WO2004061016A1 - 分散性色材とその製造方法、それを用いた水性インク、インクタンク、インクジェット記録装置、インクジェット記録方法及びインクジェット記録画像 - Google Patents
分散性色材とその製造方法、それを用いた水性インク、インクタンク、インクジェット記録装置、インクジェット記録方法及びインクジェット記録画像 Download PDFInfo
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- WO2004061016A1 WO2004061016A1 PCT/JP2003/016949 JP0316949W WO2004061016A1 WO 2004061016 A1 WO2004061016 A1 WO 2004061016A1 JP 0316949 W JP0316949 W JP 0316949W WO 2004061016 A1 WO2004061016 A1 WO 2004061016A1
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- fine particles
- dispersible
- colorant
- ink
- aqueous
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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
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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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
-
- 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 dispersible coloring material and a method for producing the same, and an ink for aqueous ink jet recording, an ink jet recording apparatus, and an ink jet recording method using the same.
- the ink-jet method is a method of recording images and characters by ejecting minute droplets of ink from nozzles to reach a recording medium (paper or the like) based on various operating principles. It is easy to use, has high flexibility in recording patterns, and does not require development and fixing operations. In particular, in recent years, the technology of full-color aqueous ink jet recording has been remarkably developed, and it is necessary to form multicolor images that are comparable to multicolor printing by conventional plate-making methods and printing by color photography. When the number of copies is small, printed matter can be obtained at a lower cost than ordinary multicolor printing or printing, and it is being widely applied to the full color single image recording field.
- the performance required of the ink jet recording ink used in the ink jet recording apparatus includes (1) bleeding and fogging on paper. (2) No clogging due to ink drying at the nozzle tip, good ejection response and stable ejection, (2) 3) good fixability of the ink on paper; (4) good image fastness (that is, weather resistance and water resistance); and (5) good long-term storage stability.
- an ink that can dry and fix the ink quickly and obtain high-quality printing even when printing on plain paper such as copy paper.
- the coloring materials used are mainly dyes and pigments.
- Water-soluble dyes have been mainly used because of their ease of handling as water-based inks and their high coloring properties.
- the development of inks that use water that is essentially insoluble in water, especially pigments, has been energetically developed as a coloring material for water-based ink jet recording that can achieve water resistance and water resistance.
- a water-insoluble coloring material, particularly a pigment it is necessary to stably disperse the coloring material in water.
- a method of stabilizing the dispersion using a surfactant or a polymer dispersant (hereinafter, also referred to as a dispersing resin) has been used.
- a method of chemically modifying the surface of a water-insoluble colorant has been proposed (for example, see Japanese Patent Application Laid-Open No. 10-195360).
- a microcapsule type pigment in which a pigment is coated with a resin has been proposed (see, for example, JP-A-8-183920 and JP-A-2000-34770). Japanese Patent Application Laid-Open No.
- a water-insoluble colorant dispersion containing a water-insoluble colorant is prepared by dispersing a water-insoluble colorant in an aqueous medium in the presence of a dispersant. It is a polymer obtained by adding a BULL monomer and polymerizing.When the dispersant disperses a water-insoluble colorant, it shows dispersion stability and when the BULL monomer is polymerized in the presence of only the dispersant. Discloses an aqueous coloring fine particle dispersion characterized by poor stability of the resulting latex, and ⁇ emulsion polymerization into a water-insoluble colorant dispersion '' is disclosed.
- the affinity of the dispersant for the vinyl monomer and the resulting polymer is not so high, so that the dispersant is less likely to be desorbed from the pigment surface and the polymerization has proceeded on the surface of the pigment to which the dispersant has been adsorbed. ''"They can be obtained in high yield without agglomeration of the fine particle dispersion coated on the pigment surface.”
- Use of the colored fine particle dispersion provides excellent dispersion stability and printability, and depends on paper type. The company claims that it has obtained an ink jet recording ink with no resistance, low metallic luster, and excellent water resistance, light resistance, and abrasion resistance. Disclosure of the invention
- the functional groups that can be modified and their densities are limited.
- the colorant is an organic pigment
- the pigment molecules which are originally insoluble in water and crystallized become pigment molecules 13 which have been hydrophilized by the bonding of the hydrophilic groups 12. It was not a satisfactory technical level, for example, it was solubilized and dissolved from pigment particles, causing so-called “pigment peeling” and causing a significant change in color tone (see Figures 6A and 6B). .
- An object of the present invention is to solve the problems of the prior art, and to provide a sufficiently high dispersion stability and a long-term stable dispersibility without detachment of the resin component from the coloring material.
- An object of the present invention is to provide a coloring material and a simple method for producing the coloring material.
- Another object of the present invention is to provide an ink for aqueous ink jet recording, an ink tank, an ink jet recording apparatus, an ink jet recording method, and an ink jet recorded image using such an excellent dispersible colorant. .
- the present inventors have intensively studied means for solving the above-mentioned problems, and as a result, by using a dispersible colorant having a novel shape, a surfactant and a polymer dispersant were essentially required.
- the development of a new dispersible colorant that maintains high dispersion stability and has long-term storage stability without detachment of the resin component from the colorant has been achieved.
- an aqueous ink jet recording ink having sufficient discharge stability and dispersion stability for use in ink jet recording and giving a printed matter having high image quality and excellent fastness was obtained. That is, the object of the present invention is achieved by the following specific means.
- a dispersive color material having a color material and chargeable resin pseudo fine particles that are smaller than the color material, wherein the color material and the charge resin pseudo fine particles are fixed. Colorant.
- a dispersible color material having a color material and chargeable resin pseudo fine particles that are smaller than the color material, wherein the color material includes a plurality of the chargeable resin pseudo fine particles fixed to the color material.
- a dispersible coloring material characterized in that it is made.
- the glass transition temperature of the copolymer component constituting the charged resin pseudo fine particles is from 140 ° C. to 60 ° C.
- chargeable resin pseudo fine particles according to any one of the above 1 to 5, wherein the chargeable resin pseudo fine particles comprise a copolymer of a monomer component containing at least one kind of hydrophobic monomer and at least one kind of hydrophilic monomer.
- hydrophobic monomer contains at least one selected from benzyl methacrylate or methyl methacrylate.
- dispersible coloring material according to any one of the above 6 to 9, further comprising at least an anionic monomer as the hydrophilic monomer.
- the dispersible coloring material according to the item 10 wherein the ayuonic monomer contains at least one selected from atalylic acid, methacrylic acid, and p-styrenesulfonate.
- a radical polymerizable monomer is subjected to aqueous precipitation polymerization using an aqueous radical polymerization initiator to integrate the water-insoluble colorant with the chargeable resin pseudo fine particles.
- an aqueous radical polymerization initiator is used to carry out aqueous precipitation polymerization of a radically polymerizable monomer.
- a method for producing a dispersible coloring material comprising: a step of integrating the water-insoluble coloring material with the chargeable resin pseudo fine particles; and (2) a step of purifying a product.
- the aqueous dispersion of a water-insoluble colorant is an aqueous pigment dispersion in which an acid value is dispersed with a polymer dispersant having an acid value of 100 or more and 250 or less. 3.
- the pigment-dispersed ice solution wherein the aqueous dispersion solution of the water-insoluble colorant is a pigment-dispersed ice solution dispersed with a polymer dispersant having an amine value of 150 or more and 300 or less. 4. The method for producing a dispersible colorant according to 4.
- the radical polymerization initiator is an aqueous azo polymerization initiator. 13. The method for producing a dispersible colorant according to any one of the above items 13 to 21.
- a water-based ink characterized by comprising at least one kind of self-dispersible resin fine particles.
- the surface zeta potential of the dispersible coloring material in the aqueous medium constituting the aqueous ink is fixed to the resin pseudo fine particles, and the average value thereof is 15 mV or less and 180 mV or more.
- An aqueous ink characterized in that the distribution has a standard deviation of less than 50.
- aqueous ink containing a dispersible colorant wherein the dispersible colorant is formed by fixing the colorant and the positively chargeable resin pseudo fine particles, and the dispersible colorant in an aqueous medium constituting the aqueous ink.
- the colorant constituting the dispersible colorant is a pigment, and the ratio of the pigment to all the resin components contained in the ink (resin mass Z pigment mass 2 B / P) is 0.3. 30.
- An ink tank comprising the water-based ink according to any one of 24 to 30.
- An ink jet recording apparatus characterized in that an ink jet recorded image is formed using the aqueous ink according to any of the above items 24 to 30.
- the colorant surface is sufficiently dispersed and stabilized at a high functional group density, a resin component is present on the surface thereof, and the dispersible colorant is free from detachment of the resin component from the colorant, and A simple method for producing the dispersible colorant is provided.
- a dispersible colorant excellent in quick drying property on a recording medium is provided.
- Another advantage of the present invention is that the recording medium The present invention provides a dispersible colorant having excellent scratch resistance in the ink jet recording apparatus, and another effect is to provide a dispersible colorant having excellent discharge characteristics in an ink jet recording apparatus.
- a dispersive colorant having excellent coloring properties on a recording medium is provided, and further, a dispersible colorant which can be stably used in a high to medium pH region, and Dispersible colorants that can be used stably in the low to high pH range are provided, and a simple production method thereof is also provided.
- an aqueous ink excellent in gloss on a glossy recording medium and an aqueous ink excellent in scratch resistance on a glossy recording medium are provided.
- an aqueous ink excellent in long-term storage stability is provided.
- the ink composition has sufficient ejection stability and dispersion stability for ink jet recording use, and has high image quality and excellent fastness.
- the present invention provides an excellent water-based ink, ink tank, ink jet recording device, ink jet recording method, and ink jet recorded image which provide printed matter having the same.
- FIG. 1A and FIG. 1B are schematic diagrams showing a basic structure of a dispersible colorant to which charged resin pseudo fine particles are fixed according to the present invention.
- FIG. 2A, FIG. 2B, FIG. 2C, and FIG. 2D are schematic diagrams of typical steps in the manufacturing method of the present invention.
- FIG. 3 is a schematic diagram showing a process of purifying charged resin pseudo fine particles and fixing the same to a coloring material in the production method of the present invention.
- FIG. 4 shows the charged resin pseudo fine particles of the present invention enlarged from the interface side where they are fixed to the coloring material.
- FIG. 5 is a schematic diagram in which the interface between the chargeable resin pseudo fine particles of the present invention and the coloring material is enlarged.
- FIG. 6A and FIG. 6B are schematic diagrams of the pigment peeling phenomenon when a hydrophilic group is directly modified on an organic pigment as represented by JP-A-10-195360.
- FIGS. 7A, 7B, and 7C are schematic diagrams showing the aggregation state of the dispersible colorant on the recording medium.
- the term “dispersible colorant” means that it is dispersible in water or an aqueous ink medium without adding a surfactant or a polymer dispersant. Is a coloring material.
- a first feature of the present invention is a dispersible color material comprising a color material and chargeable resin pseudo fine particles, wherein the color material fixes the chargeable resin pseudo fine particles.
- FIGS. 1A and 1B are schematic diagrams of a dispersible colorant which is characterized by the present invention and in which the chargeable resin pseudo fine particles 2 are fixed to the colorant 1.
- the portions 2 and 3 in FIG. 1B are portions schematically showing a state in which a part of the charged resin pseudo fine particles 2 adhered to the surface of the coloring material 1 is fused.
- the coloring material fixes the chargeable resin pseudo fine particles
- the charge of the chargeable resin pseudo fine particles is applied to the surface of the color material, and the dispersible color material can be dispersed in water or an aqueous ink medium.
- the dispersible colorant has excellent adhesiveness to the recording medium due to the presence of the resin component fixed on the surface.
- the chargeable resin pseudo fine particles which is a feature of the dispersible color material according to the present invention, are fixed to the color material, the chargeable resin pseudo fine particles are Since it does not detach from the color material surface, the dispersible color of the present invention The material is also excellent in long-term storage stability.
- the chargeable resin pseudo fine particles in the present invention are a resin aggregate in which the resin component is strongly aggregated, and preferably have a large amount of physical cross-links formed therein. Is a resin component having a stable form as a fine particle form or a microaggregate close to the fine particle form). The details of the charged resin pseudo fine particles will be described later.
- FIG. 4 shows a schematic diagram in which the interface of the charged resin pseudo-fine particles in contact with the coloring material is enlarged.
- the charged resin pseudo fine particles are formed by intertwining polymers composed of various monomer unit compositions.
- the polymer locally has various structures, and the local surface energy also has various states.
- the color material and the polymer are strongly bonded.
- the merit of the dispersible colorant according to the present invention in which the chargeable resin pseudo fine particles are fixed to the color material is that the specific surface area of the dispersible colorant is fixed by the form in which the chargeable resin pseudo fine particles are fixed. Increase.
- the charge of the chargeable resin pseudo fine particles can be converted to the surface charge of the dispersible colorant with extremely high efficiency. That is, the form of the dispersible colorant of the present invention is a form in which more surface charges are more efficiently distributed on the surface of the dispersible colorant, and is disclosed in Japanese Patent Application Laid-Open No. 8-189392. Compared with a typical form in which a coloring material is coated with a resin, a high dispersion stability can be imparted even when the resin component has a substantially smaller acid value or amine value.
- organic facial medicine is insolubilized (pigmented) by crystallization of color-forming coloring material molecules due to strong interaction.
- the colorant of the present invention is an organic face
- the chargeability is high.
- the resin pseudo fine particles are fixed over some coloring material molecules in the pigment particles. (See FIG. 5.) Therefore, the "pigment peeling" due to the localization of the coloring material molecules described in FIGS. 6A and 6B does not occur in the present invention.
- the size of the charged resin pseudo fine particles is controlled to a range smaller than the dispersed particle size of the pigment and larger than the coloring material molecules, so that An organic pigment dispersible coloring material having high dispersibility can be obtained without forming a crystal structure.
- the state in which the coloring material “fixes” the chargeable resin pseudo fine particles can be simply confirmed by the following method involving three-stage separation.
- the first separation the color material to be confirmed and contained in the ink or water dispersion And other water-soluble components (including the water-soluble resin component), and then, in the second separation, the coloring material contained in the precipitate in the first separation and the water-insoluble resin component are separated.
- the second separation the coloring material contained in the precipitate in the first separation and the water-insoluble resin component are separated.
- the resin component that is weakly adsorbed and the dispersible coloring material that fixes the charged resin pseudo fine particles are separated, and the resin component contained in the supernatant of the third separation is separated. Quantitative determination and comparison of the sediment of the second separation with the sediment of the third separation confirm the fixation between the coloring material and the chargeable resin pseudo fine particles.
- the sediment in the second separation and the sediment in the third separation were each dried to a solid content of about 0.5 g at 30 ° C. for 18 hours under reduced pressure. Observe with a scanning electron microscope at a magnification of 50,000. Then, it was confirmed that the observed dispersible colorant had a plurality of fine particle-like substances or microaggregates equivalent thereto adhered to its surface, and that each of the sedimentation from the second separation and the third separation was observed. If the object has the same form, it is determined that the coloring material has resin pseudo fine particles fixed thereon.
- the supernatant of the upper layer in the third separation is gently halved from above to about half in volume, and the solid content weight is calculated from the weight change before and after drying at 60 ° C for 8 hours. If it is less than 1%, it is considered that there is no detachment of the resin pseudo fine particles from the dispersible color material, and it can be determined that the dispersible color material has fixed the resin pseudo fine particles.
- any method that achieves the above-mentioned first separation and the second and third separations can be applied as a method for determining whether or not it is the dispersible coloring material according to the present invention. can do. That is, the first separation aims at separating the water-soluble component from the coloring material contained in the ink and the aqueous dispersion and the resin component adsorbed thereon, and the second separation is intended to The purpose is to separate the coloring material and the resin component adhered to the coloring material from other resin components adsorbed on the coloring material. Further, the third separation is intended to confirm that the resin component adhered to the coloring material does not desorb.
- any other known or newly developed separation method that achieves the purpose of each of the first, second and third separations may be used. Also, it is at least applicable.
- a second feature of the present invention resides in that the water-insoluble coloring material 1 and the chargeable resin pseudo fine particles 2 are adhered to each other and are dispersed alone to form a dispersible coloring material.
- the dispersible colorant according to the present invention can be stably dispersed in water and water-based inks without the help of other surfactants or polymer dispersants. It is a sex coloring material. This definition and determination method will be described later in detail. Therefore, to the dispersible colorant of the present invention, a polymer dispersant or other resin component or a surfactant component which may be detached in a long term is added for the purpose of stabilizing the colorant dispersion. No need.
- the dispersible colorant of the present invention when used as a water-based ink, the degree of freedom in designing components other than the dispersible colorant increases, and for example, a recording medium having a high ink permeability such as plain paper. It is also possible to use a water-based ink capable of obtaining a sufficiently high print density.
- the self-dispersibility of the dispersible colorant of the present invention can be confirmed, for example, as follows. Dilute the ink or aqueous dispersion in which the coloring material is dispersed 10 times with pure water, and concentrate it to the original concentration using an ultrafiltration filter having a molecular weight cutoff of 50,000. The concentrate is centrifuged at 1,200 rpm for 2 hours. Separate, remove the sediment and redisperse in pure water. At this time, those in which the sediment can be re-dispersed favorably are judged to have self-dispersibility.
- Good re-dispersion depends on the fact that it is visually homogeneously dispersed, that there is no noticeable sediment during standing for 1 to 2 hours, and that even if it is shaken lightly, And that the average particle size is less than twice the particle size before the operation when measuring the dispersed particle size by the dynamic light scattering method.
- the dispersible colorant according to the present invention takes a form in which the colorant has a high specific surface area by fixing the chargeable resin pseudo fine particles, and has a large amount of charge on its vast surface. Realize excellent storage stability. Therefore, more preferable results can be obtained when a large number of the chargeable resin pseudo fine particles are fixed to the coloring material in a dotted manner.
- the fixed chargeable resin pseudo fine particles have a certain distance, and are preferably uniformly distributed. More preferably, it is desirable that the surface of the coloring material is exposed between the charged resin pseudo fine particles.
- Such a form is confirmed by observing the ink for aqueous ink jet recording of the present invention with a transmission electron microscope or a scanning electron microscope.
- the chargeable resin pseudo fine particles fixed to the surface of the color material are separated by a fixed distance, or the force between the plurality of fixed charge resin pseudo fine particles, or the surface of the color material is exposed between the fixed charge resin pseudo fine particles. Can be observed.
- the charged resin pseudo fine particles are sometimes partially close to each other, and in some cases, the fused resin pseudo particles can be observed. However, there is a distance between the charged resin pseudo fine particles as a whole, If there is a portion where the resin is exposed and these states are distributed, it is considered that the charged resin pseudo fine particles are scattered and adhered to the coloring material. Is obvious.
- the aqueous ink containing the dispersible colorant according to the present invention exhibited excellent quick-drying properties on a recording medium.
- the reason for this is not clear, but it is thought to be based on the following mechanism.
- the dispersible colorant is, as described above, The chargeable resin pseudo fine particles are fixed to the surface of the coloring material and dispersed in the ink. When this ink reaches the recording medium, the solvent in the ink is converted into pores on the recording medium (capacities between cellulose fibers in the case of plain paper, and a receiving layer in the case of coated paper or glossy paper) due to the capillary phenomenon. Is absorbed into the pores.
- the chargeable resin pseudo fine particles are scattered at portions where the colorants are in contact with each other to form many fine gaps. For this reason, the ink solvent existing between the color materials causes a capillary action to be quickly absorbed into the recording medium.
- the aqueous ink according to the present invention the one using a dispersible colorant in a form in which charged resin pseudo fine particles are scattered on the surface shows a more preferable quick drying property. It is expected that has been achieved.
- Surface functional group density of the dispersible colorant according to the present invention 2 5 0 ⁇ ⁇ ⁇ than the 1, 0 0 0 mu mo is preferably less than 1 / g, 2 9 0 ⁇ mo I / g or more 9 0 0 More preferably, it is less than ⁇ o 1 Zg.
- the surface functional group density is smaller than this range, the long-term storage stability of the dispersible colorant may be deteriorated. If the surface functional group density is much larger than this range, the dispersion stability becomes too high, and the dispersibility easily penetrates on the recording medium, making it difficult to secure a high print density. There are cases.
- the surface functional group density is determined, for example, as follows, particularly when the surface charge of the dispersible colorant is anionic.
- HC 1 hydrochloric acid
- aqueous solution was added, precipitated with 2 0, 0 0 0 rpm s 1 hour condition by centrifugation apparatus dispersible colorant measured in including aqueous dispersion or Inku Let it.
- Collect sediment After redispersing in pure water, the solid content is measured by a drying method. The redispersed sediment is weighed, a known amount of sodium hydrogen carbonate is added thereto, and the stirred dispersion is further settled by a centrifuge at 80,000 rpm for 2 hours.
- the supernatant is weighed and the known amount of sodium hydrogen carbonate is subtracted from the neutralization amount obtained by neutralization titration with 0.1N hydrochloric acid to obtain the number of mo 1 per 1 g of coloring material. Functional group density is required.
- sodium hydroxide (NaOH) is used in place of hydrochloric acid and ammonium chloride is used in place of sodium bicarbonate in the same manner as described above. , Can be similarly determined.
- the surface energy of the dispersible colorant according to the present invention 7 0 111: Bruno 111 Rukoto 2 or less is also a preferred embodiment. According to the studies of the present inventors, it more possible to control the surface energy of the partial dispersion colorant to 7 O m J / m 2 or less of the range, obtain an appropriate fixing property on the recording medium it can. Wherein when the surface energy of the dispersible colorant is significantly greater than the 7 O m J / m 2, because too high hydrophilicity of the dispersible colorant table surface, the coloring material and an aqueous Inku medium on the recording medium Separation is slow, and the recorded image may not be dried easily. Further, even after the recorded image is dried, the water resistance of the printed matter may be insufficient.
- the surface energy of the dispersible coloring material used in the present invention is controlled by any of the surface charge, the functional group structure of the coloring material used, and the chemical structure and surface structure of the chargeable resin pseudo fine particles adhered to the coloring material. be able to. Further, the chemical structure and surface structure of the charged resin pseudo fine particles are controlled by any of a polymerization initiator and a monomer component used when synthesizing the charged resin pseudo fine particles.
- surface energy refers to the free energy of a material's interface and depends on the chemical structure of that interface. The higher the surface energy Indicates that it is easy to wet and has high affinity for water.
- a value obtained by using an Imperth Gas Gas Chromatograph marketed by Surface 'Measurement System Co., Ltd. is defined as a surface energy value of the dispersible colorant. Specifically, it can be determined by drying a dispersible colorant to form a powder and using it as a stationary phase, and deviating from the retention time of each gas when an organic gas having a different polarity is used as a mobile phase.
- the coloring material that is a component of the dispersible coloring material according to the present invention will be described below.
- the coloring material used in the present invention any of known or newly developed coloring materials can be used.
- hydrophobic dyes, inorganic pigments, organic pigments, metal colloids, coloring resins are used.
- Desirable is a water-insoluble coloring material such as particles that can be stably dispersed in water together with a dispersant.
- a coloring material having a dispersed particle size in the range of 0.01 to 0.5 ⁇ (10 to 500 ⁇ ), particularly preferably in the range of 0.03 to 0.3 ⁇ (30 to 300 nm) is used. use.
- the dispersible coloring material of the present invention using a coloring material dispersed in this range is a preferable dispersing coloring material which gives an image having high coloring power and high weather resistance when used as an aqueous ink.
- a dispersion particle diameter is an average value of cumulant of particle diameters measured by a dynamic light scattering method.
- examples of inorganic pigments that can be effectively used as a coloring material include car pump racks, titanium oxide, zinc oxide, zinc oxide, tripon, iron oxide, aluminum oxide, silicon dioxide, kaolinite, and montmorillonite.
- Talc Barium sulfate, Calcium carbonate, Silica, Alumina, Forced dome red, Benga, Molybdenum red, Kupa permillion, Molypdate range, Graphite, Chrome yellow, Cadmium yellow, Yellow iron oxide, Titanium yellow, Chromium oxide, Pyridian, Cobalt green, titanium cobalt Lean, cobalt chrome green, ultramarine blue, ultramarine blue, navy blue, cobalt pour, cerulean plum, manganese violet, cobalt violet, my power, and the like.
- Organic pigments that can be effectively used in the present invention include, for example, azo-based, azomethine-based, polyazo-based, phthalocyanine-based, quinatalidone-based, anthraquinone-based, indigo-based, thioindigo-based, quinophthalone-based, benzimidazolone-based, Various pigments such as isoindoline type and isoindolinone type are exemplified.
- organic insoluble coloring materials that can be used in the present invention include, for example, azo-based, anthraquinone-based, indigo-based, phthalocyanine-based, carbonyl-based, quinonimine-based, methine-based, quinoline-based, and nitro-based colorants.
- hydrophobic dyes such as dyes. Among these, disperse dyes are particularly preferred.
- Chargeable Resin Pseudo-Fine Particles-Chargeable resin pseudo-fine particles which are another component of the dispersible colorant of the present invention, are substantially insoluble in water, and are fixed in water of a colorant to be fixed.
- the dispersion unit (dispersion particle size) in (in the ink) is small, and is defined as a microparticle composed of resin components having a sufficiently high degree of polymerization.
- the shape of the microparticles may be pseudo-spherical or a plurality of microparticles (chargeable resin pseudo-fine particles) having a uniform size within a certain range.
- the resin components constituting the charged resin pseudo fine particles are preferably physically or chemically cross-linked to each other.
- the resin components constituting the charged resin pseudo fine particles are cross-linked to each other can be confirmed by using, for example, the following method.
- the resin component constituting the charged resin pseudo fine particles is estimated in advance by a known analysis method, and a linear polymer having the same chemical structure (or the same monomer unit composition) is synthesized by solution polymerization, and the Immerse the charged resin pseudo-fine particles and the polymer in an organic solvent that is a good solvent for the polymer, and compare their solubility. Then, when the solubility of the charged resin pseudo fine particles is lower than the solubility of the polymer, it is confirmed that the inside of the charged resin pseudo fine particles is crosslinked.
- the dispersed particle size of the charged resin pseudo fine particles in water can be measured by, for example, a dynamic light scattering method
- the average value of the cumulant of the dispersed particle size is used. Is preferably in the range of 10 nm or more and 200 nm or less.
- the polydispersity index of the dispersed particle size be suppressed to less than 0.2. Dispersion If the average value of the particle size is larger than 200 nm or the polydispersity index is larger than 0.2, the original purpose of colorant ⁇ finely dispersing and stabilizing is not sufficiently achieved. There is.
- the average value of the dispersed particle diameter is smaller than 10 nm, the form as the chargeable resin pseudo fine particles cannot be sufficiently maintained, and the resin is easily dissolved in water. May not be possible.
- the particle diameter is smaller than that of the coloring material particles themselves, so that the dispersion stabilization of the coloring material by fixation of the chargeable resin pseudo fine particles in the present invention is effective. Is expressed.
- the above preferred embodiment is the same even when the dispersed particle size of the chargeable resin pseudo fine particles cannot be measured. In such a case, for example, the average diameter of the chargeable resin pseudo fine particles in an electron microscope observation is as described above. It is considered to be a preferable range or a range similar thereto.
- the chargeable resin pseudo fine particles are set to a range smaller than the dispersed particle size of the pigment and larger than the coloring material molecule as described above. This is particularly desirable because a dispersible colorant that is extremely structurally stable and has high dispersibility can be obtained.
- the term "chargeable” refers to a state in which an aqueous medium itself has an ionized functional group in some form, and is preferably self-dispersible due to its chargeability. Therefore, whether or not the particles are charged resin pseudo fine particles is determined by a known and arbitrary method using the surface of the charged resin pseudo fine particles.
- the resin component constituting the chargeable resin pseudo fine particles may be any resin component, such as any commonly used natural or synthetic polymer or a polymer newly developed for the present invention. Can be used without.
- the resin component that can be used include an acrylic resin, a styrene Z acrylic resin, a polyester resin, a polyurethane resin, a polyurea resin, a polysaccharide, a polypeptide, and the like.
- polymers of monomer components having radical polymerizable unsaturated bonds such as acrylic resins and styrene Z acrylic resins, are included.
- a copolymer can be used preferably.
- Examples of the monomer having a radical polymerizable unsaturated bond preferably used in the present invention include the following.
- Classified as hydrophobic monomers for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, benzyl acrylate, benzyl methacrylate
- hydrophobic monomers for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl methacrylate, n-butyl methacrylate, isoptyl methacrylate, t-butyl methacrylate, tridecyl methacrylate, benzyl methacrylate, etc.
- Styrene-based monomers such as styrene, ⁇ -methylinolestyrene, o-methinolestyrene, m-methylstyrene, p-methylstyrene, and tert-butylstyrene; itaconate esteranol such as benzyl itaconate; Maleic esters such as dimethyl oleate; fumaric esters such as dimethyl fumarate; acrylonitrile, methacrylonitrile, vinyl acetate and the like.
- monomers having an anionic group include, for example, monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, and the like.
- Sulfonate groups such as salts thereof, styrene sulfonic acid, sulfonic acid 12-propyl pyracrylamide, acrylic acid 12-sulfonic acid ethyl ester, methacrylic acid 12-sulfonic acid ethyl ester, butyl acrylacrylamide sulfonic acid, etc.
- salts thereof, and monomers having a phosphonic acid group such as methacrylic acid 1-2-phosphonate, acrylic acid 12-phosphonate ethyl and the like.
- methacrylic acid 1-2-phosphonate acrylic acid 12-phosphonate ethyl and the like.
- Examples of the monomer having a cationic group include monomers having a primary amino group such as aminoethyl acrylate, aminopropyl acrylate, amide methacrylate, aminoethyl methacrylate, and aminopropyl methacrylate; and methyl acrylate.
- nonionic hydrophilic monomer specifically, for example, monomers having both a radical polymerizable unsaturated bond and a strong hydroxyl group in the structure at the same time are applicable.
- Hydroxymethyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. are classified into this category.
- known or new various oligomers, macromonomers, and the like can be used without limitation.
- crosslinkable monomer for example, divinyl benzene, aryl (meth) acrylate, methylenebisacrylamide, and the like can be used.
- various known or novel crosslinkable monomers can be used.
- the chargeable resin pseudo fine particles are formed of a copolymer of a monomer component containing at least one kind of hydrophobic monomer and at least one kind of hydrophilic monomer among the above-listed monomers. It is an aspect.
- hydrophobic monomer one containing at least a monomer having a methyl group at the ⁇ -position and having a radically polymerizable unsaturated double bond.
- the hydrophobic monomer contains at least an alkyl acrylate compound and an alkyl methacrylate compound (hereinafter, referred to as (meth) ⁇ '-alkyl acrylate compound). It is a form.
- the (meth) acrylic acid alkyl ester compound has excellent adhesiveness to the coloring material, as well as excellent copolymerizability with the hydrophilic monomer component, uniformity of the surface properties of the chargeable resin pseudo fine particles, and A favorable result is given from the viewpoint of uniform fixation to the colorant.
- the above-mentioned preferred hydrophobic monomers it is particularly preferable to include at least one selected from benzyl methacrylate or methyl methacrylate.
- the above-mentioned two types of monomers give the chargeable resin pseudo fine particles favorable heat resistance and transparency.
- the dispersible coloring material which is fixed exhibits excellent color development.
- the dispersible color material and the Z or the chargeable resin pseudo fine particles adhered to the color material of the present invention are appropriately selected by selecting the monomer species and the copolymerization ratio constituting the chargeable resin pseudo fine particles.
- the properties can be controlled, but the glass transition temperature of the copolymer component contained in the charged resin pseudo fine particles is 140 ° C or higher.
- the temperature is also a preferable embodiment to control the temperature to be ⁇ 25 ° C. or more and 53 ° C. or less.
- those which are known to have a low glass transition temperature of a homopolymer obtained from the monomer are selected and used.
- n-butyl acrylate and acrylic acid as monomers in an appropriate ratio.
- ethyl methacrylate and methacrylic acid as monomers at an appropriate ratio.
- the glass transition temperature of the chargeable resin pseudo fine particles can be measured by generally used differential scanning calorimetry. For example, in the present invention, a value measured using DSC822e manufactured by METTLER is used. Detailed measurement conditions will be described in Examples.
- a dispersible colorant comprising a copolymer component having a glass transition temperature of 140 ° C or higher and 60 ° C or lower is recorded by the high film forming property imparted to the chargeable resin pseudo fine particles.
- a film can be formed with adjacent colorants on paper to form a strong colored film. Therefore, the printed matter obtained by using the dispersible coloring material having such a structure not only imparts high scratch resistance, but also has a scratch resistance even on a glossy recording medium which is extremely disadvantageous in the scratch resistance. Excellent printed matter can be obtained.
- the aqueous ink containing the dispersible coloring material of the present invention comprising the copolymer component having the glass transition temperature in the above-described range has a temperature at the time of being applied on the recording medium, which is not particularly different from room temperature. Even in cases where it has excellent scratch resistance To give the printed matter. Although the reason for this has not been clarified, it is supposed as follows according to the study of the present inventors. Generally, the glass transition temperature measured by differential scanning calorimetry is the glass transition temperature of a resin in a dry state, but the glass transition temperature is known to decrease when the resin is in a water-absorbing state, for example. ing.
- the glass transition temperature of the charged resin pseudo fine particles constituting the dispersible colorant present in the aqueous medium as the aqueous ink is lower than the measured glass transition temperature, it is applied to the recording medium.
- the film exhibits its film forming property and adhesiveness when it is used. In particular, when the glass transition temperature is from 130 ° C to 55 ° C, more preferably from 125 ° C to 53 ° C, the above-mentioned film forming property and adhesiveness are preferably exhibited. Further, it has been clarified by the present inventors that a more preferable result is obtained when the resin component constituting the chargeable resin pseudo fine particles contains at least one kind of hydrophilic monomer at the same time.
- a composition containing at least an anionic monomer as a hydrophilic monomer is also a preferred mode.
- a configuration containing an anionic monomer more anionic groups can be introduced into the charged resin pseudo-fine particles, and the surface functional group density of the coloring material can be controlled to the preferable value as described above. This method is also effective.
- a composition containing an anionic monomer a dispersible colorant exhibiting high dispersion stability particularly in a high pH region to a middle pH region can be obtained.
- the anionic monomer used in the present invention is not particularly limited as long as it has a functional group exhibiting anionic properties in water.
- Acrylic acid, methacrylic acid, p-styrenesulfonic acid, and salts thereof are particularly preferably used from the viewpoints of copolymerizability, general versatility, anionic properties, and the like.
- the configuration containing at least a cationic monomer as a hydrophilic monomer is a preferable mode in which a dispersible colorant exhibiting high dispersion stability can be obtained, particularly in a medium pH region to a low pH region.
- the cationic monomer is not particularly limited as long as it is a monomer having a functional group that exhibits cationicity in water, and among the radically polymerizable monomers described above, those mentioned as monomers having a cationic group are preferably used. .
- the method and method for synthesizing the chargeable resin pseudo fine particles and the method for fixing the chargeable resin pseudo fine particles to the color material are known, and the method for synthesizing the charge resin pseudo fine particles and the color material is known. Can be implemented.
- the present inventors have conducted intensive studies and found that a dispersible colorant comprising a colorant, which is a feature of the present invention, and chargeable resin pseudo fine particles smaller than the colorant, The present inventors have invented a manufacturing method capable of easily obtaining a diffused color material in a state where the chargeable resin pseudo fine particles are fixed to the color material.
- a method for producing a dispersible colorant according to the present invention which is preferably implemented in the present invention, will be described.
- the dispersible colorant according to the present invention having the above-mentioned properties can be produced extremely easily by applying the aqueous precipitation polymerization method under the following conditions.
- a water-insoluble colorant is dispersed in a dispersant to prepare an aqueous dispersion of the water-insoluble colorant.
- the chargeable resin pseudo fine particles and the coloring material are fixed to each other by a step of subjecting a radical polymerizable monomer to aqueous precipitation polymerization using an aqueous radical polymerization initiator.
- the dispersible colorant obtained through the aqueous precipitation polymerization process is a chargeable resin pseudo fine particle synthesized in the aqueous precipitation polymerization process, It becomes a water-insoluble colorant that is strongly adhered to the colorant in a uniform and scattered state, and has excellent dispersion stability by itself. Further, in the above-mentioned aqueous precipitation polymerization process, the characteristics of the chargeable resin pseudo fine particles can be easily controlled to the preferable forms as described above. A good fixation state with the chargeable resin pseudo fine particles is achieved.
- a preferred embodiment in the above-mentioned manufacturing method will be described in more detail.
- the water-insoluble colorant preferably used in the present invention as described above is dispersed with a dispersant to obtain an aqueous dispersion.
- a dispersing agent for dispersing the coloring material in the aqueous solution any of ionic, non-ionic and the like can be used, but from the viewpoint of maintaining the dispersion stability in the subsequent polymerization step, a polymer is used. It is desirable to use a dispersant or a water-soluble polymer.
- those that have sufficient water solubility and have a hydrophobic portion that serves as an adsorption site of the radical polymerizable monomer, particularly a hydrophobic monomer, added to the oil droplet interface at the surface of the colorant fine particles and the polymerization step are preferably used.
- at least one of the hydrophobic monomers used in the subsequent polymerization step is present as a unit constituting the dispersant. It is preferable from the viewpoint that it is easy to cause sticking to the coloring material.
- the method for producing a polymer dispersant and a water-soluble polymer that functions as a dispersant that can be used in the present invention is not particularly limited.
- a monomer having an ionic group and another polymerizable monomer may be used. It can be produced by reacting in a non-reactive solvent in the presence or absence of a catalyst.
- a dispersant selected from acrylic polymer compounds if the obtained dispersible colorant is intended to have an anionic group in particular, the anionic dispersant is used.On the other hand, the obtained dispersible colorant is intended to have a cationic group in particular. In this case, it is desirable to select a dispersant having a cationic group or a nonionic dispersant.
- Anionic dispersants are used from the viewpoint of promoting the fixation of the charged resin pseudo fine particles to the coloring material and maintaining the dispersion stability of the coloring material in the polymerization process in the subsequent aqueous precipitation polymerization. It is also a desirable embodiment to use an acid value of from 100 to 250 when using a compound and an amine value of from 150 to 300 when using a cationic dispersant. When the acid value and the amine value are smaller than these ranges, the affinity between the hydrophobic monomer and the dispersant becomes higher than the affinity between the coloring material and the dispersant during the aqueous precipitation polymerization, and the chargeable resin is not charged.
- the dispersant Before the pseudo fine particles adhere to the colorant, the dispersant may be detached from the surface of the colorant and may not be able to maintain a dispersed state. If the acid value and the amine value are larger than the above ranges, the dispersing agent has a displaced volume effect on the surface of the coloring material and the electrostatic repulsion becomes too strong. Sticking may be hindered.
- an anionic dispersant it is preferable to select a dispersant having a carboxyl group as an aionic group from the viewpoint of not inhibiting the fixation of the resin fine particles to the coloring material.
- the colorant In the process of forming a water-insoluble colorant into a dispersion aqueous solution with a dispersant, the colorant preferably has a dispersed particle size of 0.01 m or more and 0.5 ⁇ m or less (10 nm or more and 500 nm or less). , And particularly preferably in the range of 0.03 / im or more and 0.3 / im or less (30 nm or more and 300 nm or less).
- the dispersion particle size in this process largely reflects on the dispersion particle size of the obtained dispersible colorant, and the above range is preferable from the viewpoint of the coloring power and the weather resistance of the image and the dispersion stability. .
- the dispersion particle size distribution of the water-insoluble colorant used in the present invention is preferably as monodisperse as possible.
- the particle size distribution of the dispersible coloring material obtained by fixing the charged resin pseudo fine particles tends to be narrower than the particle size distribution of the aqueous dispersion solution before the polymerization step shown in FIG.
- Certain forces basically depend on the particle size distribution of the aqueous dispersion described above. It is also important to narrow the particle size distribution of the coloring material in order to surely induce the fixation of the coloring material and the charged resin pseudo fine particles by hetero aggregation.
- the obtained dispersible colorant has excellent dispersion stability.
- the particle size of the colorant in a dispersed state differs depending on various measurement methods.
- the organic pigment is a spherical particle, it is extremely small, but in the present invention, ELS-800 manufactured by Otsuka Electronics Co., Ltd. is used. At 0, the average particle diameter and polydispersity index determined by dynamic light scattering based on principle and cumulant analysis were used.
- the method of dispersing the water-insoluble colorant in water may be any method among the methods in which the colorant can be stably dispersed in water under the conditions described above, as long as the method uses a dispersant as described above. It is not limited to any of the methods described. Alternatively, a dispersing method newly developed for the present invention may be used. In general, for example, when the water-insoluble colorant is a pigment, the amount of the polymer dispersant to be used is preferably from 10% by mass to 130% by mass based on the pigment. I have. In addition, when the water-insoluble colorant used has no self-dispersibility itself, the performance of the dispersible colorant obtained by the above-described preferred embodiment of the chargeable resin pseudo fine particles to be fixed can be controlled. It is preferred in that respect.
- Examples of the method of dispersing the colorant used in the present invention include, for example, a disperser such as a paint shaker, a sand mill, an agitator mill, and a three-roll mill; If it is a dispersion method generally used for each color material, such as a machine, You are not limited in any way.
- a disperser such as a paint shaker, a sand mill, an agitator mill, and a three-roll mill.
- any general water-soluble radical polymerization initiator can be used.
- the water-soluble radical polymerization initiator include persulfates and water-soluble azo compounds.
- it may be a redox initiator formed by a combination of a water-soluble radical polymerization initiator and a reducing agent.
- a polymerization initiator that gives a polymerization initiator residue having the same sign as the surface characteristics of the obtained dispersible colorant is selected.
- An embodiment in which a water-soluble azo compound (hereinafter referred to as an aqueous azo radical polymerization initiator) is used as a radical polymerization initiator is another preferred embodiment of the present invention.
- An azo-based radical polymerization initiator containing water is a compound having at least one azo group in the molecule. The azo group is cleaved by heat (or light) to generate a radical, and the polymerization is carried out. To start. Compared with the case where persulfate is used, when the aqueous azo radical polymerization initiator is used, the decrease in pH in the polymerization system due to the reaction of the initiator is smaller, so that the dispersibility in the polymerization system is reduced.
- a quinacridone pigment is a pigment having a structure represented by the following general formula (1). Specifically, P.V. Ret) 19, PR (pigment red) 122, P.R. 192, PR 202, PR 206, PR 207, PR 209 and the like.
- water-soluble azo polymerization initiator preferably used in the present application, those commonly used for conventional emulsion polymerization and the like are preferably used, and other polymerization initiators used for newly developed emulsion polymerization are used. Can also be used.
- VA-080 (2,2'-azobis (2_methyl-1N- (1,1_bis (hydroxymethyl) -2-hydroxyhydroxyethyl) propionamide))
- VA-086 (2,2, azobis ( 2-methyl-1-N- (2-hydroxyethyl) propionamide)), VA-057 (2,2, -azobis (2- (N- (2-carboxyethyl) amidino) propane)), VA- 058 (2, .2,1 azobis (2- (3,4,5,6, -tetrahydropyrimidine-12-yl) propane) dihydrochloride),
- VA-060 (2,2,1 azobis (2 — (1— (2—Hydroxitytil) 1-2—Imidazoline-1-yl) Propane) Dihydrochloride, V—50 (2,2, -azobis (2-amidinopropane) dihydrochloride), V—501 ( 4, 4, azobis (4-cyanopentanoic acid)) (all manufactured by Wako Pure Chemical
- azo radical initiators particularly those having a carboxylic acid group and an amino group, for example, VA-057 (2,2'-azobis (2- (N- (2-carboxyethyl) amidino) propane)
- VA-057 2,2'-azobis (2- (N- (2-carboxyethyl) amidino) propane
- the radically polymerizable monomer used in the production method of the present invention becomes a component constituting the charged resin pseudo fine particles through the aqueous precipitation polymerization step described above, the resin substantially insoluble in water is used. As described in the section of the fine particles, it may be appropriately selected according to the characteristics of the chargeable resin pseudo fine particles and the dispersible colorant to be obtained.
- any of conventionally known radical polymerization monomers or radically polymerizable monomers newly developed for the present invention can be used.
- FIG. 2A, FIG. 2B, FIG. 2C, and FIG. 2D are process diagrams schematically illustrating the process flow of the manufacturing method. The process until a dispersible colorant is obtained by this process is considered as follows. First, as shown in FIG. 2A, a dispersion aqueous solution in which the coloring material 1 is dispersed in the aqueous solution by the dispersant 3 is prepared.
- the coloring material is dispersion-stabilized by the adsorption of the dispersant, and the adsorption is in thermal equilibrium.
- the temperature of the dispersion aqueous solution prepared in FIG. 2A is increased while stirring, and a monomer component 4 is added to the dispersion aqueous solution together with, for example, an aqueous radical polymerization initiator 5 (see FIG. 2B).
- the added aqueous radical polymerization initiator is cleaved by raising the temperature and Of the monomer component added to the aqueous dispersion, and contributes to the reaction between the hydrophobic monomer dissolved in the aqueous phase in a small amount and the water-soluble monomer in the aqueous phase.
- FIG. 3 is a schematic diagram illustrating a process from the polymerization of the monomer 4 to the generation of the dispersible colorant 6 (FIG. 2C).
- the reaction of the monomer 4 proceeds as described above, the oligomer 7 generated by the polymerization reaction of the monomer component becomes insoluble in water and precipitates from the aqueous phase to form a precipitate 8.
- the oligomers precipitated at this time do not have sufficient dispersion stability, they form the charged resin pseudo fine particles 2 together.
- the chargeable resin pseudo-fine particles 2 further cause hetero-aggregation around the hydrophobic surface of the colorant in the aqueous dispersion as a nucleus, and the resin component forming the surface of the color material 1 and the chargeable resin pseudo-fine particles 2 Are strongly adsorbed by hydrophobic interaction.
- the polymerization reaction continues to progress inside the charged resin pseudo fine particles 2, and changes to a more energy stable form while increasing the number of adsorption points with the coloring material 1.
- the inside of the charged resin pseudo fine particles 2 is highly formed with physical crosslinking, the form in which the most stable adsorption to the coloring material 1 is fixed is fixed.
- the coloring material 1 is stabilized by the plurality of charged resin pseudo fine particles 2 being fixed, and the dispersant in the equilibrium state is separated from the surface of the coloring material 1.
- FIG. 4 shows a schematic diagram of the charged resin pseudo fine particles 2 obtained as described above on the side of the bonding interface with the coloring material 1.
- the charged resin pseudo fine particles which are aggregates of the resin components, have a hydrophilic monomer unit 911, a hydrophobic mono unit 912, etc., which are arbitrarily distributed.
- the surface energy has a distribution, and there are many adsorption points 10 which coincide with the surface energy of the coloring material.
- FIG. 5 shows an enlarged schematic diagram of the interface between a part of the charged resin pseudo fine particles 11 and a part of the color material particles 1 a.
- the interface 11 of the charged resin pseudo fine particles is shown in FIG. While adsorbing the adsorption point 10 shown in (1), the coloring material is stably fixed in a form corresponding to the surface shape of the portion 1a.
- the charged tree Since the polymerization reaction is progressing inside the fat pseudo fine particles, the adsorption is stabilized and the fixing to the coloring material is achieved.
- a dispersible colorant having the above-described configuration is easily formed (see FIG. 2D).
- the charge resin pseudo fine particles are interposed between the charged resin pseudo fine particles. Due to the mutual action of electrostatic repulsion, the charged resin pseudo fine particles are scattered and adhered to the coloring material, and the above-described preferred embodiment is obtained.
- the polymerization reaction conditions vary depending on the properties of the polymerization initiator, dispersant, and monomer used.For example, the reaction temperature is set to 10 ° C. or less, preferably
- the reaction time is 1 hour or more, preferably 6 hours or more and 30 hours or less.
- the stirring speed during the reaction is preferably from 50 rpm to 500 rpm, and more preferably from 150 rpm to 400 rpm.
- the monomer component when polymerizing a monomer component containing at least one type of hydrophobic monomer and at least one type of hydrophilic monomer to obtain charged resin pseudo fine particles, preferably the monomer component is used. It is desirable that the aqueous radical polymerization initiator be dropped into an aqueous dispersion of a water-insoluble colorant which contains a polymerization initiator in advance. Alternatively, it is also desirable to add dropwise to the aqueous dispersion of the water-insoluble colorant simultaneously or separately with the aqueous radical polymerization initiator.
- the copolymerization ratio of the monomers having the different properties should always be kept constant. Is desirable. If a mixture of the above monomers is added to the polymerization system in excess of the amount of the monomer consumed in the polymerization reaction within a fixed time, only a specific type of monomer is preliminarily polymerized, and the remaining monomers are preliminarily polymerized. The polymerized monomer tends to polymerize after consumption, and in this case, the generated chargeable resin pseudo fine particles have large non-uniform properties. Generated in this way Among the charged charged resin pseudo fine particles, those having a particularly high content of a hydrophilic monomer component may not be able to adhere to the surface of the coloring material in some cases.
- an ionic monomer such as acrylic acid or methacrylic acid
- it may be partially dependent on the properties of the polymer dispersant in which the coloring material is dispersed. In some cases, causing aggregation. In order to prevent this, it is also a preferred embodiment to neutralize the anionic monomer in advance and add it in the form of sodium salt or potassium salt.
- a further purification treatment is performed. It is desirable to carry out.
- purifying the unreacted polymerization initiator, monomer component, dispersant, water-soluble resin component that did not lead to fixation, and chargeable resin pseudo fine particles in the above means the storage stability of the dispersible colorant. It is important in keeping high.
- the purification method to be used an optimum one may be selected from the generally used purification methods and used. For example, purification using a centrifugation method or an ultrafiltration method is also a preferable embodiment.
- a dispersible colorant in which charged resin pseudo fine particles made of a desired copolymer are fixed on the surface of the colorant can be obtained by controlling many control factors.
- the dispersible colorant that has undergone the process of the present invention can obtain a large surface functional group density even when the amount of the anionic monomer used in the above process is relatively small, and high Dispersion stability can be imparted.
- the dispersion stability of the charged resin pseudo fine particles can be increased without impairing the long-term storage stability.
- the present inventors think as follows.
- the portion containing a lot of components derived from the aionic monomer is preferentially in the aqueous phase, that is, the charged resin pseudo fine particles.
- the surface of the dispersible coloring material of the present invention having a structurally large specific surface area further has an anionic property derived from an anionic monomer component. It is expected that a large number of groups will be present, and as a result, the dispersible colorant according to the production method of the present invention will be stabilized with less anionic monomer components.
- the aqueous ink according to the present invention is characterized by containing the dispersible coloring material described above.
- the coloring material used is a pigment
- the pigment content is generally 0.1% by weight to 20% by weight, preferably 0.3% by weight to 15% by weight based on the ink.
- the dispersible coloring material of the present invention is present in the ink with the chargeable resin pseudo fine particles 2 fixed to the surface of the coloring material 1. Therefore, the coloring material adheres to the recording medium and the adjacent coloring material on the recording paper via the chargeable resin pseudo fine particles fixed on the surface. Therefore, printed matter obtained by using the aqueous ink of the present invention has excellent scratch resistance.
- a water-based ink in which self-dispersible resin particles are dispersed is usually used, so that a water-insoluble coloring material such as a pigment is usually used on a glossy medium. High gloss printing is possible.
- the chargeable resin pseudo fine particles ( ⁇ ) fixed to the coloring material and the self-dispersible resin fine particles ( ⁇ ) dispersed in the ink are present.
- the monomer component constituting the fine particles ( ⁇ ) and the monomer component constituting the self-dispersing resin fine particles ( ⁇ ) contain at least one common monomer component, whereby the chargeable resin pseudo fine particles ( ⁇ ) Since the affinity between the dispersible coloring material to which the particles are fixed and the self-dispersing resin fine particles ( ⁇ ) is increased and the adhesive force is increased, the abrasion resistance of a printed matter particularly on a glossy medium is greatly improved.
- the average value of the surface zeta potential of the dispersible colorant in the aqueous medium constituting the aqueous ink is one, especially when the dispersible colorant has an anionic group.
- the range is 2 OmV or more and 18 OmV or less, and in the case of having a cationic group, the average value is +1 OmV or more and +6 OmV or less. is there.
- the zeta potential when the zeta potential is in the range of 15 mV to +1 O mV, the high dispersion stability of the dispersible colorant is hindered by the action of the aqueous medium, and the long-term storage stability of the aqueous ink is reduced. May be insufficient.
- the zeta potential when the zeta potential is lower than 18 O mV or higher than +6 O mV, the storage stability of the ink is excellent, but the water resistance of the printed matter may be insufficient. .
- zeta ( ⁇ ) potential is also called zeta potential or electrokinetic potential.
- zeta potential When a solid and a liquid that are in contact with each other make a relative motion, the potential difference generated at the interface between the two. Means It is used to analyze the surface state of a solid present in a liquid. Among the electric double layer generated at the interface between the solid and the liquid, the part close to the surroundings has a stationary phase (or adsorption phase). Opposite charge Are stuck. When a solid and a liquid make relative motion, this stationary phase moves together with the solid, so the potential difference that actually governs the movement is considered to be the potential difference between the surface of the stationary phase and the inside of the solution. This potential difference is called zeta potential.
- the zeta potential takes a positive or negative value depending on whether the charge of the stationary phase is positive or negative.
- the zeta potential of the water-insoluble colorant prevents the colorants from approaching each other and maintains the dispersed state.
- the zeta potential is an important physical property value.
- the absolute value of the zeta potential greatly contributes to dispersion stability, but also its distribution should be considered.
- the surface of the dispersion having a small absolute value and the surface of the absolute value have the same sign.
- a hetero-coagulation phenomenon is likely to occur due to an attractive force acting between large dispersion surfaces. That is, the zeta potential of the dispersible colorant in the aqueous ink according to the present invention is uniform, and the effect on the dispersion stability is exerted when the absolute value is uniform. According to the studies of the present inventors, it can be obtained the desired dispersion stability if less than 5 0 with a standard deviation becomes apparent to the zeta potential power the average value of the dispersible colorant of the present invention.
- the zeta potential is a value that changes depending on various conditions such as the dielectric constant, pH, and salt concentration of the aqueous medium in which the coloring material (the same applies to all other colloidal dispersions).
- the absolute values and distributions measured at the media conditions in which the material is used should be discussed.
- the zeta potential of the dispersible colorant in the aqueous ink can be measured by a generally known and commonly used method.
- the coloring material is diluted to an appropriate ratio in an aqueous mixed solvent used as an aqueous ink using ZEEC OM manufactured by Microtech Nichion Co., Ltd.
- the moving speed of the dispersed particles (that is, the dispersible colorant in the case of the present invention) when the above electric field is applied is defined as a value obtained by measuring by an image processing method.
- the electrical conductivity of the aqueous medium may be abnormally high, and the measurement may not be performed.
- remove or reduce the electrolyte component until it reaches 0.01 M and measure the pH of the aqueous medium in accordance with the pH when the ink is used.
- the zeta potential is preferably used in the present invention. An ink having stability can be obtained.
- the adhesion between the coloring materials and between the coloring materials and the recording medium can be enhanced, so that excellent scratch resistance can be imparted to the printed matter.
- a dispersible colorant obtained by adhering chargeable resin pseudo fine particles including a copolymer component having a glass transition temperature of 140 ° C.
- the film forming property can be more effectively expressed, and the abrasion resistance of the glossy paper can be further improved.
- B / P is significantly larger than 4.0, the ink becomes highly viscous as a whole, and the ejection stability may be impaired especially when used in an ink jet recording apparatus. Further, since the amount of the resin is extremely large relative to the coloring material, the coloring property of the coloring material on the recording medium may be hindered, and a sufficient printing density may not be obtained.
- the ink jet recording apparatus has excellent abrasion resistance and can be used in an ink jet recording apparatus.
- a water-based ink having both ejection stability can be obtained.
- resin mass refers to the total amount of the charged resin pseudo fine particles contained in the ink according to the present invention, and also includes a resin component that is clearly strongly adsorbed on the pigment surface. There is. However, water-soluble resin components that can be easily separated from pigments are not included.
- the value of B / P described above can be generally determined by a differential thermogravimetric analysis method. In the present invention, however,] / ⁇ 4 / ⁇ 0/30/85 Use the value measured and calculated in 1. That is, in the present invention, the sediment obtained by centrifuging the dispersible colorant or the aqueous ink jet recording ink containing the colorant according to the present invention at 80,000 rotations for 2 hours is dried.
- the BZP was calculated by weighing and calculating the mass change before and after the decomposition temperature of each of the pigment and the fat component when the temperature was raised in a nitrogen atmosphere or in the atmosphere.
- the ink jet recorded image according to the present invention is formed on a recording medium by an ink jet recording apparatus as described below, using the aqueous ink of the present invention containing the dispersible colorant having the above-described configuration.
- a recording medium used in the present invention any medium capable of ink jet recording can be used without limitation.
- the dispersible colorant of the present invention has a preferred form as shown in FIGS. 7A, 7B, and 7C as an action due to its characteristic shape. (Most preferably only Figure 7B or Figure 7C), but the level of implementation includes them at the same time).
- FIG. 7A is particularly likely to occur when the self-dispersible resin fine particles B are further added to the aqueous ink described above, and the charged resin pseudo fine particles are used to fill the unevenness between the coloring materials on the recording medium 14.
- a highly glossy image is realized even on a recording medium by depositing the self-dispersing resin fine particles B.
- FIG. 7B shows that the charged pseudo fine particles 2 adhered to each color material existing between the adjacent color materials, In this state, a strong colored film is formed by fixing to each of the coloring materials, and a recorded image having high durability and durability is formed. Furthermore, by making the ratio of the chargeable resin pseudo fine particles fixed to the surface of the color material relatively small, the function of FIG. A preferable form as shown in FIG. 7C is adopted.
- Figure 7C shows the electrostatic repulsion (indicated by the arrow 15 in the figure) of the chargeable resin pseudo fine particles and the surface of the coloring material during the aggregation of the dispersible coloring material in the ink attached to the recording medium. It shows that the form of aggregation is controlled by the balance with the aggregation force. By performing such control, it becomes possible to control the image density or the bleeding of the ink by controlling the aggregation of the color material on the recording medium.
- the dispersible coloring material according to the present invention and the water-based ink containing the coloring material are used for an ink jet discharge type head, or as an ink tank containing the ink, or as a filling material. It is also effective as an ink for use.
- the present invention provides an excellent effect in a bubble jet (registered trademark) type recording head and recording apparatus among the ink jet recording methods.
- the typical configuration and principle are described, for example, in the basic specifications disclosed in Japanese Patent Nos. 4,723,129 and 4,740,796. It is preferable to use the principle based on this principle.
- This method can be applied to any of the so-called on-demand type and continuous type.
- the on-demand type it is arranged corresponding to the sheet holding the ink and the liquid path.
- a full-line type recording head having a length corresponding to the width of the maximum recording medium that can be recorded by the recording apparatus a combination of a plurality of recording heads as disclosed in the above specification is used. Either a configuration that satisfies the length or a configuration as a single recording head that is integrally formed may be used, but the present invention can exert the above-described effects more effectively.
- a replaceable chip-type recording head or the recording head itself which is attached to the main body of the device and enables electrical connection with the main body and supply of ink from the main body.
- the present invention is also effective when a cartridge-type recording head provided integrally is used.
- the present invention can further stabilize the effects of the present invention by adding recovery means for the recording head, preliminary auxiliary means, and the like provided as a configuration of the recording apparatus to which the present invention is applied. It is a good thing. To be specific, these are the caps for recording heads.
- Recording ink 1 according to Example 1 was produced in the following manner. First, a mixture of 10 parts of carbon black, 6 parts of glycerin, 10 parts of a styrene-acrylic acid-based resin dispersant, and 74 parts of water was mixed at 1,500 rpm with a sand mill manufactured by Kaneda Rika Kogyo Co., Ltd. For 5 hours to obtain a pigment dispersion liquid 1. The sand mill used 0.6 mm zirconia beads and the filling rate in the pot was 70%.
- the carbon black used in this example is B lack Pearls 880 (hereinafter abbreviated as BP 880) marketed by Cabot Co. of the United States.
- an aqueous solution was prepared by previously adding water and a hydroxylic power equivalent to the above-mentioned acid value and stirring at 80 ° C.
- the resulting Pigment Dispersion Liquid 1 was stably dispersed with an average dispersed particle size of 98 nm, and the polydispersity index was 0.16.
- the pigment dispersion 1 obtained above as 100 parts, under a nitrogen atmosphere, heated to 70 ° C, and while stirring with a motor, the following mixed solution was gradually added dropwise and added for 5 hours. Polymerization was performed.
- the mixed solution was composed of 5.5 parts of methyl methacrylate, 0.5 part of acrylic acid, 0.12 part of potassium hydroxide, 0.05 part of persulfuric acid, and 20 parts of water.
- the resulting dispersion was diluted 10-fold with water, Aggregated components were removed by centrifugation at 5,000 rpm for 10 minutes. Thereafter, the mixture was further purified by centrifugation at 12,500 rpm for 2 hours to obtain a dispersible colorant 1 as a precipitate.
- This dispersible colorant 1 was dispersed in water, centrifuged at 1,200 rpm for 60 minutes, and the sediment re-dispersed in water was dried.
- the scanning electron microscope JS M When observed at 50,000 magnifications with -670 (manufactured by JEOL High-Tech Co., Ltd.), the dispersible coloring material 1 was observed to have resin fine particles fixed to the surface of carbon black. Was. The color materials after this described in the present example were confirmed in the same manner as above.
- the dispersible colorant 1 obtained above was contained in the ink at a concentration of 4%, and the following component composition was mixed with the dispersible colorant 1. Further, the dispersible coloring material 1 was mixed with a filter having a pore size of 2.5 microns. The mixture was filtered under pressure to prepare a recording ink 1 of this example.
- Example 2 Using 100 parts of the same pigment dispersion liquid 1 as prepared in Example 1, under a nitrogen atmosphere, heated to 70 ° C, and the following mixture was gradually dropped while stirring with a motor. In addition, polymerization was performed for 8 hours. The mixture used above consists of 5.7 parts of styrene, 0.3 parts of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. After the polymerization, purification was performed by centrifugation in the same manner as in Example 1 to obtain Dispersible Coloring Material 2. Further, in the same manner as in Example 1, the recording ink of the present example containing the dispersible colorant 2 obtained above at a concentration of 4% in the ink was used. 2 was prepared.
- Example 2 Using 100 parts of the same Pigment Dispersion Liquid 1 as prepared in Example 1, under a nitrogen atmosphere, heated to 70 ° C, and the following mixture was gradually added dropwise while stirring with a motor. The polymerization was carried out for 6 hours.
- the mixture used above consisted of 5.7 parts of methyl methacrylate, 0.3 part of acrylic acid, 0.07 part of potassium hydroxide, 0.05 part of potassium persulfate and 20 parts of water. After the polymerization, purification was performed by centrifugation in the same manner as in Example 1 to obtain Dispersible Coloring Material 3.
- the ink contains the dispersible colorant 3 obtained above at a concentration of 4%, and further contains the resin fine particles B1 prepared above at a concentration of 1.2%.
- a recording ink 3 of this example was prepared.
- Example 2 Observation of the obtained dispersible colorant 4 in the same manner as in Example 1 revealed that even in the dispersible colorant 4, resin fine particles were present on the surface of the carbon black. Although the state of sticking was observed, it could be confirmed that compared with the case of Example 1, the portion that had been fused was more.
- Example 5 As in the case of obtaining the fine resin particles B1 in Example 3, 100 parts of the pigment dispersion liquid 1 was replaced, polymerization was performed, and purification was performed by centrifugation to obtain the fine resin particles B2. Got. Then, in the same manner as in Example 1, the ink contains the dispersible colorant 4 obtained above at a concentration of 4%, and further contains the resin fine particles B2 prepared above at a concentration of 1.2%. A recording ink 4 of this example was prepared.
- Example 5 Example 5
- Example 2 Using 100 parts of the same pigment dispersion liquid 1 as prepared in Example 1, while heating at 50 ° C under a nitrogen atmosphere, the following mixed liquid was gradually dropped while stirring with a motor. In addition, polymerization was performed for 5 hours.
- the mixed solution used above consisted of 6 parts of butyl acrylate, 0.05 part of potassium persulfate, and 20 parts of sodium thiosulfate and water in equimolar amounts to potassium persulfate. After the polymerization, purification was performed by centrifugation in the same manner as in Example 1 to obtain Dispersible Coloring Material 5.
- Example 1 Observation of the obtained dispersible color material 5 in the same manner as in Example 1 reveals that even in the dispersible color material 5, resin fine particles are fixed to the surface of the car pump rack. As a result, it was confirmed that the number of fused portions was larger than that of Example 1. Further, in the same manner as in Example 1, a recording ink 5 of this example including the dispersible colorant 5 obtained above at a concentration of 4% in the ink was prepared.
- Example 2 Using 100 parts of the same pigment dispersion liquid 1 as prepared in Example 1, under a nitrogen atmosphere, heated to 70 ° C, and the following mixture was gradually dropped while stirring with a motor. Force U, polymerization was carried out for 5 hours.
- the mixture used above consisted of 17.2 parts of methyl methacrylate, 0.8 part of sodium p-styrenesulfonate, 0.05 part of potassium persulfate and 20 parts of water. After the polymerization, a far end was obtained in the same manner as in Example 1. Purification was performed by centrifugation to obtain dispersible coloring material 6. Further, in the same manner as in Example 1, a recording ink 6 of this example containing the dispersible colorant 6 obtained above at a concentration of 4% in the ink was prepared.
- the recording ink 7 according to this example was produced in the following manner. First, a mixed solution having a composition consisting of 10 parts of carbon black, 6 parts of glycerin, 10 parts of a styrene-dimethylaminoethyl acrylate copolymeric cationic dispersant, and 74 parts of water was passed through a sand mill manufactured by Kaneda Rika Kogyo Co., Ltd. The mixture was dispersed at 1,500 rpm for 5 hours to obtain a pigment dispersion liquid 2. The sand mill used zirconia beads with a diameter of 0.6 mm, and the filling rate in the pot was 70%.
- the dispersion was prepared by adding water and acetic acid slightly in excess of the amine value, stirring the mixture at 80 ° C., and forming a water solution.
- the obtained pigment dispersion liquid 2 was stably dispersed at an average dispersed particle diameter of 105 nm, and had a polydispersity index of 0.18.
- Example 8 It consists of 3 parts and 20 parts of water.
- the obtained dispersion was diluted 10-fold with water, and centrifuged at 50,000 rpm for 10 minutes to remove aggregated components. Thereafter, the mixture was further purified by centrifugation at 12,500 rpm for 2 hours to obtain a dispersible colorant 7 as a precipitate. Further, in the same manner as in Example 1, the dispersible color material 7 obtained above was used, and the mixture was prepared and filtered according to the same formulation as in Example 1, and the dispersible color material 7 was added to the ink by 4%.
- the recording ink 7 of this embodiment including the density Made. ⁇ Example 8 '
- the recording ink 8 according to this example was produced in the following manner.
- a coloring material a mixture having a composition consisting of 10 parts of Pigment Blue (PB) 15: 3 (manufactured by Clariant), 6 parts of dariserin, 10 parts of a styrene-acrylic acid-based dispersant, and 74 parts of water.
- the liquid was dispersed in a sand mill manufactured by Kaneda Rika Kogyo Co., Ltd. at 1,500 rpm for 5 hours to obtain Pigment Dispersion Liquid 3.
- a sand mill manufactured by Kaneda Rika Kogyo Co., Ltd. at 1,500 rpm for 5 hours to obtain Pigment Dispersion Liquid 3.
- 0.6 mm zirconia beads were used, and the filling rate in the pot was set to 70%.
- the resulting Pigment Dispersion Liquid 3 was stably dispersed at an average dispersed particle size of 108 nm, and had a polydispersity index of 0.14.
- the recording ink 9 according to the present example was produced in the following manner. First, a composition consisting of 10 parts of Pigment Yellow (PY) 180 (manufactured by Clariant) as a coloring material, 6 parts of dariserin, 10 parts of a styrene-atalylic acid-based dispersant, and 74 parts of water. was dispersed in a sand mill manufactured by Kaneda Rika Kogyo Co., Ltd. at 1,500 rpm for 5 hours to obtain a pigment dispersion 4. The sand mill used 0.6 mm zircon your beads, and the filling rate in the pot was 70%.
- PY Pigment Yellow
- Clariant manufactured by Clariant
- the resulting Pigment Dispersion Liquid 4 was stably dispersed at a mean particle size of 126 nm, and the polydispersity index was 0.16.
- Example 2 Using the dispersible color material 9 obtained above, mixing and filtering were performed in the same manner as in Example 1, and the ink of the present example including the dispersible color material 9 at a concentration of 3.5% in the ink was recorded. Ink 9 was prepared.
- the recording ink 10 according to the present example was produced in the following manner. First, 10 parts of Pigment Red (PR) 122 (manufactured by Ciba Specialty Chemicals) as a coloring material, 6 parts of glycerin, 10 parts of styrene-acrylic acid-based dispersant, and 74 parts of water
- the mixed liquid having the composition was dispersed in a sand mill manufactured by Kaneda Rika Kogyo Co., Ltd. at 1,500 rpm for 5 hours to obtain Pigment Dispersion Liquid 5.
- Zirconia beads with a diameter of 0.6 mm were used in the sand mill, and the filling rate in the pot was 70%.
- the resulting pigment dispersion 5 is an average
- the particles were dispersed stably at a dispersed particle size of 96 nm, and the polydispersity index was 0.13.
- the mixture was further centrifuged at 12,500 rpm for 2 hours to obtain a dispersible coloring material 10 as a sediment.
- the same formulation as in Example 1 was carried out, and the mixture was filtered and the dispersible color material 10 was contained in the ink at a concentration of 3.5%. Recording ink 10 was prepared.
- a 5% aqueous dispersion of each dispersible colorant is diluted 10-fold with pure water and concentrated to the original concentration using an ultrafiltration filter with a molecular weight cut-off of 500,000.
- the separated sediment is taken out, redispersed in pure water, and visually dispersed uniformly, and the average particle size measured by the dynamic light scattering method described below is 2% of the particle size before operation. It was confirmed that it was within 2 times and evaluated according to the following criteria.
- each dispersible colorant was placed in a glass sample bottle in the form of a dispersion aqueous solution, and after standing for one month at 60 ° C in a closed state, the dispersion state was visually determined.
- the evaluation criteria are as follows.
- Each dispersible colorant was measured by a dynamic light scattering method using ELS-800, manufactured by Otsuka Electronics Co., Ltd., and the average value of cumulant was defined as the average particle size.
- the glass transition temperature of the resin fine particles fixed to each dispersible colorant was determined by drying the dispersible colorant as a sample, and using a Mettler's Toledo DSC 82 22 e DSC 0.52 ° C / It was measured at a heating rate of min. • Surface functional group density
- the surface functional group density of each dispersible colorant was determined as follows. A large excess amount of hydrochloric acid (HC 1) was added to the aqueous dispersion of the coloring material, and the precipitate that had settled under a condition of a centrifuge at 200,000 rpm for 1 hour was re-dispersed in pure water to obtain a solid content. The sediment was weighed to determine the ratio, and a dispersion of a known amount of sodium bicarbonate added and stirred was further sedimented by a centrifugal separator at 80,000 rpm for 2 hours.
- HC 1 hydrochloric acid
- the supernatant was weighed, and the surface functional group density was calculated by subtracting the known amount of sodium hydrogen carbonate and the blank value obtained by measuring pure water from the neutralization amount determined by neutralization titration with a 0.1N aqueous HC1 solution. did. If it is obvious that the polar group has a cationic group, sodium hydroxide (NaH) is used in place of the HC1 aqueous solution, and ammonium chloride is used instead of sodium hydrogencarbonate. I asked.
- NaH sodium hydroxide
- Table 1 shows the compositions and evaluation results of the inks of Examples 1 to 8.
- M MA is methyl methacrylate
- AAc is acrylic acid
- St is styrene
- Bz MA is benzyl methacrylate.
- BA represents butyl acrylate
- Na SS represents sodium p-styrenesulfonate
- DMAEA dimethylaminoethyl acrylate
- KPS represents persulfuric acid lime
- NaTS represents sodium thiosulfate.
- the characteristics of the ink were evaluated as follows.
- printing on a recording medium is performed by an ink jet recording apparatus.
- the obtained images were evaluated.
- An image was formed using a BJS 600 marketed by Canon Inc. as the inkjet recording apparatus used.
- the optical density (OD), sharpness, scratch resistance, marker resistance, storage stability at room temperature and ejection stability of the printed matter were evaluated as follows, and the results are shown in Table 2. .
- BZP values were determined by differential thermogravimetry. The obtained ink was dried and used as a sample to measure and calculate with TGAZSDTA851 manufactured by METTLER TOLEDO.
- Each of the dispersible coloring materials was diluted to about 100,000 times with an aqueous solvent from which the dispersible coloring material and the resin fine particles were removed from the ink formulation described in Example 1, and the cells were diluted with a microtech Nichion ZEECOM.
- the value of the ⁇ potential on the stationary surface was measured for 100 particles, and the average value was defined as the ⁇ potential of each color material.
- the standard deviation of each of the 100 measured values was determined.
- the optical density (OD) of the printed matter after one day passed was measured and evaluated according to the following criteria.
- cyan text was printed instead of Bk text, the optical density of cyan was measured instead of black, and the case where OD was 1.0 or more was evaluated as A.
- the printed matter 00 is 1.3 or more.
- OD of printed matter is 0.8 or more and less than 1.3.
- O D of the printed matter is less than 0.8.
- Abrasion resistance of printed matter has the printed portion multiplied by the weight of 40 g / cm 2 Silbon The paper was rubbed five times, and the disorder of the printed portion was visually observed and evaluated according to the following criteria. A: There is no printing disorder due to rubbing and no stain on the white portion.
- the marker resistance of the printed matter was evaluated by the following criteria by tracing the printed part once with a fluorescent yellow marker pen (Zebra Optex), visually observing disturbance of the printed part, and evaluating the following criteria.
- the storage stability was determined by visually observing the state of dispersion in the ink after each ink was placed in a glass sample bottle and allowed to stand at room temperature for one month in that state.
- the evaluation criteria are as follows.
- the ejection stability was determined by printing 100 sheets of a specific Bk text continuously, comparing the initial printed matter with the last printed matter, and visually checking the printed matter.
- Example 3 in which self-dispersible resin fine particles were added exhibited excellent characteristics as compared with Recording Ink 1 containing a dispersible colorant synthesized from the same monomer species.
- MA Methyl methacrylate
- AAc Ataryl
- St Styrene
- BdlA methallyl undil
- BA butyl acrylate
- Example 1 2 Purification was performed by centrifugation at 2,500 rpm for 2 hours to obtain a dispersible colorant 11 as a precipitate. Further, the mixture was mixed and filtered according to the same formulation as in Example 1, to thereby prepare a recording ink 11 of the present example containing the dispersible colorant 11 obtained above at a concentration of 4% in the ink.
- Example 1 2 Purification was performed by centrifugation at 2,500 rpm for 2 hours to obtain a dispersible colorant 11 as a precipitate. Further, the mixture was mixed and filtered according to the same formulation as in Example 1, to thereby prepare a recording ink 11 of the present example containing the dispersible colorant 11 obtained above at a concentration of 4% in the ink.
- Example 1 2 Purification was performed by centrifugation at 2,500 rpm for 2 hours to obtain a dispersible colorant 11 as a precipitate. Further, the mixture was mixed and filtered according to the same formulation as in Example 1, to thereby prepare a recording ink 11 of
- Example 2 Using 100 parts of the same pigment dispersion liquid 1 as prepared in Example 1, a mixture of the following composition was gradually added dropwise while stirring with a motor while heating at 70 ° C under a nitrogen atmosphere. And polymerization was carried out. The mixture used consisted of 45.6 parts of methyl methacrylate, 2.4 parts of acrylic acid, 0.6 part of potassium hydroxide, 0.1 part of potassium persulfate and 20 parts of water. After polymerization for 5 hours as described above, purification was carried out by centrifugation in the same manner as in Example 9 to obtain a dispersible colorant 12. Further, the mixture was prepared and filtered according to the same formulation as in Example 1, and a recording ink 12 of this example containing the dispersible colorant 12 obtained above at a concentration of 4% in the ink was prepared.
- Example 2 Using 100 parts of the same pigment dispersion liquid 1 as prepared in Example 1, a mixture of the following composition was gradually added dropwise while stirring with a motor while heating at 70 ° C under a nitrogen atmosphere. And polymerization was carried out. The mixture used consisted of 5.7 parts of benzyl methacrylate, 0.3 part of acrylic acid, 0.07 part of potassium hydroxide, 0.01 part of potassium persulfate and 20 parts of water. After 5 hours of polymerization as described above, the mixture was purified by centrifugation under the same conditions as in Example 1 to obtain a dispersible colorant 13 as a precipitate. Further, the mixture was prepared and filtered according to the same formulation as in Example 1, to thereby prepare a recording ink 13 of the present example containing the dispersible colorant 13 obtained above at a concentration of 4% in the ink.
- Example 15 Using 100 parts of the same pigment dispersion liquid 1 as prepared in Example 1, a mixture of the following composition was gradually stirred with a motor while heating at 70 ° C. under a nitrogen atmosphere. Polymerization was performed by dropwise addition. The mixed solution used consisted of 10 parts of methyl methacrylate, 8 parts of atarilic acid, 1.9 parts of hydroxide hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. Perform after 7 hours of polymerization as described above. Purification was performed by centrifugation in the same manner as in Example 1 to obtain a dispersible colorant 14. Further, the mixture was prepared and filtered according to the same formulation as in Example 1 to prepare a recording ink 14 of this example containing the dispersible colorant 14 obtained above at a concentration of 4% in the ink. Example 15
- Example 2 Using 100 parts of the same pigment dispersion liquid 1 as prepared in Example 1, a mixture of the following composition was gradually added dropwise while stirring with a motor while heating at 70 ° C under a nitrogen atmosphere. And polymerization was carried out. The mixture used was 4.5 parts of benzyl methacrylate, 1.2 parts of butyl acrylate, 0.3 parts of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts of potassium persulfate and water. It consists of 20 parts. After polymerization for 5 hours as described above, purification was performed by centrifugation in the same manner as in Example 1 to obtain a dispersible colorant 15.
- the ink contains the dispersible colorant 15 obtained above at a concentration of 4%, and further contains the resin fine particles B3 prepared above at a concentration of 19.2%.
- a recording ink 15 of this example was prepared.
- Table 3 shows the results of various observations and measurements of physical properties of the dispersible colorants obtained in Examples 11 to 15 described above in the same manner as in Examples 1 to 10.
- St is styrene
- H EMA is hydroxyethyl methacrylate
- AAc is acryloline acid
- E MA is ethyl methacrylate
- MA c is methacryloline acid
- Bz MA is benzyl methacrylate
- MMA methyl methacrylate
- BA represents butyl acrylate
- KPS represents potassium persulfate.
- Printing was performed in the same manner as in Examples 1 to 10. One minute after the completion of printing, the printed portion was rubbed with a finger, and the stain on the printed portion was evaluated according to the following criteria.
- the printed matter printed in the same manner as in Examples 1 to 10 was tilted at an angle of 45 degrees from a horizontal plane with the printed surface up, and 1 m1 of water was sprayed from a height of 20 cm using a spot with Bk. Hanged on the text printing area. At this time, the degree of bleeding of the print was evaluated according to the following criteria.
- Table 2 shows the compositions, physical properties, and evaluation results of the inks of Examples 11 to 15. As shown in Table 2, in all the examples, the observation results were good, and it was confirmed that a coloring material having a monodispersity was obtained. There were many parts where the resin was relatively aggregated, and the dottedness was poor. In addition, all of the recording inks exhibited excellent printing performance, but Example 11 having a high surface energy was slightly inferior to other Examples in quick drying and water resistance. Further, in Example 13 in which the dottedness of the resin fine particles was poor, it was found that the image density, the quick drying property, and the ejection stability were slightly inferior to the others. became.
- Example 14 having a high surface functional group density, although sufficient image density and ejection stability were obtained, the marker resistance was slightly inferior, and especially the water resistance was inferior to the others.
- Example 15 having a large B / P ratio, slight print misalignment may occur occasionally at the beginning of ejection or during high-speed printing, and the ejection stability is slightly inferior to other recording inks. The result was. This is presumably because the response to high-speed ejection became poor due to the increase in the viscosity of the recording ink.
- MMA methyl methacrylate
- BA butyl acrylate 4: 1 to 15
- St Styrene
- HEMA Methacryl hiro-shetyl
- AAc Acrylic
- EMA Ethyl methacrylate
- MAc Methacrylic acid
- BzMA Benzyl methacrylate
- Comparative Ink 1 was prepared using Pigment Dispersion Liquid 1 before the polymerization step prepared in Example 1 and in the same formulation as in Example 1 so that the pigment had a concentration of 4%.
- the color material in Comparative Ink 1 was observed in the same manner as in Example 1, no resin fine particles adhered to the surface of the color material were observed.
- the resin-treated fine particles used in Example 3 were Cabojet 200 manufactured by Cabot Co., Ltd., which is a surface-treated self-dispersible carbon black, so that the solid content concentration was 4%.
- a comparative ink 2 was prepared by preparing the same formulation as in Example 1 except that the concentration of the child B1 was 1.6%.
- the coloring material in Comparative Ink 2 was observed in the same manner as in Example 1, resin fine particles adhering to the surface of the coloring material were found in some places, but the distribution was not uniform, and the aggregates of the resin fine particles were found. Was also observed.
- Comparative Examples 1 and 2 were significantly inferior to the Examples of the present invention, particularly in terms of print density, long-term storage stability, and ejection stability.
- Comparative Example 2 although it had homodispersibility, the resin particles could not be sufficiently fixed, so that the abrasion resistance, the water resistance, and the quick drying property were significantly inferior.
- BzMA benzyl methacrylate
- AAc atarilic acid
- Examples 1 to 4, 6, 12, and 15 were evaluated as follows, and the results are shown in Table 7.
- the printer used for the series of evaluations prints a 5 cm square solid patch of Bk on glossy paper PR-101 for ink jet recording from Canon Inc., and prints the image density on glossy paper. The abrasion and gloss were evaluated.
- optical density (OD) of the printed matter was measured and evaluated according to the following criteria.
- O D of printed matter is 2.3 or more.
- B OD is 1.7 or more and less than 2.3.
- C OD is less than 1.7.
- the scratch resistance of the printed matter was evaluated by the following criteria by rubbing the printed part five times with a silbon paper weighing 40 g / cm 2 and visually observing the shaving of the image part.
- the glossiness of the printed portion was visually evaluated according to the following criteria.
- Example 2 using styrene and Example 15 having a high BZP, the image density of glossy paper tended to be slightly lower than that of other examples using a methacrylate ester-based monomer. In addition, the glossiness of the glossy paper was excellent in Examples 4, 12, and 15 having a low Tg and Example 3 in which the fine resin particles B were added.
- Table 7 Ink compositions, properties, and evaluation results of applications 1 to 4 6 12 and 15
- the dispersible coloring material which has high dispersion stability, does not detach
- a dispersible color material having excellent scratch resistance on a recording medium is provided, and as another effect, a dispersible color material having excellent ejection characteristics in an ink jet recording apparatus is provided. You. Further, as another effect of the present invention, a dispersible colorant having excellent color developability on a recording medium is provided. (4) Dispersible coloring materials that can be used stably in the middle pH region to the low pH region are provided, and a simple production method thereof is also provided. Further, as another effect of the present invention, a water-based ink excellent in gloss on a glossy recording medium and a water-based ink excellent in scratch resistance on a glossy recording medium are provided. You.
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003296156A AU2003296156A1 (en) | 2002-12-27 | 2003-12-26 | Disperse color material and process for producing the same, water-color ink employing it, ink tank, inkjet recorder, inkjet recording method and inkjet recorded image |
US10/498,105 US20050043434A1 (en) | 2002-12-27 | 2003-12-26 | Dispersible color material and process for producing the same, water-color ink employing it, ink tank, inkjet recorder, inkjet recording method and inkjet recorded image |
EP20030786370 EP1593715A1 (en) | 2002-12-27 | 2003-12-26 | Disperse color material and process for producing the same, water-color ink employing it, ink tank, inkjet recorder, inkjet recording method and inkjet recorded image |
CN2003801077477A CN1732237B (zh) | 2002-12-27 | 2003-12-26 | 分散性色料及其制造方法 |
CA 2511099 CA2511099A1 (en) | 2002-12-27 | 2003-12-26 | Dispersible colorant and method for producing the same, and aqueous ink, ink tank, ink jet recorder, ink jet recording method and inkjet recorded image using the same |
US10/866,877 US20040244622A1 (en) | 2002-12-27 | 2004-06-15 | Dispersible colorant and method for producing the same, and aqueous ink, ink tank, ink jet recorder, ink jet recording method and inkjet recorded image using the same |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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JP2002382351 | 2002-12-27 | ||
JP2002-382351 | 2002-12-27 | ||
JP2003049212 | 2003-02-26 | ||
JP2003-049212 | 2003-02-26 | ||
JP2003-114956 | 2003-04-18 | ||
JP2003114956 | 2003-04-18 | ||
JP2003428400A JP2004331946A (ja) | 2002-12-27 | 2003-12-24 | 分散性色材とその製造方法、それを用いた水性インクジェット記録用インク、インクジェット記録装置、インクジェット記録方法、及びインクジェット記録画像 |
JP2003-428400 | 2003-12-24 |
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US10/866,877 Continuation US20040244622A1 (en) | 2002-12-27 | 2004-06-15 | Dispersible colorant and method for producing the same, and aqueous ink, ink tank, ink jet recorder, ink jet recording method and inkjet recorded image using the same |
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WO2004061016A1 true WO2004061016A1 (ja) | 2004-07-22 |
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US (2) | US20050043434A1 (ja) |
EP (1) | EP1593715A1 (ja) |
JP (1) | JP2004331946A (ja) |
KR (1) | KR100882065B1 (ja) |
CN (1) | CN1732237B (ja) |
AU (1) | AU2003296156A1 (ja) |
CA (1) | CA2511099A1 (ja) |
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- 2003-12-26 US US10/498,105 patent/US20050043434A1/en not_active Abandoned
- 2003-12-26 CN CN2003801077477A patent/CN1732237B/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
CN1732237B (zh) | 2010-04-28 |
KR20050088342A (ko) | 2005-09-05 |
CN1732237A (zh) | 2006-02-08 |
JP2004331946A (ja) | 2004-11-25 |
CA2511099A1 (en) | 2004-07-22 |
AU2003296156A1 (en) | 2004-07-29 |
KR100882065B1 (ko) | 2009-02-10 |
US20040244622A1 (en) | 2004-12-09 |
US20050043434A1 (en) | 2005-02-24 |
EP1593715A1 (en) | 2005-11-09 |
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