structure 1
The amide compound represented by chemical structure 1 has a high boiling point (ie 216 ° C), a high equilibrium moisture content of 39.2% in an environment of 23 ° C and a relative humidity of 80%, and an extremely low liquid viscosity of 1.48 mPa. S at 25 ° C. In addition, since the amide compound is extremely easily dissolved in water-soluble organic solvent or water, the viscosity of the inkjet ink decreases, which is extremely preferable as the ink for inkjet printing.
The inkjet engraving ink containing the amide compound represented by the chemical structure 1 has good conservation capacity and discharge stability and is favorable to the maintenance unit of the ink discharge device.
The content of the amide compound represented by the chemical structure 1 in the inkjet ink is preferably from 1% by weight to 50% by weight and more preferably from 2% by weight to 40% by weight. When the content is very small, the viscosity of the ink does not decrease easily, resulting in the deterioration of the discharge stability and fixation of the waste ink in the maintenance unit. In addition, when the content is very large, the drying of the ink in the recording media (typically paper) tends to be inferior and the quality of the text on the flat paper can deteriorate.
In addition, the water-soluble organic solvent mixed with the amide compound represented by chemical structure 1 contains at least one type of polyol having an equilibrium moisture content of 30% by weight or higher in an environment of 23 ° C and a relative humidity 80%. In addition, for example, as described above, it is preferable to contain a wetting agent A having a high equilibrium moisture content and a high boiling point (the equilibrium moisture content in an environment of 23 ° C and a relative humidity of 80% is 30% by weight or more and preferably 40% by weight or more and the boiling point is 250 ° C or higher) and a wetting agent B having a high equilibrium moisture content and a relatively low boiling point (The equilibrium moisture content in an environment of 23 ° C and 80% relative humidity is 30% by weight and the boiling point is 140 ° C to 250 ° C).
In the polyol, specific examples of wetting agent A having a boiling point of 250 ° C or higher at normal pressure include, but are not limited to, 1,2,3-butane triol (boiling point: 175 ° C / 33 hPa, 38% by weight), 1,2,4-butane triol (boiling point: 190 ° C to 191 ° C / 24 hPa, 41% by weight), glycerin (boiling point: 290 ° C, 49% by weight), diglycerin (boiling point: 270 C / 20 hPa, 38% by weight), triethylene glycol (boiling point: 285 ° C, 39% by weight), and tetraethylene glycol (boiling point: 324 ° C at 330 ° C, 37% by weight). A specific example of wetting agent B having a boiling point of 140 ° C to 250 ° C is 1,3-butane diol (boiling point: 203 ° C to 204 ° C, 35% by weight).
Both wetting agent A and wetting agent B have a high moisture absorbance so that the equilibrium moisture content is 30% by weight or more in an environment of 23 ° C and a relative humidity of 80%. However, wetting agent B has a relatively higher evaporation capacity than wetting agent A. Among these, a group of glycerin and 1,3-butane diol is preferable.
When wetting agent A and wetting agent B are used in combination, although it is difficult to specifically limit the weight ratio of wetting agent B to wetting agent A because it is significantly dependent on the content of other wetting agents such as wetting agent C and the content and type of additives such as a penetrating agent, for example, it is preferably from 10/90 to 90/10.
In the present disclosure, the equilibrium moisture content of the water-soluble organic solvent is obtained by the amount of saturated moisture measured by conserving a petri dish on which one gram of each water-soluble organic solvent is placed in a desiccator, in which the temperature and the relative humidity they are maintained at 22 ° C to 24 ° C and 77% to 83%, respectively, using a saturated solution of potassium chloride and sodium chloride.
Amount of saturated moisture = (Amount of moisture absorbed in the organic solvent / Amount of organic solvent + Amount of moisture absorbed in it) x 100
Discharge stability and prevention of fixing waste ink to the maintenance unit in an ink discharge device are excellent when the polyol mentioned above occupies 50% by weight or more in all water-soluble organic solvent.
The inkjet engraving ink for use in the present disclosure may contain wetting agent C (typically, equilibrium moisture content: less than 30% by weight in an environment of 23 ° C and a relative humidity of 80%) instead of part of or in addition to wetting agent A and wetting agent B.
Specific examples of wetting agent C include, but are not limited to, polyols, polyol alkyl ethers, polyol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonates, ethylene carbonates, and other agents humectants.
Specific examples of polyols include, but are not limited to, dipropylene glycol (boiling point: 232 ° C), 1,5-pentane diol (boiling point: 242 ° C), 3-methyl-1, 3-butane diol (boiling point: 203 ° C), propylene glycol (boiling point: 187 ° C), 2-methyl-2,4-pentane diol (boiling point: 197 ° C), ethylene glycol (boiling point: 196 ° C to 198 ° C), tripropylene glycol (boiling point: 267 ° C), hexylene glycol (boiling point: 197 ° C), polyethylene glycol (viscous solid liquid), polypropylene glycol (boiling point: 187 ° C), 1,6-hexane diol (boiling point: 253 ° C to 260 ° C), 1,2,6-hexane triol (boiling point: 178 ° C), trimethylol ethane (solid; melting point: 199 ° C to 201 ° C), and trimethylol propane (solid; melting point: 61 ° C).
Specific examples of polyol alkyl ethers include, but are not limited to, ethylene glycol ethylene glycol monoethyl ether (boiling point: 135 ° C), ethylene glycol monobutyl ether (boiling point: 171 ° C), monomethyl ether of diethylene glycol (boiling point: 194 ° C), diethylene glycol monoethyl ether (boiling point: 197 ° C), diethylene glycol monobutyl ether (boiling point: 231 ° C), ethylene mono-2-ethylhexyl ether glycol (boiling point: 229 ° C) and propylene glycol monoethyl ether (boiling point: 132 ° C).
Specific examples of polyol aryl ethers include, but are not limited to, ethylene glycol ethylene glycol monoenyl ether (boiling point: 237 ° C) and ethylene glycol monobenzyl ether.
Specific examples of heterocyclic compounds containing nitorogen include, but are not limited to, 2-pyrrolidone (boiling point: 250 ° C, melting point: 25.5 ° C, 47% by weight to 48% by weight), N- methyl-2-pyrrolidone (boiling point: 202 ° C), 1,3-dimethylimidazoline (boiling point: 226 ° C), ε-caprolactam (boiling point: 270 ° C), and y-butylolactone (boiling point) boiling: 204 ° C to 205 ° C).
Specific examples of amides include, but are not limited to, formamide (boiling point: 210 ° C), N-methyl formamide (boiling point: 199 ° C to 201 ° C), N, N-dimethylformamide (boiling point : 153 ° C), and N, N-diethylformamide (boiling point: 176 ° C to 177 ° C).
Specific examples of amines include, but are not limited to, monoethanol amine (boiling point: 170 ° C), diethanol amine (boiling point: 268 ° C), triethanol amine (boiling point: 360 ° C), N, N-dimethyl monoethanol amine (boiling point: 139 ° C), N-methyl diethanol amine (boiling point: 243 ° C) r N-methylethyl amine (boiling point: 159 ° C), N-phenyl ethanol amine ( boiling point: 282 ° C to 5,287 ° C), and 3-aminopropyl diethyl amine (boiling point: 169 ° C).
Specific examples of sulfur-containing compounds include, but are not limited to, dimethyl sulfoxide (boiling point: 139 ° C), sulfolane (boiling point: 285 ° C), and 10 thiodiglycol (boiling point: 282 ° C).
Sugar groups are also preferable as the wetting agents.
Specific examples of sugar groups include, but are not limited to, monosaccharides, disaccharides, 15 oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. Specific examples thereof include, but are not limited to, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, and 20 maltotriosis.
Polysaccharides represent sugar in a broad sense and contain materials that are widely present in nature, for example, a-cyclodextrin and cellulose.
In addition, specific examples of derivatives of these sugar groups include, but are not limited to, reducing sugars (for example, sugar alcohols (represented by HOCH2 (CHOH) nCH20H, where n represents an integer from 2 to 5), oxidized sugars (eg, aldonic acid and uronic acid), amino acid, and thioacid.
Among these, sugar alcohols are preferable and specific examples of them include, but are not limited to, maltitol and sorbit.
The weight ratio of the pigment to the wetting agent mentioned above has an impact on the discharge stability of the ink discharged from an ink jet head and also prevents the fixing of waste ink in the maintenance unit on a discharge device. of ink.
And the amount of mixing of the wetting agent is very small while the amount of the solid pigment portion is large, the evaporation of water around the nozzle paint meniscus tends to be accelerated, thus causing poor discharge performance.
The water-soluble organic solvent containing the amide compound represented by chemical structure 1, wetting agent A, wetting agent B, and wetting agent C is preferably contained in the inkjet ink in an amount of 20% by weight at 60% by weight and more preferably from 20% by weight to 50% by weight.
When the content is very small, the discharge stability and the attachment of the waste ink to the maintenance unit tend to deteriorate. When the content is very large, the ink viscosity for inkjet engraving tends to increase a lot to discharge the ink from the ink discharge device. In addition, the drying properties of ink in the recording media (e.g., paper) tend to be inferior.
To improve the quality of images printed on flat paper, it is preferable to contain a wetting agent Cl having a boiling point lower than 240 ° C and an equilibrium moisture content of less than 30% by weight (wetting agent Cl is a water-soluble organic solvent with an equilibrium moisture content of less than 30% by weight in an environment of 23 ° C and a relative humidity of 80% and a boiling point lower than 240 ° C between wetting agent C) in an appropriate relationship.
The content of the water-soluble organic solvent is preferably 50% by weight or less based on the total wetting agent in terms of discharge stability and prevention of fixing waste ink in the maintenance unit in an ink discharge device. Coloring agent
As a coloring agent, considering the weathering properties, pigments are mainly used. Optionally, dyes can also be contained in an amount in which the weathering properties are not degraded.
There is no specific limit for the selection of pigments. Black pigments and color pigments can be used. These can be used alone or in combination.
Specific examples of inorganic pigments include, but are not limited to, titanium oxide, iron oxide, calcium oxide, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black manufactured by known methods such as contact methods, oven methods and thermal methods.
Specific examples of organic pigments include, but are not limited to, azo pigments (purple azo dyes, insoluble azo pigments, condensed azo pigments, azo chelated pigments, etc.), polycyclic pigments (phthalocyanine pigments, perylene pigments, perinone pigments , anthraquinone pigments, quinacridone pigments, dioxazin pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinofuranone pigments, etc.), dye chelates (chelates of the basic pigment type and chelates of the acid dye type) r nitro pigments, nitrous pigments, and aniline black.
Among the pigments, pigments that have a good affinity for water are particularly preferable.
More preferred specific examples of black color pigments include, but are not limited to, carbon black (CI Pigment Black 7) such as oven black, lamp black, acetylene black, and channel black, metals such as copper and iron (CI Pigmento Preto 11), metal compounds such as titanium oxide, and organic pigments such as aniline black (CI Pigmento Preto 1).
Specific examples of pigments for include, but are not limited to, CI Pigment Yellow 1, 3, 12, 13, 14, 15 17, 24, 34, 35, 37, 42 (yellow titanium oxide), 53, 55, 74 , 81, 83, 95, 97, 98, 100, 101, 104, 108, 10 9, 110, 117, 120, 128, 138, 150, 151, 153, and 183, CI Pigmento Orange 5, 13, 17, 36, 43, and 51, CI Pigmento Vermelho 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 {Permanent Red 2B (Ca)}, 48: 3, 20 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 (colcothar), 104, 105, 106, 108 (cadmium red), 112, 114, 122 (magenta quinacridone), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, and 219, CI Pigment Violet (Purple Rhodamine), 3, 5: 1, 16, 19, 23, and 38, CI Pigmento Azul 1, 2, 15, 15: 1, 15: 2, 15: 3, (phthalocyanine blue), 16, 17: 1, 56, 60, 63, and CI Pigmento Verde 1, 4, 7, 8 , 10, 17, 18, and 36.
The following first to third forms are preferable in the case where the coloring agent is a pigment. 1) In the first form, the coloring agent has a pigment that has at least one type of hydrophilic group on the surface and is hydrodispersible in the absence of a dispersing agent (hereinafter referred to as self-dispersing pigment). 2) In the second form, the coloring agent is a pigment dispersion that contains a pigment, a pigment dispersant, and a polymeric dispersion stabilizer. The polymer dispersion stabilizer is at least one of a-olefin maleic anhydride copolymer represented by the following chemical structure 2, a styrene (meth) acrylic copolymer, a water-soluble polyurethane resin, and a water-soluble polyester resin.
Chemical structure 2
In chemical structure 2, R represents an alkyl group having 6 to 30 carbon atoms, preferably 12 to 22 5 carbon atoms, and more preferably 18 to 22 carbon atoms and n represents an integer.
In the present disclosure, a mixture of compounds represented by chemical structure 2 having different values for R can be used as the copolymer of 10 male α-olefin anhydrides.
In the third form, the coloring agent contains a (2) polymeric emulsion (polymeric particulate water dispersion material containing a coloring material, for example, pigment) in which the polymeric particulates contain the coloring material having no or slight water solubility.
The self-dispersing pigment of the first form is reformed on the surface so that at least one hydrophilic group is bonded to the pigment surface directly or via another atom group. To conduct this surface reform, a particular functional group (functional group such as sulfone group or carboxyl group) is chemically bonded to the pigment surface or the surface is wet oxidized using at least one of the hypoal acid or a salt thereof.
Among these, a form is preferable in which a carboxyl group is attached on the pigment surface and the pigment is dispersed in water.
Once the pigment is reformed on the surface and the carboxyl group is bonded to it, the print quality is improved and the water resistance of the post-printing media is improved, in addition to improving dispersion stability.
In addition, since the ink containing the self-dispersing pigment of the first form has excellent re-dispersibility after drying, clogging does not occur even when the moisture from the ink around the inkjet nozzle head evaporates after the printing device to be suspended for a long period. Therefore, quality images can be produced again by a simple cleaning operation. The average volumetric particle diameter (D50) of the self-dispersing pigment is preferably 0.01 μm to 0.16 μm in the paint.
For example, self-dispersing carbon black is preferably ionic and anionic or cationic charged self-dispersing carbon black is preferable.
Specific examples of anionic hydrophilic groups include, but are not limited to, -COOM, -SO3M, -PO3HM, - PO3M2, -SO2NH2, -SO2NHCOR (M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium) . R represents an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group. Among these, it is preferable to use pigments in which -COOM or -SO3M are bonded on the pigment surface.
Specific examples of alkali metal of M in the hydrophilic group include, but are not limited to, lithium, sodium, and potassium. Specific examples of organic ammonium include, but are not limited to, mono, di, or tri-methyl ammonium, mono, di, or tri-ethyl ammonium, and mono, di, or tri-methanol ammonium.
To obtain the anionic colored pigment, -COONa is introduced on the surface of the colored pigment. For example, there are oxidation methods that use sodium hypochlorite, sulfonation methods, and methods of using diazonium salt reaction.
Like the cationic hydrophilic group, quaternary ammonium groups are preferable. Among these, quaternary ammonium groups represented by the following chemical structure 3 are more preferable. In the present disclosure, a coloring material to which any of these groups are attached on the carbon black surface is suitable.
Chemical structure 3
There is no specific limit to the method of making the cationic charged self-dispersing carbon black to which the hydrophilic group is attached. For example, to bind the N-ethyl pyridine group represented by the following chemical structure 4, carbon black is treated with 3-amino-N ethyl pyridinium bromide.
Chemical structure 4
The hydrophilic group can be bonded to the carbon black surface through another atom group. Specific examples of such atom groups include, but are not limited to, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.
Specific examples of cases where the hydrophilic group is bonded to the carbon black surface through another atom group include, but are not limited to -C2H4COOM (M represents an alkali metal or quaternary ammonium), -PhSChM (Ph represents a phenyl group (M represents alkali metal or quaternary ammonium), and - C5H10NH3 +.
In the second form, the coloring agent is a pigment dispersion that contains pigments including an inorganic pigment, an organic pigment, and a complex pigment, a pigment dispersant, and a polymer dispersion stabilizer. The polymeric dispersion stabilizer is at least one of a cx-olefin- maleic anhydride copolymer represented by the following chemical structure 2, a styrene (meth) acrylic copolymer, a water-soluble polyurethane resin, and a water-soluble polyester resin.
Chemical structure 2
In chemical structure 2, R represents an alkyl group having 6 to 30 carbon atoms, preferably 12 to 22 carbon atoms, and more preferably 18 to 22 carbon atoms and n represents an integer.
The polymeric dispersion stabilizer is a material suitable for stably maintaining the dispersion state of the pigment dispersion uniformly thoroughly dispersed in water by the pigment dispersant.
The otolefin maleic anhydride copolymer represented by chemical structure 2, the styrene (meth) acrylic copolymer, the water-soluble polyurethane resin 15, and the water-soluble polyester resin are solid at room temperature and very little soluble in water icy. However, when the copolymer and resin are dissolved in an alkaline (aqueous) solution equivalent (preferably 1.0 to 1.5 times) to the acid value of the copolymer and resin, the solution demonstrates the effect of a dispersion stabilizer.
The copolymer and resin are easily dissolved in an alkaline (aqueous) solution by heating while stirring.
However, when the olefin chain is long in the olefin maleic anhydride copolymer, it is not easy to dissolve the copolymer in the alkaline (aqueous) solution and insoluble matter may remain in some cases. In that case, the solution can still be appropriately used as the polymeric dispersion stabilizer when the insoluble matter is removed with a filter, etc.
Specific examples of base in the alkaline (aqueous) solution include, but are not limited to, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide; basic materials such as ammonia, triethyl amine, and morpholine; and amine alcohol such as triethanol amine, diethanol amine, N-methyl diethanol. 2-amino-2-ethyl-1,3-propane diol, and choline.
The α-olefin maleic anhydride copolymer represented by chemical structure 2 can be synthesized or is available from the market. Specific examples of market products include, but are not limited to, T-YP112, T-YP115, T-YP114, and T-YP116 (all manufactured by SEIKO PMC CORPORATION)
The styrene (meth) acrylic copolymer can be synthesized or is available from the market. Specific examples of market products include, but are not limited to, JC-05 (manufactured by SEIKO PMC CORPORATION), ARÜFRON UC-3900, ARUFRON UC-3910, and ARUFRON UC-3920 (manufactured by TOAGOSEI CO., LTD.) .
Any commercially available water-soluble polyurethane resin products and any synthesized water-soluble polyester resin can be used appropriately.
Specific examples of products marketed include, but are not limited to, Takelac W-5025, Takelac W-6010, and Takelac W-5661 (manufactured by Mitsui Chemicals, Inc.). Any commercially available water-soluble polyester resin products and any water-soluble polyurethane resin synthesized can be appropriately used as the water-soluble polyurethane resin described above. Specific examples of products marketed therein include, but are not limited to, Nichigo Poliester W-0030, Nichigo Poliester W-0005S30WC, and Nichigo Poliester WR-961 (manufactured by Nippon Synthesis Chemical Industry Co., Ltd.), PESRESIN A- 210, and PESRESIN A-520 (manufactured by Takamatsu Oil & Fat Co., Ltd.).
The acid value of the polymeric dispersion stabilizer is preferably from 40 mgKOH / g to 400 mgKOH / g and more preferably from 60 mgKOH / g to 350 mgKOH / g. When the acid value is very small, the solubility of the alkaline solution tends to be lower. When the acid value is very large, the viscosity of the pigment tends to increase, thereby degrading the performance of the discharge ink or reducing the stability of the pigment dispersion.
The weight average molecular weight of the polymer dispersion stabilizer is preferably 20,000 or lower and more preferably 5,000 to 20,000. When the weight average molecular weight is very small, the dispersion stability of the pigment dispersion tends to deteriorate. When the weight average molecular weight is very large, the solubility of the alkaline solution tends to be lower or the viscosity tends to increase.
The polymer dispersion stabilizer content is preferably 1 part by weight to 100 parts by weight (conversion to solid portion) and more preferably from 5 parts by weight to 50 parts by weight based on 100 parts by weight of pigment. When the content of the polymeric dispersion stabilizer is very small, the effect of the polymeric dispersion stabilizer tends to be lost. When the content of the polymeric dispersion stabilizer is very large, the viscosity of the ink tends to increase, thereby degrading the performance of the discharge ink or increasing the cost. Pigment Dispersant
In the second form, it is preferable that the coloring agent contains a pigment dispersant.
As the polymeric dispersant, the anionic surface active agent and the non-ionic surface active agent that have an HLB value of 10 to 20 are preferable.
Specific examples of anionic surface active agent include, but are not limited to, polyoxyethylene alkyl ether acetates, alkyl benzene sulfonates (eg, NH4, Na, and Ca), dysphenyl alkyl ether disulfonates (eg, NH4, Na , and Ca), sodium salts of dialkyl succinate sulfonates, sodium salts condensed with naphthalene sulfonate formalin, polyoxyethylene polycyclic phenyl ether sulfuric acid esters (eg NH4 and Na), laurates, alkyl ether sulfates polyoxyethylene, and oleates.
Among these, sodium salts of dioctyl sulfosuccinate and NH4 salts of phenyl styrene polyoxyethylene ether sulfonates.
Specific examples of the nonionic surface active agent having an HLB value of 10 to 20 include, but are not limited to, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, polycyclic phenyl ether, sorbitan aliphatic acid esters, sorbitan aliphatic esters polyoxyethylene sorbitan, polyoxyethylene phenyl alkyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, and acetylene glycol.
Among these, polyoxyethylene lauryl ether, polyoxyethylene β-naphthyl ether, polyoxyethylene sorbitan monooleate, and polyoxyethylene phenyl styrene ether are particularly preferable.
The polymer dispersant content is preferably from 1 part by weight to 100 parts by weight and more preferably from 10 parts by weight to 50 parts by weight based on 100 parts by weight of the pigment.
When the pigment dispersant content is very small, the pigment tends not to be sufficiently refined. When the pigment dispersant content is too large, excess components that are not adsorbed on the pigments tend to have an impact on the properties of the paint, resulting in deterioration in image blurring, water resistance, and abrasion resistance.
The pigment dispersion evenly and thoroughly dispersed in water by the polymeric dispersant can be prepared by dissolving the polymeric dispersant in an aqueous medium, adding the pigment to the solution followed by sufficient wetting, and mixing and kneading and dispersing the mixture by stirring at high speed with a homogenizer , a disperser using balls such as a bead mill and a ball mill, a disperser mixing and kneading using a shear force such as a roller mill or an ultrasonic disperser.
However, coarse particles tend to remain after mixing and kneading and dispersing, which cause an obstruction in the inkjet nozzle or in the supply path. Therefore, such coarse particles (for example, particle diameter: 1 μm or larger) are required to be removed by a filter or centrifuge.
The average particle diameter (D50) of the pigment dispersion in the ink is preferably 150 nm or less and more preferably 100 nm or less. When the average particle diameter (D50) is very large, the discharge stability tends to deteriorate dramatically, thereby causing the nozzle to clog or displacing the ink in a recording medium. In addition, when the average particle diameter is very small, the discharge stability tends to improve, thereby improving the saturation of produced images.
In addition, as the hydrodispersible agent of the third form, in addition to the pigment specified above, it is preferable to use a polymeric emulsion in which the polymeric particulates contain the pigment. The polymeric emulsion in which the polymeric particulates contain the pigment means an emulsion in which the pigments are encapsulated in the polymeric particulates or adsorbed on the surface of polymeric particulates. In this case, it is not necessary for all pigments to be encapsulated or adsorbed and some of the pigments can be dispersed in the emulsion unless they do not have an adverse impact on the effect of the present disclosure.
Specific examples of polymers (polymer in polymeric particulates) that form polymeric emulsions include, but are not limited to, vinyl-based polymers, polyester-based polymers, and polyurethane-based polymers. In particular, the polymers specified in JP-2000-53897-A and JP-2001-139849 can be used appropriately.
The content of coloring agent in the ink is preferably from 2% by weight to 15% by weight in a solid form and more preferably from 3% by weight to 12% by weight. When the content is very small, the color of the ink tends to deteriorate and the density of the image tends to decrease. When the content is very large, the viscosity of the ink tends to increase, thereby degrading the discharge performance of the ink, which is not preferable in terms of economy. Surface active agent
As the surface active agent, it is preferable to use the surface active agent that has a low surface tension, a high permeability, and a leveling property without degrading the dispersion stability regardless of the type of coloring agent and the use in combination with the wetting agent. At least one surface active agent selected from the group consisting of surface anionic active agents, non-ionic surface active agents, silicone-containing surface active agents, and fluorine-containing surface active agents is preferable.
Among these, silicone-containing surface active agents and fluorine-containing surface active agents are particularly preferred.
These surface active agents can be used alone or in combination.
A fluorine-containing surface active agent in which the number of carbon atoms replaced with fluorine atoms is 2 to 16 is preferable and, 4 to 16, more preferable. When the number of carbon atoms replaced with fluorine atoms is very small, the effect of fluorine atoms cannot be demonstrated. When the number of carbon atoms replaced with fluorine atoms is very large, a problem can occur with respect to the ink's preservation capacity, etc.
Specific examples of fluorine-containing surface active agent include, but are not limited to, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphoric acid ester compounds, perfluoroalkyl ethylene oxide adducts, and polymeric ether ether compounds polyoxyalkylene having a perfluoroalkyl ether group on its side chain.
Among these, polyoxyalkylene ester polymeric compounds having a perfluoroalkyl ether group in their side chain are particularly preferable due to their low foaming property. Fluorine-containing surface active agents represented by the following chemical structure 5 are more preferable. CF3CF3 (CF2CF2) m * CH2CH2O (CH2CH2O) nH Chemical structure 5
In chemical structure 5, m represents zero or an integer from 1 to 10. n represents 1 or an integer from 1 to 40.
Specific examples of perfluoroalkyl sulfonic acid compounds include, but are not limited to, perfluoroalkyl sulfonic acid and perfluoroalkylsulfonic acid salts. Specific examples of perfluoroalkyl carboxylic acid compounds include, but are not limited to, perfluoroalkyl carboxylic acid and perfluoroalkyl carboxylic acid salts.
Specific examples of perfluoroalkyl phosphoric acid ester compounds include, but are not limited to, perfluoroalkyl phosphoric acid esters and perfluoroalkyl phosphoric acid esters salts.
Specific examples of polymeric polyoxyalkylene ether compounds having a perfluoroalkyl ether group in their side chain include, but are not limited to, polyoxyalkylene ether polymers having a perfluoroalkyl ether group in their side chain, acid ester salts sulfuric polyoxyalkylene ether polymer having a perfluoroalkyl ether group on its side chain, and polyoxyalkylene ether polymer salts having a perfluoroalkyl ether group on its side chain.
Salt contractions in these fluorine-containing surface active agents are, for example, Li, Ha, K, NH4, NH3CH2CH2CH, NH2 (CH2CH2OH) 2 / and NH (CH2CH2OH) 3.
Any surface active agents containing fluorine and its products available on the market can also be used.
Specific examples of products available from the market include, but are not limited to, Surflon S-lll, Surfion S-112, Surflon S-121, Surflon S-131, Surflon S-132,
Surfion S-141, and Surfion S-145 (all manufactured by ASAHI GLASS CO., LTD.); Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, and FC-431 (all manufactured by Sumitomo 3M); MegaFac F-470, F-1405, and F-474 (all manufactured by DIC Corporation); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300 UR (all manufactured by Du Pont Kabushiki Kaisha); FT-110, FT-250, FT-251, FT-400S, FT-150 and FT-400SW (all manufactured by Neos Company Limited); and Polifox PF-151N (manufactured by Omnova Solutions Inc.). Among these, in terms of improved print quality, in particular in the color properties and in the uniform drying property on paper, Du Pont Kabushiki Kaisha's FS-300, FT-110, FT-250, FT-251, FT-400S, FT-150, and FT-400SW from Neos Company Limited, and Polifox PF-151N from Omnova Solutions Inc. are particularly preferred.
As the surface active agent containing fluorine, the compound represented by the chemical structure 6 is preferable. 1. Fluid-containing anionic surface active agent
Chemical structure 6
In chemical structure 6, Rf represents a mixture of a hydrophobic group containing fluorine represented by chemical structure 7. A represents -SO3X, -COOX, or -PO3X, where X represents a counter cation. Specific examples of X include, but are not limited to, Li, Na, K, NH4,
NH3CH2CH2OH, NH2 (CH2CH2OH) 2, and NH (CH2CH2OH) 3-
Chemical structure 7
Chemical structure 8
In chemical structure 8, Rf 'represents a fluorine-containing group represented by chemical structure 9. X represents the same as above. nélou2emé2-n.
Chemical structure 9 n independently represents an integer from 3 to 10 in chemical structure 9.
Chemical structure 10
In chemical structure 10, Rf and X are the same as above.
Chemical structure 11
In chemical structure 11, Rf and X are the same as above. 2. Nonionic Fluorine-Containing surface active agent
Chemical structure 12
In chemical structure 12, Rf is the same as above, n represents an integer from 5 to 20.
Chemical structure 13
In chemical structure 13, Rf is the same as above. n represents 1 or an integer from 1 to 40. 3. Fluorine-containing amphoteric surface active agent
Chemical structure 14
In chemical structure 14, Rf is the same as above. 4. Fluorine-containing oligomeric surface active agent
Chemical structure 15
In chemical structure 15, Rf "represents a fluorine-containing group represented by chemical structure 16. n represents zero or an integer from 1 to 10. X represents the same as above.
Chemical structure 16
In chemical structure 16, n represents an integer from 1 to 4.
Chemical structure 17
In chemical structure 17, Rf "is the same as above. 1, m, and n independently represent zero or an integer from 1 to 10.
There is no specific limitation for the selection of the silicone-based surface active agent and the silicone-based surface active agent is preferable that it does not decompose even at a high pH. Specific examples thereof include, but are not limited to, modified polydimethylsiloxane in the side chain, both a modified polydimethylsiloxane at the end, a modified polydimethylsiloxane at the end, and polydimethylsiloxane both modified in the side chain and at the end. A surface active agent containing polyether modified silicone and / or a polyoxyethylene polyoxypropylene group is particularly preferable because of its good characteristics as an aqueous surface active agent.
Any appropriately synthesized surface active agent and products thereof available on the market can also be used. The products available on the market are easily obtained by Bye Chemie Japan Co., Ltd., Shin-Etsu Silicone Co., Ltd., Dow Corning Toray Co., Ltd., etc.
There is no specific limit for the surface active agent containing polyether modified silicon. For example, a compound in which the polyalkylene oxide structure represented by the following chemical structure 18 is introduced into the side chain of the Si portion of dimethyl polysiloxane.
Chemical structure 18
In the chemical structure 18, m, n, a, and b independently represent whole numbers. R and R 'independently represent alkyl groups and alkylene groups.
Specific examples of polyether-modified silicone-containing surface active agents include, but are not limited to, KF-618, KF-642, and KF-643 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Specific examples of anionic surface active agents include, but are not limited to, polyoxyethylene alkyl ether acetates, dodecyl benzene sulfonates, laurates, and polyoxyethylene alkyl ether sulfates.
Specific examples of non-ionic surface active agents include, but are not limited to, polyoxyethylene alkyl ether, polyoxypropylene polyoxyethylene alkyl ether, polyoxyethylene alkyl esters, polyoxyethylene sorbitan aliphatic esters, sorbitan aliphatic esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl amines, and polyoxyethylene alkyl amides.
The content of the surface active agents in the engraving ink is preferably from 0.01% by weight to 3.0% by weight and more preferably from 0.5% by weight to 2% by weight. When the content is very small, the effect of the surface active agent tends to be weak. When the content is very large, the penetration of the ink in a recording medium tends to become excessively high, resulting in the decrease of the image density and the occurrence of collision through. Penetrating Agent
The engraving ink for use in the present disclosure preferably has at least one type of polyol compounds or glycol ether compounds having 8 to 11 carbon atoms.
The penetrating agent is different from the wetting agent mentioned above. The penetrating agent is not completely humectable, but it is less humectable than the wetting agent. Therefore, in this context, the penetrating agent is dealt with as non-wettable.
The penetrating agent which has a solubility of 0.2% by weight to 50% by weight in water at 25 ° C is preferable.
Among these, 2-ethyl1-1,3-hexane diol (solubility: 4.2% at 25 ° C) and 2,2,4-trimethyl-1,3-pentane diol (solubility: 2.0% at 25 ° C) are particularly preferable.
Specific examples of other polyol compounds include, but are not limited to, aliphatic diols such as 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butane diol, 2,2-diethyl -1,3-propane diol, 2-methyl-2-propyl-1,3-propane diol, 2,4-dimethyl-2,4-pentane diol, 2,5-dimethyl-2,5-hexane diol, and 5-hexene-1,2-diol.
Any other permeation agents that can be dissolved in paint and adjusted to have the desired characteristics can be used in combination. Specific examples thereof include, but are not limited to, alkyl and aryl ethers of polyols such as diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoaryl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and tetraethylene glycol chlorophenyl ether and lower alcohols such as ethanol.
The permeation agent content in the engraving ink is preferably 0.1% by weight to 40% by weight. When the content is very small, the image obtained may not dry out quickly, resulting in a blurred image. When the content is very high, the dispersion stability of the coloring agent can deteriorate, the nozzles tend to clog, and the permeability tends to be excessively high, which leads to a decrease in the density of the image and the occurrence of passing collision. Hydrodexpersible Resin
Hydrodispersible resins have excellent film forming properties (image formation), water repellency, water resistance, and weathering properties. Therefore, these are suitable for image recording that requires high water resistance and high image density.
Specific examples thereof include, but are not limited to, condensation based resins, addition based resins, and natural polymers.
Specific examples of condensation-based resins include, but are not limited to, polyester resins, polyurethane resins, polyepoxy resins, polyamide resins, polyether resins, poly (meth) acrylic resins, acrylic silicone resins, and fluorine-containing resins.
Specific examples of addition-based resins include, but are not limited to, polyolefin resins, polystyrene resins, polyvinyl alcohol resins, polyvinyl ester resins, polyacrylic acid resins, and unsaturated carboxylic acid resins.
Specific examples of natural resins include, but are not limited to, celluloses, rosin resins, and natural rubber.
Among these, polyurethane resin particles, acrylic silicone resin particles, and fluorine-containing resin particles are preferable. These can be used alone or in combination.
As fluorine-containing resins, fluorine-containing resin particulates having fluoro-olefin units are preferable. Among these, fluorine-containing vinyl ether resin particles, formed from fluoro-olefin units and vinyl ether units, are particularly preferable.
There is no specific limit on the selection of fluoro-olefin units. Specific examples thereof include, but are not limited to, -CF2CF2-, -CF2CF (CF3) -, and -CF2CFCI-.
There is no specific limit on the selection of fluoro-olefin units. For example, compounds represented by the following chemical structure 19 are suitable.
Chemical structures 19
As fluorine-containing vinyl ether resin particles formed from fluoro-olefin units and vinyl ether units, alternative copolymers in which fluoro-olefin units and vinyl ether units are alternately copolymerized.
Any particulates of properly synthesized fluorine-containing resins and their products available on the market can also be used. Specific examples of products available on the market include, but are not limited to, FLUONATE FEM-500, FEM-600, DICGUARD F- 52S, F-90, F-90M, F-90N, and AQUA FURAN TE-5A (all manufactured by DIC Corporation); and LUMIFLON FE4300, FE4500, and FE4400, ASAHI GUARD AG-7105, AG-950, AG-7600, AG-7000, and AG-1100 (all manufactured by ASAHI GLASS CO., LTD.).
Hydrodispersible resins can be used as homopolymers or complex resins as copolymers. Any type of single-phase structure, core-wrap type, and power supply type emulsions are appropriate.
A hydrodispersible resin that has a hydrophilic group with self-dispersibility or no dispersibility while the dispersibility is transmitted to a surface active agent or a resin having a hydrophilic group can be like the hydrodispersible resin. Among these, resin particle emulsions obtained by emulsification polymerization or suspension polymerization of unsaturated ionomers or monomers of a polyester resin or polyurethane resin are more appropriate.
In the case of emulsification polymerization of an unsaturated monomer, since a resin emulsion is obtained by reaction in water in which an unsaturated monomer, a polymerization initiator, a surface active agent, a chain transfer agent, a chelating agent, pH adjusting agent, etc. are added, and it is easy to obtain a hydrodispersible resin and exchange the resin components. Therefore, a hydrodispersible resin having the target properties is easily obtained.
Specific examples of unsaturated monomers include, but are not limited to, unsaturated carboxylic acids, monofunctional or polyfunctional (meth) acrylic ester monomers, amide (meth) acrylic monomers, aromatic vinyl monomers, cyano vinyl monomers, vinyl monomers, monomers of aryl compounds, olefin monomers, diene monomers, and oligomers having unsaturated carbon. These can be used alone or in combination.
When these are used in combination, the properties of the resin can be easily reformed. The properties of the resin can be reformed by polymerization reaction and graft reaction using oligomer-type polymerization initiators.
Specific examples of unsaturated carboxylic acids include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid.
Specific examples of monofunctional (meth) acrylic ester monomers include, but are not limited to, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, iso methacrylate , n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadocyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate methacrylate, benzyl methacrylate 2, , 2-hydroxypropyl methacrylate, dimethyl aminoethyl methacrylate, ethyl methacryloxy salts ethyl trimethyl ammonium, 3-methacryloxy propyl trimethoxy silane, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylate, n-butyl acrylate, -amyl, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, aminoethyl dimethyl acrylate, and ethyl trimethyl ammonium acrylate salts.
Specific examples of polyfunctional (meth) acrylic ester monomers include, but are not limited to, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, dimethacrylate 1,4-butylene glycol, 1,6-hexane diol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, 2,2'-bis (4-methacryloxy diethoxyphenyl) propane, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1, 6-hexane diol diacrylate, neopent glycol diacrylate , 1,9-nonane diol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4-acryloxy propyloxyphenyl) propane triacrylate, 2,2'-bis (4-acryloxydetoxifen triacrylate) il) propane trimethylol propane, trimethylol ethane triacrylate, methane tetramethylol triacrylate, ditrimethylol tetraacrylate, methane tetramethylol tetraacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.
Specific examples of (meth) acrylic monomers include, but are not limited to, acrylic amides, methacrylic amides, N, N-dimethyl acrylic amides, methylene bis acrylic amides, and 2-acrylic amide-2-methyl propane sulfonates.
Specific examples of aromatic vinyl monomers include, but are not limited to, styrene, O-methyl styrene, vinyl toluene, 4-t-butyl styrene, chloro-styrene, vinyl anisol, vinyl naphthalene, and divinyl benzene.
Specific examples of vinyl cyan compound monomers include, but are not limited to, acrylonitrile, and methacrylonitrile.
Specific examples of vinyl monomers include, but are not limited to, vinyl acetate, vinylidene chloride, vinyl chloride, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid and its salts, trimethoxysilane vinyl, and triethoxysilane vinyl.
Specific examples of the monomers of aryl compounds include, but are not limited to, aryl sulfonic acid and its salts, aryl amine, aryl chloride, diaryl amine, and diaryl dimethyl ammonium salts.
Specific examples of olefin monomers include, but are not limited to, ethylene and propylene.
Specific examples of diene monomers include, but are not limited to, butadiene and chloroprene.
Specific examples of oligomers having unsaturated carbon include, but are not limited to, styrene oligomers having a methacryloyl group, styrene-acrylonitrile oligomers having a methacryloyl group, methyl methacrylate oligomers having a methacryloyl group, a dimethyl oligomeric group , and polyester oligomers having an acryloyl group.
Once the disruption of molecular chains, such as destruction by dispersion and hydrolytic cleavage, occurs in hydrodispersible resins in a strong alkaline or strong acid environment, the pH is preferably 4 to 12, more preferably 6 to 11, and more preferably from 7 to 9 in terms of miscibility with the color of the hydrodispersible agent.
The average particle diameter (D50) of the hydrodispersible resin is related to the viscosity of the liquid dispersion. If the composition is the same, the viscosity in the same solid portion increases as the particle diameter decreases.
In order to prevent the preparation paint from having an excessively high viscosity, the average particle diameter (D50) of the hydrodispersible resin is preferably 50 nm or more. In addition, particles that have a particle diameter larger than the nozzle size of the inkjet head nozzle are not useful. When large particles 5 smaller than the mouth of the nozzle are present in the paint, the paint discharge property deteriorates. The average particle diameter (D50) of the hydrodispersible resin is preferably 200 nm or less and more preferably 150 nm or less in order not to degrade the discharge property.
In addition, the hydrodispersible resin preferably has a fixing characteristic of the hydrodispersible agent dye in a recording medium (typically paper) and forms a film at room temperature to improve the fixing property of the coloring material. Therefore, the minimum film-forming temperature (MFT) of the hydrodispersible resin is preferably 30 ° C or lower.
In addition, when the glass transition temperature of the hydrodispersible resin is very low (for example, -40 ° C or lower), the viscosity of the resin film tends to increase, thereby causing the sheet of the image obtained to increase the grip. Therefore, the glass transition temperature of the hydrodispersible resin is preferably -30 ° C or higher. The content of the hydrodispersible resin in the engraving ink is preferably from 1% by weight to 15% by weight and more preferably from 2% by weight to 7% in a solid form. The content of the solid portion in the coloring agent, the pigment in the coloring agent, and the hydrodispersible resin can be measured, for example, by a method of separating only the coloring agent and the hydrodispersible resin from the ink.
When the pigment is used as the coloring agent, the ratio of the coloring agent to the hydrodispersible resin can be measured by evaluating the decrease in mass ratio by thermal mass analysis.
In addition, when a molecular structure of the coloring agent is known, it is possible to quantify the solid portion of the coloring agent using NMR for pigments or dyes and fluorescent X-ray analysis for heavy metal atoms and inorganic pigments, organic pigments containing metal, and dyes containing metal contained in the molecular structure.
The ink for use in the present disclosure normally has a moisture content greater than 50% by weight. Since the total amount of resin and pigment is greater than 3% by weight, the solvent evaporation ratio is from 50% by weight to 97% by weight. Other Components
There is no specific limit for the selection of other components. Optionally, pH adjusting agents, antiseptic and antifungal agents, chelate reagents, anti-corrosion agents, antioxidants, ultraviolet absorbers, oxygen absorbers, and photo-stabilizing agents can be mixed in the paint of the present disclosure.
Any pH adjusters that can adjust the pH of the prescribed ink to be from 7 to 11 without having an adverse impact on the ink can be used. Specific examples thereof include, but are not limited to, alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates.
When the pH is too high or too low, the inkjet head and an ink supply unit tend to be dissolved, which results in poor modification, leakage, ink discharge performance, etc.
Specific examples of alcohol amines include, but are not limited to, diethanol amine, triethanol amine, and 2-amino-2-ethyl-1,3-propane diol.
Specific examples of alkali metal hydroxides include, but are not limited to, lithium hydroxides, sodium hydroxides, and potassium hydroxides.
Specific examples of ammonium hydroxides include, but are not limited to, ammonium hydroxides, quaternary ammonium hydroxides, and quaternary phosphonium hydroxides.
Specific examples of alkali metal carbonates include, but are not limited to, lithium carbonate, sodium carbonate, and potassium carbonate.
Specific examples of antiseptic and antifungal agents include, but are not limited to, dehydrosodium acetate, sodium sorbinate, 2-pyridine thiol-sodium l-oxide benzoate, sodium benzoate, and sodium pentachlorophenol.
Specific examples of chelate reagents include, but are not limited to, sodium ethylene diamine tetraacetate, sodium nitrile triacetate, sodium hydroxyethylethylene diamine triacetate, diethylene sodium acetate diethyl acetate, and uramyl sodium diacetate.
Specific examples of anti-corrosion agents include, but are not limited to, acid sulfite, thiosodium sulfate, ammonium thiodiglycolate, diisopropyl ammonium nitride, quaternary pentaerythritol nitride, and dicyclohexyl ammonium nitride.
Specific examples of antioxidants include, but are not limited to, phenol-based antioxidants (including hindered enol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
Specific examples of phenol-based antioxidants (including hindered enol-based antioxidants) include, but are not limited to, butylated hydroxy anisol, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3, 5-di-tert-butyl-4-hydroxyphenyl), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4 , 4'-butylidenobis (3-methyl-6-tert-butylphenol), 3,9-bis {1,1— dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenol) propionyloxy ] ethyl} -2,4,8-10-tetraoxa spiro [5.5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetracis [(3 ', 5'-di-tert-butyl-4-methylene-3-propionate '-hydroxyphenyl)] methane.
Specific examples of amine-based antioxidants include, but are not limited to, phenyl-β-naphthylamine, α-naphthyl amine, N, N'-di-sec-butyl-p-phenylene diamine, phenothiazine, N, N'-diphenyl -p-phenylene diamine, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxy anisol, 2,2 '-methylenobis (4-methyl-6-tert-butylphenol), 4,4'-butylidenobis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol) , tetracis [methylene-3- (3,5-di-tert-butyl-4-dihydroxyphenyl) propionate] methane, and 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane .
Specific examples of sulfur-based antioxidants include, but are not limited to, dilauryl-3,3'-thiodipropionate, distearyl thiodipropionate and, laurylstearyl thiodipropionate, 3,3'-mercaptobenzo imidazole, and dilauryl sulfide.
Specific examples of phosphorus-based antioxidants include, but are not limited to, triphenylphosphite, octadecylphosphite, triisodecylphosphite, trilauryltrithiophosphite, and trinonylphenyl phosphite.
Specific examples of ultraviolet absorbers include, but are not limited to, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and complex salt-based ultraviolet absorbers of nickel.
Specific examples of benzophenone-based ultraviolet absorbers include, but are not limited to, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxy benzophenone, 2,4-dihydroxy benzophenone, 2-hydroxy-4 - methoxybenzophenone, and 2,2 ', 4'-4'-tetrahydroxy benzophenone.
Specific examples of benzotriazole-based ultraviolet absorbers include, but are not limited to, 2- (2 '-hydroxy-5' - tert-octylphenyl) benzo triazole, 2 - (2'-hydroxy-5r-methylphenyl) benzo triazole, 2- (2'-hydroxy-4'- octoxyphenyl) benzo triazole, and 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzo triazole.
Specific examples of salicylate-based ultraviolet absorbers include, but are not limited to, phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.
Specific examples of cyanoacrylate-based ultraviolet absorbers include, but are not limited to, ethyl-2-cyano-3,3'-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p- methoxyphenyl), and butyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Specific examples of ultraviolet absorbers based on complex nickel salt include, but are not limited to, nickel-bis (octylphenyl) sulfide, 2,2'-thiobis (4-tert-octyl ferrate) -n-butylamine nickel (II ), 2,2'-thiobis (4-tert-octyl ferrate) -2-ethylexyl amine nickel (II), and 2,2'-thiobis (4-tert-octyl ferrate) triethanol amine nickel (II).
The inkjet engraving ink for use in the present disclosure is manufactured by dispersing or dissolving the coloring agent, the water-soluble organic solvent, a surface-active agent, and water with optional components such as a permeation agent and a dispersed or hydrodispersible resin. dissolved in an aqueous medium for use after stirring and mixing, if desired.
The dispersion is conducted by a sand mill, a homogenizer, a ball mill, a paint stirrer, an ultrasonic dispersing agent, etc. Stirring and mixing can be conducted by a stirrer that has a stirring handle, a magnetic stirrer, a high speed dispersion device, etc.
There is no specific limit on the characteristics of the ink for inkjet engraving and any appropriate ink can be selected, for example, viscosity and surface tension with the following ranges are preferable.
The viscosity of the recording ink is 3 mPa * s at 20 mPa * s at 25 ° C. When the ink viscosity is 3 mPa • s or greater, the print density and print quality are improved. When the ink viscosity is 20 mPa * s or less, an appropriate ink discharge property is ensured.
Viscosity can be measured by a viscometer (RL-550, manufactured by TOKI SANGYO CO., LTD.) At 25 ° C.
The surface tension of the recording ink is preferably 35 mN / m or less and more preferably 32 mN / m or less. When the surface tension is very strong, the leveling of the ink in a recording medium tends to occur and hardly occurs, thus prolonging the drying time.
There is no limit to the selection of ink colors for engraving for use in this disclosure. For example, yellow, magenta, cyan, and black are appropriate. When an ink set having at least two types of colors is used for engraving, images of multiple colors are produced. When an ink set having all color combinations is used, full color images are formed.
Engraving ink for use in the present disclosure is used on any printer that has an inkjet head such as a type of piezoelectric element in which ink droplets are discharged into a vibrating plate that forms the wall of the flow path. ink using a piezoelectric element as the pressure generating device to compress the ink into the ink flow path as described in JP-H2-51734-A; a thermal type in which bubbles are produced by heating the ink in the ink flow path with a thermal element as described in JP-S61-59911-A; and an electrostatic type in which ink droplets are discharged by transforming a vibration plate by an electrostatic force generated between the vibration plate and the electrode while the vibration plate and electrode are provided facing each other as described in JP-H6 - 71882-A).
The recording ink for use in the present disclosure is used appropriately for inkjet recording, a recording pen, a scroll point pen, a magic marker, a hydrographic pen, etc. In particular, this ink can be appropriately used in an image forming apparatus (typically, a printer). 7 For example, printers on which recording media and recording ink are heated from 50 ° C to 200 ° C when, 10 before, or after printing to speed up image fixation are appropriate and particularly preferable for a recording medium with inkjet and ink set and an inkjet engraving method. recording
The inkjet and ink set recording medium of the present disclosure is a combination of inkjet recording ink and the recording medium described above.
The recording medium has a substrate and a coated layer on at least one side of the substrate. The amount of pure water transfer to the recording medium having the coated layer is 2 ml / m2 to 35 ml / m2 over a contact time of 100 ms and 3 ml / m2 at 40 ml / m2 over a contact time 400 ms when measured by a dynamic liquid absorption test device at 23 ° C and 50% RH. In addition, as long as the amount of pure water transfer to the recording medium having the coated layer is within the ranges, there is no specific limit for the recording medium so that any glossy paper, special paper, fabric, film, a transparent sheet, flat paper, etc. can be used appropriately.
When the amount of pure water transfer over a 100 ms contact time is very small, bead formation (non-uniform density) tends to occur. When the amount of pure water transfer during a contact time of 100 ms is very large, the diameter of 15 ink points after engraving is less than desired. Therefore, the recording medium for use in the present disclosure has the amount of transfer of pure water to the recording medium having the coated layer measured by a dynamic liquid absorption test device at 23 ° C and 50% RH (humidity relative) is 2 ml / m2 to 35 ml / m2, preferably 2 ml / m2 to 25 ml / m2, and more preferably from 2 ml / m2 to 10 ml / m2 for a contact time of 100 ms.
When the amount of pure water transfer during a 400 ms contact time is very small, the drying property tends to deteriorate, resulting in jagged marks. When the amount of pure water transfer over a 400 ms contact time is very high, the brightness of the imaging portion after drying 5 tends to be low. Therefore, the recording medium for use in the present disclosure has the amount of pure water transfer to the recording medium having the coated layer being 3 ml / m3 to 45 ml / m2, preferably 3 ml / m3 to 25 ml / m2 , and more preferably from 3 ml / m3 to 10 ml / m2 for a contact time of 400 ms when measured by a dynamic liquid absorption test device at 23 ° C and 50% RH. Substrate
There is no specific limitation for the selection of the substrate. For example, paper formed mainly of wood fiber and a sheet material such as a non-woven cloth mainly formed of wood fiber and a synthesized fiber.
There is no specific limitation for the selection of the paper. For example, paper pulp and 20 scrap paper pulp are used.
Specific examples of wood pulp include, but are not limited to, L-Breached Kraft Pulp (LBKP), N-Breached Kraft Pulp, N-Breached Sulfite Pulp (NBSP), L-Breached Sulfite Pulp (LBSP), Ground Pulp ( GP), and Thermo-
Mechanical Pulp (TMP).
Specific examples of the materials for the waste paper pulp include, but are not limited to, {high quality white paper (broken) from unprinted, {high quality white paper (broken) from} printing, {waste paper (broken) from} cardboard, {waste paper (broken) from} medium quality paper without printing, (waste paper from) white paper with black printing, {waste paper (broken) from } unprinted wooden paper, (waste paper) white paper with color printing, (waste paper) white paper or paper or art paper with color printing, {waste paper (broken) from} art paper without printing, (waste paper) medium quality paper with color printing, (waste paper) wooden paper with printing, newspaper waste paper, magazine waste paper, etc. specified in the waste paper quality specification list by Papel Recycling Promotion Center.
To be specific, these are chemical pulp papers and paper containing high yield pulp, which are waste paper and cardboard paper such as printing paper such as uncoated computer paper, thermal paper, and pressure sensitive paper; waste paper OA such as flat photocopy paper; coated paper such as art paper,
coated paper, micro-coated paper, and matte coated paper; uncoated paper such as high quality paper, high quality colored paper, banknote, printing letter paper, kraft paper, cover paper, medium quality paper, newsprint paper, wood paper, super wrapping paper, Japanese imitation veil, glazed poster paper machine, and paper coated with polyethylene. These can be used alone or in combination.
The waste paper pulp is manufactured by a combination of the following four processes: (1): In the maceration, the waste paper is subjected to mechanical force and drugs by a pulp former to produce non-stiffened fiber, of which the printed ink is highlighted. (2): When removing dust, foreign objects such as plastic contained in waste paper and dirt are removed by a sieve, a cleaner, etc. (3): In ink removal, printed ink detached from fiber using a surface active agent is removed from the system by a flotation method or a washing method. (4) In bleaching, the degree of white is improved using oxidation and reduction.
When the waste paper pulp is mixed, the ratio of the waste paper pulp mixture to the entire pulp is preferably 40% or less considering the curl after engraving.
As the internal filler material for use on the substrate, 5 for example, known pigments are used as a white pigment.
Specific examples of white pigments include, but are not limited to, inorganic white pigments such as light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide , zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthesized silica, aluminum hydroxide, alumina, lithopone, 15 zeolite, magnesium carbonate, and magnesium hydroxide: organic pigments such as styrene-based plastic pigment, acrylic-based plastic pigments, polyethylene, microcapsule, urea resin, and melamine resins. These can be used alone or in combination.
As internal measuring agents for use in the sheet producing the substrate, for example, sizing agents based on rosin resins, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resin sizing agents for use in the production of neutral paper they are used. Among these, sizing agents for rosin resins and alkenyl succinic anhydride are particularly preferable.
The alkyl dimers of ketene have an excellent sizing effect, meaning that the amount of addition is less. However, it reduces the friction rate of the surface of a recording medium so that the recording medium tends to become very smooth, which is not preferable in terms of transferability during inkjet recording.
There is no specific limit on the thickness of the substrate. The layer thickness can be determined and is preferably in the range of 50 μm to 300 μm. The weight of the substrate is preferably from 45 g / m2 to 290 g / m2. Coated Layer
The coated layer includes a pigment and a binder resin and optionally contains a surface active agent and other components.
As pigments, inorganic pigments, or a combination of the same inorganic pigments and organic pigments can be used.
Specific examples of inorganic pigments include, but are not limited to, kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, white titanium, magnesium carbonate, titanium dioxide, aluminum hydroxide, hydroxide calcium, magnesium hydroxide, zinc hydroxide, and chloride.
Among these, kaolin has an excellent gloss demonstration and is particularly preferable for preparing the texture close to that of offset printing paper.
With respect to kaolin, there are delaminated kaolin, cooked kaolin, engineered kaolin remodeling the surface.
Considering the gloss demonstration, kaolin which has a particle size distribution in which particles having a particle diameter of 2 μm or less occupy 80% or more is preferable.
The amount of kaolin addition is preferably 50 parts by weight or more based on 100 parts by weight of the binder resin. When the amount of addition is very small, the brightness tends to deteriorate. Although there is no specific upper limit for the addition quantity, considering the fluidity, in particular, thickening under a high shear force, the amount of kaolin addition is 90 parts by weight or less in terms of coating suitability.
Specific examples of organic pigments include, but are not limited to, aqueous liquid dispersion of styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. These can be used alone or in combination.
Since organic pigments have an excellent gloss demonstration, their specific gravity is less than that of an inorganic pigment, it is possible to obtain a bulky coated layer having a high gloss with good surface coverage property.
The amount of organic pigment addition is preferably from 2 parts by weight to 20 parts by weight based on 100 parts by weight of the total pigment in the coated layer. When the amount of addition is very small, such a coated layer is not easily obtained. When the amount of addition is very large, the fluidity of the coating liquid tends to deteriorate, thereby degrading the coating operation property. This, too, is not preferable in terms of savings.
Organic pigments are classified into solid type, hollow type, screw type, etc. Considering the balance of the gloss demonstration, the surface coverage, and the fluidity of the liquid application, the average particle diameter (D50) preferably has 0.2 μm to 3.0 μm and more preferably a hollow type that has a ratio of empty of 40% or more.
As a binder resin, aqueous resins are preferable.
As aqueous resins, at least one of the water-soluble resins and hydrodispersible resins are preferable.
There is no specific limit for water-soluble resins and any known water-soluble resins can be used appropriately. Specific examples thereof include, but are not limited to, polyvinyl alcohol, modified polyvinyl alcohols such as anion-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and acetal-modified polyvinyl alcohol; polyurethane; polyvinyl pyrrolidone and modified polyvinyl pyrrolidones such as copolymers of polyvinyl 15 pyrrolidone and vinyl acetate, vinyl pyrrolidone copolymers and methacrylic dimethyl aminoethyl acid; copolymers of quaternized vinyl pyrrolidone and methacrylic dinethyl aminoethyl acid; and copolymers of vinyl pyrrolidone and methacrylic amide propyl trimethyl ammonium chloride; celluloses 20 such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxy propyl cellulose; modified celluloses such as cationized hydroxyethyl cellulose; synthetic resins such as polyesters, polyacrylates, melamine resins, their modified products, and copolymers of polyethers and polyurethane; poly (meth) acrylic resins, poly (meth) acrylic amides, oxidized starch, phosphate starch, self-modified starch, cationized starch, other modified starches, polyethylene oxide, sodium polyacrylates, and sodium alginate. These can be used alone or in combination.
Among these, in terms of ink absorption, polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol, polyesters, polyurethanes, and polyester and polyurethane copolymers.
There is no specific limit for hydrodispersible resins and any known hydrodispersible resins can be used appropriately. Specific examples thereof include, but are not limited to, polyvinyl acetate, ethylene and vinyl acetate copolymers, polystyrene, styrene and (meth) acrylate copolymers, (meth) acrylate polymers, vinyl acetate and (meth) copolymers ) acrylate, styrene and butadiene copolymers, ethylene and propylene copolymers, polyvinyl ethers, silicone and acrylic copolymers. In addition, optionally, crosslinking agents such as methylated melamine, methylated urea, methylated hydroxy propylene urea, and isocyanate can be contained. Copolymers having a crosslinking property that contains a unit such as N-methylol acrylic amide are also suitable.
These aqueous resins can be used alone or in combination.
The aqueous resin content is 2 parts by weight to 100 parts by weight and preferably 3 parts by weight to 50 parts by weight based on 100 parts by weight of the pigment. The amount of addition of aqueous resins is determined so that the recording medium has a target liquid absorption property.
When a coloring agent having a hydrodispersion capacity is used as the coloring agent, a mixture of cationic organic compound in the coated layer is not necessary, but the cationic organic compound can be used appropriately without specific limits.
Specific examples of cationic organic compounds mixed in the coated layer include, but are not limited to, primary to tertiary amines that form insoluble salts through reaction with a sulfonic acid group, a carboxylic group, an amino group, etc. in a direct dye or an acidic dye in an aqueous paint, and monomers, oligomers, and polymers of quaternary ammonium salts. Among these, oligomers and polymers are preferable.
Specific examples of cationic organic compounds include, but are not limited to, condensation compounds of dimethyl amine epichlorohydrin, condensation compounds of dimethyl amine ammonium epichlorohydrin, poly (trimethyl aminoethyl methyl sulfate methacrylic acid), diarylamine chloride copolymers. acrylic amide, poly (diarylamine chloride. * sulfur dioxide), polyaryl amine chloride, poly (diaryl amine arylamine) chloride, acrylic amide copolymers. diaryl amine, polyvinyl amine copolymers, diciano diamida, composed of condensation of diciano diamida. ammonium chloride. urea. formaldehyde, a product of the condensation of polyalkylene polyamine salt. diciano diamide ammonium, dimethyldiaryl ammonium chloride, polydiarylmethyl amine chloride, poly (diaryldimethyl ammonium) chloride, poly (diaryldimethyl ammonium. sulfur dioxide), poly (diaryldimethylammonium chloride. diaryl amine chloride derivatives), copolymers acrylic amide. diaryl dimethyl ammonium chloride, acrylate copolymers. acrylic amide. diaryl amine chloride, polyethylene imine, ethylene imine derivatives of acrylic amine polymers, etc., and modified alkylene imine polyethylene oxides. These can be used alone or in combination.
Among these, it is preferable to use cationic organic compounds having low molecular weights such as condensation compounds of dimethyl amine epichlorohydrin and polyaryl amine chlorides and other cationic organic compounds having relatively high molecular weights such as poly (diaryldimethyl ammonium) chloride in combination.
In such use in combination r the image density is improved more than a single use of such a cationic organic compound, thereby reducing pinning.
The cationic equivalent of the cationic organic compound by the titration method (using polyvinyl potassium sulfate and toluidine blue) is preferably from 3 meq / g to 8 meq / g. When the cationic equivalent is within this range, good results are obtained within the range of the amount of dry fixation.
When the cationic equivalent is measured by the colloid titration method, the cationic organic compound is diluted with distilled water so that the solid portion is 0.1% by weight with no pH adjustment.
The amount of dry fixation of cationic organic compounds is preferably 0.3 g / m2 to 2.0 g / m2. When the amount of dry fixation is very small, the density of the image is not easily improved or the reduction pin is not easily obtained.
There is no specific limit for the surface active agent contained in the coated layer and any known surface active agent is used appropriately.
Any of the anionic active agents, cationic active agents, amphoteric active agents and nonionic active agents can be used. Among these, nonionic active agents are particularly preferred. By adding the surface active agent, the water resistance of the image is improved and the density of the image becomes high, thereby reducing runoff.
Specific examples of nonionic active agents include, but are not limited to, higher alcohol adducts with ethylene oxides, alkyl phenol adducts with ethylene oxides, aliphatic acid adducts with ethylene oxide, aliphatic acid adducts with ethylene oxide , polyol aliphatic ester adducts with ethylene oxide, superior aliphatic acid amine adducts with ethylene oxide, aliphatic acid amide ethylene oxide adducts, fat adducts with ethylene oxide, polypropylene glycol adducts with oxide ethylene, glycerol aliphatic acid esters, pentaerythritol aliphatic acid esters, sorbitol and sorbitan aliphatic acid esters, sucrose aliphatic acid esters, polyol alkyl ethers, and aliphatic alkanol acid amides. These can be used alone or in combination.
There is no specific limit for the polyol and any known polyol is used appropriately. Specific examples thereof include, but are not limited to, glycerol, trimethylol propane, pentaerythritol, sorbitol, and sucrose.
In addition, with respect to ethylene oxide adducts, it is also appropriate to use adducts in which part of ethylene oxide is replaced with alkylene oxides such as propylene oxide or butylene oxide unless the substitution has an adverse impact on water solubility . Preferably, the replacement ratio is 50% or less. The HLB (hydrophilicity / lipophilicity) of the nonionic active people is preferably from 4 to 15 and more preferably from 7 to 13.
The amount of addition of surface active agent is preferably from 0 to 10 parts by weight and more preferably from 0.1 to 1.0 parts by weight based on 100 parts by weight of the cationic organic compound.
Other components can be added to the coated layer unless they have an adverse impact on the target or the effect of the present disclosure. Like other components, aluminum powder, pH adjusting agents and antioxidants are specified.
There is no specific limit for a method of forming the coated layer. For example, methods are used in which the application of liquid to the coated layer is applied to the substrate or the substrate is impregnated thereon.
There is no specific limit for the method of impregnation or application (coating) of the liquid application for the coated layer. For example, the liquid can be coated by a conventional size compression machine, a portal cylinder size compression machine, a film transfer size compression machine, a blade coat, a rod coat, a air knife cover, and a curtain cover. In terms of cost, the substrate is impregnated in the liquid and the liquid is applied by a conventional size compression machine, a portal cylinder size compression machine, a film transfer size compression machine, etc. installed on a first paper machine followed by finishing using a machine coater.
There is no specific limit on the amount of fixation of the net application. The fixing amount of the solid portion is preferably in the range of 0.5 g / m2 to 20 g / m2 and more preferably from 1 g / m2 to 15 g / m2
The coated layer can be dried after impregnation or application. There is no specific limit for the drying temperature. A drying temperature is preferably in the range of 100 ° C to about 250 ° C.
The recording medium can have a back side of the substrate and / or another layer formed between the substrate and the coated layer and / or the back layer and the substrate. A protective layer can also be formed on the coated layer. Each layer can have a single layer structure or multiple layers of structure.
As a recording medium, in addition to the inkjet recording medium, flat printing paper on the market, coated paper for offset printing and coated paper for gravure printing can be used.
The printing paper on the market is fused coated paper, art paper (AO size, Al size), A2 size coated paper, A3 size coated paper, B2 size coated paper, light weight coated paper, coated micro-paper, etc. . used for commercial printing or printing publications such as offset printing and printmaking.
Specific examples thereof include, but are not limited to, Aurora Coat (manufactured by Nippon Papel Industries Co., Ltd.) and (POD Gloss Coat, manufactured by Oji paper Co., Ltd.). Cartridge
The ink cartridge has a container to hold the ink for inkjet engraving for use in the present disclosure and other optionally selected parts.
There is no specific limit for the container. Any shape, any structure, any size, and any material can be appropriately selected. For example, a container having at least one ink pouch formed from aluminum laminated film, a resin film, etc. can be used appropriately.
The ink cartridge is described in detail with reference to figures 1 and 2.
Figure 1 is a schematic diagram illustrating an example of the ink cartridge. Figure 2 is an example of variation of the ink cartridge illustrated in figure 1.
As illustrated in figure 1, the inkjet ink described above is loaded into an ink pouch 241 from an ink inlet 242. Subsequent to air evacuation, the ink inlet 242 is closed by melting. When ink is used, a needle provided with an inkjet engraving device (main part) 101 shown in figure 3 is pushed into an ink outlet 243 formed of rubber so that ink is supplied to the recording device with inkjet 101.
The ink pouch 241 is formed of a packaging material such as aluminum laminated film having no permeability. The ink pouch 241 is housed in a cartridge box 244 made of plastic as shown in figure 2 and detachable to an inkjet engraving device for use.
An ink cartridge 201 accommodates inkjet engraving ink for use in the present disclosure and can be used by detachably attaching to an inkjet engraving device, in particular, the inkjet engraving device described below .
Inkjet Engraving Method and Inkjet Engraving Device
In the inkjet engraving method for use in the present disclosure, images are recorded by discharging ink for inkjet engraving to a recording medium having a coated layer on at least one side thereof. The recording medium has an amount of transfer of pure water to the recording medium having the coated layer being 2 ml / m2 to 35 ml / m2 during a contact time of 100 ms and 3 ml / m2 to 40 ml / m2 during a contact time of 400 ms when compared by a dynamic liquid absorption test device at 23 ° C and 50% RH. The inkjet ink contains at least one water-soluble organic solvent, a surface active agent, and a coloring agent. The water-soluble organic solvent contains at least one amide compound represented by the following chemical structure 1.
Chemical structure 1
The method of forming images, etc. in the ink recording medium for ink jet recording includes an ink release process, preferably with suitably selected optional processes such as stimulus generation process and a control process.
The inkjet recording device that conducts the recording method includes an ink delivery device, preferably with appropriately selected optional devices such as a stimulus generating device and a control device.
As described above, the inkjet engraving method of the present disclosure is demonstrated by the inkjet engraving device and the ink launching process is suitably conducted by the ink launching device. In addition, the other processes are properly conducted by other corresponding devices.
Ink launch process and ink launch device
The ink release process applies a stimulus (energy) to the recording ink to release the ink to form an image on a recording medium.
The ink delivery device applies the stimulus (energy) to the ink to record an ink release to form the image on the recording medium. There is no specific limit on the selection of the ink delivery device. For example, ink discharge nozzles are specified.
With respect to the device, it is preferable that at least part of the liquid environment, the liquid resistance unit, the vibration plate, and the nozzle member of the inkjet head be formed of materials containing at least one of silicone and nickel .
In addition, the diameter of the inkjet nozzle is preferably 30 μm or less and more preferably from 1 μm to 20 μm.
The stimulus (energy) can be generated by the stimulus generating device, etc. There is no specific limit for the stimulus. For example, heat (temperature), pressure, vibration, and light are appropriate. These can be used alone or in combination. Among these, heat and pressure are preferable.
Specific examples of a stimulus generating device include, but are not limited to, a heating device, a pressure device, a piezoelectric element, a vibration generator, an ultrasonic oscillator, and light. To be specific, for example, a piezoelectric actuator, a thermal actuator using the exchange phases due to film evaporation using a thermoelectric conversion element such as a heat resistance, a shape and memory alloy actuator using phase shift metal by temperature exchange, and an electrostatic actuator using an electrostatic force can be used.
There is no specific limit on how the recording ink is released. How it launches exchanges depending on the type of stimulus. When the stimulus is heat, for example, there is a method in which thermal energy is imparted to the ink for engraving on the recording head using a thermal head, etc. to generate bubbles in the ink whose pressure discharges the ink from the nozzle orifices like 20 droplets.
When the stimulus is pressure, for example, there is a method of applying a voltage to the piezoelectric element fixed in the position referred to as a pressure environment located in an ink passage in the recording head to bend the piezoelectric element, thereby reducing the volume of the pressure environment to discharge ink droplets from the nozzle holes of the recording head.
The ink droplet size for engraving is preferably 5, for example, 3 x 10 ~ 15 to 40 x 10 "15 m3 (from 3 pl to 40 pl). The discharge speed is preferably from 5 m / s to 20 m / s, its trigger frequency is preferably 1 kHz or higher, and the setting is preferably 300 dpi or higher.
There is no specific limit for the control device as long as the device can control the movement of each device. Any control device can be properly selected and used. For example, devices such as a sequencer and a computer can be used.
An example of inkjet engraving of the present disclosure conducted by a series inkjet engraving device is described with reference to the accompanying drawings.
The inkjet recording device illustrated in figure 3 includes the inkjet recording device (main part) 101, a paper feed tray 102 for feeding paper to main part 101, a discharge tray 103 installed on top of the main piece 101 for stock paper on which an image is formed (engraved), and an ink cartridge loading unit 104. An operating unit 105 having operation codes and a monitor are arranged on the top surface of the loading unit of the ink cartridge 104. The ink cartridge loading unit 104 has a front cover that can be opened and closed to secure and detach the ink cartridge 201.
As illustrated in figures 4 and 5, the main piece 101 has a guide rod 131 and a tray 132 serving as the guide members that are suspended by the chassis plates provided on both sides. The guide rod 131 and tray 132 slide a carriage 133 slidably. A main scan motor moves the carriage 133 in the main scan direction indicated by the arrows in figure 5.
Car 133 has a recording head 134 that has four inkjet recording heads that discharge the ink droplets of yellow (Y), cyan (C), magenta (M), and black (Bk). The recording head 134 is arranged so that the ink discharge holes cross the main scan direction while the ink droplet discharge direction is down.
The inkjet recording heads forming the recording head 134 which have piezoelectric actuators such as piezoelectric elements, thermal actuators using phase shift due to film evaporation using thermoelectric conversion, alloy and shape actuators using phase shift metal by temperature exchange, or electrostatic actuators using an electrostatic force as power generation devices are useful.
In addition, carriage 133 has sub-tanks 135 for each color to supply each colored ink to the recording head 134. The recording ink is supplied and replenished to the sub-tanks 135 from the ink cartridge 201 mounted on the ink cartridge loading unit. 104 through an ink supply tube.
As a paper feed section, a paper fed 142 placed on a paper loading unit (plate) 141 of the paper feed tray 102, a paper feed roller 143 having a crescent shape is provided to separate a separate and fed paper 142 over the paper loading unit 141 and a separation pad 144 facing the paper feed roller 143. The separation pad 144 is formed of a material that has a high friction factor and is angled towards the side of the paper feed roller 143.
In addition, as a transfer section for transferring replenished to sub-tanks 135 from ink cartridge 201.
In this inkjet engraving device, when the ink for engraving on the ink cartridge 201 is used, the chassis in the ink cartridge 201 is disassembled to replace the ink pouch 241 inside the chassis.
In addition, the ink cartridge 201 securely supplies the ink for recording even when the ink cartridge 201 is placed vertically (on its side) and installed by the front loading.
Therefore, when main part 101 is blocked on the top side, for example, it is accommodated on a shelf or something is placed on the upper surface of main part 101, the ink cartridge 201 is easily changed.
An example of a subsystem 91 that includes a
The maintenance device for the ink discharge device is described with reference to figures 6 to 8. Figure 6 is a plan view illustrating subsystem 91, figure 7 is a schematic diagram illustrating the structure of subsystem 91, and figure 8 is a view of the right side of subsystem 91 illustrated in figure 6.
In a frame (maintenance frame) 111 of subsystem 91, two cover retainers 112A and 112B are provided as a cover maintenance mechanism, a wiper blade 93 serving as a cleaning member including an elastic body as a device cleaning, and a carriage latch 115. The wiper blade 93 and the carriage latch 115 are retained in a manner that is movable up and down.
In addition, a simulation ink discharge receiver 94 is provided between the wiper blade 93 and the cap retainer 112A. To clean the wiper blade 93, a wiper 118 is oscillately supported that serves as a cleaning device that includes a wiper cylinder 96 serving as a cleaning member to compress the wiper blade 93 from outside frame 111 to the side of a cleaner 95 serving as a cleaning member for the simulation ink discharge receiver 94.
The cap retainers 112A and 112B (referred to as the cap retainer 112 when no separation between the two is required) have two covers 92a and 92b and 92c and 92d, respectively, a cover to cover the nozzle surfaces of the two recording heads.
A piping pump (suction pump) 120 serving as a suction device is connected to the cap 92a retained by the cap retainer 112A located closest to the printing area between the four through a flexible tube 119 and not connected to the other caps 92b , 92c, and 92d. That is, only cap 92a is defined as a suction (restoration) and humidification cap (hereinafter referred to as a suction cap) and the other caps are simply defined as humidification caps.
Therefore, when restoring the recording head, a recording head that needs restoration is selectively moved to a position where the cap 92a can cover the recording head.
In addition, a cam shaft 121 pivotally supported by frame 111 is disposed below the cap retainers 112A and 112B. For the meat shaft 121, cover meat meats 122A and 122B are provided for moving the lid retainers 112A and 112B up and down, a cleaning meat 124 for moving the cleaning blade 93 up and down, a meat car lock 125 to move car lock 115 up and down through a car lock arm 117, a cylinder 126 serving as a rotating body of the simulation ink droplet grounding member in which the ink droplets simulation discharged into the simulation ink discharge receiver 94 land, and a wiper meat 128 to oscillate a wiper 118.
The lid 92 is moved up and down by the lid meats 122A and 122B.
The wiper blade 93 is moved up and down by the wiper cam 124. When the wiper blade 93 is moving downward, the wiper 118 advances. Therefore, the wiper blade 93 moves downwards while it is interspersed with wiper cylinder 96 of wiper 118 and wiper 95 of the simulation ink discharge receiver 94 so that the ink attached to wiper blade 93 is scraped downwards inward. of the simulation ink discharge receiver 94.
Car latch 115 is tilted upward (to the latch direction) by a compressed spring and moved up and down through the car latch arm 117 driven by the car latch meat 125. To rotate the tubing pump 120 and the camshaft 121, with respect to the rotation of a motor 131, a motor gear 132 provided for a motor shaft 131a is engaged with a pump gear 133 provided on a pump shaft 120a of the pipe pump 120, an intermediate gear 136 having a one-way clutch 137 is engaged with an intermediate gear 134 integrated with a pump gear 133 via an intermediate gear 135, and an intermediate gear 138 coaxial with the intermediate gear 136 is engaged with a cam gear 140 fixed to the camshaft 121 via an intermediate gear 139.
An intermediate shaft of the intermediate gear 136 having the one-way clutch 137 and the intermediate gear 138 are pivoted by frame 111.
In addition, a meat 142 for domestic position sensor to detect the domestic position of the meat axis 121 is provided therewith. When the cap 92 reaches the lowest position, a home position lever is moved to open the sensor by the home position sensor provided to subsystem 91 so that the home position of motor 131 (except pump 120) can be detected .
When the power is turned on, regardless of the position of the cap 92 (the cap retainer 112), the cap 92 (the cap retainer 112) moves down and up and does not conduct position detection until it begins to move . After the domestic position (in the center of the upward movement) of the cap 92 is detected, the cap 92 (the cap retainer 112) moves down by a predetermined amount to the bottom position.
Then, after the carriage moves left and right for position detection, it returns to the position to cap recording head 134.
Next, the simulation discharge receiving unit is described with reference to figures 9 and 10. Figure 9 is a cross section of a front view illustrating the simulation discharge receiving unit and figure 10 is a side view illustrating the same.
The simulation discharge receiving unit 200 includes the simulation ink discharge receiver 94, a cylinder 203 placed under the simulation ink discharge receiver 94 and serving as a simulation discharge ink grounding member provided for the meat shaft 121, scraping members 204A and 204B forming a scraping mechanism 204 for scraping the embossing ink attached to the inside of the cleaner 95, and a scraping member 205 for scraping the embossing tub attached to the cylinder 203 serving 10 like a rotating body. A waste ink tank 206 containing an absorber 207 is disposed under the simulation ink discharge receiver 94.
The scraping mechanism 204 for scraping the embossing ink fixed inside the cleaner 95 of the simulation ink discharge receiver 94 oscillatingly supports the bottom portions of the scraping members 204A and 204B by an extension shaft 210 provided for a retainer 201. These scraping members 204A and 204B are connected to each other by a connecting member 211 with permission.
In addition, pin members 121 contacting retaining members 204A and 204B by rotating cylinder 203 are provided on the side of cylinder 203 serving as a rotating body of the dummy ink droplet grounding member provided to the cam shaft 121. The scraping members 204A and 204B tilt the front ends 204a thereof to follow an inclined surface of the cleaner 95.
In addition, a convex portion 204b is provided on the side facing the inner wall of the simulation ink discharge receiver 94 of the scraping members 204A and 204B to reduce the contact area when oscillating.
Structured as described above, the engraving ink removed from the wiper blade 93 fixes wiper 95 when cleaning wiper blade 93.
When cylinder 203 rotates in the direction indicated by the arrow
And in figure 10 rotating the cam shaft 121, the pin member 212 of the cylinder 203 contacts the scraping members 204A and 204B. Therefore, the scraping members 204A and 204B move back and forth (between the positions indicated by the solid lines and the position indicated by the broken lines) 33 along the direction indicated by the arrows F and G in figure 10.
By this reciprocal movement of the scraping members 204A and 204B, the embossing ink attached to the cleaner 95 is scraped and collected in m or several places by the front ends 204a of the scraping members 204A and 204B. Therefore, the etching ink assembles to form blocks and flows downward by its own weight along the inner wall of the simulation ink discharge receiver 94 to drip in the waste tank ink 206 placed below it.
That is, in the case of a cleaning mechanism in which the etching ink attached to the wiper blade 93 is pressed against the wiper 95 for removal, the etching ink remains on the front end of the wiper 95 if the wiper 93 is simply moved while being compressed against the wiper blade 95.
In particular, when the etching ink has a high viscosity, the etching ink remains on the front end of the wiper 95, which tends to make it difficult to remove the etching ink attached to the wiper blade 93 during cleaning the next time.
Therefore, even if the etching ink that has a high viscosity is used, since the droplet volume of the etching ink to the surface contacting the cleaner 95 increases by scraping the etching ink attached to the cleaner 95 in one or a few places, the ink easily flows downwards from the contact surface with the cleaner 95 and therefore the cleaning blade 93 can be cleaned in a clean state for the next time, thereby improving the cleaning property of the cleaning blade 93 .
According to one experiment, when the viscosity of the etching ink at 25 ° C is very large, for example, 5 mPa • s, it is confirmed that the etching ink tends to remain on the front end of the cleaner, which tends to degrade the performance of removing the recording ink from the blade for the next time. When the scraping members 204A and 204B described above are provided, it is confirmed that the etching ink flows effectively
In addition, since the scraping members 204A and 204B are driven by the rotation of the cylinder 203 serving O as a rotating body of a dye grounding member of the simulation paint provided to the cam shaft 121, 10 the structure of the scraping 204 is simple.
In addition, since the cylinder 203 serving as a rotating body of a simulation ink droplet grounding member rotated by the meat shaft 121 is disposed within the simulation ink discharge receiver 94, at the mist velocity of the droplet of simulation ink (2) discharged is reduced or the simulation ink attached to and collected by cylinder 203.
Therefore, the diffusion of the mist from the recording ink is prevented.
Once the scraping member 205 for scraping the embossing ink attached to the cylinder 203 is provided, the embossing ink attached to the cylinder 203 is scraped by the scraping member 205 and falls into the waste ink tank 206 at its own weight.
By arranging the member to scrape the engraving ink attached to the cylinder 203 below the 203 cylinder and above the waste ink tank, it is possible to deal with the waste ink by removing the engraving ink attached to the cylinder by a simple mechanism at low cost.
A serial-type recording device (back-and-forth type) with an inkjet in which a car scan is used in this example. Also, this can be applied to a linetype inkjet recording device having a linetype head.
In addition, the inkjet engraving device and the inkjet engraving method described above are appropriately applied to engraving systems that employ inkjet engraving such as inkjet engraving printers, facsimile machines, photocopiers, multifunctional machines (printer / facsimile / photocopier). Ink Engraving Material
The ink recording material in which the images are recorded by the ink jet recording device and the ink jet recording method has an image formed on a recording medium using the recording ink described above.
In addition, the ink recording material has an image formed in the recording medium of the inkjet recording medium and ink set of the present disclosure using the set recording ink.
The recording medium has a substrate that has a coated layer on at least one side of it. The amount of pure water transfer to the recording medium that has a coated layer measured by a dynamic liquid absorption test device at 23 ° C and 50% RH (relative humidity) is 2 ml / m2 to 35 ml / m2 during a contact time of 100 ms and 3 ml / m2 to 40 ml / m2 during a contact time of 400 ms. In addition, as long as the amount of pure water transfer to the recording medium that has the coated layer is within these ranges, there is no specific limit for the recording medium so that any glossy paper, special paper, fabric, film, a transparent sheet, flat paper, etc. can be used appropriately. These can be used alone or in combination.
The ink recording material is a blur-free quality image that is stable over time so the ink recording material is. ink can be appropriately used as a material on which tests and images are recorded.
Having generally described (preferred embodiments of) this invention, another understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting. In the description in the following examples, the numbers represent the ratio in parts by weight, 5 unless otherwise specified. EXAMPLES
In the following, the present disclosure is described in detail with reference to the examples, but not limited to them. PREPARATION EXAMPLE 1
Preparation of Aqueous Solution A of Aqueous Polymer
A-olefin maleic anhydride represented by chemical structure 2 (T-YP112, Olefin chain (R): number of carbon atoms: 20 to 24 corresponding to the alkyl group having 18 to 22 carbon atoms in R of chemical structure II, 15 manufactured by SEIKO PMC CORPORATION) having an acid value of 190 mgKOH / g and a weight average molecular weight of 10,000: parts 1 normal LiOH aqueous solution (having an acid value 1.2 times of a maleic anhydride copolymer of a - 20 olefin represented by the chemical structure 1 17.34 parts
Deionized water 72.66 parts Heat and stir a mixture of the recipe specified above to dissolve the maleic anhydride of cx-olefin- represented by chemical structure 2 followed by filtration in one minute the amount of insoluble matter with the filter having an average opening of 5 μm for prepare an aqueous solution A to an aqueous solution A of aqueous polymer. PREPARATION EXAMPLE 2
Preparation of Liquid Dispersion of Black Pigment Treated on the Surface Add 90 g of carbon black having a CTAB specific surface area of 150 m2 / g and a DBP oil absorption amount of 100 ml / 100 g to 3000 ml of 2.5 ml 10 normal sodium sulfate solution and conduct the oxidation treatment reaction by shaking at 300 rpm at 60 ° C for ten hours.
Filter the reaction liquid and neutralize the sodium hydroxide-filtered carbon black followed by ultrafiltration. θ Wash the carbon black thus obtained with water. Dry the carbon black and disperse it in pure water so that the solid portion of the carbon black is 30% by weight followed by sufficient agitation to obtain the black pigment dispersion liquid. The mean particle diameter (D50) of the pigment dispersion in the liquid black pigment dispersion is 103 nm. The average particle diameter (D50) is measured by the particle size distribution measuring instrument (Nanotrac
UPA-EX-150 manufactured by Nikkiso Co., Ltd.) PREPARATION EXAMPLE 3
Preparation of Magenta Pigment containing Liquid Dispersant of Polymeric Particulates
PREPARATION OF THE POLYMERIC SOLUTION A
After sufficient replacement with nitrogen gas in a flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas introduction tube, a reflux tube, and a drip funnel, mix 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, 4.0 g of polyethylene methacrylate, 4.0 g of styrene macromer, and 0.4 g of ethanol mercapto in the flask and heat the system to 65 ° C , drip a liquid mixture of 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 hydroxyethyl methacrylate, 36 , 0 g of styrene micromer, 3.6 g of ethanol mercapto, 2.4 g of azobisdimethyl valeronitrile, and 18 g of methyl ethyl ketone in the bottle in two and a half hours; subsequently, drop a liquid mixture of 0.8 g of dimethyl valeronitrile azobis and 18 g of methyl ethyl ketone into the flask in one and a half hours; after one hour of aging at 65 ° C, add 0.8 g of azobisdimethyl valeronitrile represented by more aging in one hour; after the reaction is complete, add 364 g of methyl ethyl ketone to the flask to obtain 800 g of polymeric solution A having a concentration of 50% by weight.
Preparation of Magenta Pigment containing Liquid Dispersion of Polymeric Particulates
Sufficiently stir 28 g of polymeric solution A, 4.2 g of C.I. Pigmento Red 122, 13.6 g of 1 mol / 1 of potassium hydroxide solution, 20 g of methyl ethyl ketone, and 13.6 g of deionized water; mixing and kneading the mixture using a roller mill;
Place the obtained paste in 200 g of pure water followed by sufficient stirring. Distill methyl ethyl ketone using an evaporator and remove coarse particles by filtering the liquid dispersion thus obtained with a polyvinylidene fluoride membrane filter having an average orifice diameter of 5.0 μm under pressure to obtain a liquid dispersion of polymeric particles containing pigment magenta containing the pigment in an amount of 15% by weight and a solid portion of 20% by weight.
The average particle diameter (D50) of polymeric particles in the liquid dispersion of polymeric particles containing magenta pigment is 127 nm. The average particle diameter (D50) is measured by the particle size distribution measuring instrument (Nanotrac UPA-EX-150, manufactured by Nikkiso Co., Ltd.) PREPARATION EXAMPLE 4
Preparation of Cyan Pigment containing Liquid Dispersion of Polymeric Particulates
A liquid dispersion of polymeric particles containing cyan pigment is prepared in the same way as in preparation example 3 except that C.I. Pigmento Red 122 is replaced with phthalocyanine pigment (C.I. Pigmento Blue 15: 3).
The average particle diameter (D50) of polymeric particles in the liquid dispersion of polymeric particles containing cyan pigment is 93 nm. The average particle diameter (D50) is measured by the particle size distribution measuring instrument (Nanotrac UPA-EX-150, manufactured by Nikkiso Co., Ltd.) PREPARATION EXAMPLE 5
Preparation of Yellow Pigment Containing Liquid Dispersion of Polymeric Particulates
A liquid dispersion of polymeric particulates containing yellow pigment is prepared in the same manner as in preparation example 3 except that C.I. Pigmento Red 122 is replaced with monoazo yellow pigment (C.I. Pigmento Yellow 74).
The average particle diameter (D50) of the polymeric particles in the liquid dispersion of polymeric particles containing yellow pigment is 76 nm. The average particle diameter (D50) is measured by the particle size distribution measuring instrument (Nanotrac UPA-EX-150, manufactured by Nikkiso Co., Ltd.) PREPARATION EXAMPLE 6
Preparation of carbon black pigment containing liquid dispersion of polymeric particulates
A liquid dispersion of polymeric particulates containing carbon black pigment is prepared in the same way as in preparation example 3 except that C.I. Pigmento Red 122 is replaced with carbon black (FW100, manufactured by Degussa AG).
The average particle diameter (D50) of polymeric particles in the liquid dispersion of polymeric particles containing carbon black pigment is 104 nm. The average particle diameter (D50) is measured by the particle size distribution measuring instrument (Nanotrac UPA-EX-150, manufactured by Nikkiso Co., Ltd.) PREPARATION EXAMPLE 7
Preparation of Liquid Dispersion of Yellow Pigment Surface Active Agent
Monoazo yellow pigment (CI Pigmento Yellow 74, manufactured by Dainichiseika Color and Chemicals Mfg. Co., Ltd.): 30 parts Polyoxyethylene styrene phenyl ether (nonionic surface active agent, NOIGEN EA177, HLB value: 15.7, manufactured by DAI -ICHI KOGYO SEIYAKU CO., 5 LTD.) 10 parts
Deionized water 60.0 parts Dissolve the surface active agent specified above in the deionized water followed by mixing with the pigment specified above. After sufficient wetting, 10 disperse the resultant with a wet type dispersion device (type DYNO-MILL KDL A, manufactured by Willy A. Bachofen AG) in which zirconia beads having a diameter of 0.5 mm are loaded with the 2,000 rpm for two hours to obtain a primary pigment dispersion.
Then, add 4.26 parts of water-soluble polyurethane resin (Takelac W-5661, manufactured by Mitsui Chemicals, Inc., effective component: 35.2% by weight, acid value: 40 mgKOH / g, molecular weight: 18,000) followed by sufficient agitation to obtain a liquid dispersion of yellow pigment surface active agent.
The average particle diameter (D50) of the pigment dispersion in the yellow pigment liquid dispersion is 62 nm. The average particle diameter (D50) is measured by the particle size distribution measuring instrument (Nanotrac UPA-EX-150, manufactured by Nikkiso Co., Ltd.) EXAMPLES 1 AND 7 AND COMPARATIVE EXAMPLES 1 AND 2
Manufacture of engraving ink Each engraving ink is manufactured according to the following 5 procedure.
Mix a water-soluble organic solvent (wetting agent), a permeation agent, a surface active agent, and a mildew proof agent shown in Table 1 and water followed by an hour's stirring for uniform mixing. Add a water-soluble resin to the liquid mixture followed by an hour's stirring. Add a liquid dispersion of pigment and a defoaming agent to it followed by an hour's stirring. Filter the liquid dispersion thus obtained with a polyvinylidene fluoride membrane filter 15 having an average orifice diameter of 5.0 μm under pressure to remove coarse particles and dust. Thus, each ink for engraving examples 1 to 7 and comparative examples 1 and 2. TABLE 1




Product name: Aurora Coat Base weight = 104.7 g / m2 (manufactured by Nippon Papel Industries Co., Ltd.) 20 Embossing paper 2 Product name: POD Gloss Coat Paper <100> Base weight = 100 g / m2 (manufactured by Nippon Papel Industries Co., Ltd.) Embossing paper 3 Product name: My Paper Base weight = 67 g / m2 (manufactured by Ricoh Co., Ltd.) Measurement of the amount of pure water transfer by the device dynamic liquid absorption test Measure the amount of pure water transfer to the surface on which the coated layer is applied to embossing paper 1 to 3. A dynamic liquid absorption test device (type K350 Series D, manufactured by KYOWA CO., LTD.) Is used to measure the amount of pure water transfer.
The results are shown in table 2. TABLE 2
Evaluate each ink for inkjet engraving of examples 1 to 7 and comparative examples 1 and 2 according to the following evaluation criteria. The results are shown in table 1.
Preparation of Image Formation Assessment
In an environment where temperature and humidity are adjusted in a range of 22.5 ° C to 23.5 ° C and 45% RH (relative humidity) to 55% RH, change in the activation voltage of the piezoelectric element of so that the same amount of ink is fixed to the recording media by setting an inkjet printer (IPSiO GXe 5500, manufactured by Ricoh Co., Ltd.) to discharge the same amount of ink. Image Density
Print a graph including a 64-point character ■ designed by Microsoft Word 2000 on My Paper (manufactured by Ricoh Co., Ltd.) and measure the color of the ■ portion of the surface printed by a reflection spectrodensitometer (X-Rite 939, manufactured by by X-RITE Co., Ltd.).
The print mode is: a modified mode in which "Plain Paper - Standard Fast" is changed to "no color calibration" from a user setting to flat paper by a trigger attached to the printer. Smear Fixing Property Three hours after printing is completed, move the white cotton fabric (manufactured by TOYO SEIKI Co., Ltd.) attached to a watch meter (manufactured by TOYO SEIKI Co., Ltd.) behind and in front of the solid image portion printed ten times and observe the ink attached to the white cotton with the naked eye to assess the contamination according to the following criteria: 5: No contamination 4: Slightly contaminated 3: Contaminated, but not causing any practical problems 2: Slightly substantially contaminated 1: Substantially contaminated
Toothed mark evaluation Observe the degree of the toothed mark on each image impression with the naked eye and the degree of the toothed mark on each image impression with the naked eye and evaluate using the following criteria: Evaluation Criteria E (Excellent): No toothed marks G (Good): Slight jagged marks observed B (bad): Serious jagged marks observed Bead formation
Observe the degree of bead formation in the green solid image portion of each image print with the naked eye and evaluate by the following criteria: Evaluation Criteria E (Excellent): Uniform printing with no G-formation (Good): Slight formation of observed accounts B (Bad): formation of clear observed accounts
Brightness Issue a portion of a solid image prepared using Microsoft Word 2000 (manufactured by Microsoft Corporation) and measure the brightness at 60 ° using a gloss meter (Micro-Gross 60 °, manufactured by Atlas). Synchronization Occurrence
To check if synchronism occurs, draw a graphic to occupy everything for a solid image using Microsoft Word 2000 (manufactured by Microsoft Corporation) and make an assessment of the degree of paper curl after printing according to the following criteria: Evaluation Criteria G ( Good): No matched problem for the next discharge paper B (Bad): Both ends tangled, causing a problem for the discharge Effects of the Invention
As described above, the inkjet recording medium and ink set of the present disclosure is excellent around the image density and gloss for a recording medium having poor ink absorbing properties such as glossy gloss printing paper. commercially available commercial product that is available at low cost and furthermore produces quality recording materials without problems such as a low fixing and clocking property with respect to recording with inkjet materials using the recording medium having poor ownership of ink absorption mentioned above. Furthermore, the stability of the discharge ink for the nozzle is good, thus producing quality images so that the assembly is appropriately used for ink cartridge, ink engraving material, ink jet engraving device, and inkjet engraving methods.

权利要求:
Claims (7)
[0001]
1. Inkjet recording medium and ink set characterized by the fact that it comprises: ink comprising: water; a water-soluble organic solvent comprising an amide compound represented by the following chemical structure 1; I
[0002]
2. Inkjet recording medium and ink set, according to claim 1, characterized by the fact that an amide compound content represented by the chemical structure 1 in the inkjet recording ink in the range of 1% in weight to 50% by weight.
[0003]
3. Inkjet engraving medium and ink set according to claim 1 or 2, characterized in that the coloring agent comprises a pigment that has at least one type of hydrophilic group on its surface and is hydrodispersible in the absence of a dispersing agent.
[0004]
4. Inkjet recording medium and ink set according to claim 1 or 2, characterized in that the coloring agent comprises a pigment dispersion in which a pigment, a pigment dispersant, and a stabilizer of pigment polymeric dispersion are dispersed in water.
[0005]
5. Inkjet engraving medium and ink set according to claim 1 or 2, characterized in that the coloring agent comprises a polymeric emulsion in which water-insoluble polymeric particles and / or slightly soluble polymeric particles comprising a pigment are dispersed in water.
[0006]
6. Inkjet engraving medium and ink set according to any one of claims 1 to 5, characterized in that the ink for inkjet engraving is at least one ink selected from the group consisting of cyan ink, magenta ink, yellow ink, and black ink.
[0007]
7. Inkjet engraving method characterized by the fact that it comprises: discharging the ink for inkjet engraving on a recording medium, as defined in any one of claims 1 to 6, the layer being coated on at least one side, where the amount of pure water transfer to the recording medium is 2 ml / m2 to 35 ml / m2 during a contact time of 100 ms and 3 ml / m2 to 40 ml / m2 during a contact time. 400 ms contact as measured by a dynamic liquid absorption test device at 23 ° C and 50% RH, in which the inkjet ink comprises water, a water-soluble organic solvent comprising an amide compound represented by the following chemical structure 1, a surface active agent, and a coloring agent:

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法律状态:
2015-06-23| B03A| Publication of an application: publication of a patent application or of a certificate of addition of invention|

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2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-07-09| B06T| Formal requirements before examination|

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2020-05-12| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-11-17| B09A| Decision: intention to grant|

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2021-01-26| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2011-142598|2011-06-28|

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JP2011142598|2011-06-28|

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JP2011-240933|2011-11-02|

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JP2011240933A|JP5888589B2|2011-06-28|2011-11-02|Ink for inkjet recording-Media set for recording and inkjet recording method|

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