WO2012056932A1 - Process for production of black ink composition - Google Patents
Process for production of black ink composition Download PDFInfo
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- WO2012056932A1 WO2012056932A1 PCT/JP2011/073857 JP2011073857W WO2012056932A1 WO 2012056932 A1 WO2012056932 A1 WO 2012056932A1 JP 2011073857 W JP2011073857 W JP 2011073857W WO 2012056932 A1 WO2012056932 A1 WO 2012056932A1
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- pigment
- ink composition
- water
- aqueous dispersion
- carbon black
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Definitions
- the present invention relates to a method for producing a black ink composition.
- Inkjet technology has been applied as an image recording method for recording color images in the fields of office printers, home printers, and the like.
- a pigment is widely used as a colorant for an ink component used in inkjet.
- carbon black is often used for black ink.
- a black ink composition using carbon black is capable of improving the hue by using a color pigment in combination with carbon black (see, for example, JP 2000-318293 A).
- organic solvent-based UV curable inks it has been studied to add a phthalocyanine derivative to black ink in order to improve storage stability and curability (see, for example, JP-A-2005-264098).
- water-based inks are preferable for reducing the environmental load.
- water-based pigment inks do not necessarily have sufficient scratch resistance and the like, recently, ultraviolet curable water-based pigment inks have been studied.
- JP-A-2005-264098 contributes to the improvement of the dispersibility of the carbon black pigment, and is essentially different from a so-called pigment intended for coloring.
- the present invention provides a method for producing a black ink composition for ink-jet recording, which can be excellent in ejection stability and can form an image excellent in adhesion to a recording medium.
- ⁇ 1> Obtaining an aqueous carbon black pigment dispersion containing a carbon black pigment as a pigment, and an aqueous pigment dispersion containing at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment as a pigment And mixing a carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, a water-soluble polymerizable compound, and a polymerization initiator, to produce a black ink composition for inkjet recording Method.
- At least one of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion contains a pigment coated with a water-insoluble resin having an acidic group on at least a part of the surface thereof.
- ⁇ 3> The method for producing a black ink composition according to ⁇ 1> or ⁇ 2>, wherein the colored pigment aqueous dispersion contains at least one color pigment selected from the group consisting of a magenta pigment and a cyan pigment. .
- ⁇ 4> The method for producing a black ink composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerization initiator is a compound represented by the following general formula (1).
- n each independently represent an integer of 0 or more, and m + n represents an integer of 0 to 3)
- ⁇ 5> The above ⁇ 1> to ⁇ 4>, further comprising mixing colloidal silica with the carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator.
- the volume average secondary particle diameter of the pigment contained in at least one selected from the group consisting of the carbon black pigment aqueous dispersion and the color pigment aqueous dispersion is 40 nm to 150 nm, ⁇ 1> to ⁇ 5.
- ⁇ 7> The above-mentioned ⁇ 1>, further comprising mixing an acetylene glycol surfactant with the carbon black pigment aqueous dispersion, the colored pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator.
- the method for producing a black ink composition according to any one of to ⁇ 6>.
- the present invention it is possible to provide a method for producing a black ink composition for ink jet recording capable of forming an image having excellent ejection stability and excellent adhesion to a recording medium.
- step includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step is achieved. To do.
- a numerical range (X and Y are numerical values) indicated in the format of “X to Y” means a range including X as a minimum value and Y as a maximum value.
- the method for producing a black ink composition for ink jet recording of the present invention includes obtaining a carbon black pigment aqueous dispersion containing a carbon black pigment as a pigment, a magenta pigment, Obtaining an aqueous dispersion of a colored pigment containing, as a pigment, at least one color pigment selected from the group consisting of a cyan pigment and a yellow pigment, the aqueous dispersion of the carbon black pigment, the aqueous dispersion of the colored pigment, and a water-soluble polymerization Mixing the active compound and the polymerization initiator.
- the manufacturing method may or may not include other steps as necessary.
- the manufacturing method comprises a step of obtaining an aqueous dispersion containing at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment, independently of the step of obtaining an aqueous dispersion of a carbon black pigment.
- a black ink composition that can be excellent in ejection stability can be produced.
- an image having excellent adhesion to the recording medium can be formed.
- the aqueous dispersion of carbon black pigment is typically obtained by a step of dispersing the carbon black pigment in an aqueous medium.
- the carbon black dispersion step is not particularly limited as long as the carbon black pigment can be dispersed in an aqueous medium, and a commonly used dispersion method can be appropriately selected and applied.
- an aqueous carbon black pigment dispersion can be obtained by mixing at least one dispersant and at least one carbon black pigment in an aqueous medium, and dispersing the resulting mixture.
- the mixing method and the dispersion treatment method are not particularly limited, and a commonly used mixing and stirring device, and a dispersing device such as an ultrasonic dispersing machine, a high-pressure homogenizer, a ball mill, a roll mill, and a high-speed stirring type dispersing machine may be used as necessary. it can.
- a dispersing device such as an ultrasonic dispersing machine, a high-pressure homogenizer, a ball mill, a roll mill, and a high-speed stirring type dispersing machine may be used as necessary. it can.
- the dispersant may be either a polymer dispersant or a low molecular surfactant type dispersant.
- the polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.
- the low molecular surfactant type dispersant a commonly used low molecular surfactant can be used without particular limitation.
- examples of the water-soluble dispersant include hydrophilic polymer compounds.
- natural hydrophilic polymer compounds include plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, seaweeds such as alginic acid, carrageenan and agar.
- examples include molecules, animal polymers such as gelatin, casein, albumin and collagen, and microorganism polymers such as xanthene gum and dextran.
- fiber polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose
- starch starches such as sodium starch glycolate and sodium phosphate phosphate
- examples include molecules, seaweed polymers such as sodium alginate and propylene glycol alginate.
- Synthetic hydrophilic polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamides, polyacrylic acid or alkali metal salts thereof, and acrylics such as water-soluble styrene acrylic resins. Resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of ⁇ -naphthalene sulfonic acid formalin condensate, quaternary ammonium, amino group, etc. And a polymer compound having a cationic functional group salt in the side chain, a natural polymer compound such as shellac, and the like.
- water-soluble dispersants introduced with carboxyl groups such as homopolymers such as acrylic acid, methacrylic acid, and styrene acrylic acid, and copolymers with monomers having other hydrophilic groups are highly hydrophilic. Preferred as a molecular compound.
- water-insoluble dispersant among the polymer dispersants a water-insoluble resin having a hydrophobic constituent unit and a hydrophilic constituent unit can be used.
- hydrophilic structural unit a structural unit having an acidic group is preferable, and a structural unit having a carboxyl group is more preferable.
- water-insoluble resins include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer.
- Examples thereof include a polymer, a polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymer, a vinyl acetate-maleic acid copolymer, and a styrene-maleic acid copolymer. More specifically, for example, water-insoluble resins described in JP-A-2005-41994, JP-A-2006-273891, JP-A-2009-084494, JP-A-2009-191134, and the like can be suitably used. .
- the carbon black dispersion step uses a water-insoluble resin having an acidic group as a dispersant, and a mixture containing the carbon black pigment, a neutralizing agent, water, and a water-soluble organic solvent capable of dissolving or dispersing the water-insoluble resin.
- the method includes a step of dispersing the mixture, a step of dispersing the mixture, and a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step.
- phase inversion emulsification method Such a dispersion method is generally called a phase inversion emulsification method.
- phase inversion emulsification method For details of the phase inversion emulsification method, reference can be made to, for example, descriptions in JP-A-10-140065, JP-A-11-209672, JP-A-11-172180, and the like.
- the water-insoluble resin used for phase inversion emulsification preferably contains a water-insoluble resin having a carboxyl group, from the viewpoint of self-dispersibility and the aggregation rate when the treatment liquid described below comes into contact, and has a carboxyl group, A water-insoluble resin having an acid value of 100 mgKOH / g or less is preferable, and a water-insoluble resin having an acid value of 25 to 100 mgKOH / g is more preferable.
- a polymer dispersant having a carboxyl group and having an acid value of 25 to 100 mgKOH / g may be effective.
- the weight average molecular weight of the water-insoluble resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 40,000, and particularly preferably 10 , 40,000.
- the mixing method and the dispersion method in the phase inversion emulsification method are not particularly limited. Dispersion of a generally used mixing and stirring device, ultrasonic dispersing machine, high-pressure homogenizer, ball mill, roll mill, high-speed stirring type dispersing machine, etc. An apparatus can be used.
- the water-soluble organic solvent used in the phase inversion emulsification method is not particularly limited as long as the water-insoluble resin can be dissolved or dispersed, and can be appropriately selected according to the water-insoluble resin.
- Specific examples include alcohol solvents, ketone solvents, and ether solvents.
- the alcohol solvent include isopropyl alcohol, n-butanol, t-butanol, ethanol and the like.
- the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone.
- the ether solvent include dibutyl ether and dioxane.
- ketone solvents such as methyl ethyl ketone and alcohol solvents such as isopropyl alcohol are preferable, and ketone solvents such as methyl ethyl ketone are more preferable.
- the neutralizing agent is used to form an emulsified state or a dispersed state in which a part or all of acidic groups are neutralized and the water-insoluble resin is stable in water.
- the neutralizing agent include alcohol amines (eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol), alkali metal hydroxides (eg, lithium hydroxide, hydroxide) Sodium, potassium hydroxide, etc.), ammonium hydroxide (eg, ammonium hydroxide, quaternary ammonium hydroxide), phosphonium hydroxide, alkali metal carbonate, etc.
- alcohol amines eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol
- alkali metal hydroxides eg, lithium hydroxide, hydroxide
- ammonium hydroxide eg, ammoni
- the carbon black pigment dispersion step is a method for obtaining “a pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin”, and after dispersing the pigment using a water-soluble or water-insoluble dispersant.
- the pigment dispersion is prepared by crosslinking the dispersant with a crosslinking agent to insolubilize the water-soluble dispersant.
- the dispersant include polyvinyls, polyurethanes, polyesters, etc. Among them, polyvinyls are preferable.
- the dispersant needs to have a functional group that can be crosslinked by a crosslinking agent in the molecule.
- the crosslinkable functional group is not particularly limited, and examples thereof include a carboxyl group or a salt thereof, an isocyanate group, an epoxy group, and the like. From the viewpoint of improving dispersibility, the functional group may have a carboxyl group or a salt thereof. preferable.
- the dispersant is preferably a copolymer obtained using a carboxyl group-containing monomer as a copolymerization component.
- the carboxyl group-containing monomer include (meth) acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid and the like.
- (meth) Acrylic acid and ⁇ -carboxyethyl acrylate are preferred.
- (Meth) acrylic acid means at least one of acrylic acid and methacrylic acid.
- the copolymer component preferably contains at least one hydrophobic monomer.
- hydrophobic monomers examples include alkyl (meth) acrylates having 1 to 20 carbon atoms, (meth) acrylates having an aromatic ring group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and styrene and its derivatives. Can be mentioned.
- the dispersant is a copolymer obtained by using a carboxyl group-containing monomer and at least one of an alkyl (meth) acrylate having 1 to 20 carbon atoms and a (meth) acrylate having an aromatic ring group as a copolymerization component.
- the method for synthesizing the copolymer as a dispersant is not particularly limited, but random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.
- the acid value of the dispersant before crosslinking is preferably 60 to 250 mgKOH / g, more preferably 65 to 150 mgKOH / g, from the viewpoint of dispersibility of the pigment.
- the acid value of the dispersant after crosslinking is preferably 25 to 100 mgKOH / g from the viewpoints of stability and ink aggregation.
- the weight average molecular weight of the dispersant before crosslinking is not particularly limited, but is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint of dispersibility of the pigment. , 40,000 is more preferable.
- the cross-linking agent is not particularly limited as long as it is a compound having two or more sites that react with the dispersant, but preferably has two or more epoxy groups from the viewpoint of excellent reactivity with a carboxyl group.
- a compound having bifunctionality (a bifunctional or higher functional epoxy compound) is preferred. Specific examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl.
- Examples include ether and trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether are preferable.
- the molar ratio of the crosslinking site of the crosslinking agent to the crosslinked site of the dispersant is preferably from 1: 1.1 to 1:10, from the viewpoint of the crosslinking reaction rate and the dispersion stability after crosslinking, 1: 5 is more preferable, and 1: 1.1 to 1: 3 is most preferable.
- a pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin can be produced by the method described in JP-A-2009-190379.
- the mixing mass ratio (p: s) between the carbon black pigment (p) and the dispersant (s) is not particularly limited, and can be appropriately selected according to the dispersion method and the like.
- a range of 1: 0.06 to 1: 3 is preferable, a range of 1: 0.125 to 1: 1 is more preferable, and a range of 1: 0.125 to 1: 0.7 is more preferable.
- the average particle size of the carbon black pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 40 to 150 nm.
- the particle size distribution of the carbon black pigment aqueous dispersion is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. In some embodiments, only one or a mixture of two or more carbon black pigment aqueous dispersions having a monodisperse particle size distribution may be used.
- the average particle diameter of the carbon black pigment in a dispersed state means the average particle diameter in an ink state. The same applies to the average particle size of the carbon black pigment in the so-called concentrated ink dispersion before ink conversion.
- the average particle size and particle size distribution of the carbon black pigment in the dispersed state were measured by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). It is calculated
- Carbon black pigment There is no restriction
- TEM2010 transmission electron microscope TEM2010 (trade name, pressurization voltage 200 kV) manufactured by JEOL Ltd.
- the pH of the carbon black pigment is preferably in the acidic to neutral range because easy dispersibility is obtained, more preferably pH 2.0 to pH 8.5, and pH 2.5 to pH 8.0. It is particularly preferred.
- the pH of the carbon black pigment is measured as the pH (25 ° C.) of the aqueous dispersion of the carbon black pigment.
- the DBP absorption amount of the carbon black pigment is not particularly limited, but is preferably 30 ml / 100 g or more and 200 ml / 100 g or less, and more preferably 50 ml / 100 g or more and 150 ml / 100 g or less from the viewpoint of color tone and printing density. .
- the DBP absorption is measured by JIS K6221 A method.
- the BET specific surface area of the carbon black pigment is not particularly limited, but is preferably 30 m 2 / g or more and 450 m 2 / g or less, and 200 m 2 / g or more and 400 m 2 / g or less from the viewpoint of printing density and storage stability. It is more preferable that
- Examples of the carbon black pigment include those produced by known methods such as a contact method, a furnace method, and a thermal method. Specific examples include, for example, Raven7000, Raven5750, Raven5250, Raven5000ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1190 ULTRAII, Raven1170, Raven1255, Raven10, Raven10 REGAL400R, REGAL330R, REGAL660R, MOGUL L, BLACK PEARLS L, MONARCH 700, MONARCH 800, MONARCH 880, MONARCH 900, MONARCH 1000, MONARCH 1100, MONARCH 1300, M NARCH 1400 (above, manufactured by Cabot Corporation), COLOR BLACK FW1, COLOR BLACK FW2, COLOR BLACK FW2V, COLOR BLACK 18, COLOR BLACK FW200, COLOR BLACK S150, COLOR BLACK TE 160, COLOR BLTE TE 160, COLOR BLS PRINTE
- the above carbon black pigments may be used singly or in combination of two or more.
- the content of the carbon black pigment with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.5 to 4% by mass from the viewpoint of adhesion to a recording medium, abrasion resistance, and print density. 0.8 to 2% by mass is more preferable.
- the colored pigment aqueous dispersion is typically obtained by dispersing the colored pigment in an aqueous medium.
- the color pigment dispersion step is not particularly limited as long as at least one color pigment selected from a magenta pigment, a cyan pigment, and a yellow pigment can be dispersed in an aqueous medium, and a commonly used dispersion method is appropriately selected and applied. can do.
- an aqueous colored pigment dispersion can be obtained by mixing at least one dispersing agent and at least one coloring pigment in an aqueous medium and dispersing the resulting mixture.
- the dispersant, the mixing method, and the dispersion treatment method are as described above.
- the colored pigment is dispersed to prepare an aqueous colored pigment dispersion, and an ink composition is produced using the dispersion.
- a black ink composition that can be more excellent in dispersion stability and ejection stability can be produced.
- This effect can be considered to be obtained because, for example, the aqueous pigment dispersion can be made into a better dispersion state according to the type of pigment.
- the manufacturing method it is possible to select more appropriate dispersion conditions depending on the type of pigment.
- the color pigment dispersion step may be a step of mixing and co-dispersing two or more types of color pigments for each color pigment. It may be a step of monodisperse processing. In an embodiment, from the viewpoint of ejection stability, it is preferable to prepare an aqueous colored pigment dispersion for each colored pigment.
- the color pigment dispersion step uses the water-insoluble resin having the acidic group as a dispersant, obtains a mixture containing the color pigment, a neutralizing agent, water, and a water-soluble organic solvent, and disperses the mixture. And a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step.
- an aqueous colored pigment dispersion that can be excellent in dispersion stability can be obtained.
- the dispersant may be water-insolubilized by crosslinking the dispersant using a cross-linking agent to produce a dispersion. This is a preferred embodiment.
- the details of the color pigment dispersion step are the same as those in the carbon black dispersion step, and the preferred embodiments are also the same.
- the average particle diameter of the colored pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 40 to 150 nm.
- the particle size distribution of the color pigment aqueous dispersion is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. In an embodiment, the color pigment aqueous dispersion having a monodisperse particle size distribution may be used alone or in combination of two or more.
- the colored pigment in the present invention is at least one selected from a magenta pigment, a cyan pigment, and a yellow pigment.
- the magenta pigment, cyan pigment, and yellow pigment can be appropriately selected from known organic pigments according to the purpose. Specific examples of the organic pigment are shown below.
- magenta pigments examples include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I.
- cyan pigments examples include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment Green 7, and siloxane-crosslinked aluminum phthalocyanine described in US Pat. No. 4,311,775.
- C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. preferably at least one selected from CI Pigment Blue 16.
- yellow pigment examples include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 185.
- C.I. I. Pigment yellow 74 C.I. I. Pigment yellow 155, C.I. I. It is preferably at least one selected from Pigment Yellow 185.
- the color pigment preferably contains at least one magenta pigment and at least one cyan pigment from the viewpoint of adhesion to a recording medium.
- the content of the color pigment relative to the total mass of the carbon black pigment and the color pigment is not particularly limited. From the viewpoints of adhesion to a recording medium, abrasion resistance, and ejection properties, the content is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass.
- the content of the magenta pigment (magenta pigment / cyan pigment) with respect to the content of the cyan pigment in the ink composition is not particularly limited. From the viewpoints of adhesion to a recording medium, abrasion resistance, and color tone, it is preferably 100% by mass or more and 180% by mass or less, and more preferably 120% by mass or more and 150% by mass or less.
- the mixture obtained in the mixing step may or may not be filtered.
- the method for the filtration treatment is not particularly limited, and any of atmospheric filtration, pressure filtration, suction filtration and the like may be used.
- the filter medium used for filtration is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include filter paper and membrane filter.
- a water-soluble polymerizable compound is used for mixing.
- water-soluble means a property that can be dissolved in water so as to have a certain concentration or more.
- the solubility in water at 25 ° C. is preferably 5% by mass or more, and more preferably 10% by mass or more.
- the water-soluble polymerizable compound is preferably one that can be dissolved (desirably uniformly) in the aqueous ink composition.
- the solubility may be increased by adding a water-soluble organic solvent to be described later, and it may be dissolved (desirably uniformly) in the ink composition or not.
- the water-soluble polymerizable compound preferably contains at least one selected from the group consisting of a compound having a (meth) acrylic ester structure in the molecule and a compound having a (meth) acrylamide structure in the molecule. It is more preferable to contain at least one compound having a (meth) acrylamide structure.
- the (meth) acrylic ester structure means at least one of a methacrylic ester structure and an acrylic ester structure
- the (meth) acrylamide structure means at least one of a methacrylamide structure and an acrylamide structure.
- the polymerizable compound having a (meth) acrylic ester structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylic ester structure in the molecule.
- the polymerizable compound having a (meth) acrylic ester structure in the molecule is preferably a compound represented by the following general formula (M-1).
- Q 1 represents an i-valent linking group
- R 1 represents a hydrogen atom or a methyl group
- I represents an integer of 1 or more.
- Compound represented by the general formula (M-1) are those unsaturated monomer bonded to the linking group Q 1 by an ester bond.
- R 1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- the valence i of the linking group Q 1 preferably 2 or more, more preferably 2 to 6 or less, still more preferably 2 to 4.
- the linking group Q 1 is not particularly limited as long as it is a group that can be linked to the (meth) acrylic ester structure, but is selected from the linking groups such that the compound represented by the general formula (M-1) satisfies the aforementioned water solubility. It is preferred that Specific examples include residues from which one or more hydrogen atoms or hydroxyl groups have been removed from the following compound group X.
- Still linking group Q 1 methylene, ethylene, propylene, 4 or less of the substituted or unsubstituted alkylene chain of carbon atoms such as butylene group, more pyridine ring, an imidazole ring, a pyrazine ring, piperidine ring, piperazine ring, morpholine ring Examples thereof include a functional group having a saturated or unsaturated heterocyclic ring.
- the linking group Q 1 is preferably a residue of a polyol containing an oxyalkylene group (preferably an oxyethylene group), and contains three or more oxyalkylene groups (preferably an oxyethylene group).
- a residue of a polyol is particularly preferable.
- water-soluble polymerizable compound (M-1) having a (meth) acrylic ester structure in the molecule include, for example, the following nonionic compounds, but the present application is not limited thereto.
- nonionic polymerizable compound a (meth) acrylic acid ester having two or more acryloyl groups in one molecule derived from a polyol compound can also be used.
- the polyol compound include polyol compounds having two or more hydroxyl groups such as glycol condensates, oligoethers, oligoesters, monosaccharides, and disaccharides.
- (meth) acrylic acid esters with triethanolamine, diethanolamine, trishydroxyaminomethane, trishydroxyaminoethane, etc. are also suitable.
- water-soluble polymerizable compound (M-1) having a (meth) acrylic ester structure in the molecule include the following cationic compounds. It is not limited.
- R represents a residue of a polyol compound.
- X represents H or CH 3
- a ⁇ represents Cl ⁇ , HSO 4 — or CH 3 COO — .
- the polyol compound include glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, trimethylolpropane, trimethylolmethane, trimethylolethane, penta Examples include erythritol, bisphenol A, alicyclic bisphenol A, and condensates thereof.
- the following structures (cationic compounds 1 to 11) can also be exemplified as the polymerizable compound having a cationic group.
- the compound having a (meth) acrylamide structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylamide structure in the molecule.
- the compound having a (meth) acrylamide structure in the molecule is preferably a compound represented by the following general formula (M-2). Having the structure of the formula (M-2) is preferable because the compatibility between the compound represented by the general formula (1) described later and the polymerizable compound is improved, and the curing sensitivity and the like can be increased.
- Q 2 represents a j-valent linking group
- R 2 represents a hydrogen atom or a methyl group
- J represents an integer of 1 or more.
- the compound represented by formula (M-2) are those unsaturated monomers, bonded to the linking group Q 2 by an amide bond.
- R 2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- the linking group Q is not limited to two valence j, preferably 2 or more, more preferably 2 to 6 or less, still more preferably 2 to 4.
- the connecting group Q 2 is not particularly limited as long as it is capable of linking groups and (meth) acrylamide structure. Details of the linking group Q 2 is the same as the linking group Q 1, preferred embodiment is also the same.
- water-soluble polymerizable compound having a (meth) acrylamide structure in the molecule include the following water-soluble polymerizable compounds.
- a compound having a maleimide structure represented by the following a compound having a sulfamide structure, a compound having an N-vinylacetamide structure, or the like can be used.
- a water-soluble polymeric compound can be contained individually by 1 type or in combination of 2 or more types.
- the content of the polymerizable compound in the ink composition is preferably 3 to 50% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass with respect to the total mass of the ink composition.
- the polymerization initiator is preferably at least one water-soluble polymerization initiator.
- water-soluble means to dissolve 0.5% by mass or more in distilled water at 25 ° C.
- the water-soluble polymerization initiator is preferably dissolved at 1% by mass or more in distilled water at 25 ° C., more preferably at least 3% by mass.
- water-soluble polymerization initiator examples include compounds represented by the following general formula (1), compounds described in JP-A-2005-307198, and the like. Of these, a water-soluble polymerization initiator represented by the following general formula (1) is preferable from the viewpoints of adhesion to a recording medium and abrasion resistance.
- n and n each independently represents an integer of 0 or more, and m + n represents an integer of 0 to 3. It is preferable that m is 0 to 3 and n is 0 or 1, and it is more preferable that m is 0 or 1 and n is 0. Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
- the compound represented by the general formula (1) may be a newly synthesized compound or a commercially available compound.
- the content of the polymerization initiator with respect to the total mass of the ink composition is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 20% by mass, and 1.0%. It is more preferably in the range of ⁇ 15% by mass, most preferably in the range of 1.0 to 7.0% by mass.
- Water-soluble organic solvent In the mixing step, it is preferable that at least one water-soluble organic solvent is further subjected to mixing.
- a water-soluble organic solvent in the black ink composition, it is possible to obtain an effect of preventing drying, wetting or promoting penetration.
- the water-soluble organic solvent can function as an anti-drying agent that prevents the ink from adhering and drying to form aggregates at the ink discharge port of the ejection nozzle, thereby preventing clogging.
- a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
- the water-soluble organic solvent can function as a penetration enhancer that enhances ink permeability to paper.
- water-soluble organic solvents examples include alkanediols (polyhydric alcohols) such as glycerin, ethylene glycol, and propylene glycol; sugar alcohols; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol
- alkanediols polyhydric alcohols
- sugar alcohols alkyl alcohols having 1 to 4 carbon atoms
- alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol
- Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propy
- the mixing step further includes subjecting at least one surfactant to further mixing.
- the surfactant can be used as a surface tension adjusting agent.
- As the surface tension modifier a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used effectively.
- Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic properties Either a surfactant or a betaine surfactant can be used.
- a nonionic surfactant is preferable from the viewpoint of suppression of droplet ejection interference of the ink composition, and an acetylene glycol surfactant is more preferable.
- acetylene glycol surfactant examples include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7.
- -Alkylene oxide adducts of diols can be mentioned, and at least one selected from these is preferable.
- Examples of commercially available products of these compounds include E series such as Olphine E1010 (product names) manufactured by Nissin Chemical Industry Co., Ltd.
- the surfactant content is determined from the surface tension of the ink composition from the viewpoint of favorably discharging the ink composition by an ink jet method.
- the amount is preferably in the range of 20 to 60 mN / m, more preferably 20 to 45 mN / m, and further preferably 25 to 40 mN / m from the viewpoint of surface tension.
- the specific amount of the surfactant in the black ink composition of the surfactant is not particularly limited except that the surface tension is preferably within a range, and is preferably 0.1% by mass or more, more preferably 0. 0.1 to 10% by mass, more preferably 0.2 to 3% by mass.
- the method for producing a black ink composition of the present invention preferably includes a step of further mixing at least one colloidal silica.
- the step of mixing colloidal silica may be performed simultaneously with the mixing step or may be performed independently of the mixing step.
- the black ink composition contains colloidal silica
- the effect can be recognized particularly when silicon is used in at least a part of the ink jet head member.
- the ink composition contains colloidal silica
- the hydrolysis of the ink component is effectively suppressed, and the stability of the ink composition is improved, so that the ejection of the ink composition on the ink jet recording apparatus is stopped and fixed. It is presumed that even when the ink is left for a period of time and then the discharge is restarted, excellent discharge stability (stand-by recovery performance) can be obtained, and at the same time, the rub resistance of the image can be achieved.
- colloidal silica is moderately adsorbed on the surface of the ink jet head member to reduce the erosion of the ink jet head member surface by the ink component, thereby preventing the liquid repellency of the ink jet head member from being lowered.
- Colloidal silica is a colloid composed of inorganic oxide fine particles having an average particle size of several hundred nm or less and containing silicon. Silicon dioxide (including hydrates thereof) may be included as a main component, and aluminate may be included as a minor component. Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.
- colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.
- the colloidal silica dispersion medium is not particularly limited and may be water, an organic solvent, or a mixture thereof.
- the organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent, but is preferably a water-soluble organic solvent. Specific examples include methanol, ethanol, isopropyl alcohol, n-propanol and the like.
- colloidal silica is not particularly limited, and can be produced by a commonly used method.
- it can be produced from aerosil synthesis by thermal decomposition of silicon tetrachloride or water glass.
- it can also be produced by a liquid phase synthesis method such as hydrolysis of alkoxide (for example, see “Fiber and Industry”, Vol. 60, No. 7 (2004) P376).
- the average particle size of the particles contained in the colloidal silica is not particularly limited, but is typically 1 nm to 25 nm, preferably 3 nm to 25 nm, more preferably 3 nm to 20 nm, and further preferably 3 nm to 15 nm. Particularly preferred is 5 nm to 10 nm.
- damage for example, decrease in liquid repellency
- members constituting the inkjet head such as a base material, a protective film, a liquid repellent film, and the like is more effectively performed. Can be suppressed.
- the average particle diameter of the particles being 25 nm or less may be suitable from the viewpoint of the dischargeability of the ink composition and the abrasive effect of the particles.
- productivity can improve that an average particle diameter is 1 nm or more, and colloidal silica with few dispersion
- the average particle size of the colloidal silica particles can be measured by a method such as a light scattering method or a laser diffraction method, which is a general measurement of dispersed particles.
- a TEM transmission electron microscope
- the particle diameters of 300 colloidal silica particles were measured by the photographing method, and the average value was taken as the average particle diameter.
- the shape of the colloidal silica particles is not particularly limited as long as it does not hinder the ejection performance of the ink composition. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used. Among them, the spherical shape is preferable from the viewpoint of ink ejection.
- the colloidal silica may be produced by the above production method or may be a commercially available product.
- Commercially available products include, for example, Ludox AM, Ludox AS, Ludox LS, Ludox TM, Ludox HS, etc. (all registered trademarks, manufactured by EI Du Pont de Nemours &Co); SNOWTEX S, SNOWTEX XS , Snowtex 20, Snowtex 30, Snowtex 40, Snowtex N, Snowtex C, Snowtex O, etc. (all registered trademarks, manufactured by Nissan Chemical Co., Ltd.); Syton C-30, Symantec ZOO, etc.
- colloidal silica examples include SNOWTEX ST-UP, SNOWTEX PS-S, SNOWTEX PS-M, SNOWTEX ST-OUP, SNOWTEX PS-SO, and SNOWTEX PS.
- -MO manufactured by Nissan Chemical Co., Ltd.
- the pH of the above commercially available colloidal silica dispersion is often adjusted to be acidic or alkaline. This is because the stable dispersion region of colloidal silica exists on the acidic side or alkaline side.
- a commercially available colloidal silica dispersion is added to the ink composition, it must be added in consideration of the pH of the stable dispersion region of the colloidal silica and the pH of the ink composition.
- the colloidal silica content in the ink composition is not particularly limited, but is preferably 0.005% by mass to 0.5% by mass of the total amount of the ink composition, and more preferably 0.005% of the total amount of the ink composition. It is preferably from 0.01% by weight to 0.1% by weight, particularly preferably from 0.01% by weight to 0.1% by weight of the total amount of the ink composition.
- the content in the ink composition is not more than the above upper limit value, the dischargeability of the ink composition can be further improved, and the influence on the ink jet head due to the abrasive effect of the silica particles can be more effectively suppressed. .
- the fall of the liquid repellency of an inkjet head member can be suppressed more effectively because it is more than the said lower limit.
- the ink composition is made of colloidal silica having an average particle size (TEM imaging method) of 3 nm to 25 nm from the viewpoint of suppressing the decrease in liquid repellency of an ink jet head member and good ink ejection properties.
- the total amount is preferably 0.005% to 0.5% by mass, and the colloidal silica having an average particle size of 3 nm to 15 nm is preferably included in the total amount of the ink composition from 0.005% to 0.1% by mass. More preferred.
- the content ratio of colloidal silica to the polymerizable compound (colloidal silica / polymerizable compound) in the ink composition is preferably 0.0001 to 0.1, and preferably 0.001 to 0.05 on a mass basis. It is more preferable.
- the content ratio of colloidal silica with respect to the polymerizable compound is 0.0001 or more, a decrease in liquid repellency of the inkjet head member can be more effectively suppressed.
- discharge property can improve more because it is 0.1 or less.
- the black ink composition may contain resin particles as necessary.
- the resin particles may be subjected to mixing at the same time in the mixing step, or may be contained in the ink composition by being subjected to mixing independently of the mixing step.
- the resin particles fix the ink composition by increasing the viscosity of the ink by aggregation or dispersion instability when contacted with the treatment liquid or the region on the dried recording medium after the treatment liquid is applied. It is preferable to have a function (that is, fix an image).
- the resin particles are preferably used in a form dispersed in at least one of water and an organic solvent.
- Resin particles include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, butadiene resins, styrene resins, crosslinked acrylic resins, crosslinked styrene resins, and benzoguanamine resins.
- a phenol resin, a silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluorine resin, or a latex thereof can be used.
- Preferred examples include acrylic resins, acrylic-styrene resins, styrene resins, cross-linked acrylic resins, and cross-linked styrene resins.
- the resin particles can also be used in the form of latex.
- the weight average molecular weight of the resin particles is preferably 10,000 or more and 200,000 or less, more preferably 20,000 or more and 200,000 or less.
- the average particle size of the resin particles is preferably in the range of 1 nm to 1 ⁇ m, more preferably in the range of 1 nm to 200 nm, still more preferably in the range of 1 nm to 100 nm, and particularly preferably in the range of 1 nm to 50 nm.
- the glass transition temperature Tg of the resin particles is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
- the content of the resin particles with respect to the total mass of the black ink composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass.
- the particle size distribution of the resin fine particles is not particularly limited, and may be any having a wide particle size distribution or a monodispersed particle size distribution. Resin particles having a monodispersed particle size distribution may be used alone or in combination of two or more.
- the black ink composition may further contain various additives as other components, if necessary, in addition to the above components.
- Various additives may be used for mixing at the same time in the mixing step, or may be contained in the ink composition by being used for mixing independently of the mixing step.
- the various additives include, for example, ultraviolet absorbers, antifading agents, antifungal agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, preservatives, antifoaming agents, viscosity modifiers, and dispersions.
- Known additives such as stabilizers or chelating agents can be used.
- the content of these additives may be appropriately determined according to the application, but may be, for example, about 0.02 to 1.00% by mass with respect to the total mass of the black ink composition.
- UV absorbers examples include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, nickel complex salt UV absorbers, and the like.
- organic and metal complex anti-fading agents can be used as the anti-fading agent.
- organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and metal complexes.
- nickel complex, zinc complex and the like there are nickel complex, zinc complex and the like.
- antifungal agent examples include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, sodium sorbate, pentachlorophenol Sodium etc. are mentioned.
- the pH adjuster is not particularly limited as long as it can adjust the pH to a desired value without adversely affecting the ink composition to be prepared, and can be appropriately selected according to the purpose.
- alcohol amines eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol
- alkali metal hydroxides eg, lithium hydroxide, sodium hydroxide, potassium hydroxide) Etc.
- ammonium hydroxide for example, ammonium hydroxide, quaternary ammonium hydroxide, etc.
- phosphonium hydroxide alkali metal carbonate and the like.
- rust preventive examples include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
- antioxidants examples include phenolic antioxidants (including hindered phenolic antioxidants), amine antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
- chelating agent examples include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like.
- the surface tension (25 ° C.) of the ink composition is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 40 mN / m or less.
- the surface tension is measured using an Automatic Surface Tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) under the condition of 25 ° C.
- the viscosity of the ink composition at 25 ° C. is preferably 1.2 mPa ⁇ s or more and 15.0 mPa ⁇ s or less, more preferably 2 mPa ⁇ s or more and less than 13 mPa ⁇ s, and still more preferably 2 It is not less than 5 mPa ⁇ s and less than 10 mPa ⁇ s.
- the viscosity is measured using a VISCOMETER TV-22 (trade name, manufactured by TOKI SANGYO CO. LTD) under conditions of 25 ° C. of the ink composition.
- an aggregate can be formed by applying the black ink composition on a recording medium by an ink jet method and contacting the ink composition. Including applying a treatment liquid containing an aggregating agent on the recording medium, and irradiating the ink composition applied on the recording medium with an active energy ray to cure the ink image, and others as necessary An image forming method that can include these steps can be given.
- the black ink composition is applied onto a recording medium by an ink jet method.
- the ink composition can be selectively applied onto the recording medium, and a desired image can be formed.
- the inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method
- a charge control method that discharges ink using electrostatic attraction
- a drop-on-demand method that uses vibration pressure of a piezoelectric element
- An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure
- a thermal ink jet bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. )
- Any method may be used.
- ink jet method a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent ink are used. The method is included.
- An ink jet head used in the ink jet method may be an on-demand method or a continuous method.
- Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (eg, thermal ink jet type) Specific examples include, for example, bubble jet (registered trademark) type, electrostatic attraction type (eg, electric field control type, slit jet type), and discharge type (eg, spark jet type). Any discharge method may be used.
- the ink nozzles used when recording by the inkjet method There are no particular restrictions on the ink nozzles used when recording by the inkjet method, and they can be appropriately selected according to the purpose.
- a short serial head is used, and a recording method is arranged in correspondence with a shuttle method in which recording is performed while the head is scanned in the width direction of the recording medium, and the entire area of one side of the recording medium.
- an image can be recorded on the entire surface of the recording medium by scanning the recording medium in a direction orthogonal to the arrangement direction of the recording elements, and a carriage system such as a carriage for scanning a short head is not necessary.
- the recording speed can be increased as compared with the shuttle system.
- the ink jet recording method can be applied to any of these, but generally, when applied to a line system that does not use a dummy jet, the effect of improving ejection accuracy and image scratch resistance can be increased.
- the amount of ink droplets ejected from the inkjet head is preferably 0.5 to 6 pl (picoliter), more preferably 1 to 5 pl, and still more preferably 2 to 4 pl from the viewpoint of obtaining a high-definition image.
- a treatment liquid containing an aggregating agent capable of forming an aggregate by contact with the ink composition is applied to the recording medium, and the treatment liquid is contacted with the ink composition to form an image.
- the treatment liquid comes into contact with the ink composition, dispersed particles such as resin particles and pigment in the ink composition are aggregated, and the image is fixed on the recording medium. Details and preferred embodiments of each component in the treatment liquid will be described later.
- the treatment liquid can be applied by applying a known method such as a coating method, an inkjet method, or an immersion method.
- a coating method include known coating methods using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and the like.
- the details of the inkjet method are as described above.
- the treatment liquid may be applied either before or after the ink composition is applied to the recording medium.
- a mode in which the ink is applied onto the recording medium after the treatment liquid is applied onto the recording medium in the treatment liquid applying step is preferable. That is, before applying (discharging) the ink composition to the recording medium by the ink jet method, a processing liquid capable of aggregating the pigment in the ink composition is applied in advance, and the processing liquid applied on the recording medium is applied.
- An embodiment in which an image is formed by discharging the ink composition so as to come into contact with the ink is preferable. Thereby, inkjet recording can be speeded up, and an image with high density and resolution can be obtained even at high speed recording.
- the amount of treatment liquid applied is not particularly limited as long as the ink composition can be agglomerated, but it can be preferably an amount such that the amount of aggregating agent applied is 0.1 g / m 2 or more.
- the amount of the flocculant applied is preferably 0.1 to 1.0 g / m 2 , more preferably 0.2 to 0.8 g / m 2 .
- the amount of the aggregating component applied is 0.1 g / m 2 or more, the aggregating reaction can proceed satisfactorily, and when it is 1.0 g / m 2 or less, the glossiness can be suppressed from becoming too high.
- the treatment liquid contains at least one aggregating agent capable of forming an aggregate by contact with the black ink composition.
- the treatment liquid may or may not contain other components as required.
- the flocculant is capable of aggregating (fixing) components in the ink composition by contacting the ink composition on the recording medium, and functions as a fixing agent, for example.
- a fixing agent for example, by applying the treatment liquid to a recording medium (preferably coated paper), the ink composition is further deposited on the recording medium in a state where the aggregating agent is present on the recording medium, By contacting, the components in the ink composition can be aggregated, and the ink composition components can be fixed on the recording medium.
- the flocculant include acidic compounds, polyvalent metal salts, and cationic polymers. Among these, an acidic compound is preferable from the viewpoint of improving the cohesiveness of the ink composition component.
- a flocculant may be used individually by 1 type, or may use 2 or more types together.
- acidic compounds include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. , Lactic acid, sulfonic acid, orthophosphoric acid, metaphosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, and derivatives of these compounds, etc. Preferably mentioned.
- acidic compounds with high water solubility are preferable.
- a trivalent or less acidic compound is preferable, and a divalent or trivalent acidic compound is particularly preferable.
- An acidic compound may be used individually by 1 type, and may use 2 or more types together.
- the pH (25 ° C.) of the treatment liquid is preferably 0.1 to 6.8, more preferably 0.5 to 6.0, and 0.8 More preferably, it is -5.0.
- the content of the acidic compound is preferably 40% by mass or less, more preferably 15 to 40% by mass, and more preferably 15 to 35% by mass with respect to the total mass of the treatment liquid. Further preferred. By setting the content of the acidic compound to 40% by mass or less, the components in the ink composition can be more efficiently fixed.
- the treatment liquid preferably contains at least one water-soluble organic solvent in addition to the flocculant.
- the details of the water-soluble organic solvent are the same as those in the ink composition, and the preferred embodiments are also the same.
- the treatment liquid may or may not contain other additives as other components as long as the effects of the present invention are not impaired.
- additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, anti-foaming agents.
- Well-known additives such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned.
- ink is applied after the treatment liquid is applied, and the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied on the recording medium and before the ink composition is applied. It is preferable. By heating and drying the treatment liquid in advance before the ink application step, ink colorability such as bleeding prevention is improved, and a visible image with good color density and hue can be recorded.
- Heat drying can be performed by a known heating means such as a heater, a blowing means using blowing air such as a dryer, or a combination of these.
- a heating method for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, an infrared heater was used.
- the heating method etc. are mentioned, One of these may be used or you may heat combining a plurality.
- the image forming method preferably removes at least a part of the solvent in the ink composition by heating the ink image formed by applying the ink composition onto a recording medium after the ink ejection.
- heat-drying treatment it is possible to form an image having better adhesion to a recording medium and an abrasion resistance of an image formed by a subsequent curing step.
- the method of heating is not particularly limited, but a non-contact drying method such as a method of heating with a heating element such as a nichrome wire heater, a method of supplying warm air or hot air, a method of heating with a halogen lamp, an infrared lamp, etc. Preferably, it can be mentioned.
- the image forming method preferably includes irradiating the ink composition applied on the recording medium with an active energy ray and curing.
- the curing step of irradiating the active energy ray is a step of irradiating the ink image formed by applying the ink composition with, for example, ultraviolet rays from an ultraviolet irradiation lamp.
- the monomer component (water-soluble polymerizable compound) in the image can be surely polymerized and cured.
- the ultraviolet irradiation lamp is disposed opposite the recording surface of the recording medium and the entire recording surface is irradiated, the entire image can be cured.
- the light source for irradiating the active energy ray is not limited to the ultraviolet irradiation lamp, but a halogen lamp, a high-pressure mercury lamp, a laser, an LED, an electron beam irradiation apparatus, or the like can also be adopted.
- the curing step of irradiating the active energy ray may be placed before or after the heat drying as long as it is after ink application and treatment liquid application, and may be performed both before and after the heat drying.
- the irradiation condition of the active energy ray is not particularly limited as long as the polymerizable compound can be polymerized and cured.
- the wavelength of the active energy ray is preferably, for example, 200 to 600 nm, more preferably 300 to 450 nm, and further preferably 350 to 420 nm.
- the output of the active energy ray is preferably at 5000 mJ / cm 2 or less, more preferably 10 ⁇ 4000mJ / cm 2, further preferably 20 ⁇ 3000mJ / cm 2.
- the image forming method of the present invention records an image on a recording medium.
- the recording medium is not particularly limited, and general printing paper mainly composed of cellulose, such as so-called high-quality paper, coated paper, and art paper, used for general offset printing and the like can be used.
- General printing paper mainly composed of cellulose is relatively slow in ink absorption and drying in image recording by a general ink jet method using water-based ink, and color material movement is likely to occur after droplet ejection, and image quality is likely to deteriorate.
- the image forming method using the ink set the movement of the color material can be suppressed, and a high-quality image excellent in color density and hue can be recorded.
- the recording medium commercially available media can be used.
- Fine paper (A) such as “New NPI Fine” manufactured by Oji Paper Co., Ltd., “OK Everlight Coat” manufactured by Oji Paper Co., Ltd., and “Aurora S” manufactured by Nippon Paper Industries Co., Ltd., Oji Paper Co., Ltd.
- Lightweight coated paper (A3) such as “OK Coat L” manufactured by Nippon Paper Industries Co., Ltd. and “Aurora L” manufactured by Nippon Paper Industries Co., Ltd.
- the water absorption coefficient Ka of the recording medium is preferably 0.05 to 0 from the viewpoint that the effect of suppressing the movement of the coloring material is large and that a high-quality image with better color density and hue than before can be obtained. .5 in a mL / m 2 ⁇ ms 1/2, more preferably 0.1 ⁇ 0.4mL / m 2 ⁇ ms 1/2, more preferably 0.2 ⁇ 0.3mL / m 2 ⁇ ms 1/2 .
- the water absorption coefficient Ka is synonymous with that described in JAPANJTAPPI paper pulp test method No 51: 2000 (issued by Japan Paper Pulp Technology Association).
- the absorption coefficient Ka is an automatic scanning absorption meter. It is calculated from the difference in the amount of water transferred between the contact time of 100 ms and the contact time of 900 ms using KM500Win (manufactured by Kumagai Riki Co., Ltd.).
- coated paper used for general offset printing is preferable.
- the coated paper is obtained by applying a coating material to the surface of high-quality paper, neutral paper, or the like that is mainly surface-treated with cellulose as a main component and is not generally surface-treated.
- the coated paper tends to cause quality problems such as image gloss and scratch resistance in image formation by a normal aqueous inkjet, but the inkjet recording method can suppress gloss unevenness, gloss and abrasion resistance.
- An image with good properties can be obtained.
- the composition of the obtained water-insoluble resin P-1 was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 49400. Furthermore, when the acid value of this water-insoluble resin was determined by the method described in JIS standard (JIS K 0070: 1992), it was 84.8 mgKOH / g.
- a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Seisakusho) was used to centrifuge at a capacity of 50 mL. Centrifugal treatment was performed at 8000 rpm for 30 minutes using a spear, and the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion-exchanged water was added to obtain a carbon black pigment aqueous dispersion CB1 as a dispersion of resin-coated pigment particles (encapsulated pigment) having a pigment concentration of 15% by mass.
- Pigment Dispersion 2 was obtained as follows. 13.6 parts of carbon black pigment, 6.2 parts of the dispersant P-2, 9.3 parts of 1 mol / L NaOH aqueous solution, and 70.9 parts of ion-exchanged water were mixed, and 0. Dispersion was performed for 3 hours using 1 mm ⁇ zirconia beads. Thereafter, 0.87 part of trimethylolpropane triglycidyl ether and 0.38 part of boric acid were added and reacted at 60 ° C. for 6 hours, followed by cooling. Further, a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Corporation) was used.
- aqueous carbon black pigment dispersion CB2 as a dispersion of resin-coated pigment particles having a carbon black concentration of 13% by mass. It was 92 nm when the volume average particle diameter was measured by the method similar to the above.
- the pigment concentration was determined from the absorbance spectrum, and ion exchange water was added to obtain an aqueous carbon black pigment dispersion CB3 having a carbon black concentration of 10.0% by mass.
- the volume average particle size was measured by the same method as described above, it was 90 nm.
- a colored pigment aqueous dispersion C1 was obtained in the same manner as described above except that in the preparation of the aqueous carbon black pigment dispersion 1, Pigment Blue 15: 3 was used instead of the carbon black pigment. It was 93 nm when the volume average particle diameter was measured by the method similar to the above.
- a colored pigment aqueous dispersion M1 was obtained in the same manner as described above except that in the preparation of the colored pigment dispersion C1, Pigment Red 122 was used instead of Pigment Blue 15: 3. It was 78 nm when the volume average particle diameter was measured by the method similar to the above.
- Colored pigment aqueous dispersion Y1 was obtained in the same manner as described above except that in the preparation of Pigment Dispersion 1, Pigment Yellow 74 was used instead of Pigment Blue 15: 3. It was 95 nm when the volume average particle diameter was measured by the method similar to the above.
- the aqueous layer was extracted four times with 200 ml of ethyl acetate, and the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain 35.0 g of the target polymerizable compound 2 solid. (107 mmol, 59% yield).
- Example 1> Carbon black pigment aqueous dispersion CB1 obtained above, colored pigment aqueous dispersion C1, polymerizable compound 2, colloidal silica (Snowtex XS (registered trademark), average particle size 5 nm, Nissan Chemical Industries, Ltd. Each component was mixed so as to have the following ink composition. This was packed in a plastic disposable syringe and filtered through a PVDF 5 ⁇ m filter (Millex-SV (registered trademark), diameter 25 mm, manufactured by Millipore) to prepare a black ink composition Bk-1.
- PVDF 5 ⁇ m filter Millex-SV (registered trademark), diameter 25 mm, manufactured by Millipore
- Example 2 the black ink composition Bk was used in the same manner as in Example 1 except that the types and addition amounts of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion were changed so as to have the formulation shown in Table 1. -2 to 6 were prepared respectively. In Table 1, the addition amounts of the carbon black pigment and the color pigment each mean solid mass.
- Example 7 A black ink composition Bk-7 was prepared in the same manner as in Example 4 except that the polymerizable compound 5 was used in place of the polymerizable compound 2 in Example 4.
- Example 8 the black ink composition Bk-8 was prepared in the same manner as in Example 4 except that Zonyl FSN (registered trademark, manufactured by DuPont) was used instead of the surfactant Olfine E1010 (described above). Prepared.
- Zonyl FSN registered trademark, manufactured by DuPont
- Example 1 the black ink composition Bk-9 was prepared in the same manner as in Example 1 except that the addition amount of the carbon black pigment aqueous dispersion CB1 was changed to 20% without using the color pigment aqueous dispersion. Prepared.
- the component of the following composition was mixed and the processing liquid 1 was prepared.
- the treatment liquid 1 had a viscosity of 2.5 mPa ⁇ s, a surface tension of 40 mN / m, and a pH of 1.0 at 25 ° C.
- the surface tension is measured using a fully automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.), and the viscosity is measured using DV-III Ultra CP (trade name, manufactured by Brookfield Engineering). did.
- the pH was measured using a PH meter HM-30R (trade name, manufactured by Toa DKK Corporation).
- An ink jet head provided with a silicon nozzle plate was prepared, and the black ink composition obtained above was refilled in a storage tank connected thereto.
- the silicon nozzle plate is previously provided with a liquid repellent film using a fluorinated alkylsilane compound.
- “OK Top Coat +” (trade name, manufactured by Oji Paper Co., Ltd., basis weight 104.7 g / m 2 ) as a recording medium is cut into A5 size and on a stage that can move in a predetermined linear direction at 500 mm / sec. The stage temperature was kept at 30 ° C.
- the treatment liquid 1 obtained above was applied to this with a bar coater so as to have a thickness of about 1.2 ⁇ m, and was dried at 50 ° C. for 2 seconds immediately after the application. Thereafter, the inkjet head is fixedly arranged so that the direction of the line head in which the nozzles are arranged (main scanning direction) is inclined by 75.7 degrees with respect to the direction orthogonal to the moving direction of the stage (sub-scanning direction), and recording is performed.
- a solid image is obtained by ejecting ink over the entire surface of the recording medium in a line system under the ejection conditions of an ink droplet amount of 2.8 pL, an ejection frequency of 25.5 kHz, a resolution of 1200 dpi ⁇ 1200 dpi while moving the medium at a constant speed in the sub-scanning direction Formed. After the image was recorded, while being heated with an infrared heater from the back side (back side) of the ink landing surface, warm air of 120 ° C. and 5 m / sec was applied to the recording surface for 15 seconds and dried.
- UV light was irradiated from a metal halide lamp (manufactured by Eye Graphics Co., Ltd., maximum irradiation wavelength 365 nm) so as to obtain an integrated irradiation amount of 3 J / cm 2 , and the image was cured to obtain a print sample.
- a metal halide lamp manufactured by Eye Graphics Co., Ltd., maximum irradiation wavelength 365 nm
- the obtained print sample was visually observed to confirm that ink was ejected from all nozzles. After this line image is formed, the head is left as it is for a predetermined time, and then a new recording medium is attached to the stage, and ink is discharged again under the same conditions as above to print a print sample (line image). Produced.
- the obtained print sample (line image) was visually observed, and after standing for a predetermined time, 2000 ink droplets were ejected, and the standing restorability was evaluated using the maximum standing time during which all 96 nozzles could be ejected as an index. . The longer the standing time during which no ejection failure occurred, the better the ejection performance, and the evaluation was based on the following evaluation criteria. The evaluation results are shown in Table 1.
- a method for producing a black ink composition for ink jet recording capable of forming an image which can be excellent in ejection stability and can be excellent in adhesion to a recording medium.
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Abstract
A process for producing a black ink composition for inkjet recording, which comprises: preparing an aqueous carbon black pigment dispersion containing a carbon black pigment as a pigment; preparing an aqueous colored pigment dispersion containing at least one colored pigment selected from the group consisting of a magenta pigment as a pigment, a cyan pigment and a yellow pigment; and mixing the aqueous carbon black pigment dispersion, the aqueous colored pigment dispersion, a water-soluble polymerizable compound and a polymerization initiator together.
Description
本発明は、黒色系インク組成物の製造方法に関する。
The present invention relates to a method for producing a black ink composition.
インクジェット技術は、オフィスプリンタ、ホームプリンタ等の分野においてカラー画像を記録する画像記録方法として適用されてきた。インクジェットに用いられるインク成分の着色剤として顔料が広く用いられている。中でも黒色系インクにはカーボンブラックが用いられることが多い。
Inkjet technology has been applied as an image recording method for recording color images in the fields of office printers, home printers, and the like. A pigment is widely used as a colorant for an ink component used in inkjet. Of these, carbon black is often used for black ink.
カーボンブラックを用いた黒色系インク組成物は、カーボンブラックに加えて着色顔料を併用することで色相改良が可能とされている(例えば、特開2000-318293号公報参照)。
有機溶剤系UV硬化型インクについては、保存安定性及び硬化性改良のために黒インクにフタロシアニン誘導体を含有させることが検討されている(例えば、特開2005-264098号公報参照)。
一方、環境負荷軽減のためには水性インクが好ましいが、水性顔料インクは耐擦過性などが必ずしも十分でないため、最近では、紫外線硬化型の水性顔料インクの検討がなされている。 A black ink composition using carbon black is capable of improving the hue by using a color pigment in combination with carbon black (see, for example, JP 2000-318293 A).
Regarding organic solvent-based UV curable inks, it has been studied to add a phthalocyanine derivative to black ink in order to improve storage stability and curability (see, for example, JP-A-2005-264098).
On the other hand, water-based inks are preferable for reducing the environmental load. However, since water-based pigment inks do not necessarily have sufficient scratch resistance and the like, recently, ultraviolet curable water-based pigment inks have been studied.
有機溶剤系UV硬化型インクについては、保存安定性及び硬化性改良のために黒インクにフタロシアニン誘導体を含有させることが検討されている(例えば、特開2005-264098号公報参照)。
一方、環境負荷軽減のためには水性インクが好ましいが、水性顔料インクは耐擦過性などが必ずしも十分でないため、最近では、紫外線硬化型の水性顔料インクの検討がなされている。 A black ink composition using carbon black is capable of improving the hue by using a color pigment in combination with carbon black (see, for example, JP 2000-318293 A).
Regarding organic solvent-based UV curable inks, it has been studied to add a phthalocyanine derivative to black ink in order to improve storage stability and curability (see, for example, JP-A-2005-264098).
On the other hand, water-based inks are preferable for reducing the environmental load. However, since water-based pigment inks do not necessarily have sufficient scratch resistance and the like, recently, ultraviolet curable water-based pigment inks have been studied.
特開2000-318293号公報、および特開2005-264098号公報に記載のインク組成物では、画像を形成した場合に記録媒体に対する十分な密着性が得られない場合があった。また特開2005-264098号公報に記載の顔料誘導体は、カーボンブラック顔料の分散性向上に寄与するものであって、着色を目的としたいわゆる顔料とは本質的に異なるものである。
In the ink compositions described in Japanese Patent Application Laid-Open Nos. 2000-318293 and 2005-264098, sufficient adhesion to a recording medium may not be obtained when an image is formed. The pigment derivative described in JP-A-2005-264098 contributes to the improvement of the dispersibility of the carbon black pigment, and is essentially different from a so-called pigment intended for coloring.
本発明は、吐出安定性に優れ得るとともに、記録媒体への密着性に優れる画像を形成し得るインクジェット記録用の黒色系インク組成物の製造方法を提供する。
The present invention provides a method for producing a black ink composition for ink-jet recording, which can be excellent in ejection stability and can form an image excellent in adhesion to a recording medium.
前記課題を解決するための具体的手段は以下の通りである。
<1> カーボンブラック顔料を顔料として含むカーボンブラック顔料水性分散物を得ることと、マゼンタ顔料、シアン顔料およびイエロー顔料からなる群から選ばれる少なくとも1種の着色顔料を顔料として含む着色顔料水性分散物を得ることと、前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、水溶性の重合性化合物、および重合開始剤を混合することと、を含むインクジェット記録用の黒色系インク組成物の製造方法。 Specific means for solving the above problems are as follows.
<1> Obtaining an aqueous carbon black pigment dispersion containing a carbon black pigment as a pigment, and an aqueous pigment dispersion containing at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment as a pigment And mixing a carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, a water-soluble polymerizable compound, and a polymerization initiator, to produce a black ink composition for inkjet recording Method.
<1> カーボンブラック顔料を顔料として含むカーボンブラック顔料水性分散物を得ることと、マゼンタ顔料、シアン顔料およびイエロー顔料からなる群から選ばれる少なくとも1種の着色顔料を顔料として含む着色顔料水性分散物を得ることと、前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、水溶性の重合性化合物、および重合開始剤を混合することと、を含むインクジェット記録用の黒色系インク組成物の製造方法。 Specific means for solving the above problems are as follows.
<1> Obtaining an aqueous carbon black pigment dispersion containing a carbon black pigment as a pigment, and an aqueous pigment dispersion containing at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment as a pigment And mixing a carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, a water-soluble polymerizable compound, and a polymerization initiator, to produce a black ink composition for inkjet recording Method.
<2> 前記カーボンブラック顔料水性分散物および着色顔料水性分散物の少なくとも1種は、表面の少なくとも一部が酸性基を有する水不溶性樹脂で被覆された顔料を含む、前記<1>に記載の黒色系インク組成物の製造方法。
<2> At least one of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion contains a pigment coated with a water-insoluble resin having an acidic group on at least a part of the surface thereof. A method for producing a black ink composition.
<3> 前記着色顔料水性分散物は、マゼンタ顔料およびシアン顔料からなる群から選ばれる少なくとも1種の着色顔料を含む、前記<1>または<2>に記載の黒色系インク組成物の製造方法。
<3> The method for producing a black ink composition according to <1> or <2>, wherein the colored pigment aqueous dispersion contains at least one color pigment selected from the group consisting of a magenta pigment and a cyan pigment. .
<4> 前記重合開始剤は、下記一般式(1)で表される化合物である、前記<1>~<3>のいずれか1項に記載の黒色系インク組成物の製造方法。
<4> The method for producing a black ink composition according to any one of <1> to <3>, wherein the polymerization initiator is a compound represented by the following general formula (1).
(式中、mおよびnはそれぞれ独立に0以上の整数を表し、m+nは0~3の整数を表す)
(In the formula, m and n each independently represent an integer of 0 or more, and m + n represents an integer of 0 to 3)
<5> コロイダルシリカを前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、前記水溶性の重合性化合物、および前記重合開始剤と混合することをさらに含む、前記<1>~<4>のいずれか1項に記載の黒色系インク組成物の製造方法。
<5> The above <1> to <4>, further comprising mixing colloidal silica with the carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator. The manufacturing method of the black-type ink composition of any one of these.
<6> 前記カーボンブラック顔料水性分散物および前記着色顔料水性分散物からなる群から選ばれる少なくとも1種に含まれる顔料の体積平均二次粒子径が40nm~150nmである、前記<1>~<5>のいずれか1項に記載の黒色系インク組成物の製造方法。
<6> The volume average secondary particle diameter of the pigment contained in at least one selected from the group consisting of the carbon black pigment aqueous dispersion and the color pigment aqueous dispersion is 40 nm to 150 nm, <1> to < 5. A method for producing a black ink composition according to any one of 5>.
<7> アセチレングリコール系界面活性剤を前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、前記水溶性の重合性化合物、および前記重合開始剤と混合することをさらに含む、前記<1>~<6>のいずれか1項に記載の黒色系インク組成物の製造方法。
<7> The above-mentioned <1>, further comprising mixing an acetylene glycol surfactant with the carbon black pigment aqueous dispersion, the colored pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator. The method for producing a black ink composition according to any one of to <6>.
<8> 前記<1>~<7>のいずれか1項に記載の製造方法で製造された黒色系インク組成物。
<8> A black ink composition produced by the production method according to any one of <1> to <7>.
本発明によれば、吐出安定性に優れるとともに、記録媒体への密着性に優れる画像を形成可能なインクジェット記録用の黒色系インク組成物の製造方法を提供し得る。
According to the present invention, it is possible to provide a method for producing a black ink composition for ink jet recording capable of forming an image having excellent ejection stability and excellent adhesion to a recording medium.
本開示において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない工程であってもその工程の所期の作用を達成するものであれば、その範囲に包含する。本開示において「X~Y」の形式で示された数値範囲(X、Yは数値)は、Xを最小値、Yを最大値として含む範囲を意味する。
In the present disclosure, the term “step” includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step is achieved. To do. In the present disclosure, a numerical range (X and Y are numerical values) indicated in the format of “X to Y” means a range including X as a minimum value and Y as a maximum value.
<黒色系インク組成物の製造方法>
本発明のインクジェット記録用の黒色系インク組成物(以下、単に「インク組成物」ともいう)の製造方法は、カーボンブラック顔料を顔料として含むカーボンブラック顔料水性分散物を得ることと、マゼンタ顔料、シアン顔料およびイエロー顔料からなる群から選ばれる少なくとも1種の着色顔料を顔料として含む着色顔料水性分散物を得ることと、前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、水溶性の重合性化合物、および重合開始剤を混合することと、を少なくとも含む。前記製造方法は、必要に応じてその他の工程をさらに含んでもよく含まなくてもよい。 <Method for producing black ink composition>
The method for producing a black ink composition for ink jet recording of the present invention (hereinafter also simply referred to as “ink composition”) includes obtaining a carbon black pigment aqueous dispersion containing a carbon black pigment as a pigment, a magenta pigment, Obtaining an aqueous dispersion of a colored pigment containing, as a pigment, at least one color pigment selected from the group consisting of a cyan pigment and a yellow pigment, the aqueous dispersion of the carbon black pigment, the aqueous dispersion of the colored pigment, and a water-soluble polymerization Mixing the active compound and the polymerization initiator. The manufacturing method may or may not include other steps as necessary.
本発明のインクジェット記録用の黒色系インク組成物(以下、単に「インク組成物」ともいう)の製造方法は、カーボンブラック顔料を顔料として含むカーボンブラック顔料水性分散物を得ることと、マゼンタ顔料、シアン顔料およびイエロー顔料からなる群から選ばれる少なくとも1種の着色顔料を顔料として含む着色顔料水性分散物を得ることと、前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、水溶性の重合性化合物、および重合開始剤を混合することと、を少なくとも含む。前記製造方法は、必要に応じてその他の工程をさらに含んでもよく含まなくてもよい。 <Method for producing black ink composition>
The method for producing a black ink composition for ink jet recording of the present invention (hereinafter also simply referred to as “ink composition”) includes obtaining a carbon black pigment aqueous dispersion containing a carbon black pigment as a pigment, a magenta pigment, Obtaining an aqueous dispersion of a colored pigment containing, as a pigment, at least one color pigment selected from the group consisting of a cyan pigment and a yellow pigment, the aqueous dispersion of the carbon black pigment, the aqueous dispersion of the colored pigment, and a water-soluble polymerization Mixing the active compound and the polymerization initiator. The manufacturing method may or may not include other steps as necessary.
前記製造方法は、カーボンブラック顔料の水性分散物を得る工程とは独立して、マゼンタ顔料、シアン顔料およびイエロー顔料からなる群から選ばれる少なくとも1種の着色顔料を含む水性分散物を得る工程を含むことで、吐出安定性に優れ得る黒色系インク組成物を製造することができる。また記録媒体上に付与された該黒色系インク組成物に活性エネルギー線を照射して硬化させることで、記録媒体への密着性に優れ得る画像を形成可能となる。これらの効果は例えば、顔料としてカーボンブラック顔料のみを用いる場合に比べて、インク組成物の硬化感度が向上することに起因すると考えることができる。
The manufacturing method comprises a step of obtaining an aqueous dispersion containing at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment, independently of the step of obtaining an aqueous dispersion of a carbon black pigment. By including, a black ink composition that can be excellent in ejection stability can be produced. Further, by irradiating the black ink composition applied on the recording medium with an active energy ray and curing it, an image having excellent adhesion to the recording medium can be formed. These effects can be attributed to, for example, an improvement in the curing sensitivity of the ink composition as compared with the case where only the carbon black pigment is used as the pigment.
[カーボンブラック分散工程]
カーボンブラック顔料水性分散物は、典型的には、カーボンブラック顔料を水性媒体中に分散する工程により得ることができる。
カーボンブラック分散工程は、カーボンブラック顔料を水性媒体中に分散可能であれば特に制限されず、通常用いられる分散方法を適宜選択して適用することができる。
例えば、水性媒体中で分散剤の少なくとも1種とカーボンブラック顔料の少なくとも1種とを混合し、得られた混合物を分散処理することでカーボンブラック顔料水性分散物を得ることができる。 [Carbon black dispersion process]
The aqueous dispersion of carbon black pigment is typically obtained by a step of dispersing the carbon black pigment in an aqueous medium.
The carbon black dispersion step is not particularly limited as long as the carbon black pigment can be dispersed in an aqueous medium, and a commonly used dispersion method can be appropriately selected and applied.
For example, an aqueous carbon black pigment dispersion can be obtained by mixing at least one dispersant and at least one carbon black pigment in an aqueous medium, and dispersing the resulting mixture.
カーボンブラック顔料水性分散物は、典型的には、カーボンブラック顔料を水性媒体中に分散する工程により得ることができる。
カーボンブラック分散工程は、カーボンブラック顔料を水性媒体中に分散可能であれば特に制限されず、通常用いられる分散方法を適宜選択して適用することができる。
例えば、水性媒体中で分散剤の少なくとも1種とカーボンブラック顔料の少なくとも1種とを混合し、得られた混合物を分散処理することでカーボンブラック顔料水性分散物を得ることができる。 [Carbon black dispersion process]
The aqueous dispersion of carbon black pigment is typically obtained by a step of dispersing the carbon black pigment in an aqueous medium.
The carbon black dispersion step is not particularly limited as long as the carbon black pigment can be dispersed in an aqueous medium, and a commonly used dispersion method can be appropriately selected and applied.
For example, an aqueous carbon black pigment dispersion can be obtained by mixing at least one dispersant and at least one carbon black pigment in an aqueous medium, and dispersing the resulting mixture.
混合方法、分散処理する方法は特に制限されず、一般に用いられる混合攪拌装置や、必要に応じて超音波分散機、高圧ホモジナイザー、ボールミル、ロールミル、高速攪拌型分散機等の分散装置を用いることができる。
The mixing method and the dispersion treatment method are not particularly limited, and a commonly used mixing and stirring device, and a dispersing device such as an ultrasonic dispersing machine, a high-pressure homogenizer, a ball mill, a roll mill, and a high-speed stirring type dispersing machine may be used as necessary. it can.
前記分散剤は、ポリマー分散剤、又は低分子の界面活性剤型分散剤のいずれでもよい。ポリマー分散剤は、水溶性の分散剤、又は非水溶性の分散剤のいずれでもよい。
前記低分子の界面活性剤型分散剤としては、通常用いられる低分子界面活性剤を特に制限なく用いることができる。 The dispersant may be either a polymer dispersant or a low molecular surfactant type dispersant. The polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.
As the low molecular surfactant type dispersant, a commonly used low molecular surfactant can be used without particular limitation.
前記低分子の界面活性剤型分散剤としては、通常用いられる低分子界面活性剤を特に制限なく用いることができる。 The dispersant may be either a polymer dispersant or a low molecular surfactant type dispersant. The polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.
As the low molecular surfactant type dispersant, a commonly used low molecular surfactant can be used without particular limitation.
前記ポリマー分散剤のうち、水溶性分散剤としては、親水性高分子化合物が挙げられる。例えば、天然の親水性高分子化合物では、アラビアガム、トラガンガム、グアーガム、カラヤガム、ローカストビーンガム、アラビノガラクトン、ペクチン、クインスシードデンプン等の植物性高分子、アルギン酸、カラギーナン、寒天等の海藻系高分子、ゼラチン、カゼイン、アルブミン、コラーゲン等の動物系高分子、キサンテンガム、デキストラン等の微生物系高分子等が挙げられる。
Among the polymer dispersants, examples of the water-soluble dispersant include hydrophilic polymer compounds. For example, natural hydrophilic polymer compounds include plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, seaweeds such as alginic acid, carrageenan and agar. Examples include molecules, animal polymers such as gelatin, casein, albumin and collagen, and microorganism polymers such as xanthene gum and dextran.
天然物を原料に修飾した親水性高分子化合物では、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース等の繊維素系高分子、デンプングリコール酸ナトリウム、デンプンリン酸エステルナトリウム等のデンプン系高分子、アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等の海藻系高分子等が挙げられる。
For hydrophilic polymer compounds modified from natural products, fiber polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose, starch starches such as sodium starch glycolate and sodium phosphate phosphate Examples include molecules, seaweed polymers such as sodium alginate and propylene glycol alginate.
合成系の親水性高分子化合物としては、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル等のビニル系高分子、非架橋ポリアクリルアミド、ポリアクリル酸又はそのアルカリ金属塩、水溶性スチレンアクリル樹脂等のアクリル系樹脂、水溶性スチレンマレイン酸樹脂、水溶性ビニルナフタレンアクリル樹脂、水溶性ビニルナフタレンマレイン酸樹脂、ポリビニルピロリドン、ポリビニルアルコール、β-ナフタレンスルホン酸ホルマリン縮合物のアルカリ金属塩、四級アンモニウムやアミノ基等のカチオン性官能基の塩を側鎖に有する高分子化合物、セラック等の天然高分子化合物等が挙げられる。
Synthetic hydrophilic polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamides, polyacrylic acid or alkali metal salts thereof, and acrylics such as water-soluble styrene acrylic resins. Resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalene sulfonic acid formalin condensate, quaternary ammonium, amino group, etc. And a polymer compound having a cationic functional group salt in the side chain, a natural polymer compound such as shellac, and the like.
これらの中でも、アクリル酸、メタクリル酸、スチレンアクリル酸等のホモポリマーや、他の親水基を有するモノマーとの共重合体などのように、カルボキシル基が導入された水溶性分散剤が親水性高分子化合物として好ましい。
Among these, water-soluble dispersants introduced with carboxyl groups such as homopolymers such as acrylic acid, methacrylic acid, and styrene acrylic acid, and copolymers with monomers having other hydrophilic groups are highly hydrophilic. Preferred as a molecular compound.
ポリマー分散剤のうち非水溶性分散剤としては、疎水性構成単位と親水性構成単位とを有する水不溶性樹脂を用いることができる。前記親水性構成単位としては、酸性基を有する構成単位が好ましく、カルボキシル基を有する構成単位がより好ましい。
水不溶性樹脂としては、例えば、スチレン-(メタ)アクリル酸共重合体、スチレン-(メタ)アクリル酸-(メタ)アクリル酸エステル共重合体、(メタ)アクリル酸エステル-(メタ)アクリル酸共重合体、ポリエチレングリコール(メタ)アクリレート-(メタ)アクリル酸共重合体、酢酸ビニル-マレイン酸共重合体、スチレン-マレイン酸共重合体等が挙げられる。
より具体的には例えば、特開2005-41994号公報、特開2006-273891号公報、特開2009-084494号公報、特開2009-191134等に記載の水不溶性樹脂を好適に用いることができる。 As the water-insoluble dispersant among the polymer dispersants, a water-insoluble resin having a hydrophobic constituent unit and a hydrophilic constituent unit can be used. As the hydrophilic structural unit, a structural unit having an acidic group is preferable, and a structural unit having a carboxyl group is more preferable.
Examples of water-insoluble resins include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer. Examples thereof include a polymer, a polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymer, a vinyl acetate-maleic acid copolymer, and a styrene-maleic acid copolymer.
More specifically, for example, water-insoluble resins described in JP-A-2005-41994, JP-A-2006-273891, JP-A-2009-084494, JP-A-2009-191134, and the like can be suitably used. .
水不溶性樹脂としては、例えば、スチレン-(メタ)アクリル酸共重合体、スチレン-(メタ)アクリル酸-(メタ)アクリル酸エステル共重合体、(メタ)アクリル酸エステル-(メタ)アクリル酸共重合体、ポリエチレングリコール(メタ)アクリレート-(メタ)アクリル酸共重合体、酢酸ビニル-マレイン酸共重合体、スチレン-マレイン酸共重合体等が挙げられる。
より具体的には例えば、特開2005-41994号公報、特開2006-273891号公報、特開2009-084494号公報、特開2009-191134等に記載の水不溶性樹脂を好適に用いることができる。 As the water-insoluble dispersant among the polymer dispersants, a water-insoluble resin having a hydrophobic constituent unit and a hydrophilic constituent unit can be used. As the hydrophilic structural unit, a structural unit having an acidic group is preferable, and a structural unit having a carboxyl group is more preferable.
Examples of water-insoluble resins include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer. Examples thereof include a polymer, a polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymer, a vinyl acetate-maleic acid copolymer, and a styrene-maleic acid copolymer.
More specifically, for example, water-insoluble resins described in JP-A-2005-41994, JP-A-2006-273891, JP-A-2009-084494, JP-A-2009-191134, and the like can be suitably used. .
前記カーボンブラック分散工程は、分散剤として酸性基を有する水不溶性樹脂を用い、これとカーボンブラック顔料、中和剤、水、および該水不溶性樹脂を溶解または分散可能な水溶性有機溶剤を含む混合物を得る工程と、前記混合物を分散処理する工程と、分散処理工程後に水溶性有機溶剤の少なくとも一部を除去する工程と、を含むことが好ましい。かかる分散処理方法であることで、顔料表面のすくなくとも一部が酸性基を有する水不溶性樹脂によって被覆され、分散安定性に優れ得るカーボンブラック顔料水性分散物を得ることができる。
このような分散方法は一般的に転相乳化法と呼ばれている。転相乳化法の詳細については、例えば特開平10-140065号公報、特開平11-209672号公報、特開平11-172180号公報等の記載を参照することができる。 The carbon black dispersion step uses a water-insoluble resin having an acidic group as a dispersant, and a mixture containing the carbon black pigment, a neutralizing agent, water, and a water-soluble organic solvent capable of dissolving or dispersing the water-insoluble resin. Preferably, the method includes a step of dispersing the mixture, a step of dispersing the mixture, and a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step. By such a dispersion treatment method, it is possible to obtain an aqueous carbon black pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin having an acidic group and can be excellent in dispersion stability.
Such a dispersion method is generally called a phase inversion emulsification method. For details of the phase inversion emulsification method, reference can be made to, for example, descriptions in JP-A-10-140065, JP-A-11-209672, JP-A-11-172180, and the like.
このような分散方法は一般的に転相乳化法と呼ばれている。転相乳化法の詳細については、例えば特開平10-140065号公報、特開平11-209672号公報、特開平11-172180号公報等の記載を参照することができる。 The carbon black dispersion step uses a water-insoluble resin having an acidic group as a dispersant, and a mixture containing the carbon black pigment, a neutralizing agent, water, and a water-soluble organic solvent capable of dissolving or dispersing the water-insoluble resin. Preferably, the method includes a step of dispersing the mixture, a step of dispersing the mixture, and a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step. By such a dispersion treatment method, it is possible to obtain an aqueous carbon black pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin having an acidic group and can be excellent in dispersion stability.
Such a dispersion method is generally called a phase inversion emulsification method. For details of the phase inversion emulsification method, reference can be made to, for example, descriptions in JP-A-10-140065, JP-A-11-209672, JP-A-11-172180, and the like.
転相乳化に用いられる水不溶性樹脂は、自己分散性、及び後述する処理液が接触したときの凝集速度の観点から、カルボキシル基を有する水不溶性樹脂を含むことが好ましく、カルボキシル基を有し、酸価が100mgKOH/g以下の水不溶性樹脂であることが好ましく、25~100mgKOH/gの水不溶性樹脂を含むことがより好ましい。特に前記インク組成物をインク組成物中の成分を凝集させる処理液と組み合わせて用いる場合には、カルボキシル基を有し、かつ酸価が25~100mgKOH/gのポリマー分散剤が有効であり得る。
The water-insoluble resin used for phase inversion emulsification preferably contains a water-insoluble resin having a carboxyl group, from the viewpoint of self-dispersibility and the aggregation rate when the treatment liquid described below comes into contact, and has a carboxyl group, A water-insoluble resin having an acid value of 100 mgKOH / g or less is preferable, and a water-insoluble resin having an acid value of 25 to 100 mgKOH / g is more preferable. In particular, when the ink composition is used in combination with a treatment liquid that aggregates the components in the ink composition, a polymer dispersant having a carboxyl group and having an acid value of 25 to 100 mgKOH / g may be effective.
前記水不溶性樹脂の重量平均分子量は、3,000~100,000が好ましく、より好ましくは5,000~50,000であり、更に好ましくは5,000~40,000であり、特に好ましくは10,000~40,000である。
The weight average molecular weight of the water-insoluble resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 40,000, and particularly preferably 10 , 40,000.
転相乳化法における混合方法、分散処理する方法は特に制限されず、一般に用いられる混合攪拌装置や、必要に応じて超音波分散機、高圧ホモジナイザー、ボールミル、ロールミル、高速攪拌型分散機等の分散装置を用いることができる。
The mixing method and the dispersion method in the phase inversion emulsification method are not particularly limited. Dispersion of a generally used mixing and stirring device, ultrasonic dispersing machine, high-pressure homogenizer, ball mill, roll mill, high-speed stirring type dispersing machine, etc. An apparatus can be used.
溶剤除去工程には、特に制限はなく、減圧蒸留等の常法により有機溶剤を留去する方法等を適用することができる。このとき水溶性有機溶剤の少なくとも一部に加えて、水の一部が除去されてもよい。
水溶性有機溶剤を除去して水系へと転相することで、カーボンブラックの粒子表面の少なくとも一部が、水不溶性樹脂で被覆された樹脂被覆カーボンブラック粒子の分散物を得ることができる。得られた分散物は、有機溶剤が実質的に除去された状態であることが好ましい。その有機溶剤の量は、好ましくは0.2質量%以下であり、更に好ましくは0.1質量%以下である。 There is no restriction | limiting in particular in a solvent removal process, The method etc. which distill off an organic solvent by conventional methods, such as vacuum distillation, are applicable. At this time, in addition to at least a part of the water-soluble organic solvent, a part of the water may be removed.
By removing the water-soluble organic solvent and carrying out phase inversion to an aqueous system, a dispersion of resin-coated carbon black particles in which at least a part of the surface of the carbon black particles is coated with a water-insoluble resin can be obtained. The obtained dispersion is preferably in a state in which the organic solvent is substantially removed. The amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.
水溶性有機溶剤を除去して水系へと転相することで、カーボンブラックの粒子表面の少なくとも一部が、水不溶性樹脂で被覆された樹脂被覆カーボンブラック粒子の分散物を得ることができる。得られた分散物は、有機溶剤が実質的に除去された状態であることが好ましい。その有機溶剤の量は、好ましくは0.2質量%以下であり、更に好ましくは0.1質量%以下である。 There is no restriction | limiting in particular in a solvent removal process, The method etc. which distill off an organic solvent by conventional methods, such as vacuum distillation, are applicable. At this time, in addition to at least a part of the water-soluble organic solvent, a part of the water may be removed.
By removing the water-soluble organic solvent and carrying out phase inversion to an aqueous system, a dispersion of resin-coated carbon black particles in which at least a part of the surface of the carbon black particles is coated with a water-insoluble resin can be obtained. The obtained dispersion is preferably in a state in which the organic solvent is substantially removed. The amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.
転相乳化法に用いられる水溶性有機溶剤は、前記水不溶性樹脂を溶解または分散可能であれば特に制限されず、水不溶性樹脂に応じて適宜選択できる。具体的は例えば、アルコール系溶剤、ケトン系溶剤、及びエーテル系溶剤が好ましく挙げられる。前記アルコール系溶剤としては、イソプロピルアルコール、n-ブタノール、t-ブタノール、エタノール等が挙げられる。前記ケトン系溶剤としては、アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン等が挙げられる。前記エーテル系溶剤としては、ジブチルエーテル、ジオキサン等が挙げられる。これらの溶媒の中では、メチルエチルケトン等のケトン系溶剤とイソプロピルアルコール等のアルコール系溶剤が好ましく、メチルエチルケトン等のケトン系溶剤がさらに好ましい。
The water-soluble organic solvent used in the phase inversion emulsification method is not particularly limited as long as the water-insoluble resin can be dissolved or dispersed, and can be appropriately selected according to the water-insoluble resin. Specific examples include alcohol solvents, ketone solvents, and ether solvents. Examples of the alcohol solvent include isopropyl alcohol, n-butanol, t-butanol, ethanol and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone. Examples of the ether solvent include dibutyl ether and dioxane. Among these solvents, ketone solvents such as methyl ethyl ketone and alcohol solvents such as isopropyl alcohol are preferable, and ketone solvents such as methyl ethyl ketone are more preferable.
前記中和剤は、酸性基の一部又は全部が中和され、水不溶性樹脂が水中で安定した乳化状態又は分散状態を形成するために用いられる。
中和剤としては、例えば、アルコールアミン類(例えば、ジエタノールアミン、トリエタノールアミン、2-アミノ-2-エチル-1,3プロパンジオールなど)、アルカリ金属水酸化物(例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなど)、アンモニウム水酸化物(例えば、水酸化アンモニウム、第4級アンモニウム水酸化物)、ホスホニウム水酸化物、アルカリ金属炭酸塩などが挙げられ、水酸化ナトリウム、水酸化カリウムが好適に用いられる。 The neutralizing agent is used to form an emulsified state or a dispersed state in which a part or all of acidic groups are neutralized and the water-insoluble resin is stable in water.
Examples of the neutralizing agent include alcohol amines (eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol), alkali metal hydroxides (eg, lithium hydroxide, hydroxide) Sodium, potassium hydroxide, etc.), ammonium hydroxide (eg, ammonium hydroxide, quaternary ammonium hydroxide), phosphonium hydroxide, alkali metal carbonate, etc. Preferably used.
中和剤としては、例えば、アルコールアミン類(例えば、ジエタノールアミン、トリエタノールアミン、2-アミノ-2-エチル-1,3プロパンジオールなど)、アルカリ金属水酸化物(例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなど)、アンモニウム水酸化物(例えば、水酸化アンモニウム、第4級アンモニウム水酸化物)、ホスホニウム水酸化物、アルカリ金属炭酸塩などが挙げられ、水酸化ナトリウム、水酸化カリウムが好適に用いられる。 The neutralizing agent is used to form an emulsified state or a dispersed state in which a part or all of acidic groups are neutralized and the water-insoluble resin is stable in water.
Examples of the neutralizing agent include alcohol amines (eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol), alkali metal hydroxides (eg, lithium hydroxide, hydroxide) Sodium, potassium hydroxide, etc.), ammonium hydroxide (eg, ammonium hydroxide, quaternary ammonium hydroxide), phosphonium hydroxide, alkali metal carbonate, etc. Preferably used.
また、前記カーボンブラック顔料分散工程は、「顔料表面の少なくとも一部が水不溶性樹脂で被覆された顔料分散物」を得る方法として、顔料を水溶性もしくは水不溶性の分散剤を用いて分散した後に、架橋剤を用いて分散剤を架橋することにより水溶性の分散剤を水不溶化して顔料分散物を作製する方法であることもまた好ましい。
前記分散剤としてはポリビニル類、ポリウレタン類、ポリエステル類等が挙げられるが、その中でもポリビニル類が好ましい。
前記分散剤は、分子内に、架橋剤により架橋可能な官能基を有することが必要である。該架橋可能な官能基としては、特に限定されず、カルボキシル基またはその塩、イソシアナート基、エポキシ基等が挙げられるが、分散性向上の観点からカルボキシル基またはその塩を有していることが好ましい。 In addition, the carbon black pigment dispersion step is a method for obtaining “a pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin”, and after dispersing the pigment using a water-soluble or water-insoluble dispersant. It is also preferable that the pigment dispersion is prepared by crosslinking the dispersant with a crosslinking agent to insolubilize the water-soluble dispersant.
Examples of the dispersant include polyvinyls, polyurethanes, polyesters, etc. Among them, polyvinyls are preferable.
The dispersant needs to have a functional group that can be crosslinked by a crosslinking agent in the molecule. The crosslinkable functional group is not particularly limited, and examples thereof include a carboxyl group or a salt thereof, an isocyanate group, an epoxy group, and the like. From the viewpoint of improving dispersibility, the functional group may have a carboxyl group or a salt thereof. preferable.
前記分散剤としてはポリビニル類、ポリウレタン類、ポリエステル類等が挙げられるが、その中でもポリビニル類が好ましい。
前記分散剤は、分子内に、架橋剤により架橋可能な官能基を有することが必要である。該架橋可能な官能基としては、特に限定されず、カルボキシル基またはその塩、イソシアナート基、エポキシ基等が挙げられるが、分散性向上の観点からカルボキシル基またはその塩を有していることが好ましい。 In addition, the carbon black pigment dispersion step is a method for obtaining “a pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin”, and after dispersing the pigment using a water-soluble or water-insoluble dispersant. It is also preferable that the pigment dispersion is prepared by crosslinking the dispersant with a crosslinking agent to insolubilize the water-soluble dispersant.
Examples of the dispersant include polyvinyls, polyurethanes, polyesters, etc. Among them, polyvinyls are preferable.
The dispersant needs to have a functional group that can be crosslinked by a crosslinking agent in the molecule. The crosslinkable functional group is not particularly limited, and examples thereof include a carboxyl group or a salt thereof, an isocyanate group, an epoxy group, and the like. From the viewpoint of improving dispersibility, the functional group may have a carboxyl group or a salt thereof. preferable.
前記分散剤としては、共重合成分としてカルボキシル基含有モノマーを用いて得られる共重合体であることが好ましい。カルボキシル基含有モノマーとしては、(メタ)アクリル酸、β-カルボキシエチルアクリレート、フマル酸、イタコン酸、マレイン酸、クロトン酸等が挙げられ、中でも、架橋性および分散安定性の観点から、(メタ)アクリル酸やβ-カルボキシエチルアクリレートが好ましい。尚、(メタ)アクリル酸はアクリル酸およびメタクリル酸の少なくとも一方を意味する。
前記共重合成分は疎水性モノマーの少なくとも1種を含むことが好ましい。疎水性モノマーとしては、炭素数1~20のアルキル(メタ)アクリレート、ベンジル(メタ)アクリレートやフェノキシエチル(メタ)アクリレート等の芳香環基を有する(メタ)アクリレート、ならびに、スチレンおよびその誘導体等を挙げることができる。 The dispersant is preferably a copolymer obtained using a carboxyl group-containing monomer as a copolymerization component. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, β-carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid and the like. Among these, from the viewpoint of crosslinkability and dispersion stability, (meth) Acrylic acid and β-carboxyethyl acrylate are preferred. (Meth) acrylic acid means at least one of acrylic acid and methacrylic acid.
The copolymer component preferably contains at least one hydrophobic monomer. Examples of hydrophobic monomers include alkyl (meth) acrylates having 1 to 20 carbon atoms, (meth) acrylates having an aromatic ring group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and styrene and its derivatives. Can be mentioned.
前記共重合成分は疎水性モノマーの少なくとも1種を含むことが好ましい。疎水性モノマーとしては、炭素数1~20のアルキル(メタ)アクリレート、ベンジル(メタ)アクリレートやフェノキシエチル(メタ)アクリレート等の芳香環基を有する(メタ)アクリレート、ならびに、スチレンおよびその誘導体等を挙げることができる。 The dispersant is preferably a copolymer obtained using a carboxyl group-containing monomer as a copolymerization component. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, β-carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid and the like. Among these, from the viewpoint of crosslinkability and dispersion stability, (meth) Acrylic acid and β-carboxyethyl acrylate are preferred. (Meth) acrylic acid means at least one of acrylic acid and methacrylic acid.
The copolymer component preferably contains at least one hydrophobic monomer. Examples of hydrophobic monomers include alkyl (meth) acrylates having 1 to 20 carbon atoms, (meth) acrylates having an aromatic ring group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and styrene and its derivatives. Can be mentioned.
前記分散剤は、共重合成分として、カルボキシル基含有モノマーと、炭素数1~20のアルキル(メタ)アクリレートおよび芳香環基を有する(メタ)アクリレートの少なくとも一方とを用いて得られる共重合体であることが好ましい。
分散剤としての共重合体の合成方法は特に限定されないが、ビニルモノマーのランダム重合が分散安定性の点で好ましい。 The dispersant is a copolymer obtained by using a carboxyl group-containing monomer and at least one of an alkyl (meth) acrylate having 1 to 20 carbon atoms and a (meth) acrylate having an aromatic ring group as a copolymerization component. Preferably there is.
The method for synthesizing the copolymer as a dispersant is not particularly limited, but random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.
分散剤としての共重合体の合成方法は特に限定されないが、ビニルモノマーのランダム重合が分散安定性の点で好ましい。 The dispersant is a copolymer obtained by using a carboxyl group-containing monomer and at least one of an alkyl (meth) acrylate having 1 to 20 carbon atoms and a (meth) acrylate having an aromatic ring group as a copolymerization component. Preferably there is.
The method for synthesizing the copolymer as a dispersant is not particularly limited, but random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.
架橋前の分散剤の酸価は、顔料の分散性の観点から60~250mgKOH/gが好ましく、65~150mgKOH/gがさらに好ましい。
架橋後の分散剤の酸価は25~100mgKOH/gが、安定性、インク凝集性の観点で好ましい。
架橋前の分散剤の重量平均分子量は特に制限されないが、顔料の分散性の観点から3,000~100,000であることが好ましく、5,000~50,000であることがより好ましく、10,000~40,000がさらに好ましい。 The acid value of the dispersant before crosslinking is preferably 60 to 250 mgKOH / g, more preferably 65 to 150 mgKOH / g, from the viewpoint of dispersibility of the pigment.
The acid value of the dispersant after crosslinking is preferably 25 to 100 mgKOH / g from the viewpoints of stability and ink aggregation.
The weight average molecular weight of the dispersant before crosslinking is not particularly limited, but is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint of dispersibility of the pigment. , 40,000 is more preferable.
架橋後の分散剤の酸価は25~100mgKOH/gが、安定性、インク凝集性の観点で好ましい。
架橋前の分散剤の重量平均分子量は特に制限されないが、顔料の分散性の観点から3,000~100,000であることが好ましく、5,000~50,000であることがより好ましく、10,000~40,000がさらに好ましい。 The acid value of the dispersant before crosslinking is preferably 60 to 250 mgKOH / g, more preferably 65 to 150 mgKOH / g, from the viewpoint of dispersibility of the pigment.
The acid value of the dispersant after crosslinking is preferably 25 to 100 mgKOH / g from the viewpoints of stability and ink aggregation.
The weight average molecular weight of the dispersant before crosslinking is not particularly limited, but is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint of dispersibility of the pigment. , 40,000 is more preferable.
前記架橋剤は分散剤と反応する部位を2つ以上有している化合物であれば、特に限定されないが、中でもカルボキシル基との反応性に優れている点から、好ましくは2つ以上のエポキシ基を有している化合物(2官能以上のエポキシ化合物)が好ましい。
具体例としては、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、1,6-へキサンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等が挙げられ、ポリエチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルが好ましい。 The cross-linking agent is not particularly limited as long as it is a compound having two or more sites that react with the dispersant, but preferably has two or more epoxy groups from the viewpoint of excellent reactivity with a carboxyl group. A compound having bifunctionality (a bifunctional or higher functional epoxy compound) is preferred.
Specific examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl. Examples include ether and trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether are preferable.
具体例としては、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、1,6-へキサンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等が挙げられ、ポリエチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルが好ましい。 The cross-linking agent is not particularly limited as long as it is a compound having two or more sites that react with the dispersant, but preferably has two or more epoxy groups from the viewpoint of excellent reactivity with a carboxyl group. A compound having bifunctionality (a bifunctional or higher functional epoxy compound) is preferred.
Specific examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl. Examples include ether and trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether are preferable.
架橋剤の架橋部位と分散剤の被架橋部位のモル比は、架橋反応速度、架橋後の分散液安定性の観点から、1:1.1~1:10が好ましく、1:1.1~1:5がより好ましく、1:1.1~1:3が最も好ましい。
The molar ratio of the crosslinking site of the crosslinking agent to the crosslinked site of the dispersant is preferably from 1: 1.1 to 1:10, from the viewpoint of the crosslinking reaction rate and the dispersion stability after crosslinking, 1: 5 is more preferable, and 1: 1.1 to 1: 3 is most preferable.
具体的には例えば、特開2009-190379号公報に記載の方法によって顔料表面の少なくとも一部が水不溶性樹脂で被覆された顔料分散物を製造することができる。
Specifically, for example, a pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin can be produced by the method described in JP-A-2009-190379.
前記カーボンブラック顔料(p)と分散剤(s)との混合質量比(p:s)は特に制限されず、分散方法等に応じて適宜選択できる。例えば、1:0.06~1:3の範囲が好ましく、1:0.125~1:1の範囲がより好ましく、更に好ましくは1:0.125~1:0.7である。
The mixing mass ratio (p: s) between the carbon black pigment (p) and the dispersant (s) is not particularly limited, and can be appropriately selected according to the dispersion method and the like. For example, a range of 1: 0.06 to 1: 3 is preferable, a range of 1: 0.125 to 1: 1 is more preferable, and a range of 1: 0.125 to 1: 0.7 is more preferable.
分散状態でのカーボンブラック顔料の平均粒子径は、10~200nmが好ましく、10~150nmがより好ましく、40~150nmがさらに好ましい。平均粒子径は、200nm以下であると色再現性が良好になり得、インクジェット法で打滴する際の打滴特性が良好になり得、10nm以上であると耐光性が良好になり得る。カーボンブラック顔料水性分散物の粒径分布に関しては、特に制限はなく、広い粒径分布又は単分散性の粒径分布のいずれであってもよい。ある実施形態においては、単分散性の粒径分布を持つカーボンブラック顔料水性分散物を1種のみ又は2種以上混合して使用してもよい。
ここで、分散状態でのカーボンブラック顔料の平均粒子径とは、インク化した状態での平均粒子径を意味する。インク化する前段階のいわゆる濃縮インク分散物におけるカーボンブラック顔料の平均粒子径も同様である。 The average particle size of the carbon black pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 40 to 150 nm. When the average particle size is 200 nm or less, the color reproducibility can be improved, the droplet ejection characteristics when ejected by the ink jet method can be improved, and when it is 10 nm or more, the light resistance can be improved. The particle size distribution of the carbon black pigment aqueous dispersion is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. In some embodiments, only one or a mixture of two or more carbon black pigment aqueous dispersions having a monodisperse particle size distribution may be used.
Here, the average particle diameter of the carbon black pigment in a dispersed state means the average particle diameter in an ink state. The same applies to the average particle size of the carbon black pigment in the so-called concentrated ink dispersion before ink conversion.
ここで、分散状態でのカーボンブラック顔料の平均粒子径とは、インク化した状態での平均粒子径を意味する。インク化する前段階のいわゆる濃縮インク分散物におけるカーボンブラック顔料の平均粒子径も同様である。 The average particle size of the carbon black pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 40 to 150 nm. When the average particle size is 200 nm or less, the color reproducibility can be improved, the droplet ejection characteristics when ejected by the ink jet method can be improved, and when it is 10 nm or more, the light resistance can be improved. The particle size distribution of the carbon black pigment aqueous dispersion is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. In some embodiments, only one or a mixture of two or more carbon black pigment aqueous dispersions having a monodisperse particle size distribution may be used.
Here, the average particle diameter of the carbon black pigment in a dispersed state means the average particle diameter in an ink state. The same applies to the average particle size of the carbon black pigment in the so-called concentrated ink dispersion before ink conversion.
なお、分散状態でのカーボンブラック顔料の平均粒子径及び粒径分布は、ナノトラック粒度分布測定装置UPA-EX150(商品名、日機装(株)製)を用いて、動的光散乱法により体積平均粒子径を測定することにより求められるものである。
The average particle size and particle size distribution of the carbon black pigment in the dispersed state were measured by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). It is calculated | required by measuring a particle diameter.
(カーボンブラック顔料)
前記カーボンブラック顔料には特に制限はない。画像の記録媒体への密着性、耐擦性、画像濃度等の観点から、pHが酸性から中性の領域であるカーボンブラック顔料であることが好ましい。さらにカーボンブラック顔料の平均一次粒子径は10~50nmであることが好ましく、10~30nmがさらに好ましい。
尚、平均一次粒子径は、日本電子(株)社製の透過型電子顕微鏡TEM2010(商品名、加圧電圧200kV)を用いて撮影された画像から、任意に選択した一次粒子1000個の粒子径(円相当径)を測定してその算術平均として算出される。 (Carbon black pigment)
There is no restriction | limiting in particular in the said carbon black pigment. From the viewpoint of adhesion of an image to a recording medium, abrasion resistance, image density and the like, a carbon black pigment having a pH range from acidic to neutral is preferable. Further, the average primary particle size of the carbon black pigment is preferably 10 to 50 nm, more preferably 10 to 30 nm.
The average primary particle size is a particle size of 1000 primary particles arbitrarily selected from an image taken using a transmission electron microscope TEM2010 (trade name, pressurization voltage 200 kV) manufactured by JEOL Ltd. (Equivalent circle diameter) is measured and calculated as the arithmetic average.
前記カーボンブラック顔料には特に制限はない。画像の記録媒体への密着性、耐擦性、画像濃度等の観点から、pHが酸性から中性の領域であるカーボンブラック顔料であることが好ましい。さらにカーボンブラック顔料の平均一次粒子径は10~50nmであることが好ましく、10~30nmがさらに好ましい。
尚、平均一次粒子径は、日本電子(株)社製の透過型電子顕微鏡TEM2010(商品名、加圧電圧200kV)を用いて撮影された画像から、任意に選択した一次粒子1000個の粒子径(円相当径)を測定してその算術平均として算出される。 (Carbon black pigment)
There is no restriction | limiting in particular in the said carbon black pigment. From the viewpoint of adhesion of an image to a recording medium, abrasion resistance, image density and the like, a carbon black pigment having a pH range from acidic to neutral is preferable. Further, the average primary particle size of the carbon black pigment is preferably 10 to 50 nm, more preferably 10 to 30 nm.
The average primary particle size is a particle size of 1000 primary particles arbitrarily selected from an image taken using a transmission electron microscope TEM2010 (trade name, pressurization voltage 200 kV) manufactured by JEOL Ltd. (Equivalent circle diameter) is measured and calculated as the arithmetic average.
前記カーボンブラック顔料のpHは、酸性乃至中性の領域であると、易分散性が得られるため好ましく、pH2.0~pH8.5であることがより好ましく、pH2.5~pH8.0であることが特に好ましい。
カーボンブラック顔料のpHは、カーボンブラック顔料の水分散物のpH(25℃)として測定される。 The pH of the carbon black pigment is preferably in the acidic to neutral range because easy dispersibility is obtained, more preferably pH 2.0 to pH 8.5, and pH 2.5 to pH 8.0. It is particularly preferred.
The pH of the carbon black pigment is measured as the pH (25 ° C.) of the aqueous dispersion of the carbon black pigment.
カーボンブラック顔料のpHは、カーボンブラック顔料の水分散物のpH(25℃)として測定される。 The pH of the carbon black pigment is preferably in the acidic to neutral range because easy dispersibility is obtained, more preferably pH 2.0 to pH 8.5, and pH 2.5 to pH 8.0. It is particularly preferred.
The pH of the carbon black pigment is measured as the pH (25 ° C.) of the aqueous dispersion of the carbon black pigment.
前記カーボンブラック顔料のDBP吸収量は特に制限されないが、色調と印画濃度の観点から、30ml/100g以上200ml/100g以下であることが好ましく、50ml/100g以上150ml/100g以下であることがより好ましい。
DBP吸収量は、JIS K6221 A法によって測定される。 The DBP absorption amount of the carbon black pigment is not particularly limited, but is preferably 30 ml / 100 g or more and 200 ml / 100 g or less, and more preferably 50 ml / 100 g or more and 150 ml / 100 g or less from the viewpoint of color tone and printing density. .
The DBP absorption is measured by JIS K6221 A method.
DBP吸収量は、JIS K6221 A法によって測定される。 The DBP absorption amount of the carbon black pigment is not particularly limited, but is preferably 30 ml / 100 g or more and 200 ml / 100 g or less, and more preferably 50 ml / 100 g or more and 150 ml / 100 g or less from the viewpoint of color tone and printing density. .
The DBP absorption is measured by JIS K6221 A method.
前記カーボンブラック顔料のBET比表面積は特に制限されないが、印画濃度と保存安定性の観点から、30m2/g以上450m2/g以下であることが好ましく、200m2/g以上400m2/g以下であることがより好ましい。
The BET specific surface area of the carbon black pigment is not particularly limited, but is preferably 30 m 2 / g or more and 450 m 2 / g or less, and 200 m 2 / g or more and 400 m 2 / g or less from the viewpoint of printing density and storage stability. It is more preferable that
カーボンブラック顔料としては、例えば、コンタクト法、ファーネス法、サーマル法などの公知の方法によって製造されたものが挙げられる。
具体例としては例えば、RAVEN7000、RAVEN5750、RAVEN5250、RAVEN5000ULTRAII、RAVEN3500、RAVEN2000、RAVEN1500、RAVEN1250、RAVEN1200、RAVEN1190 ULTRAII、RAVEN1170、RAVEN1255、RAVEN1080、RAVEN1060、RAVEN700(以上全て登録商標、コロンビアン・カーボン社製)、REGAL400R、REGAL330R、REGAL660R、MOGUL L、BLACK PEARLS L、MONARCH 700、MONARCH 800、MONARCH 880、MONARCH 900、MONARCH 1000、MONARCH 1100、MONARCH 1300、MONARCH 1400(以上、キャボット社製)、COLOR BLACK FW1、 COLOR BLACK FW2、COLOR BLACK FW2V、COLOR BLACK 18、COLOR BLACK FW200、COLOR BLACK S150、COLOR BLACK S160、COLOR BLACK S170、PRINTEX35、PRINTEX U、PRINTEX V、PRINTEX140U、PRINTEX140V、SPECIAL BLACK 6、SPECIAL BLACK 5、SPECIAL BLACK 4A、SPECIAL BLACK4、NIPEX180-IQ、NIPEX170-IQ(以上商品名、デグッサ社製)、No.25、No.33、No.40、No.45、No.47、No.52、No.900、No.2200B、No.2300、No.990、No.980、No.970、No.960、No.950、No.850、MCF-88、MA600、MA7、MA8、MA100(以上商品名、三菱化学社製)等を挙げることができる。但し、これらに限定されるものではない。 Examples of the carbon black pigment include those produced by known methods such as a contact method, a furnace method, and a thermal method.
Specific examples include, for example, Raven7000, Raven5750, Raven5250, Raven5000ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1190 ULTRAII, Raven1170, Raven1255, Raven10, Raven10 REGAL400R, REGAL330R, REGAL660R, MOGUL L, BLACK PEARLS L, MONARCH 700, MONARCH 800, MONARCH 880, MONARCH 900, MONARCH 1000, MONARCH 1100, MONARCH 1300, M NARCH 1400 (above, manufactured by Cabot Corporation), COLOR BLACK FW1, COLOR BLACK FW2, COLOR BLACK FW2V, COLOR BLACK 18, COLOR BLACK FW200, COLOR BLACK S150, COLOR BLACK TE 160, COLOR BLTE TE 160, COLOR BLS PRINTEX140U, PRINTEX140V, SPECIAL BLACK 6, SPECIAL BLACK 5, SPECIAL BLACK 4A, SPECIAL BLACK4, NIPEX180-IQ, NIPEX170-IQ (above trade names, manufactured by Degussa), No. 25, no. 33, no. 40, no. 45, no. 47, no. 52, no. 900, no. 2200B, no. 2300, no. 990, no. 980, no. 970, no. 960, no. 950, no. 850, MCF-88, MA600, MA7, MA8, MA100 (trade names, manufactured by Mitsubishi Chemical Corporation) and the like. However, it is not limited to these.
具体例としては例えば、RAVEN7000、RAVEN5750、RAVEN5250、RAVEN5000ULTRAII、RAVEN3500、RAVEN2000、RAVEN1500、RAVEN1250、RAVEN1200、RAVEN1190 ULTRAII、RAVEN1170、RAVEN1255、RAVEN1080、RAVEN1060、RAVEN700(以上全て登録商標、コロンビアン・カーボン社製)、REGAL400R、REGAL330R、REGAL660R、MOGUL L、BLACK PEARLS L、MONARCH 700、MONARCH 800、MONARCH 880、MONARCH 900、MONARCH 1000、MONARCH 1100、MONARCH 1300、MONARCH 1400(以上、キャボット社製)、COLOR BLACK FW1、 COLOR BLACK FW2、COLOR BLACK FW2V、COLOR BLACK 18、COLOR BLACK FW200、COLOR BLACK S150、COLOR BLACK S160、COLOR BLACK S170、PRINTEX35、PRINTEX U、PRINTEX V、PRINTEX140U、PRINTEX140V、SPECIAL BLACK 6、SPECIAL BLACK 5、SPECIAL BLACK 4A、SPECIAL BLACK4、NIPEX180-IQ、NIPEX170-IQ(以上商品名、デグッサ社製)、No.25、No.33、No.40、No.45、No.47、No.52、No.900、No.2200B、No.2300、No.990、No.980、No.970、No.960、No.950、No.850、MCF-88、MA600、MA7、MA8、MA100(以上商品名、三菱化学社製)等を挙げることができる。但し、これらに限定されるものではない。 Examples of the carbon black pigment include those produced by known methods such as a contact method, a furnace method, and a thermal method.
Specific examples include, for example, Raven7000, Raven5750, Raven5250, Raven5000ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1190 ULTRAII, Raven1170, Raven1255, Raven10, Raven10 REGAL400R, REGAL330R, REGAL660R, MOGUL L, BLACK PEARLS L, MONARCH 700, MONARCH 800, MONARCH 880, MONARCH 900, MONARCH 1000, MONARCH 1100, MONARCH 1300, M NARCH 1400 (above, manufactured by Cabot Corporation), COLOR BLACK FW1, COLOR BLACK FW2, COLOR BLACK FW2V, COLOR BLACK 18, COLOR BLACK FW200, COLOR BLACK S150, COLOR BLACK TE 160, COLOR BLTE TE 160, COLOR BLS PRINTEX140U, PRINTEX140V, SPECIAL BLACK 6, SPECIAL BLACK 5, SPECIAL BLACK 4A, SPECIAL BLACK4, NIPEX180-IQ, NIPEX170-IQ (above trade names, manufactured by Degussa), No. 25, no. 33, no. 40, no. 45, no. 47, no. 52, no. 900, no. 2200B, no. 2300, no. 990, no. 980, no. 970, no. 960, no. 950, no. 850, MCF-88, MA600, MA7, MA8, MA100 (trade names, manufactured by Mitsubishi Chemical Corporation) and the like. However, it is not limited to these.
上記のカーボンブラック顔料は、1種単独でも、2種以上を組み合わせて使用してもよい。
前記インク組成物の全質量に対するカーボンブラック顔料の含有量は、特に制限されないが、記録媒体への密着性、耐擦性、印画濃度の観点から、0.5~4質量%であることが好ましく、0.8~2質量%であることがより好ましい。 The above carbon black pigments may be used singly or in combination of two or more.
The content of the carbon black pigment with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.5 to 4% by mass from the viewpoint of adhesion to a recording medium, abrasion resistance, and print density. 0.8 to 2% by mass is more preferable.
前記インク組成物の全質量に対するカーボンブラック顔料の含有量は、特に制限されないが、記録媒体への密着性、耐擦性、印画濃度の観点から、0.5~4質量%であることが好ましく、0.8~2質量%であることがより好ましい。 The above carbon black pigments may be used singly or in combination of two or more.
The content of the carbon black pigment with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.5 to 4% by mass from the viewpoint of adhesion to a recording medium, abrasion resistance, and print density. 0.8 to 2% by mass is more preferable.
[着色顔料分散工程]
着色顔料水性分散物は、典型的には、着色顔料を水性媒体中に分散することにより得ることができる。
前記着色顔料分散工程は、マゼンタ顔料、シアン顔料およびイエロー顔料から選ばれる少なくとも1種の着色顔料を水性媒体中に分散可能であれば特に制限されず、通常用いられる分散方法を適宜選択して適用することができる。
例えば、水性媒体中で分散剤の少なくとも1種と着色顔料の少なくとも1種とを混合し、得られた混合物を分散処理することで着色顔料水性分散物を得ることができる。分散剤、混合方法および分散処理する方法については上述の通りである。 [Coloring pigment dispersion process]
The colored pigment aqueous dispersion is typically obtained by dispersing the colored pigment in an aqueous medium.
The color pigment dispersion step is not particularly limited as long as at least one color pigment selected from a magenta pigment, a cyan pigment, and a yellow pigment can be dispersed in an aqueous medium, and a commonly used dispersion method is appropriately selected and applied. can do.
For example, an aqueous colored pigment dispersion can be obtained by mixing at least one dispersing agent and at least one coloring pigment in an aqueous medium and dispersing the resulting mixture. The dispersant, the mixing method, and the dispersion treatment method are as described above.
着色顔料水性分散物は、典型的には、着色顔料を水性媒体中に分散することにより得ることができる。
前記着色顔料分散工程は、マゼンタ顔料、シアン顔料およびイエロー顔料から選ばれる少なくとも1種の着色顔料を水性媒体中に分散可能であれば特に制限されず、通常用いられる分散方法を適宜選択して適用することができる。
例えば、水性媒体中で分散剤の少なくとも1種と着色顔料の少なくとも1種とを混合し、得られた混合物を分散処理することで着色顔料水性分散物を得ることができる。分散剤、混合方法および分散処理する方法については上述の通りである。 [Coloring pigment dispersion process]
The colored pigment aqueous dispersion is typically obtained by dispersing the colored pigment in an aqueous medium.
The color pigment dispersion step is not particularly limited as long as at least one color pigment selected from a magenta pigment, a cyan pigment, and a yellow pigment can be dispersed in an aqueous medium, and a commonly used dispersion method is appropriately selected and applied. can do.
For example, an aqueous colored pigment dispersion can be obtained by mixing at least one dispersing agent and at least one coloring pigment in an aqueous medium and dispersing the resulting mixture. The dispersant, the mixing method, and the dispersion treatment method are as described above.
前記製造方法においては、カーボンブラック顔料の分散処理とは独立して、着色顔料を分散処理して着色顔料水性分散物を調製し、これを用いてインク組成物を製造する。これにより、分散安定性、吐出安定性により優れ得る黒色系インク組成物を製造することができる。
この効果は例えば、顔料水性分散物を、顔料の種類に応じたより良好な分散状態とすることができるために得られると考えることができる。これに関連して、前記製造方法では、顔料の種類に応じてより適切な分散条件を選択することが可能である。 In the production method, independent of the dispersion treatment of the carbon black pigment, the colored pigment is dispersed to prepare an aqueous colored pigment dispersion, and an ink composition is produced using the dispersion. Thereby, a black ink composition that can be more excellent in dispersion stability and ejection stability can be produced.
This effect can be considered to be obtained because, for example, the aqueous pigment dispersion can be made into a better dispersion state according to the type of pigment. In this regard, in the manufacturing method, it is possible to select more appropriate dispersion conditions depending on the type of pigment.
この効果は例えば、顔料水性分散物を、顔料の種類に応じたより良好な分散状態とすることができるために得られると考えることができる。これに関連して、前記製造方法では、顔料の種類に応じてより適切な分散条件を選択することが可能である。 In the production method, independent of the dispersion treatment of the carbon black pigment, the colored pigment is dispersed to prepare an aqueous colored pigment dispersion, and an ink composition is produced using the dispersion. Thereby, a black ink composition that can be more excellent in dispersion stability and ejection stability can be produced.
This effect can be considered to be obtained because, for example, the aqueous pigment dispersion can be made into a better dispersion state according to the type of pigment. In this regard, in the manufacturing method, it is possible to select more appropriate dispersion conditions depending on the type of pigment.
前記黒色系インク組成物が2種以上の着色顔料を含む場合、前記着色顔料分散工程は、2種以上の着色顔料を混合して共分散処理する工程であっても、それぞれの着色顔料毎に単分散処理する工程であってもよい。ある実施形態においては吐出安定性の観点から、それぞれの着色顔料毎に着色顔料水性分散物を調製することが好ましい。
When the black ink composition contains two or more types of color pigments, the color pigment dispersion step may be a step of mixing and co-dispersing two or more types of color pigments for each color pigment. It may be a step of monodisperse processing. In an embodiment, from the viewpoint of ejection stability, it is preferable to prepare an aqueous colored pigment dispersion for each colored pigment.
前記着色顔料分散工程は、分散剤として前記酸性基を有する水不溶性樹脂を用い、これと着色顔料、中和剤、水、および水溶性有機溶剤を含む混合物を得る工程と、前記混合物を分散処理する工程と、分散処理工程後に水溶性有機溶剤の少なくとも一部を除去する工程と、を含むことが好ましい。かかる分散工程であることで、分散安定性に優れ得る着色顔料水性分散物を得ることができる。
前記カーボンブラック分散工程と同様、顔料を水溶性もしくは水不溶性分散剤を用いて分散した後に、架橋剤を用いて分散剤を架橋することにより分散剤を水不溶化して分散物を作製することも好ましい態様である。
かかる着色顔料分散工程の詳細は、前記カーボンブラック分散工程と同様であり、好ましい態様も同様である。 The color pigment dispersion step uses the water-insoluble resin having the acidic group as a dispersant, obtains a mixture containing the color pigment, a neutralizing agent, water, and a water-soluble organic solvent, and disperses the mixture. And a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step. By this dispersion step, an aqueous colored pigment dispersion that can be excellent in dispersion stability can be obtained.
Similarly to the carbon black dispersion step, after dispersing the pigment using a water-soluble or water-insoluble dispersant, the dispersant may be water-insolubilized by crosslinking the dispersant using a cross-linking agent to produce a dispersion. This is a preferred embodiment.
The details of the color pigment dispersion step are the same as those in the carbon black dispersion step, and the preferred embodiments are also the same.
前記カーボンブラック分散工程と同様、顔料を水溶性もしくは水不溶性分散剤を用いて分散した後に、架橋剤を用いて分散剤を架橋することにより分散剤を水不溶化して分散物を作製することも好ましい態様である。
かかる着色顔料分散工程の詳細は、前記カーボンブラック分散工程と同様であり、好ましい態様も同様である。 The color pigment dispersion step uses the water-insoluble resin having the acidic group as a dispersant, obtains a mixture containing the color pigment, a neutralizing agent, water, and a water-soluble organic solvent, and disperses the mixture. And a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step. By this dispersion step, an aqueous colored pigment dispersion that can be excellent in dispersion stability can be obtained.
Similarly to the carbon black dispersion step, after dispersing the pigment using a water-soluble or water-insoluble dispersant, the dispersant may be water-insolubilized by crosslinking the dispersant using a cross-linking agent to produce a dispersion. This is a preferred embodiment.
The details of the color pigment dispersion step are the same as those in the carbon black dispersion step, and the preferred embodiments are also the same.
分散状態での着色顔料の平均粒子径は、10~200nmが好ましく、10~150nmがより好ましく、40~150nmがさらに好ましい。平均粒子径は、200nm以下であると色再現性が良好になり得、インクジェット法で打滴する際の打滴特性が良好になり得、10nm以上であると耐光性が良好になり得る。着色顔料水性分散物の粒径分布には、特に制限はなく、広い粒径分布又は単分散性の粒径分布のいずれであってもよい。ある実施形態においては、単分散性の粒径分布を持つ着色顔料水性分散物を1種のみ又は2種以上混合して使用してもよい。
The average particle diameter of the colored pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 40 to 150 nm. When the average particle size is 200 nm or less, the color reproducibility can be improved, the droplet ejection characteristics when ejected by the ink jet method can be improved, and when it is 10 nm or more, the light resistance can be improved. The particle size distribution of the color pigment aqueous dispersion is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. In an embodiment, the color pigment aqueous dispersion having a monodisperse particle size distribution may be used alone or in combination of two or more.
(着色顔料)
本発明における着色顔料は、マゼンタ顔料、シアン顔料およびイエロー顔料から選ばれる少なくとも1種である。前記マゼンタ顔料、シアン顔料およびイエロー顔料は、目的に応じて公知の有機顔料から適宜選択することができる。前記有機顔料の具体的な例を以下に示す。 (Color pigment)
The colored pigment in the present invention is at least one selected from a magenta pigment, a cyan pigment, and a yellow pigment. The magenta pigment, cyan pigment, and yellow pigment can be appropriately selected from known organic pigments according to the purpose. Specific examples of the organic pigment are shown below.
本発明における着色顔料は、マゼンタ顔料、シアン顔料およびイエロー顔料から選ばれる少なくとも1種である。前記マゼンタ顔料、シアン顔料およびイエロー顔料は、目的に応じて公知の有機顔料から適宜選択することができる。前記有機顔料の具体的な例を以下に示す。 (Color pigment)
The colored pigment in the present invention is at least one selected from a magenta pigment, a cyan pigment, and a yellow pigment. The magenta pigment, cyan pigment, and yellow pigment can be appropriately selected from known organic pigments according to the purpose. Specific examples of the organic pigment are shown below.
マゼンタ顔料としては、例えば、C.I.ピグメント・レッド2、C.I.ピグメント・レッド3、C.I.ピグメント・レッド5、C.I.ピグメント・レッド6、C.I.ピグメント・レッド7、C.I.ピグメント・レッド15、C.I.ピグメント・レッド16、C.I.ピグメント・レッド48:1、C.I.ピグメント・レッド53:1、C.I.ピグメント・レッド57:1、C.I.ピグメント・レッド122、C.I.ピグメント・レッド123、C.I.ピグメント・レッド139、C.I.ピグメント・レッド144、C.I.ピグメント・レッド149、C.I.ピグメント・レッド166、C.I.ピグメント・レッド177、C.I.ピグメント・レッド178、C.I.ピグメント・レッド222、C.I.ピグメントバイオレット19等が挙げられる。
これらの中でも、記録媒体への密着性と耐擦性の観点から、C.I.ピグメント・レッド122、C.I.ピグメント・レッド202、C.I.ピグメント・レッド209、C.I.ピグメントバイオレット19から選ばれる少なくとも1種であることが好ましい。 Examples of magenta pigments include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 222, C.I. I. Pigment violet 19 and the like.
Among these, from the viewpoint of adhesion to a recording medium and abrasion resistance, C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. It is preferably at least one selected from pigment violet 19.
これらの中でも、記録媒体への密着性と耐擦性の観点から、C.I.ピグメント・レッド122、C.I.ピグメント・レッド202、C.I.ピグメント・レッド209、C.I.ピグメントバイオレット19から選ばれる少なくとも1種であることが好ましい。 Examples of magenta pigments include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 222, C.I. I. Pigment violet 19 and the like.
Among these, from the viewpoint of adhesion to a recording medium and abrasion resistance, C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. It is preferably at least one selected from pigment violet 19.
シアン顔料としては、例えばC.I.ピグメント・ブルー15、C.I.ピグメント・ブルー15:2、C.I.ピグメント・ブルー15:3、C.I.ピグメント・ブルー15:4、C.I.ピグメント・ブルー16、C.I.ピグメント・ブルー60、C.I.ピグメント・グリーン7、及び米国特許4311775号明細書に記載のシロキサン架橋アルミニウムフタロシアニン等が挙げられる。
これらの中でも、記録媒体への密着性と耐擦性の観点から、C.I.ピグメント・ブルー15:3、C.I.ピグメント・ブルー15:4、C.I.ピグメント・ブルー16から選ばれる少なくとも1種であることが好ましく、C.I.ピグメント・ブルー15:3、C.I.ピグメント・ブルー15:4から選ばれる少なくとも1種であることがより好ましい。 Examples of cyan pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment Green 7, and siloxane-crosslinked aluminum phthalocyanine described in US Pat. No. 4,311,775.
Among these, from the viewpoint of adhesion to a recording medium and abrasion resistance, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. preferably at least one selected from CI Pigment Blue 16. I. Pigment blue 15: 3, C.I. I. More preferably, it is at least one selected from CI Pigment Blue 15: 4.
これらの中でも、記録媒体への密着性と耐擦性の観点から、C.I.ピグメント・ブルー15:3、C.I.ピグメント・ブルー15:4、C.I.ピグメント・ブルー16から選ばれる少なくとも1種であることが好ましく、C.I.ピグメント・ブルー15:3、C.I.ピグメント・ブルー15:4から選ばれる少なくとも1種であることがより好ましい。 Examples of cyan pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment Green 7, and siloxane-crosslinked aluminum phthalocyanine described in US Pat. No. 4,311,775.
Among these, from the viewpoint of adhesion to a recording medium and abrasion resistance, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. preferably at least one selected from CI Pigment Blue 16. I. Pigment blue 15: 3, C.I. I. More preferably, it is at least one selected from CI Pigment Blue 15: 4.
イエロー顔料としては、例えば、C.I.ピグメント・オレンジ31、C.I.ピグメント・オレンジ43、C.I.ピグメント・イエロー12、C.I.ピグメント・イエロー13、C.I.ピグメント・イエロー14、C.I.ピグメント・イエロー15、C.I.ピグメント・イエロー17、C.I.ピグメント・イエロー74、C.I.ピグメント・イエロー93、C.I.ピグメント・イエロー94、C.I.ピグメント・イエロー128、C.I.ピグメント・イエロー138、C.I.ピグメント・イエロー151、C.I.ピグメント・イエロー155、C.I.ピグメント・イエロー180、C.I.ピグメント・イエロー185等が挙げられる。
これらの中でも、記録媒体への密着性と耐擦性の観点から、C.I.ピグメント・イエロー74、C.I.ピグメント・イエロー155、C.I.ピグメント・イエロー185から選ばれる少なくとも1種であることが好ましい。 Examples of the yellow pigment include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 185.
Among these, from the viewpoint of adhesion to a recording medium and abrasion resistance, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 155, C.I. I. It is preferably at least one selected from Pigment Yellow 185.
これらの中でも、記録媒体への密着性と耐擦性の観点から、C.I.ピグメント・イエロー74、C.I.ピグメント・イエロー155、C.I.ピグメント・イエロー185から選ばれる少なくとも1種であることが好ましい。 Examples of the yellow pigment include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 185.
Among these, from the viewpoint of adhesion to a recording medium and abrasion resistance, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 155, C.I. I. It is preferably at least one selected from Pigment Yellow 185.
前記着色顔料は、記録媒体への密着性の観点から、マゼンタ顔料の少なくとも1種とシアン顔料の少なくとも1種とを含むことがより好ましい。
The color pigment preferably contains at least one magenta pigment and at least one cyan pigment from the viewpoint of adhesion to a recording medium.
前記インク組成物において、前記カーボンブラック顔料および着色顔料の総質量に対する前記着色顔料の含有量(着色顔料/(カーボンブラック顔料+着色顔料))は特に制限されない。記録媒体への密着性、耐擦性、吐出性の観点から、5質量%以上60質量%以下であることが好ましく、10質量%以上50質量%以下であることがより好ましい。
In the ink composition, the content of the color pigment relative to the total mass of the carbon black pigment and the color pigment (color pigment / (carbon black pigment + color pigment)) is not particularly limited. From the viewpoints of adhesion to a recording medium, abrasion resistance, and ejection properties, the content is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass.
前記着色顔料がマゼンタ顔料とシアン顔料とを含む場合、前記インク組成物におけるシアン顔料の含有量に対するマゼンタ顔料の含有量(マゼンタ顔料/シアン顔料)は特に制限されない。記録媒体への密着性、耐擦性、色調の観点から、100質量%以上180質量%以下であることが好ましく、120質量%以上150質量%以下であることがより好ましい。
When the colored pigment includes a magenta pigment and a cyan pigment, the content of the magenta pigment (magenta pigment / cyan pigment) with respect to the content of the cyan pigment in the ink composition is not particularly limited. From the viewpoints of adhesion to a recording medium, abrasion resistance, and color tone, it is preferably 100% by mass or more and 180% by mass or less, and more preferably 120% by mass or more and 150% by mass or less.
[混合工程]
混合工程においては、前記カーボンブラック顔料水性分散物の少なくとも1種と、前記着色顔料水性分散物の少なくとも1種と、水溶性の重合性化合物の少なくとも1種と、重合開始剤の少なくとも1種とを混合する。必要に応じて水溶性有機溶剤の少なくとも1種、及び/又は界面活性剤の少なくとも1種をさらに混合してもよく、混合しなくてもよい。
混合工程における混合方法には特に制限はない。通常用いられる液体の混合方法を適宜選択することができ、例えば、一般的な攪拌装置を用いることができる。 [Mixing process]
In the mixing step, at least one carbon black pigment aqueous dispersion, at least one color pigment aqueous dispersion, at least one water-soluble polymerizable compound, and at least one polymerization initiator, Mix. If necessary, at least one water-soluble organic solvent and / or at least one surfactant may or may not be further mixed.
There is no restriction | limiting in particular in the mixing method in a mixing process. A commonly used liquid mixing method can be appropriately selected. For example, a general stirring device can be used.
混合工程においては、前記カーボンブラック顔料水性分散物の少なくとも1種と、前記着色顔料水性分散物の少なくとも1種と、水溶性の重合性化合物の少なくとも1種と、重合開始剤の少なくとも1種とを混合する。必要に応じて水溶性有機溶剤の少なくとも1種、及び/又は界面活性剤の少なくとも1種をさらに混合してもよく、混合しなくてもよい。
混合工程における混合方法には特に制限はない。通常用いられる液体の混合方法を適宜選択することができ、例えば、一般的な攪拌装置を用いることができる。 [Mixing process]
In the mixing step, at least one carbon black pigment aqueous dispersion, at least one color pigment aqueous dispersion, at least one water-soluble polymerizable compound, and at least one polymerization initiator, Mix. If necessary, at least one water-soluble organic solvent and / or at least one surfactant may or may not be further mixed.
There is no restriction | limiting in particular in the mixing method in a mixing process. A commonly used liquid mixing method can be appropriately selected. For example, a general stirring device can be used.
[濾過工程]
必要に応じて、前記混合工程で得られた混合物を濾過処理してもよく、しなくてもよい。濾過処理の方法は特に制限されず、常圧濾過、加圧濾過、吸引濾過等のいずれであってもよい。また濾過に用いる濾材も特に制限されず、目的に応じて適宜選択することができる。例えば濾紙、メンブレンフィルタ等を挙げることができる。 [Filtering process]
If necessary, the mixture obtained in the mixing step may or may not be filtered. The method for the filtration treatment is not particularly limited, and any of atmospheric filtration, pressure filtration, suction filtration and the like may be used. The filter medium used for filtration is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include filter paper and membrane filter.
必要に応じて、前記混合工程で得られた混合物を濾過処理してもよく、しなくてもよい。濾過処理の方法は特に制限されず、常圧濾過、加圧濾過、吸引濾過等のいずれであってもよい。また濾過に用いる濾材も特に制限されず、目的に応じて適宜選択することができる。例えば濾紙、メンブレンフィルタ等を挙げることができる。 [Filtering process]
If necessary, the mixture obtained in the mixing step may or may not be filtered. The method for the filtration treatment is not particularly limited, and any of atmospheric filtration, pressure filtration, suction filtration and the like may be used. The filter medium used for filtration is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include filter paper and membrane filter.
(重合性化合物)
前記混合工程においては、水溶性の重合性化合物が混合に供される。ここで水溶性とは、水に一定濃度以上になるよう溶解できる性質をいう。具体的には25℃の水に対する溶解度が5質量%以上であることが好ましく、10質量%以上であることがより好ましい。水溶性の重合性化合物は、水性のインク組成物中に(望ましくは均一に)溶解し得るものであることが好ましい。後述する水溶性有機溶剤を添加することにより溶解度が上昇してインク組成物中に(望ましくは均一に)溶解するものであってもそうでないものでもよい。 (Polymerizable compound)
In the mixing step, a water-soluble polymerizable compound is used for mixing. Here, water-soluble means a property that can be dissolved in water so as to have a certain concentration or more. Specifically, the solubility in water at 25 ° C. is preferably 5% by mass or more, and more preferably 10% by mass or more. The water-soluble polymerizable compound is preferably one that can be dissolved (desirably uniformly) in the aqueous ink composition. The solubility may be increased by adding a water-soluble organic solvent to be described later, and it may be dissolved (desirably uniformly) in the ink composition or not.
前記混合工程においては、水溶性の重合性化合物が混合に供される。ここで水溶性とは、水に一定濃度以上になるよう溶解できる性質をいう。具体的には25℃の水に対する溶解度が5質量%以上であることが好ましく、10質量%以上であることがより好ましい。水溶性の重合性化合物は、水性のインク組成物中に(望ましくは均一に)溶解し得るものであることが好ましい。後述する水溶性有機溶剤を添加することにより溶解度が上昇してインク組成物中に(望ましくは均一に)溶解するものであってもそうでないものでもよい。 (Polymerizable compound)
In the mixing step, a water-soluble polymerizable compound is used for mixing. Here, water-soluble means a property that can be dissolved in water so as to have a certain concentration or more. Specifically, the solubility in water at 25 ° C. is preferably 5% by mass or more, and more preferably 10% by mass or more. The water-soluble polymerizable compound is preferably one that can be dissolved (desirably uniformly) in the aqueous ink composition. The solubility may be increased by adding a water-soluble organic solvent to be described later, and it may be dissolved (desirably uniformly) in the ink composition or not.
前記水溶性の重合性化合物は、分子内に(メタ)アクリルエステル構造を有する化合物及び分子内に(メタ)アクリルアミド構造を有する化合物からなる群から選ばれる少なくとも1種を含むことが好ましく、分子内に(メタ)アクリルアミド構造を有する化合物を少なくとも1種含むことがより好ましい。ここで、(メタ)アクリルエステル構造とは、メタクリルエステル構造及びアクリルエステル構造の少なくとも一方を意味し、(メタ)アクリルアミド構造とは、メタクリルアミド構造及びアクリルアミド構造の少なくとも一方を意味する。
The water-soluble polymerizable compound preferably contains at least one selected from the group consisting of a compound having a (meth) acrylic ester structure in the molecule and a compound having a (meth) acrylamide structure in the molecule. It is more preferable to contain at least one compound having a (meth) acrylamide structure. Here, the (meth) acrylic ester structure means at least one of a methacrylic ester structure and an acrylic ester structure, and the (meth) acrylamide structure means at least one of a methacrylamide structure and an acrylamide structure.
-分子内に(メタ)アクリルエステル構造を有する化合物-
分子内に(メタ)アクリルエステル構造を有する重合性化合物は、分子内に(メタ)アクリルエステル構造を有する重合性化合物であれば限定されない。
分子内に(メタ)アクリルエステル構造を有する重合性化合物は、下記一般式(M-1)で表される化合物であることが好ましい。 -Compounds with (meth) acrylic ester structure in the molecule-
The polymerizable compound having a (meth) acrylic ester structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylic ester structure in the molecule.
The polymerizable compound having a (meth) acrylic ester structure in the molecule is preferably a compound represented by the following general formula (M-1).
分子内に(メタ)アクリルエステル構造を有する重合性化合物は、分子内に(メタ)アクリルエステル構造を有する重合性化合物であれば限定されない。
分子内に(メタ)アクリルエステル構造を有する重合性化合物は、下記一般式(M-1)で表される化合物であることが好ましい。 -Compounds with (meth) acrylic ester structure in the molecule-
The polymerizable compound having a (meth) acrylic ester structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylic ester structure in the molecule.
The polymerizable compound having a (meth) acrylic ester structure in the molecule is preferably a compound represented by the following general formula (M-1).
一般式(M-1)中、Q1はi価の連結基を表し、R1は水素原子またはメチル基を表す。また、iは1以上の整数を表す。
In general formula (M-1), Q 1 represents an i-valent linking group, and R 1 represents a hydrogen atom or a methyl group. I represents an integer of 1 or more.
一般式(M-1)で表される化合物は、不飽和単量体がエステル結合により連結基Q1に結合したものである。R1は、水素原子、またはメチル基を表し、好ましくは水素原子である。連結基Q1の価数iに制限はないが、2以上であることが好ましく、2以上6以下であることがより好ましく、2以上4以下であることがさらに好ましい。
Compound represented by the general formula (M-1) are those unsaturated monomer bonded to the linking group Q 1 by an ester bond. R 1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Although there is no limit to the valence i of the linking group Q 1, preferably 2 or more, more preferably 2 to 6 or less, still more preferably 2 to 4.
連結基Q1は(メタ)アクリルエステル構造と連結可能な基であれば特に制限はないが、一般式(M-1)で表される化合物が前述の水溶性を満たすような連結基から選択されることが好ましい。具体的には以下の化合物群Xから1以上の水素原子またはヒドロキシル基が除去された残基を挙げることができる。
The linking group Q 1 is not particularly limited as long as it is a group that can be linked to the (meth) acrylic ester structure, but is selected from the linking groups such that the compound represented by the general formula (M-1) satisfies the aforementioned water solubility. It is preferred that Specific examples include residues from which one or more hydrogen atoms or hydroxyl groups have been removed from the following compound group X.
-化合物群X-
エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール,2,3-ブタンジオール、1,5-ペンタンジオール、1,4-ペンタンジオール、2,4-ペンタンジオール、3-メチル-1,5-ペンタンジオール、2-メチル-2,4-ペンタンジオール、1,5-ヘキサンジオール、1,6-ヘキサンジオール、2,5-ヘキサンジオール、グリセリン、1,2,4-ブタントリオール、1,2,6-ヘキサントリオール、1,2,5-ペンタントリオール、チオグリコール、トリメチロールプロパン、ジトリメチロールプロパン、トリメチロールエタン、ジトリメチロールエタン、ネオペンチルグリコール、ペンタエリスリトール、ジペンタエリスリトール、及びこれらの縮合体、低分子ポリビニルアルコール、または糖類などのポリオール類、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ポリエチレンイミン、ポリプロピレンジアミン、などのポリアミン類。 -Compound group X-
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4 -Pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5 -Pentanetriol, thioglycol, Methylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, neopentyl glycol, pentaerythritol, dipentaerythritol, and their condensates, low molecular weight polyvinyl alcohol, or polyols such as sugars, ethylenediamine, diethylenetriamine, triethylene Polyamines such as tetramine, polyethyleneimine, and polypropylenediamine.
エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール,2,3-ブタンジオール、1,5-ペンタンジオール、1,4-ペンタンジオール、2,4-ペンタンジオール、3-メチル-1,5-ペンタンジオール、2-メチル-2,4-ペンタンジオール、1,5-ヘキサンジオール、1,6-ヘキサンジオール、2,5-ヘキサンジオール、グリセリン、1,2,4-ブタントリオール、1,2,6-ヘキサントリオール、1,2,5-ペンタントリオール、チオグリコール、トリメチロールプロパン、ジトリメチロールプロパン、トリメチロールエタン、ジトリメチロールエタン、ネオペンチルグリコール、ペンタエリスリトール、ジペンタエリスリトール、及びこれらの縮合体、低分子ポリビニルアルコール、または糖類などのポリオール類、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ポリエチレンイミン、ポリプロピレンジアミン、などのポリアミン類。 -Compound group X-
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4 -Pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5 -Pentanetriol, thioglycol, Methylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, neopentyl glycol, pentaerythritol, dipentaerythritol, and their condensates, low molecular weight polyvinyl alcohol, or polyols such as sugars, ethylenediamine, diethylenetriamine, triethylene Polyamines such as tetramine, polyethyleneimine, and polypropylenediamine.
さらに連結基Q1としては、メチレン、エチレン、プロピレン、ブチレン基等の炭素数4以下の置換又は無置換のアルキレン鎖、更にはピリジン環、イミダゾール環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環などの飽和もしくは不飽和のヘテロ環を有する官能基などを例示することができる。
Still linking group Q 1, methylene, ethylene, propylene, 4 or less of the substituted or unsubstituted alkylene chain of carbon atoms such as butylene group, more pyridine ring, an imidazole ring, a pyrazine ring, piperidine ring, piperazine ring, morpholine ring Examples thereof include a functional group having a saturated or unsaturated heterocyclic ring.
連結基Q1としては、これらの中でも、オキシアルキレン基(好ましくは、オキシエチレン基)を含むポリオール類の残基であることが好ましく、オキシアルキレン基(好ましくは、オキシエチレン基)を3以上含むポリオール類の残基であることが特に好ましい。
Among these, the linking group Q 1 is preferably a residue of a polyol containing an oxyalkylene group (preferably an oxyethylene group), and contains three or more oxyalkylene groups (preferably an oxyethylene group). A residue of a polyol is particularly preferable.
前記分子内に(メタ)アクリルエステル構造を有する水溶性の重合性化合物(M-1)の具体例としては、例えば以下に示すノニオン性化合物を挙げることができるが、本願はこれに限定されない。
Specific examples of the water-soluble polymerizable compound (M-1) having a (meth) acrylic ester structure in the molecule include, for example, the following nonionic compounds, but the present application is not limited thereto.
また、ノニオン性の重合性化合物としては、ポリオール化合物から誘導される1分子中に2以上のアクリロイル基を有する(メタ)アクリル酸エステルも用いることができる。前記ポリオール化合物としては、例えば、グリコール類の縮合物、オリゴエーテル、オリゴエステル類等や、単糖類、2糖類などの2以上の水酸基を有するポリオール化合物が挙げられる。
Further, as the nonionic polymerizable compound, a (meth) acrylic acid ester having two or more acryloyl groups in one molecule derived from a polyol compound can also be used. Examples of the polyol compound include polyol compounds having two or more hydroxyl groups such as glycol condensates, oligoethers, oligoesters, monosaccharides, and disaccharides.
またトリエタノールアミン、ジエタノールアミン、トリスヒドロキシアミノメタン、トリスヒドロキシアミノエタン等との(メタ)アクリル酸エステル等も好適である。
Further, (meth) acrylic acid esters with triethanolamine, diethanolamine, trishydroxyaminomethane, trishydroxyaminoethane, etc. are also suitable.
さらに、前記分子内に(メタ)アクリルエステル構造を有する水溶性の重合性化合物(M-1)の具体例としては、例えば以下に示すカチオン性化合物を挙げることができるが、本発明はこれに限定されない。
Furthermore, specific examples of the water-soluble polymerizable compound (M-1) having a (meth) acrylic ester structure in the molecule include the following cationic compounds. It is not limited.
前記構造において、Rは、ポリオール化合物の残基を表す。また、Xは、H又はCH3を表し、A-はCl-、HSO4
-又はCH3COO-を表す。前記ポリオール化合物としては、例えば、グリセリン、1,2,4-ブタントリオール、1,2,5-ペンタントリオール、1,2,6-ヘキサントリオール、トリメチロールプロパン、トリメチロールメタン、トリメチロールエタン、ペンタエリスリトール、ビスフェノールA、脂環型ビスフェノールA及びこれらの縮合物等を挙げることができる。さらに、カチオン基を有する重合性化合物として以下の構造(カチオン性化合物1~11)も挙げることができる。
In the above structure, R represents a residue of a polyol compound. X represents H or CH 3 , and A − represents Cl − , HSO 4 — or CH 3 COO — . Examples of the polyol compound include glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, trimethylolpropane, trimethylolmethane, trimethylolethane, penta Examples include erythritol, bisphenol A, alicyclic bisphenol A, and condensates thereof. Furthermore, the following structures (cationic compounds 1 to 11) can also be exemplified as the polymerizable compound having a cationic group.
-分子内に(メタ)アクリルアミド構造を有する化合物-
分子内に(メタ)アクリルアミド構造を有する化合物は、分子内に(メタ)アクリルアミド構造を有する重合性化合物であれば限定されない。
分子内に(メタ)アクリルアミド構造を有する化合物は、下記一般式(M-2)で表される化合物であることが好ましい。式(M-2)の構造を有することで、後述する一般式(1)で表される化合物と重合性化合物との相溶性が向上し、硬化感度等を高めることが可能となるため好ましい。 -Compounds with (meth) acrylamide structure in the molecule-
The compound having a (meth) acrylamide structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylamide structure in the molecule.
The compound having a (meth) acrylamide structure in the molecule is preferably a compound represented by the following general formula (M-2). Having the structure of the formula (M-2) is preferable because the compatibility between the compound represented by the general formula (1) described later and the polymerizable compound is improved, and the curing sensitivity and the like can be increased.
分子内に(メタ)アクリルアミド構造を有する化合物は、分子内に(メタ)アクリルアミド構造を有する重合性化合物であれば限定されない。
分子内に(メタ)アクリルアミド構造を有する化合物は、下記一般式(M-2)で表される化合物であることが好ましい。式(M-2)の構造を有することで、後述する一般式(1)で表される化合物と重合性化合物との相溶性が向上し、硬化感度等を高めることが可能となるため好ましい。 -Compounds with (meth) acrylamide structure in the molecule-
The compound having a (meth) acrylamide structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylamide structure in the molecule.
The compound having a (meth) acrylamide structure in the molecule is preferably a compound represented by the following general formula (M-2). Having the structure of the formula (M-2) is preferable because the compatibility between the compound represented by the general formula (1) described later and the polymerizable compound is improved, and the curing sensitivity and the like can be increased.
一般式(M-2)中、Q2はj価の連結基を表し、R2は水素原子またはメチル基を表す。また、jは1以上の整数を表す。
In general formula (M-2), Q 2 represents a j-valent linking group, and R 2 represents a hydrogen atom or a methyl group. J represents an integer of 1 or more.
一般式(M-2)で表される化合物は不飽和単量体が、アミド結合により連結基Q2に結合したものである。R2は、水素原子、またはメチル基を表し、好ましくは水素原子である。連結基Q2の価数jに制限はないが、2以上であることが好ましく、2以上6以下であることがより好ましく、2以上4以下であることがさらに好ましい。
The compound represented by formula (M-2) are those unsaturated monomers, bonded to the linking group Q 2 by an amide bond. R 2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. While the linking group Q is not limited to two valence j, preferably 2 or more, more preferably 2 to 6 or less, still more preferably 2 to 4.
また、連結基Q2は(メタ)アクリルアミド構造と連結可能な基であれば特に制限はない。連結基Q2の詳細は前記連結基Q1と同様であり、好ましい態様も同様である。
The connecting group Q 2 is not particularly limited as long as it is capable of linking groups and (meth) acrylamide structure. Details of the linking group Q 2 is the same as the linking group Q 1, preferred embodiment is also the same.
前記分子内に(メタ)アクリルアミド構造を有する水溶性の重合性化合物の具体例としては、例えば以下に示す水溶性の重合性化合物を挙げることができる。
Specific examples of the water-soluble polymerizable compound having a (meth) acrylamide structure in the molecule include the following water-soluble polymerizable compounds.
上記重合性化合物以外にも、例えば、下記に代表されるマレイミド構造を有する化合物、スルファミド構造を有する化合物又はN-ビニルアセトアミド構造を有する化合物等も使用することができる。
In addition to the polymerizable compound, for example, a compound having a maleimide structure represented by the following, a compound having a sulfamide structure, a compound having an N-vinylacetamide structure, or the like can be used.
水溶性の重合性化合物は、1種単独又は2種以上を組み合わせて含有することができる。
重合性化合物のインク組成物中における含有量は、インク組成物全質量に対して、3~50質量%が好ましく、10~30質量%がより好ましく、15~25質量%がさらに好ましい。 A water-soluble polymeric compound can be contained individually by 1 type or in combination of 2 or more types.
The content of the polymerizable compound in the ink composition is preferably 3 to 50% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass with respect to the total mass of the ink composition.
重合性化合物のインク組成物中における含有量は、インク組成物全質量に対して、3~50質量%が好ましく、10~30質量%がより好ましく、15~25質量%がさらに好ましい。 A water-soluble polymeric compound can be contained individually by 1 type or in combination of 2 or more types.
The content of the polymerizable compound in the ink composition is preferably 3 to 50% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass with respect to the total mass of the ink composition.
(重合開始剤)
前記混合工程においては、重合開始剤の少なくとも1種が混合に供される。前記重合開始剤は水溶性の重合開始剤の少なくとも1種であることが好ましい。ここで水溶性とは、25℃において蒸留水に0.5質量%以上溶解することを意味する。前記水溶性の重合開始剤は、25℃において蒸留水に1質量%以上溶解することが好ましく、3質量%以上溶解することがより好ましい。 (Polymerization initiator)
In the mixing step, at least one polymerization initiator is used for mixing. The polymerization initiator is preferably at least one water-soluble polymerization initiator. Here, water-soluble means to dissolve 0.5% by mass or more in distilled water at 25 ° C. The water-soluble polymerization initiator is preferably dissolved at 1% by mass or more in distilled water at 25 ° C., more preferably at least 3% by mass.
前記混合工程においては、重合開始剤の少なくとも1種が混合に供される。前記重合開始剤は水溶性の重合開始剤の少なくとも1種であることが好ましい。ここで水溶性とは、25℃において蒸留水に0.5質量%以上溶解することを意味する。前記水溶性の重合開始剤は、25℃において蒸留水に1質量%以上溶解することが好ましく、3質量%以上溶解することがより好ましい。 (Polymerization initiator)
In the mixing step, at least one polymerization initiator is used for mixing. The polymerization initiator is preferably at least one water-soluble polymerization initiator. Here, water-soluble means to dissolve 0.5% by mass or more in distilled water at 25 ° C. The water-soluble polymerization initiator is preferably dissolved at 1% by mass or more in distilled water at 25 ° C., more preferably at least 3% by mass.
前記水溶性の重合開始剤としては、例えば、下記一般式(1)で表される化合物や、特開2005―307198号公報に記載の化合物等を挙げることができる。中でも、記録媒体への密着性と耐擦性の観点から、下記一般式(1)で表される水溶性の重合開始剤が好ましい。
Examples of the water-soluble polymerization initiator include compounds represented by the following general formula (1), compounds described in JP-A-2005-307198, and the like. Of these, a water-soluble polymerization initiator represented by the following general formula (1) is preferable from the viewpoints of adhesion to a recording medium and abrasion resistance.
一般式(1)中、mおよびnはそれぞれ独立に0以上の整数を表し、m+nは0~3の整数を表す。mが0~3であってnが0または1であることが好ましく、mが0または1であってnが0であることがより好ましい。
一般式(1)で表される化合物の具体例を以下に示すが、本発明はこれらに限定されない。 In general formula (1), m and n each independently represents an integer of 0 or more, and m + n represents an integer of 0 to 3. It is preferable that m is 0 to 3 and n is 0 or 1, and it is more preferable that m is 0 or 1 and n is 0.
Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
一般式(1)で表される化合物の具体例を以下に示すが、本発明はこれらに限定されない。 In general formula (1), m and n each independently represents an integer of 0 or more, and m + n represents an integer of 0 to 3. It is preferable that m is 0 to 3 and n is 0 or 1, and it is more preferable that m is 0 or 1 and n is 0.
Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
一般式(1)で表される化合物は、新たに合成した化合物であっても、市販の化合物であってもよい。一般式(1)で表される市販の化合物としては例えば、イルガキュア2959(登録商標;m=0、n=0;BASFジャパン社製)を挙げることができる。
The compound represented by the general formula (1) may be a newly synthesized compound or a commercially available compound. Examples of commercially available compounds represented by the general formula (1) include Irgacure 2959 (registered trademark; m = 0, n = 0; manufactured by BASF Japan).
前記インク組成物の全質量に対する重合開始剤の含有量は、0.1~30質量%の範囲であることが好ましく、0.5~20質量%の範囲であることがより好ましく、1.0~15質量%の範囲であることがさらに好ましく、1.0~7.0質量%の範囲であることが最も好ましい。
The content of the polymerization initiator with respect to the total mass of the ink composition is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 20% by mass, and 1.0%. It is more preferably in the range of ˜15% by mass, most preferably in the range of 1.0 to 7.0% by mass.
(水溶性有機溶剤)
前記混合工程においては、水溶性有機溶剤の少なくとも1種をさらに混合に供することが好ましい。水溶性有機溶剤を黒色系インク組成物に含有させることで、乾燥防止、湿潤化あるいは浸透促進の効果を得うる。水溶性有機溶剤は、噴射ノズルのインク吐出口においてインクが付着乾燥して凝集体ができ、目詰まりするのを防止する乾燥防止剤の機能を奏し得る。乾燥防止や湿潤化の目的には、水より蒸気圧の低い水溶性有機溶剤が好ましい。また、水溶性有機溶剤は、紙へのインク浸透性を高める浸透促進剤の機能を奏し得る。 (Water-soluble organic solvent)
In the mixing step, it is preferable that at least one water-soluble organic solvent is further subjected to mixing. By including a water-soluble organic solvent in the black ink composition, it is possible to obtain an effect of preventing drying, wetting or promoting penetration. The water-soluble organic solvent can function as an anti-drying agent that prevents the ink from adhering and drying to form aggregates at the ink discharge port of the ejection nozzle, thereby preventing clogging. For the purpose of preventing drying or wetting, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. In addition, the water-soluble organic solvent can function as a penetration enhancer that enhances ink permeability to paper.
前記混合工程においては、水溶性有機溶剤の少なくとも1種をさらに混合に供することが好ましい。水溶性有機溶剤を黒色系インク組成物に含有させることで、乾燥防止、湿潤化あるいは浸透促進の効果を得うる。水溶性有機溶剤は、噴射ノズルのインク吐出口においてインクが付着乾燥して凝集体ができ、目詰まりするのを防止する乾燥防止剤の機能を奏し得る。乾燥防止や湿潤化の目的には、水より蒸気圧の低い水溶性有機溶剤が好ましい。また、水溶性有機溶剤は、紙へのインク浸透性を高める浸透促進剤の機能を奏し得る。 (Water-soluble organic solvent)
In the mixing step, it is preferable that at least one water-soluble organic solvent is further subjected to mixing. By including a water-soluble organic solvent in the black ink composition, it is possible to obtain an effect of preventing drying, wetting or promoting penetration. The water-soluble organic solvent can function as an anti-drying agent that prevents the ink from adhering and drying to form aggregates at the ink discharge port of the ejection nozzle, thereby preventing clogging. For the purpose of preventing drying or wetting, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. In addition, the water-soluble organic solvent can function as a penetration enhancer that enhances ink permeability to paper.
水溶性有機溶剤の例としては、グリセリン、エチレングリコール、プロピレングリコール等のアルカンジオール(多価アルコール類);糖アルコール類;エタノール、メタノール、ブタノール、プロパノール、イソプロパノールなどの炭素数1~4のアルキルアルコール類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-プロピルエーテル、エチレングリコールモノ-iso-プロピルエーテル、ジエチレングリコールモノ-iso-プロピルエーテル、エチレングリコールモノ-n-ブチルエーテル、エチレングリコールモノ-t-ブチルエーテル、ジエチレングリコールモノ-t-ブチルエーテル、トリエチレングリコールモノエチルエーテル、1-メチル-1-メトキシブタノール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-t-ブチルエーテル、プロピレングリコールモノ-n-プロピルエーテル、プロピレングリコールモノ-iso-プロピルエーテル、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ-n-プロピルエーテル、ジプロピレングリコールモノ-iso-プロピルエーテル、トリプロピレングリコールモノメチルエーテルなどのグリコールエーテル類等が挙げられる。これらは、1種単独で又は2種以上を組み合わせて用いることができる。
Examples of water-soluble organic solvents include alkanediols (polyhydric alcohols) such as glycerin, ethylene glycol, and propylene glycol; sugar alcohols; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, Diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n Butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monoethyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t- Butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol Mono-iso-propyl ether, tripropylene glycol monomethyl ether What glycol ethers. These can be used individually by 1 type or in combination of 2 or more types.
(界面活性剤)
前記混合工程は、界面活性剤の少なくとも1種をさらに混合に供することを含むことが好ましい。界面活性剤は、表面張力調整剤として用いることができる。
表面張力調整剤として、分子内に親水部と疎水部を合わせ持つ構造を有する化合物等を有効に使用することができ、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、ノニオン性界面活性剤、ベタイン系界面活性剤のいずれも使用することができる。
ある実施形態においては、インク組成物の打滴干渉抑制の観点から、ノニオン性界面活性剤が好ましく、中でもアセチレングリコール系界面活性剤がより好ましい。 (Surfactant)
It is preferable that the mixing step further includes subjecting at least one surfactant to further mixing. The surfactant can be used as a surface tension adjusting agent.
As the surface tension modifier, a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used effectively. Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic properties Either a surfactant or a betaine surfactant can be used.
In one embodiment, a nonionic surfactant is preferable from the viewpoint of suppression of droplet ejection interference of the ink composition, and an acetylene glycol surfactant is more preferable.
前記混合工程は、界面活性剤の少なくとも1種をさらに混合に供することを含むことが好ましい。界面活性剤は、表面張力調整剤として用いることができる。
表面張力調整剤として、分子内に親水部と疎水部を合わせ持つ構造を有する化合物等を有効に使用することができ、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、ノニオン性界面活性剤、ベタイン系界面活性剤のいずれも使用することができる。
ある実施形態においては、インク組成物の打滴干渉抑制の観点から、ノニオン性界面活性剤が好ましく、中でもアセチレングリコール系界面活性剤がより好ましい。 (Surfactant)
It is preferable that the mixing step further includes subjecting at least one surfactant to further mixing. The surfactant can be used as a surface tension adjusting agent.
As the surface tension modifier, a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used effectively. Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic properties Either a surfactant or a betaine surfactant can be used.
In one embodiment, a nonionic surfactant is preferable from the viewpoint of suppression of droplet ejection interference of the ink composition, and an acetylene glycol surfactant is more preferable.
アセチレングリコール系界面活性剤としては、例えば、2,4,7,9-テトラメチル-5-デシン-4,7-ジオール及び2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのアルキレンオキシド付加物等を挙げることができ、これから選ばれる少なくとも1種であることが好ましい。これらの化合物の市販品としては例えば、日信化学工業社のオルフィンE1010(諸品名)などのEシリーズを挙げることができる。
Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7. -Alkylene oxide adducts of diols can be mentioned, and at least one selected from these is preferable. Examples of commercially available products of these compounds include E series such as Olphine E1010 (product names) manufactured by Nissin Chemical Industry Co., Ltd.
黒色系インク組成物が界面活性剤(表面張力調整剤)を含有する場合、界面活性剤の含有量は、インクジェット方式によりインク組成物の吐出を良好に行う観点から、インク組成物の表面張力を20~60mN/mに調整できる範囲の量であるのが好ましく、表面張力の点からはより好ましくは20~45mN/mであり、更に好ましくは25~40mN/mである。
界面活性剤の黒色系インク組成物中における界面活性剤の具体的な量は、前記表面張力となる範囲が好ましいこと以外は特に制限はなく、0.1質量%以上が好ましく、より好ましくは0.1~10質量%であり、更に好ましくは0.2~3質量%である。 When the black ink composition contains a surfactant (surface tension adjusting agent), the surfactant content is determined from the surface tension of the ink composition from the viewpoint of favorably discharging the ink composition by an ink jet method. The amount is preferably in the range of 20 to 60 mN / m, more preferably 20 to 45 mN / m, and further preferably 25 to 40 mN / m from the viewpoint of surface tension.
The specific amount of the surfactant in the black ink composition of the surfactant is not particularly limited except that the surface tension is preferably within a range, and is preferably 0.1% by mass or more, more preferably 0. 0.1 to 10% by mass, more preferably 0.2 to 3% by mass.
界面活性剤の黒色系インク組成物中における界面活性剤の具体的な量は、前記表面張力となる範囲が好ましいこと以外は特に制限はなく、0.1質量%以上が好ましく、より好ましくは0.1~10質量%であり、更に好ましくは0.2~3質量%である。 When the black ink composition contains a surfactant (surface tension adjusting agent), the surfactant content is determined from the surface tension of the ink composition from the viewpoint of favorably discharging the ink composition by an ink jet method. The amount is preferably in the range of 20 to 60 mN / m, more preferably 20 to 45 mN / m, and further preferably 25 to 40 mN / m from the viewpoint of surface tension.
The specific amount of the surfactant in the black ink composition of the surfactant is not particularly limited except that the surface tension is preferably within a range, and is preferably 0.1% by mass or more, more preferably 0. 0.1 to 10% by mass, more preferably 0.2 to 3% by mass.
(コロイダルシリカ)
本発明の黒色系インク組成物の製造方法は、コロイダルシリカの少なくとも1種をさらに混合する工程を含むことが好ましい。コロイダルシリカを混合する工程は、前記混合工程と同時に行なっても、前記混合工程とは独立に行なってもよい。 (Colloidal silica)
The method for producing a black ink composition of the present invention preferably includes a step of further mixing at least one colloidal silica. The step of mixing colloidal silica may be performed simultaneously with the mixing step or may be performed independently of the mixing step.
本発明の黒色系インク組成物の製造方法は、コロイダルシリカの少なくとも1種をさらに混合する工程を含むことが好ましい。コロイダルシリカを混合する工程は、前記混合工程と同時に行なっても、前記混合工程とは独立に行なってもよい。 (Colloidal silica)
The method for producing a black ink composition of the present invention preferably includes a step of further mixing at least one colloidal silica. The step of mixing colloidal silica may be performed simultaneously with the mixing step or may be performed independently of the mixing step.
黒色系インク組成物がコロイダルシリカを含むことで、吐出安定性が向上し得ると共にインクジェットヘッド部材における撥液性の低下を抑制し得る。特にインクジェットヘッド部材の少なくとも一部にシリコンが使用されている場合に、特にその効果が認められ得る。
前記インク組成物がコロイダルシリカを含むことでインク成分の加水分解が効果的に抑制され、インク組成物の安定性が向上することにより、インクジェット記録装置上でインク組成物の吐出を止めて一定の時間放置し、その後吐出を再開した場合でも、優れた吐出安定性(放置回復性)が得られ、かつ画像の耐擦性も両立できるものと推察される。さらに、コロイダルシリカがインクジェットヘッド部材の表面に適度に吸着して、インク成分によるインクジェットヘッド部材表面の侵食を緩和することにより、インクジェットヘッド部材の撥液性の低下を防止できるものと推察される。 When the black ink composition contains colloidal silica, it is possible to improve ejection stability and suppress a decrease in liquid repellency in the ink jet head member. The effect can be recognized particularly when silicon is used in at least a part of the ink jet head member.
When the ink composition contains colloidal silica, the hydrolysis of the ink component is effectively suppressed, and the stability of the ink composition is improved, so that the ejection of the ink composition on the ink jet recording apparatus is stopped and fixed. It is presumed that even when the ink is left for a period of time and then the discharge is restarted, excellent discharge stability (stand-by recovery performance) can be obtained, and at the same time, the rub resistance of the image can be achieved. Further, it is presumed that colloidal silica is moderately adsorbed on the surface of the ink jet head member to reduce the erosion of the ink jet head member surface by the ink component, thereby preventing the liquid repellency of the ink jet head member from being lowered.
前記インク組成物がコロイダルシリカを含むことでインク成分の加水分解が効果的に抑制され、インク組成物の安定性が向上することにより、インクジェット記録装置上でインク組成物の吐出を止めて一定の時間放置し、その後吐出を再開した場合でも、優れた吐出安定性(放置回復性)が得られ、かつ画像の耐擦性も両立できるものと推察される。さらに、コロイダルシリカがインクジェットヘッド部材の表面に適度に吸着して、インク成分によるインクジェットヘッド部材表面の侵食を緩和することにより、インクジェットヘッド部材の撥液性の低下を防止できるものと推察される。 When the black ink composition contains colloidal silica, it is possible to improve ejection stability and suppress a decrease in liquid repellency in the ink jet head member. The effect can be recognized particularly when silicon is used in at least a part of the ink jet head member.
When the ink composition contains colloidal silica, the hydrolysis of the ink component is effectively suppressed, and the stability of the ink composition is improved, so that the ejection of the ink composition on the ink jet recording apparatus is stopped and fixed. It is presumed that even when the ink is left for a period of time and then the discharge is restarted, excellent discharge stability (stand-by recovery performance) can be obtained, and at the same time, the rub resistance of the image can be achieved. Further, it is presumed that colloidal silica is moderately adsorbed on the surface of the ink jet head member to reduce the erosion of the ink jet head member surface by the ink component, thereby preventing the liquid repellency of the ink jet head member from being lowered.
コロイダルシリカは、平均粒子径が数百nm以下であり且つケイ素を含む無機酸化物の微粒子からなるコロイドである。主成分として二酸化ケイ素(その水和物を含む)を含み、少量成分としてアルミン酸塩を含んでいてもよい。少量成分として含まれることがあるアルミン酸塩としては、アルミン酸ナトリウム、アルミン酸カリウムなどが挙げられる。
またコロイダルシリカには、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化アンモニウム等の無機塩類やテトラメチルアンモニウムヒドロキシド等の有機塩類が含まれていてもよい。これらの無機塩類および有機塩類は、例えば、コロイドの安定化剤として作用する。 Colloidal silica is a colloid composed of inorganic oxide fine particles having an average particle size of several hundred nm or less and containing silicon. Silicon dioxide (including hydrates thereof) may be included as a main component, and aluminate may be included as a minor component. Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.
In addition, colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.
またコロイダルシリカには、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化アンモニウム等の無機塩類やテトラメチルアンモニウムヒドロキシド等の有機塩類が含まれていてもよい。これらの無機塩類および有機塩類は、例えば、コロイドの安定化剤として作用する。 Colloidal silica is a colloid composed of inorganic oxide fine particles having an average particle size of several hundred nm or less and containing silicon. Silicon dioxide (including hydrates thereof) may be included as a main component, and aluminate may be included as a minor component. Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.
In addition, colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.
コロイダルシリカの分散媒には特に制限はなく、水、有機溶剤、およびこれらの混合物のいずれであってもよい。前記有機溶剤は水溶性有機溶剤であっても非水溶性有機溶剤であってもよいが、水溶性有機溶剤であることが好ましい。具体的には例えば、メタノール、エタノール、イソプロピルアルコール、n-プロパノール等を挙げることができる。
The colloidal silica dispersion medium is not particularly limited and may be water, an organic solvent, or a mixture thereof. The organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent, but is preferably a water-soluble organic solvent. Specific examples include methanol, ethanol, isopropyl alcohol, n-propanol and the like.
コロイダルシリカの製造方法には特に制限はなく、通常用いられる方法で製造することができる。例えば、四塩化ケイ素の熱分解によるアエロジル合成や水ガラスから製造することができる。あるいは、アルコキシドの加水分解といった液相合成法(例えば、「繊維と工業」、Vol.60、No.7(2004)P376参照)などによっても製造することができる。
The production method of colloidal silica is not particularly limited, and can be produced by a commonly used method. For example, it can be produced from aerosil synthesis by thermal decomposition of silicon tetrachloride or water glass. Alternatively, it can also be produced by a liquid phase synthesis method such as hydrolysis of alkoxide (for example, see “Fiber and Industry”, Vol. 60, No. 7 (2004) P376).
コロイダルシリカに含まれる粒子の平均粒子径には特に制限はないが、典型的には1nm~25nm、好ましくは3nm~25nm、より好ましくは3nm~20nmであり、さらに好ましくは3nm~15nmであり、特に好ましくは5nm~10nmである。
平均粒子径が25nm以下であると、インクジェットヘッドを構成する部材、例えば、基材、保護膜、撥液膜等に対するインク組成物によるダメージ(例えば、撥液性の低下等)をより効果的に抑制し得る。これは、平均粒子径が小さいことで、粒子の総表面積が大きくなり、インクジェットヘッドを構成する部材に対するダメージを、より効果的に抑制するためと推測し得る。またさらに、粒子の平均粒子径が25nm以下であることは、インク組成物の吐出性、粒子による研磨剤効果の観点からも好適であり得る。また、平均粒子径が1nm以上であると、生産性が向上し得、また性能のバラツキの少ないコロイダルシリカを得ることができる。 The average particle size of the particles contained in the colloidal silica is not particularly limited, but is typically 1 nm to 25 nm, preferably 3 nm to 25 nm, more preferably 3 nm to 20 nm, and further preferably 3 nm to 15 nm. Particularly preferred is 5 nm to 10 nm.
When the average particle diameter is 25 nm or less, damage (for example, decrease in liquid repellency) due to the ink composition to members constituting the inkjet head, such as a base material, a protective film, a liquid repellent film, and the like is more effectively performed. Can be suppressed. This can be presumed to be because the total surface area of the particles is increased because the average particle diameter is small, and damage to the members constituting the inkjet head is more effectively suppressed. Furthermore, the average particle diameter of the particles being 25 nm or less may be suitable from the viewpoint of the dischargeability of the ink composition and the abrasive effect of the particles. Moreover, productivity can improve that an average particle diameter is 1 nm or more, and colloidal silica with few dispersion | variation in performance can be obtained.
平均粒子径が25nm以下であると、インクジェットヘッドを構成する部材、例えば、基材、保護膜、撥液膜等に対するインク組成物によるダメージ(例えば、撥液性の低下等)をより効果的に抑制し得る。これは、平均粒子径が小さいことで、粒子の総表面積が大きくなり、インクジェットヘッドを構成する部材に対するダメージを、より効果的に抑制するためと推測し得る。またさらに、粒子の平均粒子径が25nm以下であることは、インク組成物の吐出性、粒子による研磨剤効果の観点からも好適であり得る。また、平均粒子径が1nm以上であると、生産性が向上し得、また性能のバラツキの少ないコロイダルシリカを得ることができる。 The average particle size of the particles contained in the colloidal silica is not particularly limited, but is typically 1 nm to 25 nm, preferably 3 nm to 25 nm, more preferably 3 nm to 20 nm, and further preferably 3 nm to 15 nm. Particularly preferred is 5 nm to 10 nm.
When the average particle diameter is 25 nm or less, damage (for example, decrease in liquid repellency) due to the ink composition to members constituting the inkjet head, such as a base material, a protective film, a liquid repellent film, and the like is more effectively performed. Can be suppressed. This can be presumed to be because the total surface area of the particles is increased because the average particle diameter is small, and damage to the members constituting the inkjet head is more effectively suppressed. Furthermore, the average particle diameter of the particles being 25 nm or less may be suitable from the viewpoint of the dischargeability of the ink composition and the abrasive effect of the particles. Moreover, productivity can improve that an average particle diameter is 1 nm or more, and colloidal silica with few dispersion | variation in performance can be obtained.
コロイダルシリカ粒子の平均粒子径は、分散粒子の一般的な測定である光散乱法、レーザー回折法などの手法により測定できるが、本開示では、より直接的な手法として、TEM(透過型電子顕微鏡)撮影法により300個のコロイダルシリカ粒子の粒径を実測し、その平均値を平均粒子径とした。
コロイダルシリカ粒子の形状は、インク組成物の吐出性能を妨げない限り、特に限定されない。例えば、球状、長尺の形状、針状、数珠状のいずれであってもよい。中でも、インクの吐出性の観点から、球状であることが好ましい。 The average particle size of the colloidal silica particles can be measured by a method such as a light scattering method or a laser diffraction method, which is a general measurement of dispersed particles. In this disclosure, as a more direct method, a TEM (transmission electron microscope) is used. ) The particle diameters of 300 colloidal silica particles were measured by the photographing method, and the average value was taken as the average particle diameter.
The shape of the colloidal silica particles is not particularly limited as long as it does not hinder the ejection performance of the ink composition. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used. Among them, the spherical shape is preferable from the viewpoint of ink ejection.
コロイダルシリカ粒子の形状は、インク組成物の吐出性能を妨げない限り、特に限定されない。例えば、球状、長尺の形状、針状、数珠状のいずれであってもよい。中でも、インクの吐出性の観点から、球状であることが好ましい。 The average particle size of the colloidal silica particles can be measured by a method such as a light scattering method or a laser diffraction method, which is a general measurement of dispersed particles. In this disclosure, as a more direct method, a TEM (transmission electron microscope) is used. ) The particle diameters of 300 colloidal silica particles were measured by the photographing method, and the average value was taken as the average particle diameter.
The shape of the colloidal silica particles is not particularly limited as long as it does not hinder the ejection performance of the ink composition. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used. Among them, the spherical shape is preferable from the viewpoint of ink ejection.
前記コロイダルシリカは、上記製造方法で製造されたものであっても、市販品であってもよい。市販品の具体例としては例えば、 Ludox AM、Ludox AS、Ludox LS、Ludox TM、Ludox HSなど(以上全て登録商標、E.I.Du Pont de Nemouvs & Co製);スノーテックスS、スノーテックスXS、スノーテックス20、スノーテックス30、スノーテックス40、スノーテックスN、スノーテックスC、スノーテックスOなど(以上全て登録商標、日産化学社製);Syton C-30、Syton ZOOなど(以上全て登録商標、Monsanto Co製);Nalcoag-1060 、Nalcoag-ID21~64(以上全て登録商標、Nalco Chem Co製);メタノールゾル、イソプロピルアルコール(IPA)ゾル、メチルエチルケトン(MEK)ゾル、およびトルエンゾル(以上、扶桑化学工業製);Cataloid-S、Cataloid-F120、Cataloid SI-350、Cataloid SI-500、Cataloid SI-30、Cataloid S-20L、Cataloid S-20H、CataloidS-30L、Cataloid S-30H、Cataloid SI-40、OSCAL-1432(イソプロピルアルコールゾル)など(以上全て商品名、日揮触媒化成製);アデライト(商品名、旭電化社製);数珠状粒子を含むコロイダルシリカとして、例えば、スノーテックスST-UP、スノーテックスPS-S、スノーテックスPS-M、スノーテックスST-OUP、スノーテックスPS-SO、スノーテックスPS-MO(以上、日産化学社製)などを挙げることができ、これらは容易に入手することが出来る。
The colloidal silica may be produced by the above production method or may be a commercially available product. Specific examples of commercially available products include, for example, Ludox AM, Ludox AS, Ludox LS, Ludox TM, Ludox HS, etc. (all registered trademarks, manufactured by EI Du Pont de Nemours &Co); SNOWTEX S, SNOWTEX XS , Snowtex 20, Snowtex 30, Snowtex 40, Snowtex N, Snowtex C, Snowtex O, etc. (all registered trademarks, manufactured by Nissan Chemical Co., Ltd.); Syton C-30, Symantec ZOO, etc. (all registered trademarks above) , Manufactured by Monsanto Co); Nalcoag-1060, Nalcoag-ID 21 to 64 (all registered trademarks, manufactured by Nalco Chem Co); methanol sol, isopropyl alcohol (IPA) sol, methyl ethyl keto (MEK) sol, and toluene sol (manufactured by Fuso Chemical Industries); Cataloid-S, Cataloid-F120, CataloidCSI-350, Cataloid SI-500, Cataloid SI-30, Cataloid S-20L, Cataloid S-20H, CataloidS -30L, Cataloid S-30H, Cataloid SI-40, OSCAL-1432 (isopropyl alcohol sol), etc. (all trade names, manufactured by JGC Catalysts &Chemicals); Adelite (trade name, manufactured by Asahi Denka Co., Ltd.); including beads Examples of colloidal silica include SNOWTEX ST-UP, SNOWTEX PS-S, SNOWTEX PS-M, SNOWTEX ST-OUP, SNOWTEX PS-SO, and SNOWTEX PS. -MO (manufactured by Nissan Chemical Co., Ltd.) and the like can be mentioned, and these can be easily obtained.
上記市販のコロイダルシリカ分散液のpHは、酸性またはアルカリ性に調整されているものが多い。これは、コロイダルシリカの安定分散領域が酸性側またはアルカリ性側に存在するためである。市販のコロイダルシリカ分散液をインク組成物中に添加する場合は、コロイダルシリカの安定分散領域のpHとインク組成物のpHとを考慮して添加する必要がある。
The pH of the above commercially available colloidal silica dispersion is often adjusted to be acidic or alkaline. This is because the stable dispersion region of colloidal silica exists on the acidic side or alkaline side. When a commercially available colloidal silica dispersion is added to the ink composition, it must be added in consideration of the pH of the stable dispersion region of the colloidal silica and the pH of the ink composition.
前記インク組成物におけるコロイダルシリカの含有量には特に制限はないが、好ましくはインク組成物総量の0.005質量%~0.5質量%であり、より好ましくはインク組成物総量の0.005質量%~0.1質量%であり、特に好ましくはインク組成物総量の0.01質量%~0.1質量%である。インク組成物中の含有量が前記上限値以下であることで、インク組成物の吐出性がより向上し得、またシリカ粒子の研磨剤効果によるインクジェットヘッドへの影響をより効果的に抑制し得る。また前記下限値以上であることで、インクジェットヘッド部材の撥液性の低下をより効果的に抑制し得る。
The colloidal silica content in the ink composition is not particularly limited, but is preferably 0.005% by mass to 0.5% by mass of the total amount of the ink composition, and more preferably 0.005% of the total amount of the ink composition. It is preferably from 0.01% by weight to 0.1% by weight, particularly preferably from 0.01% by weight to 0.1% by weight of the total amount of the ink composition. When the content in the ink composition is not more than the above upper limit value, the dischargeability of the ink composition can be further improved, and the influence on the ink jet head due to the abrasive effect of the silica particles can be more effectively suppressed. . Moreover, the fall of the liquid repellency of an inkjet head member can be suppressed more effectively because it is more than the said lower limit.
ある実施形態においては、前記インク組成物は、インクジェットヘッド部材の撥液性低下抑制と良好なインク吐出性の観点から、平均粒子径(TEM撮影法)が3nm~25nmのコロイダルシリカをインク組成物総量の0.005質量%~0.5質量%含有することが好ましく、平均粒子径が3nm~15nmのコロイダルシリカをインク組成物総量の0.005質量%~0.1質量%含有することがより好ましい。
In one embodiment, the ink composition is made of colloidal silica having an average particle size (TEM imaging method) of 3 nm to 25 nm from the viewpoint of suppressing the decrease in liquid repellency of an ink jet head member and good ink ejection properties. The total amount is preferably 0.005% to 0.5% by mass, and the colloidal silica having an average particle size of 3 nm to 15 nm is preferably included in the total amount of the ink composition from 0.005% to 0.1% by mass. More preferred.
前記インク組成物における重合性化合物に対するコロイダルシリカの含有量比(コロイダルシリカ/重合性化合物)は、質量基準で0.0001~0.1であることが好ましく、0.001~0.05であることがより好ましい。
重合性化合物に対するコロイダルシリカの含有比が0.0001以上であることで、インクジェットヘッド部材の撥液性の低下がより効果的に抑制され得る。また0.1以下であることで吐出性がより向上し得る。 The content ratio of colloidal silica to the polymerizable compound (colloidal silica / polymerizable compound) in the ink composition is preferably 0.0001 to 0.1, and preferably 0.001 to 0.05 on a mass basis. It is more preferable.
When the content ratio of colloidal silica with respect to the polymerizable compound is 0.0001 or more, a decrease in liquid repellency of the inkjet head member can be more effectively suppressed. Moreover, discharge property can improve more because it is 0.1 or less.
重合性化合物に対するコロイダルシリカの含有比が0.0001以上であることで、インクジェットヘッド部材の撥液性の低下がより効果的に抑制され得る。また0.1以下であることで吐出性がより向上し得る。 The content ratio of colloidal silica to the polymerizable compound (colloidal silica / polymerizable compound) in the ink composition is preferably 0.0001 to 0.1, and preferably 0.001 to 0.05 on a mass basis. It is more preferable.
When the content ratio of colloidal silica with respect to the polymerizable compound is 0.0001 or more, a decrease in liquid repellency of the inkjet head member can be more effectively suppressed. Moreover, discharge property can improve more because it is 0.1 or less.
(樹脂粒子)
前記黒色系インク組成物は、必要に応じて樹脂粒子を含有することができる。樹脂粒子は前記混合工程において同時に混合に供されてもよく、また前記混合工程とは独立して混合に供されることによりインク組成物中に含有されてもよい。
前記樹脂粒子は、処理液又は処理液が付与された後に乾燥した記録媒体上の領域と接触した際に凝集、又は分散不安定化してインクを増粘させることにより、インク組成物を固定化させる(すなわち画像を固定化させる)機能を有することが好ましい。樹脂粒子は、水および有機溶剤の少なくとも1種に分散された形態で用いられることが好ましい。 (Resin particles)
The black ink composition may contain resin particles as necessary. The resin particles may be subjected to mixing at the same time in the mixing step, or may be contained in the ink composition by being subjected to mixing independently of the mixing step.
The resin particles fix the ink composition by increasing the viscosity of the ink by aggregation or dispersion instability when contacted with the treatment liquid or the region on the dried recording medium after the treatment liquid is applied. It is preferable to have a function (that is, fix an image). The resin particles are preferably used in a form dispersed in at least one of water and an organic solvent.
前記黒色系インク組成物は、必要に応じて樹脂粒子を含有することができる。樹脂粒子は前記混合工程において同時に混合に供されてもよく、また前記混合工程とは独立して混合に供されることによりインク組成物中に含有されてもよい。
前記樹脂粒子は、処理液又は処理液が付与された後に乾燥した記録媒体上の領域と接触した際に凝集、又は分散不安定化してインクを増粘させることにより、インク組成物を固定化させる(すなわち画像を固定化させる)機能を有することが好ましい。樹脂粒子は、水および有機溶剤の少なくとも1種に分散された形態で用いられることが好ましい。 (Resin particles)
The black ink composition may contain resin particles as necessary. The resin particles may be subjected to mixing at the same time in the mixing step, or may be contained in the ink composition by being subjected to mixing independently of the mixing step.
The resin particles fix the ink composition by increasing the viscosity of the ink by aggregation or dispersion instability when contacted with the treatment liquid or the region on the dried recording medium after the treatment liquid is applied. It is preferable to have a function (that is, fix an image). The resin particles are preferably used in a form dispersed in at least one of water and an organic solvent.
樹脂粒子としては、アクリル系樹脂、酢酸ビニル系樹脂、スチレン-ブタジエン系樹脂、塩化ビニル系樹脂、アクリル-スチレン系樹脂、ブタジエン系樹脂、スチレン系樹脂、架橋アクリル樹脂、架橋スチレン系樹脂、ベンゾグアナミン樹脂、フェノール樹脂、シリコーン樹脂、エポキシ樹脂、ウレタン系樹脂、パラフィン系樹脂、フッ素系樹脂等あるいはそのラテックスを用いることができる。アクリル系樹脂、アクリル-スチレン系樹脂、スチレン系樹脂、架橋アクリル樹脂、架橋スチレン系樹脂を好ましい例として挙げることができる。
また樹脂粒子はラテックスの形態で用いることもできる。 Resin particles include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, butadiene resins, styrene resins, crosslinked acrylic resins, crosslinked styrene resins, and benzoguanamine resins. A phenol resin, a silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluorine resin, or a latex thereof can be used. Preferred examples include acrylic resins, acrylic-styrene resins, styrene resins, cross-linked acrylic resins, and cross-linked styrene resins.
The resin particles can also be used in the form of latex.
また樹脂粒子はラテックスの形態で用いることもできる。 Resin particles include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, butadiene resins, styrene resins, crosslinked acrylic resins, crosslinked styrene resins, and benzoguanamine resins. A phenol resin, a silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluorine resin, or a latex thereof can be used. Preferred examples include acrylic resins, acrylic-styrene resins, styrene resins, cross-linked acrylic resins, and cross-linked styrene resins.
The resin particles can also be used in the form of latex.
樹脂粒子の重量平均分子量は1万以上、20万以下が好ましく、より好ましくは2万以上、20万以下である。
また樹脂粒子の平均粒径は、1nm~1μmの範囲が好ましく、1nm~200nmの範囲がより好ましく、1nm~100nmの範囲が更に好ましく、1nm~50nmの範囲が特に好ましい。
樹脂粒子のガラス転移温度Tgは30℃以上であることが好ましく、40℃以上がより好ましく、50℃以上がさらに好ましい。 The weight average molecular weight of the resin particles is preferably 10,000 or more and 200,000 or less, more preferably 20,000 or more and 200,000 or less.
The average particle size of the resin particles is preferably in the range of 1 nm to 1 μm, more preferably in the range of 1 nm to 200 nm, still more preferably in the range of 1 nm to 100 nm, and particularly preferably in the range of 1 nm to 50 nm.
The glass transition temperature Tg of the resin particles is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
また樹脂粒子の平均粒径は、1nm~1μmの範囲が好ましく、1nm~200nmの範囲がより好ましく、1nm~100nmの範囲が更に好ましく、1nm~50nmの範囲が特に好ましい。
樹脂粒子のガラス転移温度Tgは30℃以上であることが好ましく、40℃以上がより好ましく、50℃以上がさらに好ましい。 The weight average molecular weight of the resin particles is preferably 10,000 or more and 200,000 or less, more preferably 20,000 or more and 200,000 or less.
The average particle size of the resin particles is preferably in the range of 1 nm to 1 μm, more preferably in the range of 1 nm to 200 nm, still more preferably in the range of 1 nm to 100 nm, and particularly preferably in the range of 1 nm to 50 nm.
The glass transition temperature Tg of the resin particles is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
黒色系インク組成物の全質量に対する樹脂粒子の含有量は、0.1~20質量%が好ましく、0.1~10質量%がより好ましく、0.1~5質量%がさらに好ましい。
樹脂微子の粒径分布には、特に制限は無く、広い粒径分布を持つもの、又は単分散の粒径分布を持つもの、いずれでもよい。単分散の粒径分布を持つ樹脂粒子を、1種のみ又は2種以上混合して使用してもよい。 The content of the resin particles with respect to the total mass of the black ink composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass.
The particle size distribution of the resin fine particles is not particularly limited, and may be any having a wide particle size distribution or a monodispersed particle size distribution. Resin particles having a monodispersed particle size distribution may be used alone or in combination of two or more.
樹脂微子の粒径分布には、特に制限は無く、広い粒径分布を持つもの、又は単分散の粒径分布を持つもの、いずれでもよい。単分散の粒径分布を持つ樹脂粒子を、1種のみ又は2種以上混合して使用してもよい。 The content of the resin particles with respect to the total mass of the black ink composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass.
The particle size distribution of the resin fine particles is not particularly limited, and may be any having a wide particle size distribution or a monodispersed particle size distribution. Resin particles having a monodispersed particle size distribution may be used alone or in combination of two or more.
(その他の成分)
前記黒色系インク組成物は、上記の成分に加え、必要に応じて更にその他成分として各種の添加剤を含むことができる。各種の添加剤は前記混合工程において同時に混合に供されてもよく、また前記混合工程とは独立して混合に供されることによりインク組成物中に含有されてもよい。
前記各種の添加剤としては、例えば、紫外線吸収剤、褪色防止剤、防黴剤、pH調整剤、防錆剤、酸化防止剤、乳化安定剤、防腐剤、消泡剤、粘度調整剤、分散安定剤、又はキレート剤等の公知の添加剤が挙げられる。これらの添加剤の含有量はその用途に応じて適宜決定すればよいが、例えば、黒色系インク組成物の全質量に対して各々0.02~1.00質量%程度とすればよい。 (Other ingredients)
The black ink composition may further contain various additives as other components, if necessary, in addition to the above components. Various additives may be used for mixing at the same time in the mixing step, or may be contained in the ink composition by being used for mixing independently of the mixing step.
Examples of the various additives include, for example, ultraviolet absorbers, antifading agents, antifungal agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, preservatives, antifoaming agents, viscosity modifiers, and dispersions. Known additives such as stabilizers or chelating agents can be used. The content of these additives may be appropriately determined according to the application, but may be, for example, about 0.02 to 1.00% by mass with respect to the total mass of the black ink composition.
前記黒色系インク組成物は、上記の成分に加え、必要に応じて更にその他成分として各種の添加剤を含むことができる。各種の添加剤は前記混合工程において同時に混合に供されてもよく、また前記混合工程とは独立して混合に供されることによりインク組成物中に含有されてもよい。
前記各種の添加剤としては、例えば、紫外線吸収剤、褪色防止剤、防黴剤、pH調整剤、防錆剤、酸化防止剤、乳化安定剤、防腐剤、消泡剤、粘度調整剤、分散安定剤、又はキレート剤等の公知の添加剤が挙げられる。これらの添加剤の含有量はその用途に応じて適宜決定すればよいが、例えば、黒色系インク組成物の全質量に対して各々0.02~1.00質量%程度とすればよい。 (Other ingredients)
The black ink composition may further contain various additives as other components, if necessary, in addition to the above components. Various additives may be used for mixing at the same time in the mixing step, or may be contained in the ink composition by being used for mixing independently of the mixing step.
Examples of the various additives include, for example, ultraviolet absorbers, antifading agents, antifungal agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, preservatives, antifoaming agents, viscosity modifiers, and dispersions. Known additives such as stabilizers or chelating agents can be used. The content of these additives may be appropriately determined according to the application, but may be, for example, about 0.02 to 1.00% by mass with respect to the total mass of the black ink composition.
紫外線吸収剤としては、例えば、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、サリチレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、ニッケル錯塩系紫外線吸収剤、などが挙げられる。
Examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, nickel complex salt UV absorbers, and the like.
褪色防止剤としては、各種の有機系および金属錯体系の褪色防止剤を使用することができる。有機の褪色防止剤としては、例えば、ハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、ヘテロ環類などがあり、金属錯体としてはニッケル錯体、亜鉛錯体などがある。
As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Examples of organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and metal complexes. There are nickel complex, zinc complex and the like.
防黴剤としては、例えば、デヒドロ酢酸ナトリウム、安息香酸ナトリウム、ナトリウムピリジンチオン-1-オキシド、p-ヒドロキシ安息香酸エチルエステル、1,2-ベンズイソチアゾリン-3-オン、ソルビン酸ナトリウム、ペンタクロロフェノールナトリウムなどが挙げられる。
Examples of the antifungal agent include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, sodium sorbate, pentachlorophenol Sodium etc. are mentioned.
pH調整剤としては、調合されるインク組成物に悪影響を及ぼさずにpHを所望の値に調整できるものであれば、特に制限はなく、目的に応じて適宜選択することができる。例えば、アルコールアミン類(例えば、ジエタノールアミン、トリエタノールアミン、2-アミノ-2-エチル-1,3-プロパンジオールなど)、アルカリ金属水酸化物(例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなど)、アンモニウム水酸化物(例えば、水酸化アンモニウム、第4級アンモニウム水酸化物など)、ホスホニウム水酸化物、アルカリ金属炭酸塩などが挙げられる。
The pH adjuster is not particularly limited as long as it can adjust the pH to a desired value without adversely affecting the ink composition to be prepared, and can be appropriately selected according to the purpose. For example, alcohol amines (eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol), alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide) Etc.), ammonium hydroxide (for example, ammonium hydroxide, quaternary ammonium hydroxide, etc.), phosphonium hydroxide, alkali metal carbonate and the like.
防錆剤としては、例えば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオジグリコール酸アンモン、ジイソプロピルアンモニウムニトライト、四硝酸ペンタエリスリトール、ジシクロヘキシルアンモニウムニトライトなどが挙げられる。
Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
酸化防止剤としては、例えば、フェノール系酸化防止剤(ヒンダードフェノール系酸化防止剤を含む)、アミン系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤などが挙げられる。
Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
キレート剤としては、例えば、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸ナトリウム、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸ナトリウム、ウラミル二酢酸ナトリウムなどが挙げられる。
Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like.
(インク組成物の物性)
前記インク組成物の表面張力(25℃)は、20mN/m以上60mN/m以下であることが好ましい。より好ましくは、20mN/m以上45mN/m以下であり、更に好ましくは、25mN/m以上40mN/m以下である。
表面張力は、Automatic Surface Tensiometer CBVP-Z(商品名、協和界面科学株式会社製)を用い、インク組成物を25℃の条件下で測定される。 (Physical properties of ink composition)
The surface tension (25 ° C.) of the ink composition is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 40 mN / m or less.
The surface tension is measured using an Automatic Surface Tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) under the condition of 25 ° C.
前記インク組成物の表面張力(25℃)は、20mN/m以上60mN/m以下であることが好ましい。より好ましくは、20mN/m以上45mN/m以下であり、更に好ましくは、25mN/m以上40mN/m以下である。
表面張力は、Automatic Surface Tensiometer CBVP-Z(商品名、協和界面科学株式会社製)を用い、インク組成物を25℃の条件下で測定される。 (Physical properties of ink composition)
The surface tension (25 ° C.) of the ink composition is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 40 mN / m or less.
The surface tension is measured using an Automatic Surface Tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) under the condition of 25 ° C.
また、前記インク組成物の25℃での粘度は、1.2mPa・s以上15.0mPa・s以下であることが好ましく、より好ましくは2mPa・s以上13mPa・s未満であり、更に好ましくは2.5mPa・s以上10mPa・s未満である。
粘度は、VISCOMETER TV-22(商品名、TOKI SANGYO CO.LTD製)を用い、インク組成物を25℃の条件下で測定される。 The viscosity of the ink composition at 25 ° C. is preferably 1.2 mPa · s or more and 15.0 mPa · s or less, more preferably 2 mPa · s or more and less than 13 mPa · s, and still more preferably 2 It is not less than 5 mPa · s and less than 10 mPa · s.
The viscosity is measured using a VISCOMETER TV-22 (trade name, manufactured by TOKI SANGYO CO. LTD) under conditions of 25 ° C. of the ink composition.
粘度は、VISCOMETER TV-22(商品名、TOKI SANGYO CO.LTD製)を用い、インク組成物を25℃の条件下で測定される。 The viscosity of the ink composition at 25 ° C. is preferably 1.2 mPa · s or more and 15.0 mPa · s or less, more preferably 2 mPa · s or more and less than 13 mPa · s, and still more preferably 2 It is not less than 5 mPa · s and less than 10 mPa · s.
The viscosity is measured using a VISCOMETER TV-22 (trade name, manufactured by TOKI SANGYO CO. LTD) under conditions of 25 ° C. of the ink composition.
[画像形成方法]
前記黒色系インク組成物を用いる画像形成方法としては、例えば、記録媒体上に前記黒色系インク組成物をインクジェット法で付与することと、前記インク組成物と接触することで凝集体を形成可能な凝集剤を含む処理液を記録媒体上に付与することと、記録媒体上に付与されたインク組成物に活性エネルギー線を照射してインク画像を硬化することと、を含み、必要に応じてその他の工程を含み得る画像形成方法を挙げることができる。 [Image forming method]
As an image forming method using the black ink composition, for example, an aggregate can be formed by applying the black ink composition on a recording medium by an ink jet method and contacting the ink composition. Including applying a treatment liquid containing an aggregating agent on the recording medium, and irradiating the ink composition applied on the recording medium with an active energy ray to cure the ink image, and others as necessary An image forming method that can include these steps can be given.
前記黒色系インク組成物を用いる画像形成方法としては、例えば、記録媒体上に前記黒色系インク組成物をインクジェット法で付与することと、前記インク組成物と接触することで凝集体を形成可能な凝集剤を含む処理液を記録媒体上に付与することと、記録媒体上に付与されたインク組成物に活性エネルギー線を照射してインク画像を硬化することと、を含み、必要に応じてその他の工程を含み得る画像形成方法を挙げることができる。 [Image forming method]
As an image forming method using the black ink composition, for example, an aggregate can be formed by applying the black ink composition on a recording medium by an ink jet method and contacting the ink composition. Including applying a treatment liquid containing an aggregating agent on the recording medium, and irradiating the ink composition applied on the recording medium with an active energy ray to cure the ink image, and others as necessary An image forming method that can include these steps can be given.
処理液に含まれる凝集剤によってインク組成物の成分を凝集状態にし、これに活性エネルギー線を照射して重合性化合物を重合、硬化させることで、記録媒体への密着性、耐擦過性により優れた画像を形成し得る。また硬化して得られる画像は膜強度がより向上し得る。
By coagulating the components of the ink composition with an aggregating agent contained in the treatment liquid and irradiating this with active energy rays to polymerize and cure the polymerizable compound, it is superior in adhesion to the recording medium and scratch resistance. Images can be formed. Moreover, the film | membrane intensity | strength can improve more the image obtained by hardening.
(インク付与工程)
インク付与工程では、前記黒色系インク組成物が、記録媒体上にインクジェット法で付与される。本工程では、記録媒体上に選択的にインク組成物を付与でき、所望の画像を形成できる。 (Ink application process)
In the ink application process, the black ink composition is applied onto a recording medium by an ink jet method. In this step, the ink composition can be selectively applied onto the recording medium, and a desired image can be formed.
インク付与工程では、前記黒色系インク組成物が、記録媒体上にインクジェット法で付与される。本工程では、記録媒体上に選択的にインク組成物を付与でき、所望の画像を形成できる。 (Ink application process)
In the ink application process, the black ink composition is applied onto a recording medium by an ink jet method. In this step, the ink composition can be selectively applied onto the recording medium, and a desired image can be formed.
インクジェット法は、特に制限はなく、公知の方式、例えば、静電誘引力を利用してインクを吐出させる電荷制御方式、ピエゾ素子の振動圧力を利用するドロップオンデマンド方式(圧力パルス方式)、電気信号を音響ビームに変えインクに照射して放射圧を利用してインクを吐出させる音響インクジェット方式、及びインクを加熱して気泡を形成し、生じた圧力を利用するサーマルインクジェット(バブルジェット(登録商標))方式等のいずれであってもよい。前記インクジェット法には、フォトインクと称する濃度の低いインクを小さい体積で多数射出する方式、実質的に同じ色相で濃度の異なる複数のインクを用いて画質を改良する方式や無色透明のインクを用いる方式が含まれる。
The inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. )) Any method may be used. In the ink jet method, a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent ink are used. The method is included.
インクジェット法で用いるインクジェットヘッドは、オンデマンド方式でもコンティニュアス方式でも構わない。吐出方式としては、電気-機械変換方式(例えば、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型、シェアードウォール型等)、電気-熱変換方式(例えば、サーマルインクジェット型、バブルジェット(登録商標)型等)、静電吸引方式(例えば、電界制御型、スリットジェット型等)及び放電方式(例えば、スパークジェット型等)などを具体的な例として挙げることができるが、いずれの吐出方式を用いても構わない。
前記インクジェット法により記録を行う際に使用するインクノズル等については特に制限はなく、目的に応じて、適宜選択することができる。 An ink jet head used in the ink jet method may be an on-demand method or a continuous method. Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (eg, thermal ink jet type) Specific examples include, for example, bubble jet (registered trademark) type, electrostatic attraction type (eg, electric field control type, slit jet type), and discharge type (eg, spark jet type). Any discharge method may be used.
There are no particular restrictions on the ink nozzles used when recording by the inkjet method, and they can be appropriately selected according to the purpose.
前記インクジェット法により記録を行う際に使用するインクノズル等については特に制限はなく、目的に応じて、適宜選択することができる。 An ink jet head used in the ink jet method may be an on-demand method or a continuous method. Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (eg, thermal ink jet type) Specific examples include, for example, bubble jet (registered trademark) type, electrostatic attraction type (eg, electric field control type, slit jet type), and discharge type (eg, spark jet type). Any discharge method may be used.
There are no particular restrictions on the ink nozzles used when recording by the inkjet method, and they can be appropriately selected according to the purpose.
インクジェット法の方式としては、短尺のシリアルヘッドを用い、ヘッドを記録媒体の幅方向に走査させながら記録を行うシャトル方式と、記録媒体の1辺の全域に対応して記録素子が配列されているラインヘッドを用いたライン方式とがある。ライン方式では、記録素子の配列方向と直交する方向に記録媒体を走査させることで記録媒体の全面に画像記録を行うことができ、短尺ヘッドを走査するキャリッジ等の搬送系が不要となる。また、キャリッジの移動と記録媒体との複雑な走査制御が不要になり、記録媒体だけが移動するので、シャトル方式に比べて記録速度の高速化が実現できる。前記インクジェット記録方法は、これらのいずれにも適用可能であるが、一般にダミージェットを行わないライン方式に適用した場合に、吐出精度及び画像の耐擦過性の向上効果が大きくなり得る。
As a method of the ink jet method, a short serial head is used, and a recording method is arranged in correspondence with a shuttle method in which recording is performed while the head is scanned in the width direction of the recording medium, and the entire area of one side of the recording medium. There is a line system using a line head. In the line method, an image can be recorded on the entire surface of the recording medium by scanning the recording medium in a direction orthogonal to the arrangement direction of the recording elements, and a carriage system such as a carriage for scanning a short head is not necessary. Further, since complicated scanning control of the carriage movement and the recording medium is not required, and only the recording medium is moved, the recording speed can be increased as compared with the shuttle system. The ink jet recording method can be applied to any of these, but generally, when applied to a line system that does not use a dummy jet, the effect of improving ejection accuracy and image scratch resistance can be increased.
インクジェットヘッドから吐出されるインクの液滴量は、高精細な画像を得る観点で、0.5~6pl(ピコリットル)が好ましく、1~5plがより好ましく、更に好ましくは2~4plである。
The amount of ink droplets ejected from the inkjet head is preferably 0.5 to 6 pl (picoliter), more preferably 1 to 5 pl, and still more preferably 2 to 4 pl from the viewpoint of obtaining a high-definition image.
(処理液付与工程)
処理液付与工程は、インク組成物と接触することで凝集体を形成可能な凝集剤を含む処理液を記録媒体に付与し、処理液をインク組成物と接触させて画像化する。処理液がインク組成物と接触すると、インク組成物中の樹脂粒子や顔料などの分散粒子が凝集し、記録媒体上に画像が固定化される。処理液における各成分の詳細及び好ましい態様については後述する。 (Processing liquid application process)
In the treatment liquid application step, a treatment liquid containing an aggregating agent capable of forming an aggregate by contact with the ink composition is applied to the recording medium, and the treatment liquid is contacted with the ink composition to form an image. When the treatment liquid comes into contact with the ink composition, dispersed particles such as resin particles and pigment in the ink composition are aggregated, and the image is fixed on the recording medium. Details and preferred embodiments of each component in the treatment liquid will be described later.
処理液付与工程は、インク組成物と接触することで凝集体を形成可能な凝集剤を含む処理液を記録媒体に付与し、処理液をインク組成物と接触させて画像化する。処理液がインク組成物と接触すると、インク組成物中の樹脂粒子や顔料などの分散粒子が凝集し、記録媒体上に画像が固定化される。処理液における各成分の詳細及び好ましい態様については後述する。 (Processing liquid application process)
In the treatment liquid application step, a treatment liquid containing an aggregating agent capable of forming an aggregate by contact with the ink composition is applied to the recording medium, and the treatment liquid is contacted with the ink composition to form an image. When the treatment liquid comes into contact with the ink composition, dispersed particles such as resin particles and pigment in the ink composition are aggregated, and the image is fixed on the recording medium. Details and preferred embodiments of each component in the treatment liquid will be described later.
処理液の付与は、塗布法、インクジェット法、浸漬法などの公知の方法を適用して行うことができる。塗布法としては、バーコーター、エクストルージョンダイコーター、エアードクターコーター、ブレードコーター、ロッドコーター、ナイフコーター、スクイズコーター、リバースロールコーター等を用いた公知の塗布方法が挙げられる。インクジェット法の詳細については、既述の通りである。
The treatment liquid can be applied by applying a known method such as a coating method, an inkjet method, or an immersion method. Examples of the coating method include known coating methods using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and the like. The details of the inkjet method are as described above.
処理液付与は、インク組成物の記録媒体上への付与の前又は後のいずれに行われてもよい。
ある実施形態においては、処理液付与工程で処理液を記録媒体上に付与した後に、インクを記録媒体上に付与する態様が好ましい。すなわち、記録媒体上に、インク組成物をインクジェット法で付与(吐出)する前に、予めインク組成物中の顔料を凝集可能な処理液を付与しておき、記録媒体上に付与された処理液に接触するようにインク組成物を吐出して画像化する態様が好ましい。これにより、インクジェット記録を高速化でき、高速記録しても濃度、解像度の高い画像を得うる。 The treatment liquid may be applied either before or after the ink composition is applied to the recording medium.
In an embodiment, a mode in which the ink is applied onto the recording medium after the treatment liquid is applied onto the recording medium in the treatment liquid applying step is preferable. That is, before applying (discharging) the ink composition to the recording medium by the ink jet method, a processing liquid capable of aggregating the pigment in the ink composition is applied in advance, and the processing liquid applied on the recording medium is applied. An embodiment in which an image is formed by discharging the ink composition so as to come into contact with the ink is preferable. Thereby, inkjet recording can be speeded up, and an image with high density and resolution can be obtained even at high speed recording.
ある実施形態においては、処理液付与工程で処理液を記録媒体上に付与した後に、インクを記録媒体上に付与する態様が好ましい。すなわち、記録媒体上に、インク組成物をインクジェット法で付与(吐出)する前に、予めインク組成物中の顔料を凝集可能な処理液を付与しておき、記録媒体上に付与された処理液に接触するようにインク組成物を吐出して画像化する態様が好ましい。これにより、インクジェット記録を高速化でき、高速記録しても濃度、解像度の高い画像を得うる。 The treatment liquid may be applied either before or after the ink composition is applied to the recording medium.
In an embodiment, a mode in which the ink is applied onto the recording medium after the treatment liquid is applied onto the recording medium in the treatment liquid applying step is preferable. That is, before applying (discharging) the ink composition to the recording medium by the ink jet method, a processing liquid capable of aggregating the pigment in the ink composition is applied in advance, and the processing liquid applied on the recording medium is applied. An embodiment in which an image is formed by discharging the ink composition so as to come into contact with the ink is preferable. Thereby, inkjet recording can be speeded up, and an image with high density and resolution can be obtained even at high speed recording.
処理液の付与量は、インク組成物を凝集可能であれば特に制限はないが、好ましくは、凝集剤の付与量が0.1g/m2以上となる付与量とすることができる。中でも、凝集剤の付与量が0.1~1.0g/m2となる量が好ましく、より好ましくは0.2~0.8g/m2である。凝集成分の付与量は、0.1g/m2以上であると凝集反応が良好に進行し得、1.0g/m2以下であると光沢度が高くなり過ぎることを抑制し得る。
The amount of treatment liquid applied is not particularly limited as long as the ink composition can be agglomerated, but it can be preferably an amount such that the amount of aggregating agent applied is 0.1 g / m 2 or more. In particular, the amount of the flocculant applied is preferably 0.1 to 1.0 g / m 2 , more preferably 0.2 to 0.8 g / m 2 . When the amount of the aggregating component applied is 0.1 g / m 2 or more, the aggregating reaction can proceed satisfactorily, and when it is 1.0 g / m 2 or less, the glossiness can be suppressed from becoming too high.
[処理液]
処理液は、前記黒色系インク組成物と接触することで凝集体を形成可能な凝集剤の少なくとも1種を含む。処理液は、必要に応じて、さらに他の成分を含んでも含まなくてもよい。 [Treatment solution]
The treatment liquid contains at least one aggregating agent capable of forming an aggregate by contact with the black ink composition. The treatment liquid may or may not contain other components as required.
処理液は、前記黒色系インク組成物と接触することで凝集体を形成可能な凝集剤の少なくとも1種を含む。処理液は、必要に応じて、さらに他の成分を含んでも含まなくてもよい。 [Treatment solution]
The treatment liquid contains at least one aggregating agent capable of forming an aggregate by contact with the black ink composition. The treatment liquid may or may not contain other components as required.
凝集剤は、記録媒体上においてインク組成物と接触することにより、インク組成物中の成分を凝集(固定化)可能なものであり、例えば、固定化剤として機能する。例えば、処理液を記録媒体(好ましくは、塗工紙)に付与することにより記録媒体上に凝集剤が存在している状態で、インク組成物がさらに記録媒体上に着滴して凝集剤と接触することにより、インク組成物中の成分を凝集させて、インク組成物成分を記録媒体上に固定化することができる。
凝集剤としては、酸性化合物、多価金属塩、およびカチオン性ポリマー等を挙げることができる。中でもインク組成物成分の凝集性向上の観点から、酸性化合物であることが好ましい。凝集剤は1種単独で用いても、2種以上を併用してもよい。 The flocculant is capable of aggregating (fixing) components in the ink composition by contacting the ink composition on the recording medium, and functions as a fixing agent, for example. For example, by applying the treatment liquid to a recording medium (preferably coated paper), the ink composition is further deposited on the recording medium in a state where the aggregating agent is present on the recording medium, By contacting, the components in the ink composition can be aggregated, and the ink composition components can be fixed on the recording medium.
Examples of the flocculant include acidic compounds, polyvalent metal salts, and cationic polymers. Among these, an acidic compound is preferable from the viewpoint of improving the cohesiveness of the ink composition component. A flocculant may be used individually by 1 type, or may use 2 or more types together.
凝集剤としては、酸性化合物、多価金属塩、およびカチオン性ポリマー等を挙げることができる。中でもインク組成物成分の凝集性向上の観点から、酸性化合物であることが好ましい。凝集剤は1種単独で用いても、2種以上を併用してもよい。 The flocculant is capable of aggregating (fixing) components in the ink composition by contacting the ink composition on the recording medium, and functions as a fixing agent, for example. For example, by applying the treatment liquid to a recording medium (preferably coated paper), the ink composition is further deposited on the recording medium in a state where the aggregating agent is present on the recording medium, By contacting, the components in the ink composition can be aggregated, and the ink composition components can be fixed on the recording medium.
Examples of the flocculant include acidic compounds, polyvalent metal salts, and cationic polymers. Among these, an acidic compound is preferable from the viewpoint of improving the cohesiveness of the ink composition component. A flocculant may be used individually by 1 type, or may use 2 or more types together.
-酸性化合物-
酸性化合物としては、例えば、硫酸、塩酸、硝酸、リン酸、ポリアクリル酸、酢酸、グリコール酸、マロン酸、リンゴ酸、マレイン酸、アスコルビン酸、コハク酸、グルタル酸、フマル酸、クエン酸、酒石酸、乳酸、スルホン酸、オルトリン酸、メタリン酸、ピロリドンカルボン酸、ピロンカルボン酸、ピロールカルボン酸、フランカルボン酸、ピリジンカルボン酸、クマリン酸、チオフェンカルボン酸、ニコチン酸、およびこれらの化合物の誘導体等が好適に挙げられる。 -Acid compounds-
Examples of acidic compounds include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. , Lactic acid, sulfonic acid, orthophosphoric acid, metaphosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, and derivatives of these compounds, etc. Preferably mentioned.
酸性化合物としては、例えば、硫酸、塩酸、硝酸、リン酸、ポリアクリル酸、酢酸、グリコール酸、マロン酸、リンゴ酸、マレイン酸、アスコルビン酸、コハク酸、グルタル酸、フマル酸、クエン酸、酒石酸、乳酸、スルホン酸、オルトリン酸、メタリン酸、ピロリドンカルボン酸、ピロンカルボン酸、ピロールカルボン酸、フランカルボン酸、ピリジンカルボン酸、クマリン酸、チオフェンカルボン酸、ニコチン酸、およびこれらの化合物の誘導体等が好適に挙げられる。 -Acid compounds-
Examples of acidic compounds include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. , Lactic acid, sulfonic acid, orthophosphoric acid, metaphosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, and derivatives of these compounds, etc. Preferably mentioned.
これらの中でも、水溶性の高い酸性化合物が好ましい。インク組成物成分と反応してインク全体を固定化させる観点から、3価以下の酸性化合物が好ましく、2価または3価の酸性化合物が特に好ましい。
酸性化合物は、1種単独で用いてもよく、2種以上を併用してもよい。 Among these, acidic compounds with high water solubility are preferable. From the viewpoint of fixing the whole ink by reacting with the ink composition component, a trivalent or less acidic compound is preferable, and a divalent or trivalent acidic compound is particularly preferable.
An acidic compound may be used individually by 1 type, and may use 2 or more types together.
酸性化合物は、1種単独で用いてもよく、2種以上を併用してもよい。 Among these, acidic compounds with high water solubility are preferable. From the viewpoint of fixing the whole ink by reacting with the ink composition component, a trivalent or less acidic compound is preferable, and a divalent or trivalent acidic compound is particularly preferable.
An acidic compound may be used individually by 1 type, and may use 2 or more types together.
前記処理液が酸性化合物を含む場合、処理液のpH(25℃)は、0.1~6.8であることが好ましく、0.5~6.0であることがより好ましく、0.8~5.0であることがさらに好ましい。
When the treatment liquid contains an acidic compound, the pH (25 ° C.) of the treatment liquid is preferably 0.1 to 6.8, more preferably 0.5 to 6.0, and 0.8 More preferably, it is -5.0.
前記酸性化合物の含有量は、前記処理液の全質量に対し、40質量%以下であることが好ましく、15~40質量%であることがより好ましく、15質量%~35質量%であることがさらに好ましい。酸性化合物の含有量を40質量%以下とすることでインク組成物中の成分をより効率的に固定化することができる。
The content of the acidic compound is preferably 40% by mass or less, more preferably 15 to 40% by mass, and more preferably 15 to 35% by mass with respect to the total mass of the treatment liquid. Further preferred. By setting the content of the acidic compound to 40% by mass or less, the components in the ink composition can be more efficiently fixed.
処理液は前記凝集剤に加えて、水溶性有機溶剤の少なくとも1種を含むことが好ましい。水溶性有機溶剤の詳細は、インク組成物におけるそれと同様であり、好ましい態様も同様である。
The treatment liquid preferably contains at least one water-soluble organic solvent in addition to the flocculant. The details of the water-soluble organic solvent are the same as those in the ink composition, and the preferred embodiments are also the same.
処理液は、本発明の効果を損なわない範囲内で、更にその他の成分として他の添加剤を含有してもよく、含有しなくてもよい。他の添加剤としては、例えば、乾燥防止剤(湿潤剤)、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤、pH調整剤、表面張力調整剤、消泡剤、粘度調整剤、分散剤、分散安定剤、防錆剤、キレート剤等の公知の添加剤が挙げられる。
The treatment liquid may or may not contain other additives as other components as long as the effects of the present invention are not impaired. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, anti-foaming agents. Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned.
また、ある実施形態においては、処理液付与後にインク付与を行い、処理液を記録媒体上に付与した後、インク組成物が付与されるまでの間に、記録媒体上の処理液を加熱乾燥することが好ましい。インク付与工程前に予め処理液を加熱乾燥させることにより、滲み防止などのインク着色性が良好になり、色濃度及び色相の良好な可視画像を記録し得る。
In some embodiments, ink is applied after the treatment liquid is applied, and the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied on the recording medium and before the ink composition is applied. It is preferable. By heating and drying the treatment liquid in advance before the ink application step, ink colorability such as bleeding prevention is improved, and a visible image with good color density and hue can be recorded.
加熱乾燥は、ヒーター等の公知の加熱手段やドライヤ等の送風を利用した送風手段、あるいはこれらを組み合わせた手段により行うことができる。加熱方法としては、例えば、記録媒体の処理液の付与面と反対側からヒーター等で熱を与える方法や、記録媒体の処理液の付与面に温風又は熱風をあてる方法、赤外線ヒーターを用いた加熱法などが挙げられ、これらのうち一つを用いても、複数を組み合わせて加熱してもよい。
Heat drying can be performed by a known heating means such as a heater, a blowing means using blowing air such as a dryer, or a combination of these. As the heating method, for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, an infrared heater was used. The heating method etc. are mentioned, One of these may be used or you may heat combining a plurality.
(加熱乾燥工程)
前記画像形成方法は、前記インク吐出の後、インク組成物の記録媒体上への付与により形成されたインク画像を加熱して、インク組成物中の溶媒の少なくとも一部を除去することが好ましい。加熱乾燥処理により、後の硬化工程によって形成される画像の記録媒体への密着性と耐擦性がより優れた画像を形成することができる。 (Heat drying process)
The image forming method preferably removes at least a part of the solvent in the ink composition by heating the ink image formed by applying the ink composition onto a recording medium after the ink ejection. By heat-drying treatment, it is possible to form an image having better adhesion to a recording medium and an abrasion resistance of an image formed by a subsequent curing step.
前記画像形成方法は、前記インク吐出の後、インク組成物の記録媒体上への付与により形成されたインク画像を加熱して、インク組成物中の溶媒の少なくとも一部を除去することが好ましい。加熱乾燥処理により、後の硬化工程によって形成される画像の記録媒体への密着性と耐擦性がより優れた画像を形成することができる。 (Heat drying process)
The image forming method preferably removes at least a part of the solvent in the ink composition by heating the ink image formed by applying the ink composition onto a recording medium after the ink ejection. By heat-drying treatment, it is possible to form an image having better adhesion to a recording medium and an abrasion resistance of an image formed by a subsequent curing step.
加熱の方法は、特に制限されないが、ニクロム線ヒーター等の発熱体で加熱する方法、温風又は熱風を供給する方法、ハロゲンランプ、赤外線ランプなどで加熱する方法など、非接触で乾燥させる方法を好適に挙げることができる。
The method of heating is not particularly limited, but a non-contact drying method such as a method of heating with a heating element such as a nichrome wire heater, a method of supplying warm air or hot air, a method of heating with a halogen lamp, an infrared lamp, etc. Preferably, it can be mentioned.
(硬化工程)
前記画像形成方法は、記録媒体上に付与されたインク組成物に活性エネルギー線を照射して硬化することを含むことが好ましい。活性エネルギー線を照射する硬化工程は、インク組成物の付与により形成されたインク画像に、例えば、紫外線照射ランプから紫外線を照射する工程である。これにより、画像中のモノマー成分(水溶性の重合性化合物)を確実に重合硬化し得る。このとき、紫外線照射ランプを記録媒体の記録面に対向配置し、記録面の全体を照射すれば、画像全体の硬化を行うことができる。活性エネルギー線を照射する光源は、紫外線照射ランプに限らず、ハロゲンランプ、高圧水銀灯、レーザー、LED、電子線照射装置などを採用することもできる。
活性エネルギー線を照射する硬化工程は、インク付与および処理液付与の後であれば、前記加熱乾燥の前後のいずれに設置されていてもよく、加熱乾燥の前後両方に実施してもよい。 (Curing process)
The image forming method preferably includes irradiating the ink composition applied on the recording medium with an active energy ray and curing. The curing step of irradiating the active energy ray is a step of irradiating the ink image formed by applying the ink composition with, for example, ultraviolet rays from an ultraviolet irradiation lamp. Thereby, the monomer component (water-soluble polymerizable compound) in the image can be surely polymerized and cured. At this time, if the ultraviolet irradiation lamp is disposed opposite the recording surface of the recording medium and the entire recording surface is irradiated, the entire image can be cured. The light source for irradiating the active energy ray is not limited to the ultraviolet irradiation lamp, but a halogen lamp, a high-pressure mercury lamp, a laser, an LED, an electron beam irradiation apparatus, or the like can also be adopted.
The curing step of irradiating the active energy ray may be placed before or after the heat drying as long as it is after ink application and treatment liquid application, and may be performed both before and after the heat drying.
前記画像形成方法は、記録媒体上に付与されたインク組成物に活性エネルギー線を照射して硬化することを含むことが好ましい。活性エネルギー線を照射する硬化工程は、インク組成物の付与により形成されたインク画像に、例えば、紫外線照射ランプから紫外線を照射する工程である。これにより、画像中のモノマー成分(水溶性の重合性化合物)を確実に重合硬化し得る。このとき、紫外線照射ランプを記録媒体の記録面に対向配置し、記録面の全体を照射すれば、画像全体の硬化を行うことができる。活性エネルギー線を照射する光源は、紫外線照射ランプに限らず、ハロゲンランプ、高圧水銀灯、レーザー、LED、電子線照射装置などを採用することもできる。
活性エネルギー線を照射する硬化工程は、インク付与および処理液付与の後であれば、前記加熱乾燥の前後のいずれに設置されていてもよく、加熱乾燥の前後両方に実施してもよい。 (Curing process)
The image forming method preferably includes irradiating the ink composition applied on the recording medium with an active energy ray and curing. The curing step of irradiating the active energy ray is a step of irradiating the ink image formed by applying the ink composition with, for example, ultraviolet rays from an ultraviolet irradiation lamp. Thereby, the monomer component (water-soluble polymerizable compound) in the image can be surely polymerized and cured. At this time, if the ultraviolet irradiation lamp is disposed opposite the recording surface of the recording medium and the entire recording surface is irradiated, the entire image can be cured. The light source for irradiating the active energy ray is not limited to the ultraviolet irradiation lamp, but a halogen lamp, a high-pressure mercury lamp, a laser, an LED, an electron beam irradiation apparatus, or the like can also be adopted.
The curing step of irradiating the active energy ray may be placed before or after the heat drying as long as it is after ink application and treatment liquid application, and may be performed both before and after the heat drying.
活性エネルギー線の照射条件としては、重合性化合物が重合硬化可能であれば特に制限されない。例えば活性エネルギー線の波長としては、例えば、200~600nmであることが好ましく、300~450nmであることがより好ましく、350~420nmであることがさらに好ましい。
活性エネルギー線の出力は、5000mJ/cm2以下であることが好ましく、10~4000mJ/cm2であることがより好ましく、20~3000mJ/cm2であることがさらに好ましい。 The irradiation condition of the active energy ray is not particularly limited as long as the polymerizable compound can be polymerized and cured. For example, the wavelength of the active energy ray is preferably, for example, 200 to 600 nm, more preferably 300 to 450 nm, and further preferably 350 to 420 nm.
The output of the active energy ray is preferably at 5000 mJ / cm 2 or less, more preferably 10 ~ 4000mJ / cm 2, further preferably 20 ~ 3000mJ / cm 2.
活性エネルギー線の出力は、5000mJ/cm2以下であることが好ましく、10~4000mJ/cm2であることがより好ましく、20~3000mJ/cm2であることがさらに好ましい。 The irradiation condition of the active energy ray is not particularly limited as long as the polymerizable compound can be polymerized and cured. For example, the wavelength of the active energy ray is preferably, for example, 200 to 600 nm, more preferably 300 to 450 nm, and further preferably 350 to 420 nm.
The output of the active energy ray is preferably at 5000 mJ / cm 2 or less, more preferably 10 ~ 4000mJ / cm 2, further preferably 20 ~ 3000mJ / cm 2.
-記録媒体-
本発明の画像形成方法は、記録媒体に上に画像を記録するものである。
記録媒体には、特に制限はないが、一般のオフセット印刷などに用いられる、いわゆる上質紙、コート紙、アート紙などのセルロースを主体とする一般印刷用紙を用いることができる。セルロースを主体とする一般印刷用紙は、水性インクを用いた一般のインクジェット法による画像記録においては比較的インクの吸収、乾燥が遅く、打滴後に色材移動が起こりやすく、画像品質が低下しやすいが、前記インクセットを用いた画像形成方法によると、色材移動を抑制し得、色濃度および色相に優れた高品位の画像を記録し得る。 -recoding media-
The image forming method of the present invention records an image on a recording medium.
The recording medium is not particularly limited, and general printing paper mainly composed of cellulose, such as so-called high-quality paper, coated paper, and art paper, used for general offset printing and the like can be used. General printing paper mainly composed of cellulose is relatively slow in ink absorption and drying in image recording by a general ink jet method using water-based ink, and color material movement is likely to occur after droplet ejection, and image quality is likely to deteriorate. However, according to the image forming method using the ink set, the movement of the color material can be suppressed, and a high-quality image excellent in color density and hue can be recorded.
本発明の画像形成方法は、記録媒体に上に画像を記録するものである。
記録媒体には、特に制限はないが、一般のオフセット印刷などに用いられる、いわゆる上質紙、コート紙、アート紙などのセルロースを主体とする一般印刷用紙を用いることができる。セルロースを主体とする一般印刷用紙は、水性インクを用いた一般のインクジェット法による画像記録においては比較的インクの吸収、乾燥が遅く、打滴後に色材移動が起こりやすく、画像品質が低下しやすいが、前記インクセットを用いた画像形成方法によると、色材移動を抑制し得、色濃度および色相に優れた高品位の画像を記録し得る。 -recoding media-
The image forming method of the present invention records an image on a recording medium.
The recording medium is not particularly limited, and general printing paper mainly composed of cellulose, such as so-called high-quality paper, coated paper, and art paper, used for general offset printing and the like can be used. General printing paper mainly composed of cellulose is relatively slow in ink absorption and drying in image recording by a general ink jet method using water-based ink, and color material movement is likely to occur after droplet ejection, and image quality is likely to deteriorate. However, according to the image forming method using the ink set, the movement of the color material can be suppressed, and a high-quality image excellent in color density and hue can be recorded.
記録媒体としては、一般に市販されているものを使用することができ、例えば、王子製紙(株)製の「OKプリンス上質」、日本製紙(株)製の「しらおい」、及び日本製紙(株)製の「ニューNPI上質」等の上質紙(A)、王子製紙(株)製の「OKエバーライトコート」及び日本製紙(株)製の「オーロラS」等の微塗工紙、王子製紙(株)製の「OKコートL」及び日本製紙(株)製の「オーロラL」等の軽量コート紙(A3)、王子製紙(株)製の「OKトップコート+」及び日本製紙(株)製の「オーロラコート」等のコート紙(A2、B2)、王子製紙(株)製の「OK金藤+」及び三菱製紙(株)製の「特菱アート」等のアート紙(A1)等(以上全て商品名)が挙げられる。また、インクジェット記録用の各種写真専用紙を用いることも可能である。
As the recording medium, commercially available media can be used. For example, “OK Prince Quality” manufactured by Oji Paper Co., Ltd., “Shiraoi” manufactured by Nippon Paper Industries Co., Ltd., and Nippon Paper Industries Co., Ltd. Fine paper (A) such as “New NPI Fine” manufactured by Oji Paper Co., Ltd., “OK Everlight Coat” manufactured by Oji Paper Co., Ltd., and “Aurora S” manufactured by Nippon Paper Industries Co., Ltd., Oji Paper Co., Ltd. Lightweight coated paper (A3) such as “OK Coat L” manufactured by Nippon Paper Industries Co., Ltd. and “Aurora L” manufactured by Nippon Paper Industries Co., Ltd. “OK Top Coat +” manufactured by Oji Paper Co., Ltd. and Nippon Paper Industries Co., Ltd. Coated paper (A2, B2) such as “Aurora Coat” manufactured by Oji Paper Co., Ltd. Art paper (A1) such as “OK Kanfuji +” manufactured by Oji Paper Co., Ltd. and “Tokuhishi Art” manufactured by Mitsubishi Paper Industries Co., Ltd. ( All of the above are trade names). It is also possible to use various photographic papers for ink jet recording.
上記の中でも、色材移動の抑制効果が大きく、従来以上に色濃度及び色相の良好な高品位な画像を得うる観点からは、記録媒体の水の吸収係数Kaが好ましくは0.05~0.5でmL/m2・ms1/2であり、より好ましくは0.1~0.4mL/m2・ms1/2であり、更に好ましくは0.2~0.3mL/m2・ms1/2である。
Among the above, the water absorption coefficient Ka of the recording medium is preferably 0.05 to 0 from the viewpoint that the effect of suppressing the movement of the coloring material is large and that a high-quality image with better color density and hue than before can be obtained. .5 in a mL / m 2 · ms 1/2, more preferably 0.1 ~ 0.4mL / m 2 · ms 1/2, more preferably 0.2 ~ 0.3mL / m 2 · ms 1/2 .
水の吸収係数Kaは、JAPAN TAPPI 紙パルプ試験方法No51:2000(発行:紙パルプ技術協会)に記載されているものと同義であり、具体的には、吸収係数Kaは、自動走査吸液計KM500Win(熊谷理機(株)製)を用いて接触時間100msと接触時間900msにおける水の転移量の差から算出されるものである。
The water absorption coefficient Ka is synonymous with that described in JAPANJTAPPI paper pulp test method No 51: 2000 (issued by Japan Paper Pulp Technology Association). Specifically, the absorption coefficient Ka is an automatic scanning absorption meter. It is calculated from the difference in the amount of water transferred between the contact time of 100 ms and the contact time of 900 ms using KM500Win (manufactured by Kumagai Riki Co., Ltd.).
記録媒体の中でも、一般のオフセット印刷などに用いられるいわゆる塗工紙が好ましい。塗工紙は、セルロースを主体とした一般に表面処理されていない上質紙や中性紙等の表面にコート材を塗布してコート層を設けたものである。塗工紙は、通常の水性インクジェットによる画像形成においては、画像の光沢や擦過耐性など、品質上の問題を生じやすいが、前記インクジェット記録方法では、光沢ムラが抑制され得、光沢性、耐擦性の良好な画像を得うる。特に、原紙とカオリン及び/又は重炭酸カルシウムを含むコート層とを有する塗工紙を用いるのが好ましい。より具体的には、アート紙、コート紙、軽量コート紙、又は微塗工紙がより好ましい。
Of the recording media, so-called coated paper used for general offset printing is preferable. The coated paper is obtained by applying a coating material to the surface of high-quality paper, neutral paper, or the like that is mainly surface-treated with cellulose as a main component and is not generally surface-treated. The coated paper tends to cause quality problems such as image gloss and scratch resistance in image formation by a normal aqueous inkjet, but the inkjet recording method can suppress gloss unevenness, gloss and abrasion resistance. An image with good properties can be obtained. In particular, it is preferable to use a coated paper having a base paper and a coat layer containing kaolin and / or calcium bicarbonate. More specifically, art paper, coated paper, lightweight coated paper, or finely coated paper is more preferable.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。尚、特に断りのない限り、「部」及び「%」は質量基準である。
Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
(水不溶性樹脂(ポリマー分散剤)P-1の合成)
攪拌機、冷却管を備えた1000mlの三口フラスコに、メチルエチルケトン88gを加えて窒素雰囲気下で72℃に加熱し、これにメチルエチルケトン50gにジメチル-2,2’-アゾビスイソブチレート0.85g、フェノキシエチルメタクリレート50g、メタクリル酸13g、及びメチルメタクリレート37gを溶解した溶液を3時間かけて滴下した。滴下終了後、さらに1時間反応した後、メチルエチルケトン2gにジメチル-2,2’-アゾビスイソブチレート0.42gを溶解した溶液を加え、78℃に昇温して4時間加熱した。得られた反応溶液は過剰量のヘキサンに2回再沈殿させ、析出した樹脂を乾燥させて、フェノキシエチルメタクリレート/メチルメタクリレート/メタクリル酸(共重合比[質量%比]=50/37/13)共重合体(水不溶性樹脂P-1)96.5gを得た。
得られた水不溶性樹脂P-1の組成は、1H-NMRで確認し、GPCより求めた重量平均分子量(Mw)は49400であった。さらに、JIS規格(JIS K 0070:1992)記載の方法により、この水不溶性樹脂の酸価を求めたところ、84.8mgKOH/gであった。 (Synthesis of water-insoluble resin (polymer dispersant) P-1)
To a 1000 ml three-necked flask equipped with a stirrer and a condenser tube, 88 g of methyl ethyl ketone was added and heated to 72 ° C. under a nitrogen atmosphere. To this, 50 g of methyl ethyl ketone was mixed with 0.85 g of dimethyl-2,2′-azobisisobutyrate, phenoxy. A solution in which 50 g of ethyl methacrylate, 13 g of methacrylic acid, and 37 g of methyl methacrylate were dissolved was dropped over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour, and then a solution of 0.42 g of dimethyl-2,2′-azobisisobutyrate dissolved in 2 g of methyl ethyl ketone was added, heated to 78 ° C. and heated for 4 hours. The obtained reaction solution was reprecipitated twice in an excess amount of hexane, and the precipitated resin was dried to obtain phenoxyethyl methacrylate / methyl methacrylate / methacrylic acid (copolymerization ratio [mass% ratio] = 50/37/13). 96.5 g of copolymer (water-insoluble resin P-1) was obtained.
The composition of the obtained water-insoluble resin P-1 was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 49400. Furthermore, when the acid value of this water-insoluble resin was determined by the method described in JIS standard (JIS K 0070: 1992), it was 84.8 mgKOH / g.
攪拌機、冷却管を備えた1000mlの三口フラスコに、メチルエチルケトン88gを加えて窒素雰囲気下で72℃に加熱し、これにメチルエチルケトン50gにジメチル-2,2’-アゾビスイソブチレート0.85g、フェノキシエチルメタクリレート50g、メタクリル酸13g、及びメチルメタクリレート37gを溶解した溶液を3時間かけて滴下した。滴下終了後、さらに1時間反応した後、メチルエチルケトン2gにジメチル-2,2’-アゾビスイソブチレート0.42gを溶解した溶液を加え、78℃に昇温して4時間加熱した。得られた反応溶液は過剰量のヘキサンに2回再沈殿させ、析出した樹脂を乾燥させて、フェノキシエチルメタクリレート/メチルメタクリレート/メタクリル酸(共重合比[質量%比]=50/37/13)共重合体(水不溶性樹脂P-1)96.5gを得た。
得られた水不溶性樹脂P-1の組成は、1H-NMRで確認し、GPCより求めた重量平均分子量(Mw)は49400であった。さらに、JIS規格(JIS K 0070:1992)記載の方法により、この水不溶性樹脂の酸価を求めたところ、84.8mgKOH/gであった。 (Synthesis of water-insoluble resin (polymer dispersant) P-1)
To a 1000 ml three-necked flask equipped with a stirrer and a condenser tube, 88 g of methyl ethyl ketone was added and heated to 72 ° C. under a nitrogen atmosphere. To this, 50 g of methyl ethyl ketone was mixed with 0.85 g of dimethyl-2,2′-azobisisobutyrate, phenoxy. A solution in which 50 g of ethyl methacrylate, 13 g of methacrylic acid, and 37 g of methyl methacrylate were dissolved was dropped over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour, and then a solution of 0.42 g of dimethyl-2,2′-azobisisobutyrate dissolved in 2 g of methyl ethyl ketone was added, heated to 78 ° C. and heated for 4 hours. The obtained reaction solution was reprecipitated twice in an excess amount of hexane, and the precipitated resin was dried to obtain phenoxyethyl methacrylate / methyl methacrylate / methacrylic acid (copolymerization ratio [mass% ratio] = 50/37/13). 96.5 g of copolymer (water-insoluble resin P-1) was obtained.
The composition of the obtained water-insoluble resin P-1 was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 49400. Furthermore, when the acid value of this water-insoluble resin was determined by the method described in JIS standard (JIS K 0070: 1992), it was 84.8 mgKOH / g.
(水溶性樹脂(ポリマー分散剤)P-2の合成)
イソプロパノール(187.5部)を窒素雰囲気下、80℃に加温した中に、メタクリル酸(216部)/メタクリル酸ベンジル(784部)/2,2’―アゾビス(2-メチルブチロニトリル)(22.05部)の混合液を2時間かけて滴下した。滴下終了後、更に4時間、80℃に保った後に、25℃まで冷却した。溶媒を減圧除去することにより、重量平均分子量約30000、酸価 140mgKOH/gの水溶性樹脂分散剤P-2(水溶性分散剤)を得た。 (Synthesis of water-soluble resin (polymer dispersant) P-2)
While isopropanol (187.5 parts) was heated to 80 ° C. under a nitrogen atmosphere, methacrylic acid (216 parts) / benzyl methacrylate (784 parts) / 2,2′-azobis (2-methylbutyronitrile) The liquid mixture (22.05 parts) was dripped over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for further 4 hours, and then cooled to 25 ° C. By removing the solvent under reduced pressure, a water-soluble resin dispersant P-2 (water-soluble dispersant) having a weight average molecular weight of about 30,000 and an acid value of 140 mgKOH / g was obtained.
イソプロパノール(187.5部)を窒素雰囲気下、80℃に加温した中に、メタクリル酸(216部)/メタクリル酸ベンジル(784部)/2,2’―アゾビス(2-メチルブチロニトリル)(22.05部)の混合液を2時間かけて滴下した。滴下終了後、更に4時間、80℃に保った後に、25℃まで冷却した。溶媒を減圧除去することにより、重量平均分子量約30000、酸価 140mgKOH/gの水溶性樹脂分散剤P-2(水溶性分散剤)を得た。 (Synthesis of water-soluble resin (polymer dispersant) P-2)
While isopropanol (187.5 parts) was heated to 80 ° C. under a nitrogen atmosphere, methacrylic acid (216 parts) / benzyl methacrylate (784 parts) / 2,2′-azobis (2-methylbutyronitrile) The liquid mixture (22.05 parts) was dripped over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for further 4 hours, and then cooled to 25 ° C. By removing the solvent under reduced pressure, a water-soluble resin dispersant P-2 (water-soluble dispersant) having a weight average molecular weight of about 30,000 and an acid value of 140 mgKOH / g was obtained.
(水溶性樹脂(ポリマー分散剤)P-3の合成)
フェノキシエチルメタクリレート/メチルメタクリレート/メタクリル酸の共重合比[質量%比]が50/11/39)となるように変えた以外は水不溶性樹脂P-1と同様の方法で共重合体(水溶性樹脂P-3)96.5gを得た。
得られた水溶性樹脂P-3の組成は、1H-NMRで確認し、GPCより求めた重量平均分子量(Mw)は48900であった。このポリマーの酸価は、248.8mgKOH/gであった。 (Synthesis of water-soluble resin (polymer dispersant) P-3)
A copolymer (water-soluble) was prepared in the same manner as the water-insoluble resin P-1, except that the copolymerization ratio [mass% ratio] of phenoxyethyl methacrylate / methyl methacrylate / methacrylic acid was 50/11/39). Resin P-3) 96.5 g was obtained.
The composition of the obtained water-soluble resin P-3 was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 48900. The acid value of this polymer was 248.8 mgKOH / g.
フェノキシエチルメタクリレート/メチルメタクリレート/メタクリル酸の共重合比[質量%比]が50/11/39)となるように変えた以外は水不溶性樹脂P-1と同様の方法で共重合体(水溶性樹脂P-3)96.5gを得た。
得られた水溶性樹脂P-3の組成は、1H-NMRで確認し、GPCより求めた重量平均分子量(Mw)は48900であった。このポリマーの酸価は、248.8mgKOH/gであった。 (Synthesis of water-soluble resin (polymer dispersant) P-3)
A copolymer (water-soluble) was prepared in the same manner as the water-insoluble resin P-1, except that the copolymerization ratio [mass% ratio] of phenoxyethyl methacrylate / methyl methacrylate / methacrylic acid was 50/11/39). Resin P-3) 96.5 g was obtained.
The composition of the obtained water-soluble resin P-3 was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 48900. The acid value of this polymer was 248.8 mgKOH / g.
(カーボンブラック顔料水性分散物CB1の調製)
カーボンブラック顔料(商品名:NIPEX170-IQ、Degussa社製)13部と、前記ポリマー分散剤P-1を5.9部と、メチルエチルケトン20部と、1mol/L NaOH水溶液8.3部と、イオン交換水52.8部とを混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて3時間分散した。
得られた分散物を減圧下、55℃でメチルエチルケトンを除去し、更に一部の水を除去した後、更に、高速冷却遠心機7550(商品名、久保田製作所製)を用いて、容量50mLの遠心菅を使用し、8000rpmで30分間遠心処理を行い、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、イオン交換水を加えて顔料濃度15質量%の樹脂被覆顔料粒子(カプセル化顔料)の分散物として、カーボンブラック顔料水性分散物CB1を得た。
ナノトラック粒度分布測定装置UPA-EX150(商品名、日機装(株)製)を用いて、動的光散乱法によりカーボンブラック顔料水性分散物CB1に含まれる粒子の体積平均粒子径を測定したところ、87nmであった。 (Preparation of carbon black pigment aqueous dispersion CB1)
13 parts of carbon black pigment (trade name: NIPEX170-IQ, manufactured by Degussa), 5.9 parts of the polymer dispersant P-1, 20 parts of methyl ethyl ketone, 8.3 parts of 1 mol / L NaOH aqueous solution, ions The mixture was mixed with 52.8 parts of exchange water and dispersed with a bead mill for 3 hours using 0.1 mmφ zirconia beads.
Methyl ethyl ketone was removed from the obtained dispersion under reduced pressure at 55 ° C., and a part of the water was further removed. Then, a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Seisakusho) was used to centrifuge at a capacity of 50 mL. Centrifugal treatment was performed at 8000 rpm for 30 minutes using a spear, and the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion-exchanged water was added to obtain a carbon black pigment aqueous dispersion CB1 as a dispersion of resin-coated pigment particles (encapsulated pigment) having a pigment concentration of 15% by mass.
When the volume average particle size of the particles contained in the carbon black pigment aqueous dispersion CB1 was measured by a dynamic light scattering method using Nanotrac particle size distribution analyzer UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.), It was 87 nm.
カーボンブラック顔料(商品名:NIPEX170-IQ、Degussa社製)13部と、前記ポリマー分散剤P-1を5.9部と、メチルエチルケトン20部と、1mol/L NaOH水溶液8.3部と、イオン交換水52.8部とを混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて3時間分散した。
得られた分散物を減圧下、55℃でメチルエチルケトンを除去し、更に一部の水を除去した後、更に、高速冷却遠心機7550(商品名、久保田製作所製)を用いて、容量50mLの遠心菅を使用し、8000rpmで30分間遠心処理を行い、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、イオン交換水を加えて顔料濃度15質量%の樹脂被覆顔料粒子(カプセル化顔料)の分散物として、カーボンブラック顔料水性分散物CB1を得た。
ナノトラック粒度分布測定装置UPA-EX150(商品名、日機装(株)製)を用いて、動的光散乱法によりカーボンブラック顔料水性分散物CB1に含まれる粒子の体積平均粒子径を測定したところ、87nmであった。 (Preparation of carbon black pigment aqueous dispersion CB1)
13 parts of carbon black pigment (trade name: NIPEX170-IQ, manufactured by Degussa), 5.9 parts of the polymer dispersant P-1, 20 parts of methyl ethyl ketone, 8.3 parts of 1 mol / L NaOH aqueous solution, ions The mixture was mixed with 52.8 parts of exchange water and dispersed with a bead mill for 3 hours using 0.1 mmφ zirconia beads.
Methyl ethyl ketone was removed from the obtained dispersion under reduced pressure at 55 ° C., and a part of the water was further removed. Then, a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Seisakusho) was used to centrifuge at a capacity of 50 mL. Centrifugal treatment was performed at 8000 rpm for 30 minutes using a spear, and the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion-exchanged water was added to obtain a carbon black pigment aqueous dispersion CB1 as a dispersion of resin-coated pigment particles (encapsulated pigment) having a pigment concentration of 15% by mass.
When the volume average particle size of the particles contained in the carbon black pigment aqueous dispersion CB1 was measured by a dynamic light scattering method using Nanotrac particle size distribution analyzer UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.), It was 87 nm.
(カーボンブラック顔料水性分散物CB2の調製)
水溶性樹脂P-2を用いて以下のようにして顔料分散物2を得た。
カーボンブラック顔料を13.6部と、前記分散剤P-2を6.2部と、1mol/L NaOH水溶液9.3部と、イオン交換水70.9部とを混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて3時間分散した。
その後、トリメチロールプロパントリグリシジルエーテル 0.87部とホウ酸0.38部を添加し60℃で6時間反応させた後冷却し、更に、高速冷却遠心機7550(商品名、久保田製作所製)を用いて、容量50mLの遠心菅を使用し、8000rpmで30分間遠心処理を行い、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、イオン交換水を加えてカーボンブラック濃度13質量%の樹脂被覆顔料粒子の分散物として、カーボンブラック顔料水性分散物CB2を得た。
上記と同様の方法で体積平均粒子径を測定したところ、92nmであった。 (Preparation of carbon black pigment aqueous dispersion CB2)
Using water-soluble resin P-2, Pigment Dispersion 2 was obtained as follows.
13.6 parts of carbon black pigment, 6.2 parts of the dispersant P-2, 9.3 parts of 1 mol / L NaOH aqueous solution, and 70.9 parts of ion-exchanged water were mixed, and 0. Dispersion was performed for 3 hours using 1 mmφ zirconia beads.
Thereafter, 0.87 part of trimethylolpropane triglycidyl ether and 0.38 part of boric acid were added and reacted at 60 ° C. for 6 hours, followed by cooling. Further, a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Corporation) was used. Using a centrifuge tube with a capacity of 50 mL, centrifugation was performed at 8000 rpm for 30 minutes, and the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion-exchanged water was added to obtain an aqueous carbon black pigment dispersion CB2 as a dispersion of resin-coated pigment particles having a carbon black concentration of 13% by mass.
It was 92 nm when the volume average particle diameter was measured by the method similar to the above.
水溶性樹脂P-2を用いて以下のようにして顔料分散物2を得た。
カーボンブラック顔料を13.6部と、前記分散剤P-2を6.2部と、1mol/L NaOH水溶液9.3部と、イオン交換水70.9部とを混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて3時間分散した。
その後、トリメチロールプロパントリグリシジルエーテル 0.87部とホウ酸0.38部を添加し60℃で6時間反応させた後冷却し、更に、高速冷却遠心機7550(商品名、久保田製作所製)を用いて、容量50mLの遠心菅を使用し、8000rpmで30分間遠心処理を行い、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、イオン交換水を加えてカーボンブラック濃度13質量%の樹脂被覆顔料粒子の分散物として、カーボンブラック顔料水性分散物CB2を得た。
上記と同様の方法で体積平均粒子径を測定したところ、92nmであった。 (Preparation of carbon black pigment aqueous dispersion CB2)
Using water-soluble resin P-2, Pigment Dispersion 2 was obtained as follows.
13.6 parts of carbon black pigment, 6.2 parts of the dispersant P-2, 9.3 parts of 1 mol / L NaOH aqueous solution, and 70.9 parts of ion-exchanged water were mixed, and 0. Dispersion was performed for 3 hours using 1 mmφ zirconia beads.
Thereafter, 0.87 part of trimethylolpropane triglycidyl ether and 0.38 part of boric acid were added and reacted at 60 ° C. for 6 hours, followed by cooling. Further, a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Corporation) was used. Using a centrifuge tube with a capacity of 50 mL, centrifugation was performed at 8000 rpm for 30 minutes, and the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion-exchanged water was added to obtain an aqueous carbon black pigment dispersion CB2 as a dispersion of resin-coated pigment particles having a carbon black concentration of 13% by mass.
It was 92 nm when the volume average particle diameter was measured by the method similar to the above.
(カーボンブラック顔料水性分散物CB3の調製)
カーボンブラック顔料を11.3部と、前記水溶性分散剤P-3を5.1部と、1mol/L NaOH水溶液21部と、イオン交換水62.6部とを混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて3時間分散した。
得られた分散物を、高速冷却遠心機7550(商品名、久保田製作所製)を用いて、容量50mLの遠心菅を使用し、8000rpmで30分間遠心処理を行い、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、イオン交換水を加えてカーボンブラック濃度10.0質量%のカーボンブラック顔料水性分散物CB3を得た。
上記と同様の方法で体積平均粒子径を測定したところ、90nmであった。 (Preparation of carbon black pigment aqueous dispersion CB3)
11.3 parts of carbon black pigment, 5.1 parts of the water-soluble dispersant P-3, 21 parts of 1 mol / L NaOH aqueous solution, and 62.6 parts of ion-exchanged water were mixed, and the mixture was mixed with a bead mill. Dispersion was performed for 3 hours using 1 mmφ zirconia beads.
The obtained dispersion was centrifuged at 8000 rpm for 30 minutes using a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Seisakusho), and the supernatant liquid other than the precipitate was collected. did. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion exchange water was added to obtain an aqueous carbon black pigment dispersion CB3 having a carbon black concentration of 10.0% by mass.
When the volume average particle size was measured by the same method as described above, it was 90 nm.
カーボンブラック顔料を11.3部と、前記水溶性分散剤P-3を5.1部と、1mol/L NaOH水溶液21部と、イオン交換水62.6部とを混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて3時間分散した。
得られた分散物を、高速冷却遠心機7550(商品名、久保田製作所製)を用いて、容量50mLの遠心菅を使用し、8000rpmで30分間遠心処理を行い、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、イオン交換水を加えてカーボンブラック濃度10.0質量%のカーボンブラック顔料水性分散物CB3を得た。
上記と同様の方法で体積平均粒子径を測定したところ、90nmであった。 (Preparation of carbon black pigment aqueous dispersion CB3)
11.3 parts of carbon black pigment, 5.1 parts of the water-soluble dispersant P-3, 21 parts of 1 mol / L NaOH aqueous solution, and 62.6 parts of ion-exchanged water were mixed, and the mixture was mixed with a bead mill. Dispersion was performed for 3 hours using 1 mmφ zirconia beads.
The obtained dispersion was centrifuged at 8000 rpm for 30 minutes using a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Seisakusho), and the supernatant liquid other than the precipitate was collected. did. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion exchange water was added to obtain an aqueous carbon black pigment dispersion CB3 having a carbon black concentration of 10.0% by mass.
When the volume average particle size was measured by the same method as described above, it was 90 nm.
(着色顔料水性分散物C1の調製)
カーボンブラック顔料水性分散物1の調製において、カーボンブラック顔料の代わりに、ピグメント・ブルー15:3を用いたこと以外は、上記と同様にして着色顔料水性分散物C1を得た。
上記と同様の方法で体積平均粒子径を測定したところ、93nmであった。 (Preparation of Colored Pigment Aqueous Dispersion C1)
A colored pigment aqueous dispersion C1 was obtained in the same manner as described above except that in the preparation of the aqueous carbon black pigment dispersion 1, Pigment Blue 15: 3 was used instead of the carbon black pigment.
It was 93 nm when the volume average particle diameter was measured by the method similar to the above.
カーボンブラック顔料水性分散物1の調製において、カーボンブラック顔料の代わりに、ピグメント・ブルー15:3を用いたこと以外は、上記と同様にして着色顔料水性分散物C1を得た。
上記と同様の方法で体積平均粒子径を測定したところ、93nmであった。 (Preparation of Colored Pigment Aqueous Dispersion C1)
A colored pigment aqueous dispersion C1 was obtained in the same manner as described above except that in the preparation of the aqueous carbon black pigment dispersion 1, Pigment Blue 15: 3 was used instead of the carbon black pigment.
It was 93 nm when the volume average particle diameter was measured by the method similar to the above.
(着色顔料水性分散物M1の調製)
着色顔料分散物C1の調製において、ピグメント・ブルー15:3の代わりにピグメント・レッド122を用いたこと以外は、上記と同様にして着色顔料水性分散物M1を得た。
上記と同様の方法で体積平均粒子径を測定したところ、78nmであった。 (Preparation of colored pigment aqueous dispersion M1)
A colored pigment aqueous dispersion M1 was obtained in the same manner as described above except that in the preparation of the colored pigment dispersion C1, Pigment Red 122 was used instead of Pigment Blue 15: 3.
It was 78 nm when the volume average particle diameter was measured by the method similar to the above.
着色顔料分散物C1の調製において、ピグメント・ブルー15:3の代わりにピグメント・レッド122を用いたこと以外は、上記と同様にして着色顔料水性分散物M1を得た。
上記と同様の方法で体積平均粒子径を測定したところ、78nmであった。 (Preparation of colored pigment aqueous dispersion M1)
A colored pigment aqueous dispersion M1 was obtained in the same manner as described above except that in the preparation of the colored pigment dispersion C1, Pigment Red 122 was used instead of Pigment Blue 15: 3.
It was 78 nm when the volume average particle diameter was measured by the method similar to the above.
(着色顔料水性分散物Y1の調製)
顔料分散物1の調製において、ピグメント・ブルー15:3の代わりにピグメント・イエロー74を用いたこと以外は、上記と同様にして着色顔料水性分散物Y1を得た。
上記と同様の方法で体積平均粒子径を測定したところ、95nmであった。 (Preparation of colored pigment aqueous dispersion Y1)
Colored pigment aqueous dispersion Y1 was obtained in the same manner as described above except that in the preparation of Pigment Dispersion 1, Pigment Yellow 74 was used instead of Pigment Blue 15: 3.
It was 95 nm when the volume average particle diameter was measured by the method similar to the above.
顔料分散物1の調製において、ピグメント・ブルー15:3の代わりにピグメント・イエロー74を用いたこと以外は、上記と同様にして着色顔料水性分散物Y1を得た。
上記と同様の方法で体積平均粒子径を測定したところ、95nmであった。 (Preparation of colored pigment aqueous dispersion Y1)
Colored pigment aqueous dispersion Y1 was obtained in the same manner as described above except that in the preparation of Pigment Dispersion 1, Pigment Yellow 74 was used instead of Pigment Blue 15: 3.
It was 95 nm when the volume average particle diameter was measured by the method similar to the above.
(重合性化合物2の合成)
攪拌機を備えた1Lの三口フラスコに4,7,10-トリオキサ-1,13-トリデカンジアミン40.0g(182mmol)、炭酸水素ナトリウム37.8g(450mmol)、水100g、テトラヒドロフラン300gを加えて、氷浴下、アクリル酸クロリド35.2g(389mmol)を20分かけて滴下した。滴下後、室温で5時間攪拌した後、得られた反応混合物から減圧下でテトラヒドロフランを留去した。次に水層を酢酸エチル200mlで4回抽出し、得られた有機層を硫酸マグネシウムで乾燥後、ろ過を行い、減圧下溶媒留去することにより目的の重合性化合物2の固体を35.0g(107mmol、収率59%)得た。 (Synthesis of polymerizable compound 2)
To a 1 L three-necked flask equipped with a stirrer was added 4,7,10-trioxa-1,13-tridecanediamine 40.0 g (182 mmol), sodium bicarbonate 37.8 g (450 mmol), water 100 g and tetrahydrofuran 300 g. In an ice bath, 35.2 g (389 mmol) of acrylic acid chloride was added dropwise over 20 minutes. After dropping, the mixture was stirred at room temperature for 5 hours, and then tetrahydrofuran was distilled off from the obtained reaction mixture under reduced pressure. Next, the aqueous layer was extracted four times with 200 ml of ethyl acetate, and the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain 35.0 g of the target polymerizable compound 2 solid. (107 mmol, 59% yield).
攪拌機を備えた1Lの三口フラスコに4,7,10-トリオキサ-1,13-トリデカンジアミン40.0g(182mmol)、炭酸水素ナトリウム37.8g(450mmol)、水100g、テトラヒドロフラン300gを加えて、氷浴下、アクリル酸クロリド35.2g(389mmol)を20分かけて滴下した。滴下後、室温で5時間攪拌した後、得られた反応混合物から減圧下でテトラヒドロフランを留去した。次に水層を酢酸エチル200mlで4回抽出し、得られた有機層を硫酸マグネシウムで乾燥後、ろ過を行い、減圧下溶媒留去することにより目的の重合性化合物2の固体を35.0g(107mmol、収率59%)得た。 (Synthesis of polymerizable compound 2)
To a 1 L three-necked flask equipped with a stirrer was added 4,7,10-trioxa-1,13-tridecanediamine 40.0 g (182 mmol), sodium bicarbonate 37.8 g (450 mmol), water 100 g and tetrahydrofuran 300 g. In an ice bath, 35.2 g (389 mmol) of acrylic acid chloride was added dropwise over 20 minutes. After dropping, the mixture was stirred at room temperature for 5 hours, and then tetrahydrofuran was distilled off from the obtained reaction mixture under reduced pressure. Next, the aqueous layer was extracted four times with 200 ml of ethyl acetate, and the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain 35.0 g of the target polymerizable compound 2 solid. (107 mmol, 59% yield).
<実施例1>
(黒色系インク組成物Bk-1の調製)
上記で得られたカーボンブラック顔料水性分散物CB1と、着色顔料水性分散物C1と,重合性化合物2と、コロイダルシリカ(スノーテックスXS(登録商標)、平均粒子径5nm、日産化学工業(株)製)とを用い、下記のインク組成になるように各成分を混合した。これをプラスチック製のディスポーザブルシリンジに詰め、PVDF5μmフィルター(Millex-SV(登録商標)、直径25mm、ミリポア社製)で濾過し、黒色系インク組成物Bk-1を調製した。 <Example 1>
(Preparation of black ink composition Bk-1)
Carbon black pigment aqueous dispersion CB1 obtained above, colored pigment aqueous dispersion C1, polymerizable compound 2, colloidal silica (Snowtex XS (registered trademark), average particle size 5 nm, Nissan Chemical Industries, Ltd. Each component was mixed so as to have the following ink composition. This was packed in a plastic disposable syringe and filtered through a PVDF 5 μm filter (Millex-SV (registered trademark), diameter 25 mm, manufactured by Millipore) to prepare a black ink composition Bk-1.
(黒色系インク組成物Bk-1の調製)
上記で得られたカーボンブラック顔料水性分散物CB1と、着色顔料水性分散物C1と,重合性化合物2と、コロイダルシリカ(スノーテックスXS(登録商標)、平均粒子径5nm、日産化学工業(株)製)とを用い、下記のインク組成になるように各成分を混合した。これをプラスチック製のディスポーザブルシリンジに詰め、PVDF5μmフィルター(Millex-SV(登録商標)、直径25mm、ミリポア社製)で濾過し、黒色系インク組成物Bk-1を調製した。 <Example 1>
(Preparation of black ink composition Bk-1)
Carbon black pigment aqueous dispersion CB1 obtained above, colored pigment aqueous dispersion C1, polymerizable compound 2, colloidal silica (Snowtex XS (registered trademark), average particle size 5 nm, Nissan Chemical Industries, Ltd. Each component was mixed so as to have the following ink composition. This was packed in a plastic disposable syringe and filtered through a PVDF 5 μm filter (Millex-SV (registered trademark), diameter 25 mm, manufactured by Millipore) to prepare a black ink composition Bk-1.
~インク組成~
・カーボンブラック顔料水性分散物CB1 ・・・17.3%
・着色顔料水性分散物C1 ・・・2.7%
・重合性化合物2 ・・・19%
・ジエチレングリコールモノエチルエーテル ・・・1%
(DEGmEE、和光純薬工業(株)製)
・コロイダルシリカ(固形分) ・・・0.05%
(スノーテックスXS(登録商標)、固形分濃度20%、日産化学工業(株)製)
・オルフィンE1010(商品名、日信化学工業(株)製) ・・・1%
・イルガキュア2959(登録商標、BASF・ジャパン社製) ・・・2.9%
・イオン交換水 ・・・残量(全量で100質量%となるよう加えた) ~ Ink composition ~
-Carbon black pigment aqueous dispersion CB1 ... 17.3%
-Colored pigment aqueous dispersion C1 2.7%
・ Polymerizable compound 2 ... 19%
・ Diethylene glycol monoethyl ether ・ ・ ・ 1%
(DEGmEE, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Colloidal silica (solid content) 0.05%
(Snowtex XS (registered trademark), solid concentration 20%, manufactured by Nissan Chemical Industries, Ltd.)
・ Orphine E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.) 1%
・ Irgacure 2959 (registered trademark, manufactured by BASF Japan) 2.9%
・ Ion-exchanged water ・ ・ ・ Remaining amount (added to 100% by mass in total)
・カーボンブラック顔料水性分散物CB1 ・・・17.3%
・着色顔料水性分散物C1 ・・・2.7%
・重合性化合物2 ・・・19%
・ジエチレングリコールモノエチルエーテル ・・・1%
(DEGmEE、和光純薬工業(株)製)
・コロイダルシリカ(固形分) ・・・0.05%
(スノーテックスXS(登録商標)、固形分濃度20%、日産化学工業(株)製)
・オルフィンE1010(商品名、日信化学工業(株)製) ・・・1%
・イルガキュア2959(登録商標、BASF・ジャパン社製) ・・・2.9%
・イオン交換水 ・・・残量(全量で100質量%となるよう加えた) ~ Ink composition ~
-Carbon black pigment aqueous dispersion CB1 ... 17.3%
-Colored pigment aqueous dispersion C1 2.7%
・ Polymerizable compound 2 ... 19%
・ Diethylene glycol monoethyl ether ・ ・ ・ 1%
(DEGmEE, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Colloidal silica (solid content) 0.05%
(Snowtex XS (registered trademark), solid concentration 20%, manufactured by Nissan Chemical Industries, Ltd.)
・ Orphine E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.) 1%
・ Irgacure 2959 (registered trademark, manufactured by BASF Japan) 2.9%
・ Ion-exchanged water ・ ・ ・ Remaining amount (added to 100% by mass in total)
<実施例2~6>
実施例1において、表1に示す処方となるようにカーボンブラック顔料水性分散物および着色顔料水性分散物の種類と添加量を変更したこと以外は実施例1と同様にして黒色系インク組成物Bk-2~6をそれぞれ調製した。
尚、表1中、カーボンブラック顔料、着色顔料の添加量は、それぞれ固形分質量を意味する。 <Examples 2 to 6>
In Example 1, the black ink composition Bk was used in the same manner as in Example 1 except that the types and addition amounts of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion were changed so as to have the formulation shown in Table 1. -2 to 6 were prepared respectively.
In Table 1, the addition amounts of the carbon black pigment and the color pigment each mean solid mass.
実施例1において、表1に示す処方となるようにカーボンブラック顔料水性分散物および着色顔料水性分散物の種類と添加量を変更したこと以外は実施例1と同様にして黒色系インク組成物Bk-2~6をそれぞれ調製した。
尚、表1中、カーボンブラック顔料、着色顔料の添加量は、それぞれ固形分質量を意味する。 <Examples 2 to 6>
In Example 1, the black ink composition Bk was used in the same manner as in Example 1 except that the types and addition amounts of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion were changed so as to have the formulation shown in Table 1. -2 to 6 were prepared respectively.
In Table 1, the addition amounts of the carbon black pigment and the color pigment each mean solid mass.
<実施例7>
実施例4において、重合性化合物2に代えて重合性化合物5を用いたこと以外は、実施例4と同様にして黒色系インク組成物Bk-7を調製した。 <Example 7>
A black ink composition Bk-7 was prepared in the same manner as in Example 4 except that the polymerizable compound 5 was used in place of the polymerizable compound 2 in Example 4.
実施例4において、重合性化合物2に代えて重合性化合物5を用いたこと以外は、実施例4と同様にして黒色系インク組成物Bk-7を調製した。 <Example 7>
A black ink composition Bk-7 was prepared in the same manner as in Example 4 except that the polymerizable compound 5 was used in place of the polymerizable compound 2 in Example 4.
<実施例8>
実施例4において、界面活性剤オルフィンE1010(上述)に代えてZonyl FSN(登録商標、デュポン株式会社製)を用いたこと以外は、実施例4と同様にして黒色系インク組成物Bk-8を調製した。 <Example 8>
In Example 4, the black ink composition Bk-8 was prepared in the same manner as in Example 4 except that Zonyl FSN (registered trademark, manufactured by DuPont) was used instead of the surfactant Olfine E1010 (described above). Prepared.
実施例4において、界面活性剤オルフィンE1010(上述)に代えてZonyl FSN(登録商標、デュポン株式会社製)を用いたこと以外は、実施例4と同様にして黒色系インク組成物Bk-8を調製した。 <Example 8>
In Example 4, the black ink composition Bk-8 was prepared in the same manner as in Example 4 except that Zonyl FSN (registered trademark, manufactured by DuPont) was used instead of the surfactant Olfine E1010 (described above). Prepared.
<比較例1>
実施例1において、着色顔料水性分散物を用いずに、カーボンブラック顔料水性分散物CB1の添加量を20%に変更したこと以外は実施例1と同様にして黒色系インク組成物Bk-9を調製した。 <Comparative Example 1>
In Example 1, the black ink composition Bk-9 was prepared in the same manner as in Example 1 except that the addition amount of the carbon black pigment aqueous dispersion CB1 was changed to 20% without using the color pigment aqueous dispersion. Prepared.
実施例1において、着色顔料水性分散物を用いずに、カーボンブラック顔料水性分散物CB1の添加量を20%に変更したこと以外は実施例1と同様にして黒色系インク組成物Bk-9を調製した。 <Comparative Example 1>
In Example 1, the black ink composition Bk-9 was prepared in the same manner as in Example 1 except that the addition amount of the carbon black pigment aqueous dispersion CB1 was changed to 20% without using the color pigment aqueous dispersion. Prepared.
<処理液1の調製>
下記組成の成分を混合して、処理液1を調製した。処理液1は、粘度2.5mPa・s、表面張力40mN/m、25℃におけるpH1.0を有していた。表面張力は全自動表面張力計CBVP-Z(商品名、協和界面科学(株)製)を用いて測定し、粘度はDV-III Ultra CP(商品名、ブルックフィールドエンジニアリング社製)を用いて測定した。pHは、PHメーター HM-30R(商品名、東亜ディーケーケー(株)製)を用いて測定した。
~処理液1の組成~
・マロン酸(和光純薬(株)製) ・・・25.0%
・ジエチレングリコールモノメチルエーテル ・・・20.0%
(和光純薬(株)製)
・エマルゲンP109 ・・・1.0%
(商品名、花王(株)製、ノニオン性界面活性剤)
・イオン交換水 ・・・54.0% <Preparation of treatment liquid 1>
The component of the following composition was mixed and the processing liquid 1 was prepared. The treatment liquid 1 had a viscosity of 2.5 mPa · s, a surface tension of 40 mN / m, and a pH of 1.0 at 25 ° C. The surface tension is measured using a fully automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.), and the viscosity is measured using DV-III Ultra CP (trade name, manufactured by Brookfield Engineering). did. The pH was measured using a PH meter HM-30R (trade name, manufactured by Toa DKK Corporation).
-Composition of treatment liquid 1-
・ Malonic acid (Wako Pure Chemical Industries, Ltd.) 25.0%
・ Diethylene glycol monomethyl ether 20.0%
(Wako Pure Chemical Industries, Ltd.)
・ Emulgen P109 ・ ・ ・ 1.0%
(Trade name, manufactured by Kao Corporation, nonionic surfactant)
・ Ion-exchanged water: 54.0%
下記組成の成分を混合して、処理液1を調製した。処理液1は、粘度2.5mPa・s、表面張力40mN/m、25℃におけるpH1.0を有していた。表面張力は全自動表面張力計CBVP-Z(商品名、協和界面科学(株)製)を用いて測定し、粘度はDV-III Ultra CP(商品名、ブルックフィールドエンジニアリング社製)を用いて測定した。pHは、PHメーター HM-30R(商品名、東亜ディーケーケー(株)製)を用いて測定した。
~処理液1の組成~
・マロン酸(和光純薬(株)製) ・・・25.0%
・ジエチレングリコールモノメチルエーテル ・・・20.0%
(和光純薬(株)製)
・エマルゲンP109 ・・・1.0%
(商品名、花王(株)製、ノニオン性界面活性剤)
・イオン交換水 ・・・54.0% <Preparation of treatment liquid 1>
The component of the following composition was mixed and the processing liquid 1 was prepared. The treatment liquid 1 had a viscosity of 2.5 mPa · s, a surface tension of 40 mN / m, and a pH of 1.0 at 25 ° C. The surface tension is measured using a fully automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.), and the viscosity is measured using DV-III Ultra CP (trade name, manufactured by Brookfield Engineering). did. The pH was measured using a PH meter HM-30R (trade name, manufactured by Toa DKK Corporation).
-Composition of treatment liquid 1-
・ Malonic acid (Wako Pure Chemical Industries, Ltd.) 25.0%
・ Diethylene glycol monomethyl ether 20.0%
(Wako Pure Chemical Industries, Ltd.)
・ Emulgen P109 ・ ・ ・ 1.0%
(Trade name, manufactured by Kao Corporation, nonionic surfactant)
・ Ion-exchanged water: 54.0%
<画像形成および評価>
シリコンノズルプレートを備えたインクジェットヘッドを用意し、これに繋がる貯留タンクに上記で得た黒色系インク組成物を詰め替えた。尚、シリコンノズルプレートには、フッ化アルキルシラン化合物を用いて撥液膜が予め設けられている。記録媒体として「OKトップコート+」(商品名、王子製紙(株)製、坪量104.7g/m2)をA5サイズにカットし、500mm/秒で所定の直線方向に移動可能なステージ上に固定し、ステージ温度を30℃に保持した。これに上記で得た処理液1をバーコーターで約1.2μmの厚みとなるように塗布し、塗布直後に50℃で2秒間乾燥させた。
その後、インクジェットヘッドを、前記ステージの移動方向(副走査方向)と直交する方向に対して、ノズルが並ぶラインヘッドの方向(主走査方向)が75.7度傾斜するように固定配置し、記録媒体を副走査方向に定速移動させながらインク液滴量2.8pL、吐出周波数25.5kHz、解像度1200dpi×1200dpiの吐出条件にてライン方式で、記録媒体の全面にインクを吐出してベタ画像を形成した。画像を記録した後、インク着滴面の裏側(背面)から赤外線ヒーターで加熱しながら、送風器により120℃、5m/secの温風を記録面に15秒間あてて乾燥させた。画像乾燥後、UV光をメタルハライドランプ(アイグラフィックス(株)製、最大照射波長365nm)から積算照射量3J/cm2になるように照射して画像を硬化して印画サンプルを得た。 <Image formation and evaluation>
An ink jet head provided with a silicon nozzle plate was prepared, and the black ink composition obtained above was refilled in a storage tank connected thereto. The silicon nozzle plate is previously provided with a liquid repellent film using a fluorinated alkylsilane compound. “OK Top Coat +” (trade name, manufactured by Oji Paper Co., Ltd., basis weight 104.7 g / m 2 ) as a recording medium is cut into A5 size and on a stage that can move in a predetermined linear direction at 500 mm / sec. The stage temperature was kept at 30 ° C. The treatment liquid 1 obtained above was applied to this with a bar coater so as to have a thickness of about 1.2 μm, and was dried at 50 ° C. for 2 seconds immediately after the application.
Thereafter, the inkjet head is fixedly arranged so that the direction of the line head in which the nozzles are arranged (main scanning direction) is inclined by 75.7 degrees with respect to the direction orthogonal to the moving direction of the stage (sub-scanning direction), and recording is performed. A solid image is obtained by ejecting ink over the entire surface of the recording medium in a line system under the ejection conditions of an ink droplet amount of 2.8 pL, an ejection frequency of 25.5 kHz, a resolution of 1200 dpi × 1200 dpi while moving the medium at a constant speed in the sub-scanning direction Formed. After the image was recorded, while being heated with an infrared heater from the back side (back side) of the ink landing surface, warm air of 120 ° C. and 5 m / sec was applied to the recording surface for 15 seconds and dried. After the image was dried, UV light was irradiated from a metal halide lamp (manufactured by Eye Graphics Co., Ltd., maximum irradiation wavelength 365 nm) so as to obtain an integrated irradiation amount of 3 J / cm 2 , and the image was cured to obtain a print sample.
シリコンノズルプレートを備えたインクジェットヘッドを用意し、これに繋がる貯留タンクに上記で得た黒色系インク組成物を詰め替えた。尚、シリコンノズルプレートには、フッ化アルキルシラン化合物を用いて撥液膜が予め設けられている。記録媒体として「OKトップコート+」(商品名、王子製紙(株)製、坪量104.7g/m2)をA5サイズにカットし、500mm/秒で所定の直線方向に移動可能なステージ上に固定し、ステージ温度を30℃に保持した。これに上記で得た処理液1をバーコーターで約1.2μmの厚みとなるように塗布し、塗布直後に50℃で2秒間乾燥させた。
その後、インクジェットヘッドを、前記ステージの移動方向(副走査方向)と直交する方向に対して、ノズルが並ぶラインヘッドの方向(主走査方向)が75.7度傾斜するように固定配置し、記録媒体を副走査方向に定速移動させながらインク液滴量2.8pL、吐出周波数25.5kHz、解像度1200dpi×1200dpiの吐出条件にてライン方式で、記録媒体の全面にインクを吐出してベタ画像を形成した。画像を記録した後、インク着滴面の裏側(背面)から赤外線ヒーターで加熱しながら、送風器により120℃、5m/secの温風を記録面に15秒間あてて乾燥させた。画像乾燥後、UV光をメタルハライドランプ(アイグラフィックス(株)製、最大照射波長365nm)から積算照射量3J/cm2になるように照射して画像を硬化して印画サンプルを得た。 <Image formation and evaluation>
An ink jet head provided with a silicon nozzle plate was prepared, and the black ink composition obtained above was refilled in a storage tank connected thereto. The silicon nozzle plate is previously provided with a liquid repellent film using a fluorinated alkylsilane compound. “OK Top Coat +” (trade name, manufactured by Oji Paper Co., Ltd., basis weight 104.7 g / m 2 ) as a recording medium is cut into A5 size and on a stage that can move in a predetermined linear direction at 500 mm / sec. The stage temperature was kept at 30 ° C. The treatment liquid 1 obtained above was applied to this with a bar coater so as to have a thickness of about 1.2 μm, and was dried at 50 ° C. for 2 seconds immediately after the application.
Thereafter, the inkjet head is fixedly arranged so that the direction of the line head in which the nozzles are arranged (main scanning direction) is inclined by 75.7 degrees with respect to the direction orthogonal to the moving direction of the stage (sub-scanning direction), and recording is performed. A solid image is obtained by ejecting ink over the entire surface of the recording medium in a line system under the ejection conditions of an ink droplet amount of 2.8 pL, an ejection frequency of 25.5 kHz, a resolution of 1200 dpi × 1200 dpi while moving the medium at a constant speed in the sub-scanning direction Formed. After the image was recorded, while being heated with an infrared heater from the back side (back side) of the ink landing surface, warm air of 120 ° C. and 5 m / sec was applied to the recording surface for 15 seconds and dried. After the image was dried, UV light was irradiated from a metal halide lamp (manufactured by Eye Graphics Co., Ltd., maximum irradiation wavelength 365 nm) so as to obtain an integrated irradiation amount of 3 J / cm 2 , and the image was cured to obtain a print sample.
[密着性評価]
上記で得られた印画サンプルを25℃、50%RHの環境下に24時間放置した。放置後の印画サンプルのベタ画像表面に、幅12mm、長さ3cmのセロハンテープ(セロテープ(登録商標)LP-12、ニチバン株式会社製)を貼り、5秒後に前記セロハンテープを剥離させた。サンプルと剥離させた前記セロハンテープとを目視で観察し、下記の評価基準にしたがって評価した。評価結果を表1に示す。 [Adhesion evaluation]
The print sample obtained above was left in an environment of 25 ° C. and 50% RH for 24 hours. A cellophane tape (cello tape (registered trademark) LP-12, manufactured by Nichiban Co., Ltd.) having a width of 12 mm and a length of 3 cm was applied to the surface of the solid image of the printed sample after being left, and the cellophane tape was peeled off after 5 seconds. The sample and the peeled cellophane tape were visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
上記で得られた印画サンプルを25℃、50%RHの環境下に24時間放置した。放置後の印画サンプルのベタ画像表面に、幅12mm、長さ3cmのセロハンテープ(セロテープ(登録商標)LP-12、ニチバン株式会社製)を貼り、5秒後に前記セロハンテープを剥離させた。サンプルと剥離させた前記セロハンテープとを目視で観察し、下記の評価基準にしたがって評価した。評価結果を表1に示す。 [Adhesion evaluation]
The print sample obtained above was left in an environment of 25 ° C. and 50% RH for 24 hours. A cellophane tape (cello tape (registered trademark) LP-12, manufactured by Nichiban Co., Ltd.) having a width of 12 mm and a length of 3 cm was applied to the surface of the solid image of the printed sample after being left, and the cellophane tape was peeled off after 5 seconds. The sample and the peeled cellophane tape were visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
~評価基準~
A:テープへの色の付着がなく、サンプルのベタ画像の劣化も認められなかった。
B:テープには色が付着したが、サンプルのベタ画像の劣化は認められなかった。
C:テープには色が付着し、サンプルのベタ画像の劣化も認められた。
D:テープの半分以上の面積に色が付着し、サンプルのベタ画像が脱落した。
※Dは実用上問題となるレベルである。 -Evaluation criteria-
A: There was no color adhesion to the tape, and no deterioration of the solid image of the sample was observed.
B: Although the color adhered to the tape, no deterioration of the solid image of the sample was observed.
C: Color adhered to the tape, and deterioration of the solid image of the sample was also observed.
D: Color adhered to more than half the area of the tape, and the solid image of the sample dropped out.
* D is a level that is problematic in practice.
A:テープへの色の付着がなく、サンプルのベタ画像の劣化も認められなかった。
B:テープには色が付着したが、サンプルのベタ画像の劣化は認められなかった。
C:テープには色が付着し、サンプルのベタ画像の劣化も認められた。
D:テープの半分以上の面積に色が付着し、サンプルのベタ画像が脱落した。
※Dは実用上問題となるレベルである。 -Evaluation criteria-
A: There was no color adhesion to the tape, and no deterioration of the solid image of the sample was observed.
B: Although the color adhered to the tape, no deterioration of the solid image of the sample was observed.
C: Color adhered to the tape, and deterioration of the solid image of the sample was also observed.
D: Color adhered to more than half the area of the tape, and the solid image of the sample dropped out.
* D is a level that is problematic in practice.
[放置回復性評価](インクジェット記録装置上でインク組成物の吐出を止めて一定の時間放置し、その後吐出を再開した場合の吐出安定性)
記録媒体として富士フイルム(株)製の画彩写真仕上げPro(商品名)を使用した。記録媒体を保持したステージを248mm/分で移動させ、インク滴量3.4pL、吐出周波数10kHz、ノズル配列方向×搬送方向75×1200dpiで96本のラインを搬送方向に対して平行に1ノズル当り2000発のインク滴を吐出して、印画サンプル(ライン画像)を作製した。これ以外の画像形成の詳細な条件は、前述のベタ画像の形成と同様とした。
得られた印画サンプルを目視で観察して、すべてのノズルからインクが吐出されていることを確認した。
このライン画像を形成した後、所定時間ヘッドをそのままの状態で放置し、続いて新しい記録媒体をステージに貼り付けて、再び上記と同様の条件でインクを吐出して印画サンプル(ライン画像)を作製した。得られた印画サンプル(ライン画像)を目視で観察し、所定時間放置後にインク滴を2000発吐出して96本のノズルすべてが吐出可能であった最大放置時間を指標として放置回復性を評価した。吐出不良が発生しない放置時間が長いほど吐出性が良好であり、以下の評価基準に基づいて評価した。評価結果を表1に示す。 [Evaluation of neglectability] (Discharge stability when the ink composition is stopped on the ink jet recording apparatus and allowed to stand for a certain period of time, and then the ejection is resumed)
As a recording medium, Fuji Photo Film Co., Ltd. painting photo finishing Pro (trade name) was used. The stage holding the recording medium is moved at 248 mm / min, and the ink droplet volume is 3.4 pL, the ejection frequency is 10 kHz, the nozzle arrangement direction × transport direction is 75 × 1200 dpi, and 96 lines per nozzle are parallel to the transport direction. A print sample (line image) was prepared by discharging 2000 ink droplets. The other detailed conditions for image formation were the same as those for the above-described solid image formation.
The obtained print sample was visually observed to confirm that ink was ejected from all nozzles.
After this line image is formed, the head is left as it is for a predetermined time, and then a new recording medium is attached to the stage, and ink is discharged again under the same conditions as above to print a print sample (line image). Produced. The obtained print sample (line image) was visually observed, and after standing for a predetermined time, 2000 ink droplets were ejected, and the standing restorability was evaluated using the maximum standing time during which all 96 nozzles could be ejected as an index. . The longer the standing time during which no ejection failure occurred, the better the ejection performance, and the evaluation was based on the following evaluation criteria. The evaluation results are shown in Table 1.
記録媒体として富士フイルム(株)製の画彩写真仕上げPro(商品名)を使用した。記録媒体を保持したステージを248mm/分で移動させ、インク滴量3.4pL、吐出周波数10kHz、ノズル配列方向×搬送方向75×1200dpiで96本のラインを搬送方向に対して平行に1ノズル当り2000発のインク滴を吐出して、印画サンプル(ライン画像)を作製した。これ以外の画像形成の詳細な条件は、前述のベタ画像の形成と同様とした。
得られた印画サンプルを目視で観察して、すべてのノズルからインクが吐出されていることを確認した。
このライン画像を形成した後、所定時間ヘッドをそのままの状態で放置し、続いて新しい記録媒体をステージに貼り付けて、再び上記と同様の条件でインクを吐出して印画サンプル(ライン画像)を作製した。得られた印画サンプル(ライン画像)を目視で観察し、所定時間放置後にインク滴を2000発吐出して96本のノズルすべてが吐出可能であった最大放置時間を指標として放置回復性を評価した。吐出不良が発生しない放置時間が長いほど吐出性が良好であり、以下の評価基準に基づいて評価した。評価結果を表1に示す。 [Evaluation of neglectability] (Discharge stability when the ink composition is stopped on the ink jet recording apparatus and allowed to stand for a certain period of time, and then the ejection is resumed)
As a recording medium, Fuji Photo Film Co., Ltd. painting photo finishing Pro (trade name) was used. The stage holding the recording medium is moved at 248 mm / min, and the ink droplet volume is 3.4 pL, the ejection frequency is 10 kHz, the nozzle arrangement direction × transport direction is 75 × 1200 dpi, and 96 lines per nozzle are parallel to the transport direction. A print sample (line image) was prepared by discharging 2000 ink droplets. The other detailed conditions for image formation were the same as those for the above-described solid image formation.
The obtained print sample was visually observed to confirm that ink was ejected from all nozzles.
After this line image is formed, the head is left as it is for a predetermined time, and then a new recording medium is attached to the stage, and ink is discharged again under the same conditions as above to print a print sample (line image). Produced. The obtained print sample (line image) was visually observed, and after standing for a predetermined time, 2000 ink droplets were ejected, and the standing restorability was evaluated using the maximum standing time during which all 96 nozzles could be ejected as an index. . The longer the standing time during which no ejection failure occurred, the better the ejection performance, and the evaluation was based on the following evaluation criteria. The evaluation results are shown in Table 1.
~評価基準~
A:最大放置時間が45分以上であった。
B:最大放置時間が30分以上45分未満であった。
C:最大放置時間が20分以上30分未満であった。
D:最大放置時間が20分未満であった。
※Dは実用上問題となるレベルである。 -Evaluation criteria-
A: The maximum standing time was 45 minutes or more.
B: The maximum standing time was 30 minutes or more and less than 45 minutes.
C: The maximum standing time was 20 minutes or more and less than 30 minutes.
D: The maximum standing time was less than 20 minutes.
* D is a level that is problematic in practice.
A:最大放置時間が45分以上であった。
B:最大放置時間が30分以上45分未満であった。
C:最大放置時間が20分以上30分未満であった。
D:最大放置時間が20分未満であった。
※Dは実用上問題となるレベルである。 -Evaluation criteria-
A: The maximum standing time was 45 minutes or more.
B: The maximum standing time was 30 minutes or more and less than 45 minutes.
C: The maximum standing time was 20 minutes or more and less than 30 minutes.
D: The maximum standing time was less than 20 minutes.
* D is a level that is problematic in practice.
表1から、本発明の黒色系インク組成物を用いて画像形成することにより、記録媒体への密着性と耐擦性に優れた画像を形成可能し得ることが分かる。
From Table 1, it can be seen that by forming an image using the black ink composition of the present invention, an image excellent in adhesion to a recording medium and abrasion resistance can be formed.
日本特許出願2010-243482の開示はその全体が参照により本明細書に取り込まれる。
本明細書に記載された全ての文献、特許、特許出願、および技術規格は、個々の文献、特許、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application 2010-243482 is incorporated herein by reference in its entirety.
All documents, patents, patent applications, and technical standards described herein are specifically and individually described as individual documents, patents, patent applications, and technical standards are incorporated by reference. To the same extent, it is incorporated herein by reference.
本明細書に記載された全ての文献、特許、特許出願、および技術規格は、個々の文献、特許、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application 2010-243482 is incorporated herein by reference in its entirety.
All documents, patents, patent applications, and technical standards described herein are specifically and individually described as individual documents, patents, patent applications, and technical standards are incorporated by reference. To the same extent, it is incorporated herein by reference.
本発明によれば、吐出安定性に優れ得るとともに、記録媒体への密着性に優れ得る画像を形成可能なインクジェット記録用の黒色系インク組成物の製造方法を提供することができる。
According to the present invention, it is possible to provide a method for producing a black ink composition for ink jet recording capable of forming an image which can be excellent in ejection stability and can be excellent in adhesion to a recording medium.
Claims (8)
- カーボンブラック顔料を顔料として含むカーボンブラック顔料水性分散物を得ることと、
マゼンタ顔料、シアン顔料およびイエロー顔料からなる群から選ばれる少なくとも1種の着色顔料を顔料として含む着色顔料水性分散物を得ることと、
前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、水溶性の重合性化合物、および重合開始剤を混合することと、
を含むインクジェット記録用の黒色系インク組成物の製造方法。 Obtaining an aqueous dispersion of carbon black pigment containing carbon black pigment as a pigment;
Obtaining a colored pigment aqueous dispersion containing as a pigment at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment;
Mixing the carbon black pigment aqueous dispersion, the colored pigment aqueous dispersion, a water-soluble polymerizable compound, and a polymerization initiator;
A method for producing a black ink composition for ink jet recording comprising: - 前記カーボンブラック顔料水性分散物および着色顔料水性分散物の少なくとも1種は、表面の少なくとも一部が酸性基を有する水不溶性樹脂で被覆された顔料を含む、請求項1に記載の黒色系インク組成物の製造方法。 2. The black ink composition according to claim 1, wherein at least one of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion contains a pigment having a surface coated with a water-insoluble resin having an acidic group. Manufacturing method.
- 前記着色顔料水性分散物は、マゼンタ顔料およびシアン顔料からなる群から選ばれる少なくとも1種の着色顔料を含む、請求項1または請求項2に記載の黒色系インク組成物の製造方法。 The method for producing a black ink composition according to claim 1 or 2, wherein the colored pigment aqueous dispersion contains at least one color pigment selected from the group consisting of a magenta pigment and a cyan pigment.
- 前記重合開始剤は、下記一般式(1)で表される化合物である、請求項1~請求項3のいずれか1項に記載の黒色系インク組成物の製造方法。
(式中、mおよびnはそれぞれ独立に0以上の整数を表し、m+nは0~3の整数を表す) The method for producing a black ink composition according to any one of claims 1 to 3, wherein the polymerization initiator is a compound represented by the following general formula (1).
(In the formula, m and n each independently represent an integer of 0 or more, and m + n represents an integer of 0 to 3) - コロイダルシリカを前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、前記水溶性の重合性化合物、および前記重合開始剤と混合することをさらに含む、請求項1~請求項4のいずれか1項に記載の黒色系インク組成物の製造方法。 5. The method according to claim 1, further comprising mixing colloidal silica with the carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator. The manufacturing method of the black-type ink composition as described in a term.
- 前記カーボンブラック顔料水性分散物および前記着色顔料水性分散物からなる群から選ばれる少なくとも1種に含まれる顔料の体積平均二次粒子径が40nm~150nmである、請求項1~請求項5のいずれか1項に記載の黒色系インク組成物の製造方法。 The volume average secondary particle diameter of the pigment contained in at least one selected from the group consisting of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion is 40 nm to 150 nm. A method for producing the black ink composition according to claim 1.
- アセチレングリコール系界面活性剤を前記カーボンブラック顔料水性分散物、前記着色顔料水性分散物、前記水溶性の重合性化合物、および前記重合開始剤と混合することをさらに含む、請求項1~請求項6のいずれか1項に記載の黒色系インク組成物の製造方法。 The method further comprises mixing an acetylene glycol surfactant with the carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator. The manufacturing method of the black-type ink composition of any one of these.
- 請求項1~請求項7のいずれか1項に記載の製造方法で製造された黒色系インク組成物。 A black ink composition produced by the production method according to any one of claims 1 to 7.
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JP2023092978A (en) * | 2021-12-22 | 2023-07-04 | 東洋インキScホールディングス株式会社 | ink set |
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JPH10130558A (en) * | 1996-09-03 | 1998-05-19 | Fujitsu Isotec Ltd | Water-based pigment-based ink and ink-jet printer |
JPH10287035A (en) * | 1997-04-16 | 1998-10-27 | Seiko Epson Corp | Ink-jet record method, recorded object, and ink-jet recording apparatus |
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JP2000186242A (en) * | 1998-04-28 | 2000-07-04 | Canon Inc | Ink, ink jet recording method using same, and photopolymerization initiator |
JP2005320541A (en) * | 2004-05-06 | 2005-11-17 | Agfa Gevaert Nv | Radiation-curable ink-jet printing |
JP2007217508A (en) * | 2006-02-15 | 2007-08-30 | Canon Inc | Inkjet ink, inkjet recording method, ink cartridge, recording unit and inkjet recording apparatus |
JP2009144007A (en) * | 2007-12-12 | 2009-07-02 | Kao Corp | Water-based ink for ink-jet recording |
JP2009190379A (en) * | 2008-02-18 | 2009-08-27 | Fujifilm Corp | Ink composition, ink set, and image forming method |
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2011
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JPH10130558A (en) * | 1996-09-03 | 1998-05-19 | Fujitsu Isotec Ltd | Water-based pigment-based ink and ink-jet printer |
JPH10287035A (en) * | 1997-04-16 | 1998-10-27 | Seiko Epson Corp | Ink-jet record method, recorded object, and ink-jet recording apparatus |
JPH11228886A (en) * | 1998-02-09 | 1999-08-24 | Seiko Epson Corp | Black ink excellent in reproducibility of black |
JP2000186242A (en) * | 1998-04-28 | 2000-07-04 | Canon Inc | Ink, ink jet recording method using same, and photopolymerization initiator |
JP2005320541A (en) * | 2004-05-06 | 2005-11-17 | Agfa Gevaert Nv | Radiation-curable ink-jet printing |
JP2007217508A (en) * | 2006-02-15 | 2007-08-30 | Canon Inc | Inkjet ink, inkjet recording method, ink cartridge, recording unit and inkjet recording apparatus |
JP2009144007A (en) * | 2007-12-12 | 2009-07-02 | Kao Corp | Water-based ink for ink-jet recording |
JP2009190379A (en) * | 2008-02-18 | 2009-08-27 | Fujifilm Corp | Ink composition, ink set, and image forming method |
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JP2023092978A (en) * | 2021-12-22 | 2023-07-04 | 東洋インキScホールディングス株式会社 | ink set |
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