WO2006001546A1 - 分散性色材の製造方法及びインクジェット記録用インク - Google Patents
分散性色材の製造方法及びインクジェット記録用インク Download PDFInfo
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- WO2006001546A1 WO2006001546A1 PCT/JP2005/012294 JP2005012294W WO2006001546A1 WO 2006001546 A1 WO2006001546 A1 WO 2006001546A1 JP 2005012294 W JP2005012294 W JP 2005012294W WO 2006001546 A1 WO2006001546 A1 WO 2006001546A1
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- dispersible
- color material
- water
- fine particles
- dispersible colorant
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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
Definitions
- the present invention relates to a method for producing a dispersible color material and an ink jet recording ink containing the dispersible color material obtained by the method.
- the inkjet method is a method of recording images, characters, etc. by ejecting fine ink droplets from nozzles to reach a recording medium (paper, etc.) based on various operating principles. It is easy to use, has high flexibility in recording patterns, and does not require development and fixing operations. It is rapidly spreading in various applications. In particular, in recent years, the full-color water-based ink jet recording system technology has made remarkable progress, and it is possible to form multicolored images that are inferior to multicolored printing by conventional plate-making methods or color photographic methods. If the number of copies to be created is small, printed materials can be obtained at a lower cost than ordinary multi-color printing and printing, so that they are being widely applied to the field of full-color image recording.
- the ink jet recording apparatus and the recording method have been improved.
- the performance required for an ink jet recording ink used in an ink jet recording apparatus is as follows: (1) A uniform image can be obtained on paper with no blur or fog, high resolution and high density (2) Clogging due to ink drying at the nozzle tip does not occur, and ejection responsiveness and ejection stability are always good. (3) Ink fixability on paper is good. (4 ) The fastness (scratch resistance, etc.) of the formed image is good. (5) The long-term storage stability is good. The In particular, with the recent increase in printing speed, there is a demand for ink that can be dried and fixed quickly and that can provide high-quality recording.
- Color materials used in ink jet recording systems mainly include dyes and pigments, and water-soluble dyes have been used mainly because of their ease of handling as water-based inks and high color development.
- a water-based ink coloring material that can realize the weather resistance of images
- the development of inks that use essentially water-insoluble coloring materials, especially pigments has been energetically advanced.
- a coloring material insoluble in water, 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 dispersion resin
- the vinyl monomer was added and polymerized after dispersion, and when the dispersant was dispersed with a water-insoluble colorant, it showed dispersion stability, and the vinyl monomer was present in the presence of the dispersant alone.
- ⁇ Aqueous colored fine particle dispersions characterized by poor stability of latex produced when polymerizing one '' is disclosed as ⁇ vinyl monomer and produced when emulsion-polymerized into a water-insoluble colorant dispersion ''. Since the affinity of the dispersant for the polymer is not so high, it is difficult for the dispersant to desorb from the pigment surface, and the polymerization proceeds on the pigment surface where the dispersant is adsorbed.
- the colored fine particle dispersion By using the colored fine particle dispersion, it is excellent in dispersion stability and printability, is not dependent on the paper type, has a low metallic luster, and is water resistant. , If It is said that a water-based ink having excellent light resistance and scratch resistance is obtained. Disclosure of the invention
- the dispersion stability of the color material and the glossiness of the recorded image may not be sufficient. According to the study by the present inventors, it is necessary to increase the surface functional group density of the coloring material in order to enhance the dispersion stability.
- the conventional technique using a polymer dispersant, and JP-A-8-1 In the method of making a pigment covered with a resin disclosed in Japanese Patent No. 8 3 9 20, if the acid value of the resin is increased in order to increase the dispersion stability, the hydrophilicity of the resin also increases. At the same time, the resin easily deviated from the color material, and long-term storage stability could not be maintained.
- the inventors of the present invention have achieved a high dispersion stability by using a dispersible color material having a novel shape, and the resin component is a color material.
- the ejection stability is sufficient for inkjet recording applications. High-quality images with excellent stability and dispersion stability, scratch resistance, etc. are obtained, the head face surface is not soiled, and the ink jet recording ink is less likely to cause kogation on the heater port. It was.
- the present invention relates to a method for producing a dispersible colorant using aqueous precipitation polymerization, a dispersion step of dispersing a colorant in an aqueous solution using a dispersant, and a resin monomer in an aqueous solution in which the colorant is dispersed.
- a radical polymerization initiator, and an aqueous precipitation polymerization process for producing a dispersible color material in which the chargeable resin pseudo fine particles are fixed on the color material by aqueous precipitation polymerization, and an aqueous solution containing the dispersible color material is limited. It is a method for producing a dispersible color material, characterized by having at least an ultrafiltration step of obtaining a dispersible color material by external filtration.
- the present invention is an ink jet recording ink characterized by containing a dispersible color material obtained by the above production method.
- an ultrafiltration process is provided after that, so that charged resin pseudo fine particles suitable for ink jet recording ink can be obtained.
- a dispersible colorant formed by fixation can be selectively obtained with a high degree of purification.
- the ink containing the dispersible color material obtained by fixing the chargeable resin pseudo fine particles obtained by the production method is an ink in which the color material is dispersed with the resin, but has extremely excellent ejection stability. It will be.
- FIG. 1A and 1B are schematic views showing the basic structure of a dispersible color material to which the chargeable resin pseudo fine particles obtained by the present invention are fixed (fused).
- FIG. 3 is a schematic diagram showing the process of refining the charged resin pseudo fine particles and fixing (fusing) them to the color material in the production method of the present invention.
- FIG. 4 is a schematic diagram in which the charged resin pseudo fine particles obtained by the present invention are enlarged from the interface side where they are fixed (fused) to the coloring material.
- FIG. 5 is an enlarged schematic view of the interface where the chargeable resin pseudo fine particles obtained by the present invention and the coloring material are fixed (fused).
- FIGS. 6A and 6B are schematic diagrams of a pigment peeling phenomenon when a hydrophilic group is directly modified on an organic pigment, as represented by Japanese Patent Application Laid-Open No. 10-1953. BEST MODE FOR CARRYING OUT THE INVENTION
- the first feature of the dispersible color material produced by the present invention is a dispersible color material comprising a color material and a chargeable resin pseudo fine particle, wherein the color material fixes the chargeable resin pseudo fine particle. It is in the point.
- FIGS. 1A and 1B show schematic diagrams of a dispersible color material, which characterizes the present invention, in which chargeable resin pseudo fine particles 2 are fixed to color material 1.
- FIG. The part 2 ′ in FIG. 1B is a part schematically showing a state in which a part of the chargeable resin pseudo fine particles 2 fixed on the surface of the coloring material 1 is fused.
- the charge of the chargeable resin pseudo fine particles is imparted to the surface of the color material, so that the dispersible color material can be dispersed in water or an aqueous ink medium.
- the dispersible colorant has excellent adhesion to the recording medium due to the presence of the resin component adhering to the surface.
- the charged resin pseudo fine particles which are the characteristics of the dispersible color material used in the present invention, are fixed to the color material. Since the fine particles are not detached from the surface of the color material, the dispersible color material used in the present invention is excellent in long-term storage stability.
- the chargeable resin pseudo fine particles in the present invention are those in which the resin component is strongly agglomerated.
- the resin aggregate is in a state in which many physical crosslinks are formed inside (the resin aggregate has a stable form in which the resin component is in the form of fine particles or a microaggregate close thereto. What you are doing). Details of the chargeable resin pseudo fine particles will be described later.
- the state in which the chargeable resin pseudo fine particles are fixed to the color material in the present invention is due to strong interaction between the color material surface and the chargeable resin pseudo fine particles, and is considered to be achieved in the following state.
- Figure 4 shows an enlarged schematic diagram of the interface in contact with the coloring material of the chargeable resin pseudo fine particles.
- the chargeable resin pseudo fine particles 2 are formed by intertwining polymers composed of various monomer unit compositions (indicated by 9 1 1 and 9 1 2 in the figure). Since the polymer has various structures locally at the interface with the colorant, the local surface energy is distributed in various states.
- the color material and the polymer are firmly bonded in that the surface energy generated from the chemical structure and surface structure of the color material and the surface energy generated from the chemical structure and surface structure of the polymer are well matched locally. (The part indicated by a black circle in the figure). Furthermore, at the interface where one chargeable resin pseudo fine particle is in contact with the color material, there are a plurality of points where the surface energies of both coincide locally as shown in FIG. It is expected that the solid state of the present application is established by the strong interaction at these multiple locations. In the present invention, a state in which, for example, 30% or more of the surface area of the chargeable pseudo fine particles, such as 2 ′ in FIG. 1B, is in contact with the coloring material is referred to as “fusion” for convenience. This is a form of fixation, and it is not necessary for the charged pseudo fine particles and the color material to melt together at the interface.
- the dispersible color material used in the present invention has an advantage that the chargeable resin pseudo fine particles are fixed to the color material.
- the specific surface area of the dispersible color material increases depending on the form, and the color material surface It is mentioned that the charge of the chargeable resin pseudo fine particles can be distributed on many parts of the surface.
- the form of the dispersive color material used in the present invention is a form in which more surface charges are more efficiently arranged on the surface of the dispersible color material. High dispersion stability can be imparted even when the substantial acid value or amine value of the resin component is smaller than that of a form in which a color material is coated with a resin, as represented by the publication.
- organic pigments are insolubilized (pigmented) by crystallizing chromogenic colorant molecules through strong interaction.
- a plurality of interaction points are distributed at the interface between the chargeable resin pseudo fine particles and the color material. Charged resin pseudo fine particles
- the size of the charged resin pseudo fine particles is controlled to be within a range smaller than the dispersed particle diameter of the pigment and larger than the coloring material molecule.
- a dispersible colorant of an organic pigment imparted with high dispersibility can be obtained without breaking the crystal structure.
- the state in which the coloring material “fixes” the chargeable resin pseudo fine particles is as follows: In a simple manner, it can be confirmed by the following method involving three stages of separation. First, in the first separation, the color material to be confirmed is separated from other water-soluble components (including water-soluble resin components) contained in the ink or water dispersion, In the second separation, the coloring material and the water-insoluble resin component contained in the precipitate in the first separation are separated. Furthermore, in the third separation, the weakly adsorbed resin component is separated from the dispersible colorant to which the charged resin pseudo fine particles are fixed, and the resin component contained in the third separation supernatant is quantified. The adhesion between the coloring material and the chargeable resin pseudo fine particles is confirmed by comparing the precipitate of the second separation with the precipitate of the third separation.
- the ink or water dispersion in which the color material is dispersed Take 20 g of the ink or water dispersion in which the color material is dispersed, adjust the total solids mass to about 1 Q%, and rotate it with a centrifuge at 1, 2, 0 0 0 The first separation is performed at 60 minutes. Of the separated material, the sediment in the lower layer containing the colorant is redispersed in about 3 times as much pure water as the sediment, and then subjected to the conditions of 80, 00 rotation, 90 minutes. Then perform the second separation. The lower layer sediment containing the color material is re-dispersed in 3 times the amount of pure water, and then the third separation is performed again under the conditions of 80,000 rotation and 90 minutes. Remove the underlying sediment.
- the separation conditions described above are preferable examples, and any other separation method or separation condition can be used as long as the method achieves the purpose of the first separation and the second and third separations described above. It can be applied as a method for determining whether or not a dispersible colorant is used in the invention.
- the first separation is intended to separate the coloring material contained in the ink and water dispersion and the resin component adsorbed on the coloring material, and the water-soluble component
- the second separation is the coloring material.
- the purpose is to separate the resin component adhering to the coloring material and the other resin component adsorbing to the coloring material.
- the third separation is intended to confirm that the resin component adhering to the colorant does not desorb.
- any other separation method that is publicly known or newly developed may be used, and the procedure is more than three steps. Also, it can be applied at least.
- the second feature of the dispersible colorant used in the present invention is a dispersible colorant that can be dispersed alone in an aqueous medium in a state where the water-insoluble colorant 1 is fixed to the chargeable lunar pseudo fine particles 2.
- the dispersible colorant used in the present invention is essentially capable of being dispersed in water and water-based inks without the aid of other surfactants or polymer dispersants. It is a sex color material. This definition and determination method will be described in detail later. Therefore, the dispersible colorant used in the present invention is added with a polymer dispersant or other resin component or surfactant component that may be released for a long term for the purpose of stabilizing the dispersion of the colorant.
- the dispersible color material used in the present invention is used as a water-based ink
- the degree of design freedom regarding components other than the dispersible color material is increased.
- the penetration of ink such as plain paper It is also possible to use a water-based ink that can obtain a sufficiently high print density even on a recording medium having high properties.
- the self-dispersibility of the dispersible colorant used in the present invention can be confirmed, for example, as follows.
- the ink or water dispersion in which the color material is dispersed is diluted 10 times with pure water, and concentrated to the original concentration using an ultrafiltration filter with a molecular weight cut off of 50, 00. 0
- This concentrated solution is separated in a centrifuge at 1 2,000 rpm for 2 hours, and the sediment is taken out and redispersed in pure water.
- it is judged that the sediment that can redisperse well has self-dispersibility. Whether it is well redispersed, it must be evenly distributed visually, or noticeable sediment may not be generated after standing for 1 to 2 hours. For example, it can be comprehensively judged from the fact that the average particle size is less than twice the particle size before operation when the dispersed particle size is measured by the dynamic light scattering method.
- the dispersible colorant used in 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. In this way, excellent storage stability is achieved. Therefore, a more preferable result can be obtained by the fact that a large number of charged resin pseudo fine particles are scattered and fixed to the color material.
- Such a form is confirmed by observing the water-based ink according to the present invention with a transmission electron microscope or a scanning electron microscope.
- a plurality of charged fine resin particles adhering to the color material surface are fixed at a certain distance, or the surface of the color material is exposed between the adhering charged resin pseudo fine particles. You can observe the current state. In addition, the charged resin pseudo fine particles are sometimes close to each other, and in some cases, fused particles can be observed, but even in this case, the distance between the charged resin pseudo fine particles as a whole is small. Yes, or there is a portion where the surface of the color material is exposed, and when these states are distributed, the charged resin pseudo fine particles are scattered and fixed to the color material. It is clear to those skilled in the art that .
- the aqueous ink containing the dispersible colorant having the above-described characteristics used in the present invention exhibits excellent quick drying on a recording medium. I'm sure why However, it is based on the following mechanism.
- the dispersed 14-color material is dispersed in the ink in a form in which charged resin pseudo fine particles are fixed to the surface of the color material.
- the aqueous solvent in the ink (hereinafter referred to as “ink solvent”) is a pore on the recording medium due to capillarity (in the case of plain paper, it is a gap between cellulose fibers, and coated paper) Or in the case of glossy paper, it is absorbed into the pores of the receiving layer).
- the dispersible color material used in the present invention has many fine gaps due to the scattered characteristic of the chargeable resin pseudo fine particles at the portions where the color materials are in contact with each other due to their morphological characteristics. For this reason, a capillary action acts on the ink solvent existing between the color materials, and it is quickly absorbed into the recording medium.
- the dispersible colorant having a form in which the chargeable resin pseudo fine particles are scattered on the surface exhibits a more preferable quick drying property. Therefore, it is expected that quick drying is achieved.
- the surface functional group density of the dispersible colorant according to the present invention is preferably 2 5 0 Li mo 1 Z g or more and less than 1, 0 0 0 ⁇ mo 1 Z g, and 2 9 0 o 1 Z g or more 9 0 0 mo More preferred is less than 1 Zg.
- the surface functional group density is smaller than this range, the long-term storage stability of the dispersible colorant may be deteriorated. Further, if it has a rather large surface functional group density than this range, too high dispersion stability, easily penetrates on the recording medium, Ru if there f where it is difficult to ensure high print density .
- the surface functional group density is obtained, for example, as follows. First, a large excess amount of aqueous hydrochloric acid (HC 1) solution is added to an aqueous dispersion or ink containing a dispersible colorant to be measured, and then settled in a centrifuge at 20 and 00 rpm for 1 hour. Let Collect the sediment and re-disperse it in pure water, then measure the solid content by the drying method. The re-dispersed sediment is weighed, and a dispersion obtained by adding a known amount of sodium hydrogen carbonate and stirring is further sedimented in a centrifuge at 80, 00 rpm for 2 hours.
- HC 1 aqueous hydrochloric acid
- the surface functional group density is calculated as the number of mo 1 per gram of colorant.
- the color material that is a constituent component of the dispersible color material used in the present invention will be described below.
- the color material used in the present invention among color materials known or newly developed, it is desirable to use a color material that is insoluble in water and that can be stably dispersed in water together with a dispersant.
- examples of such materials include hydrophobic dyes, inorganic pigments, organic pigments, metal colloids, and colored resin particles.
- the dispersed particle size is in the range of 0.01 to 0.5 m (10 to & 0 nm), particularly preferably 0.03 to 0.3 u rn (30 to 300 nm) Use color materials that fall within the range.
- a dispersible color material using a color material dispersed in this range is a preferable dispersible color material that gives an image having high coloring power and high weather resistance when used as an aqueous ink.
- a dispersed particle size is a cumulant average value of particle sizes measured by a dynamic light scattering method.
- examples of the inorganic pigment that can be effectively used for the coloring material include carbon black, titanium oxide, zinc white, zinc oxide, tripon, iron oxide, cadmium red, molybdenum red, chromium vermilion, and molybdenum.
- organic pigments examples include azo, azomethine, polyazo, phthalocyanine, quinacridone, anthraquinone, indigo, thioindigo, quinophthalone, benzimidazolone, Various pigments such as isoindoline and isoindolinone are listed.
- organic insoluble colorants that can be used in the present invention include, for example, azo, anthraquinone, indigo, phthalocyanine, carbonyl, quinoneimine, methine, quinoline, and nitro. Examples include hydrophobic dyes. Of these, disperse dyes are particularly preferable.
- the charged resin pseudo fine particles which are another component of the dispersible color material used in the present invention, are substantially insoluble in water, and the color material to be fixed in water (or in ink).
- the dispersion unit (dispersion particle size) in is small, and is defined as a micro-assembly made up of resin components with a sufficiently high degree of polymerization.
- the form of the micro body is pseudo close to a sphere, or a plurality of micro bodies (chargeable resin pseudo fine particles) are arranged within a certain range.
- the resin components constituting the chargeable resin pseudo fine particles are physically or chemically cross-linked with each other. Whether the resin components constituting the charged resin pseudo fine particles are cross-linked with each other can be confirmed, for example, by using the following method.
- the resin component constituting the chargeable 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 polymer is obtained.
- a linear polymer having the same chemical structure or the same monomer unit composition
- the solubility of the chargeable tree B pseudo fine particles was higher than the solubility of the polymer. If the value is too low, it can be confirmed that the inside of the charged shelf pseudo-particle is cross-linked.
- the dispersed particle size of the chargeable resin pseudo fine particles in water can be measured by, for example, a dynamic light scattering method, preferably the average particle size of the cumulan dispersion It is desirable that the value be in the range of 10 nm or more and 20 00 nm or less. Furthermore, from the viewpoint of long-term storage stability of the dispersible colorant, it is more preferable that the polydispersity index of the dispersed particle size is suppressed to less than 0.2. If the median value of the dispersed particle size is greater than 20 O nm or the polydispersity index is greater than 0.2, The original purpose of finely dispersing and stabilizing the color material may not be sufficiently achieved.
- the average value of the dispersed particle diameter is smaller than 1 O nm, the form as the charged resin pseudo fine particles cannot be sufficiently maintained, and the resin is easily dissolved in water. It may not be obtained.
- the particle diameter is smaller than the color material particles themselves, so that the dispersion of the color material can be effectively stabilized by fixing the charged resin pseudo fine particles in the present invention.
- the above-mentioned preferable mode is the same even when the dispersed particle size of the charged resin pseudo fine particles cannot be measured.
- the average diameter of the charged resin pseudo fine particles in the electron microscope observation is as described above. Is considered to be the preferred range or the equivalent range.
- the charged resin pseudo fine particles should be smaller than the pigment dispersed particle size and larger than the color material molecule. Is particularly desirable because it provides a dispersible colorant that is extremely structurally stable and has high dispersibility.
- the chargeability in the present invention refers to a state in which the functional group itself is ionized in some form in an aqueous medium, and is preferably dispersible by its chargeability. Therefore, as to whether or not it is a chargeable resin pseudo fine particle, a method of measuring the surface potential of the charge resin pseudo fine particle by a known and arbitrary method, or a potentiometric titration by the method described later.
- a method for calculating the functional group density, a method for confirming the dependency of dispersion stability on the electrolyte concentration by adding an electrolyte to the aqueous dispersion of the charged resin pseudo fine particles, or a chemical structure analysis of the charged resin pseudo fine particles Can be confirmed by any of the following methods: a method for examining the presence or absence of an ionic functional group.
- the resin component constituting the chargeable resin pseudo fine particles can be any resin component such as any commonly used natural or synthetic polymer, or a newly developed polymer for the present invention. it can.
- resin components that can be used examples include acrylic resins, styrene Z acrylic resins, polyester resins, polyurethane resins, polyurea resins, polysaccharides, polypeptides and the like.
- a polymer of a monomer component having a radical polymerizable unsaturated bond such as an acrylic resin or a styrene / acrylic resin, or the like
- a copolymer can be preferably used.
- monomers having a force loxyl group such as acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, prozelacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, and salts thereof, styrene sulfone Monomers having sulfonic acid groups such as acid, sulfonic acid-2-propylacrylamide, ethyl 2-sulfonic acid ethyl, ethyl 2-sulfonic acid ethyl, butylacrylamide sulfonic acid, etc., and salts thereof, methacrylic acid Monomers having a phosphonic acid group such as ethyl 2-phosphonate, ethyl 2-phosphonate, and the like.
- the chargeable resin pseudo fine particles preferably used in the present invention preferably have a glass transition temperature of the resin of ⁇ 40 to 60. By being in this range, a high film-forming property is imparted to the chargeable resin simulated fine particles, and the color materials adjacent to each other on the recording paper can be formed to form a strong colored film. Accordingly, it is possible to impart a high level of scratching to printed matter obtained using the dispersible color material having such a configuration.
- the glass transition temperature of the chargeable resin pseudo fine particles can be measured by the following procedure.
- the dispersible colorant is subjected to acid precipitation with hydrochloric acid or the like to recover the precipitate.
- the charged resin pseudo fine particles fixed to the coloring material can be obtained by Soxhlet extraction of the precipitate using an organic solvent such as THF (tetrahydrofuran) and distilling off the organic solvent.
- the glass transition temperature can be measured by differential scanning calorimetric analysis of the obtained chargeable resin pseudo fine particle component.
- a device such as DSC 8 2 2 e manufactured by ME TTLER may be used.
- aqueous dispersion in which a dispersible colorant and a water-soluble nonionic resin coexist, it can be separated using a centrifuge. 6
- a centrifuge for example, when the separation is performed under a centrifugal separation condition of 1 200 rpm, a dispersible colorant can be obtained as a sediment.
- the dispersible colorant of the present invention can be selected by appropriately selecting the monomer type and copolymerization ratio having a radically polymerizable unsaturated bond of the resin component constituting the chargeable resin pseudo fine particles while satisfying the above conditions.
- the monomer species include a hydrophobic monomer, an anionic hydrophilic monomer as described above, and a nonionic hydrophilic monomer.
- hydrophobic monomers examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-propyl acrylate, 1 t-butyl acrylate, benzyl acrylate, methyl methacrylate, (Meth) such as ethyl ethyl acrylate, isopropyl methacrylate, 1-n-propyl methacrylate, 1-n-butyl methacrylate, isoptyl methacrylate, 1-tert-butyl methacrylate, tridecyl methacrylate, benzyl methacrylate Acrylic acid esters; styrene monomers such as styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene; benzyl itaconate,
- hydrophilic monomer having an anionic group examples include those described above.
- nonionic hydrophilic monomer specifically, there are a radical polymerizable unsaturated bond and strong hydrophilicity in a structure such as hydroxymethyl (meth) acrylate and hydroxylpropyl (meth) acrylate.
- alkylene oxide groups such as ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , epoxy polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, other known or novel oligomers, macromonomers, etc. Can be used without any restrictions.
- the alkylene oxide group-containing monomer is excellent in copolymerizability with the hydrophobic monomer component, the uniformity of the surface properties of the charged resin pseudo fine particles, and the uniform fixing property to the colorant, and the fusing property Gives favorable results.
- the charged resin pseudo fine particles may be composed of a copolymer of monomer components including at least one hydrophobic monomer and at least one hydrophilic monomer among the monomers listed above. This is a desirable mode.
- good form control can be achieved by using at least one type of hydrophilic monomer to achieve good adhesion to the colorant and thermal stability. And dispersion stability. Therefore, by using these monomers simultaneously, it is possible to obtain charged resin pseudo fine particles that are always well fixed to the colorant and can impart good dispersion stability.
- the weight average molecular weight of the resin obtained from the above-described monomer using a water-soluble radical polymerization initiator is 2,00 or more, It is preferable to be 0 0 0 or less. Within this range, the resin that has been polymerized in the ultrafiltration step after the aqueous precipitation polymerization step but has dissolved in the solution without becoming pseudo charged fine resin particles is more efficiently removed. be able to.
- a chain transfer agent as the molecular weight modifier.
- chain transfer agent Various chain transfer agents can be used as the chain transfer agent, but lauryl mercabtan, octyl mercabtan, 2-mercaptophenol, octyl thioglycolate, or 3-mercapto are particularly effective. Examples include thiol compounds such as propionic acid.
- the weight average molecular weight of the resin constituting the dispersible pigment formed by fixing the charged resin pseudo fine particles can be reduced to 20 or less. If the weight average molecular weight of the resin is larger than this, the viscosity becomes high when used in ink, and it becomes difficult to obtain the discharge stability intended in the present invention.
- the aqueous precipitation polymerization step is a first step in which one or more hydrophobic monomers and one or more hydrophilic monomers are added, and the aqueous precipitation polymerization is performed with a water-soluble radical polymerization initiator.
- the first stage reaction is completed, as the second stage reaction, one or more kinds of hydrophilic stopper monomers are further added, followed by aqueous precipitation polymerization with a water-soluble radical polymerization initiator. It is preferable to divide into. By adopting such a configuration, it is possible to increase the hydrophilicity of the resin that is not fixed to the coloring material, so that it is easy to remove the resin that is not fixed to the coloring material after the ultrafiltration step. Because you can.
- the hydrophobic monomer includes at least a component selected from benzyl methacrylate or (meth) alkyl acrylate esters, and a hydrophilic monomer (meta) And those containing at least a component selected from acrylic acid, (meth) acrylic acid methoxypolyethylene glycols and carbon chain 4 to 40 (meth) acrylic acid long chain alkyl esters.
- the hydrophobic monomer used in the first stage reaction is benzyl methacrylate or (meth) acrylic acid alkyl esters.
- a hydrophilic monomer used in the first-stage reaction comprising at least a component selected from Evening) Contains at least a component selected from acrylic acid and (meth) acrylic acid methoxypolyethylene glycols, and mentions that the aqueous monomer used in the subsequent second-stage reaction contains (meth) acrylic acid. It is done.
- the amount of each monomer used is such that the hydrophobic monomer used in the first stage reaction contains 95 to 30 parts by mass of benzyl methacrylate with respect to 100 parts by mass of the total monomer.
- the hydrophilic monomer used in the reaction is 1 to 30 parts by mass of (meth) acrylic acid with respect to 100 parts by mass of all monomers, and (meth) acrylic acid methoxypolyethylene glycols or carbon chains 4 to 40 It is preferable to use a mixture containing one or more components selected from (meth) acrylic acid long-chain alkyl esters in the range of 40 to 40 parts by mass.
- hydrophobic monomer used in the first stage reaction contains benzyl methacrylate and the first
- the hydrophilic monomer used in the reaction of the stage is selected from (meth) alkylamine acrylate, and (meth) methoxyethylene glycol glycols or (meth) acrylic acid long chain alkyl esters having 4 to 40 carbon chains
- the hydrophilic monomer used in the second stage reaction includes (meth) alkylamine acrylate.
- the method for synthesizing the chargeable resin pseudo fine particles and the method for fixing to the color material are carried out by a method for synthesizing the chargeable resin pseudo fine particles or a method for combining the charge resin pseudo fine particles and the color material.
- a method for synthesizing the chargeable resin pseudo fine particles or a method for combining the charge resin pseudo fine particles and the color material can do.
- the present inventors as a result of intensive studies, are a dispersible color material having a color material and a chargeable resin pseudo fine particle smaller than the color material, which is a feature of the present invention.
- the inventors have invented a production method capable of easily obtaining a dispersive color material in a state where the chargeable resin pseudo fine particles are fixed to the material.
- the dispersible color material used in the present invention can be easily obtained. A suitable manufacturing method will be described.
- the dispersible colorant used in the present invention having the above-described characteristics can be manufactured very easily by applying the aqueous precipitation polymerization method under the following conditions. It became.
- a water-insoluble colorant is dispersed in a dispersant to prepare a dispersed aqueous solution of the water-insoluble colorant.
- the charged resin pseudo fine particles are fixed to the coloring material by a step of aqueous precipitation polymerization of the radically polymerizable monomer using the aqueous radical polymerization initiator in this dispersed aqueous solution.
- the dispersible colorant obtained through this aqueous precipitation polymerization process is a water-insoluble color in which the chargeable resin pseudo fine particles synthesized in the aqueous precipitation polymerization process are strongly and firmly adhered to the colorant. It becomes a material and has excellent dispersion stability by itself. Further, in the above-described aqueous precipitation polymerization process, the characteristics of the chargeable resin pseudo fine particles can be easily controlled to the preferred form as described above. The fixing state between the coloring material and the chargeable resin pseudo fine particles is achieved satisfactorily.
- preferred embodiments of the 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 dispersant for dispersing the coloring material in the aqueous solution, any of ionicity, nonionicity, etc. can be used.
- the dispersing agent is either a polymer dispersing agent or an aqueous solution. It is desirable to use a functional polymer.
- the hydrophobic portion serves as an adsorption site for the surface of the colorant fine particles and the radically polymerizable monomer added in the polymerization process, particularly the hydrophobic monomer, to the oil droplet interface.
- the hydrophobic monomers used in the subsequent polymerization step is present as a unit constituting the dispersant. From the viewpoint of easily inducing fixation to the color material, preferable.
- the production method of the polymer dispersant and the water-soluble polymer functioning as a dispersant that can be used in the present invention is not particularly limited.
- a monomer having an ionic group and other polymerizable monomers are used. It can be produced by reacting in a non-reactive solvent in the presence or absence of a catalyst.
- the affinity between the hydrophobic monomer and the dispersant becomes higher than the affinity between the colorant and the dispersant during the aqueous precipitation polymerization, and the chargeable resin pseudo
- the dispersant may be detached from the color material surface, and the dispersed state may not be maintained.
- the acid value and amine value are larger than these ranges, the excluded volume effect of the dispersing agent on the surface of the color material and the electrostatic repulsion force become too strong. Sticking may be inhibited.
- an anionic dispersant from the viewpoint of not inhibiting the adhesion of the resin fine particles to the color material, It is preferable to select a dispersant having a xyl group.
- the colorant preferably has a dispersed particle diameter of from 0.0111 to 0.5 m (from 10 nm to 500 nm). ), Particularly preferably in the range of 0.03 ⁇ 111 or more and 0.3 m or less (30 nm or more and 300 nm or less).
- the dispersed particle diameter in this process greatly reflects the dispersed particle diameter of the resulting dispersible colorant, and the above range is preferable from the viewpoint of the above-described coloring power, weather resistance of the image, and dispersion stability. .
- the dispersion particle size distribution of the water-insoluble colorant used in the present invention is preferably monodispersed as much as possible.
- the particle size distribution of the dispersible colorant obtained by fixing the charged resin pseudo fine particles tends to be narrower than the particle size distribution of the dispersed aqueous solution before the polymerization step shown in FIG. 2B.
- it depends on the particle size distribution of the above-mentioned dispersed aqueous solution.
- the dispersion stability of the dispersible colorant obtained is excellent.
- the particle size of the colorant in a dispersed state differs depending on various measurement methods.
- the organic pigment is very small in the case of spherical particles.
- ELS-8O 0 manufactured by Otsuka Electronics Co., Ltd. The average particle size and polydispersity index determined by measuring the dynamic light scattering method at 0 and using cumulant analysis were used.
- the method of dispersing the water-insoluble coloring material in water may be any method that uses a dispersing agent as described above, among the methods in which the coloring material can be stably dispersed in water under the conditions described above. It is not limited to any conventionally known method. Alternatively, it may be a dispersion method newly developed for the present invention. In general, for example, when the water-insoluble colorant is a pigment, the addition amount of the polymer dispersant to be used is preferably 10% by mass or more and 130% by mass or less based on the pigment. ing.
- Examples of the method for dispersing the color material used in the present invention include a paint shaker, Dispersers such as sand mills, agitator mills, three-roll mills, high-pressure homogenizers such as microfluidizers, nanomizers, and optimizers, ultrasonic dispersers, etc. Any method is not limited.
- FIG. 2A a dispersed aqueous solution in which the coloring material 1 is dispersed with the dispersant 3 in the aqueous solution is prepared.
- the coloring material is dispersed and stabilized by the adsorption of the dispersing agent, and this adsorption is in a thermal equilibrium state.
- the temperature of the dispersion aqueous solution prepared in FIG. 2A is raised while stirring, and the monomer component 4 is added to this together with, for example, the aqueous radical polymerization initiator 5 (see FIG. 2B).
- the added aqueous radical polymerization initiator cleaves when heated to generate radicals.
- a small amount of a hydrophobic monomer dissolved in the aqueous phase and water Contributes to the reaction with water-soluble monomers in the phase.
- FIG. 3 is a schematic diagram illustrating the process from the polymerization of monomer 4 to the production of a dispersible colorant.
- the reaction of the monomer 4 proceeds as described above, the oligomer 7 formed by the monomer component combining reaction becomes insoluble in water, and precipitates from the aqueous phase to become a precipitate 8.
- the charged resin pseudo fine particles 2 are formed together.
- the charged resin pseudo fine particles 2 further cause heteroaggregation with the hydrophobic surface of the coloring material in the aqueous dispersion as a nucleus, and the resin component constituting the surface of the coloring material 1 and the charging resin pseudo fine particles 2 is hydrophobic. Strongly adsorbed by sexual interaction.
- the chargeable resin pseudo fine The polymerization reaction continues in the interior of the particle 2 and changes to a more energy-stable form while increasing the adsorption point with the colorant 1.
- the inside of the charged resin simulated fine particles 2 is highly physically cross-linked, so that the most stable adsorbing form with the coloring material 1 is fixed and fixed.
- coloring material 1 is stabilized by the adhering of a plurality of chargeable resin pseudo fine particles 2 and dispersing agent 3 in an equilibrium state is detached from the surface of coloring material 1 (Fig. 2C ⁇ 2 D).
- the dispersing agent 3 detached at this time but also water-based precipitation polymerization, it is possible to efficiently remove not only the chargeable resin pseudo fine particles but also the resin dissolved in the solution. it can.
- FIG. 4 shows a schematic diagram of the charge resin pseudo fine particles 2 obtained as described above on the fixing interface side with the coloring material 1.
- the charged resin pseudo fine particles which are aggregates of resin components, have hydrophilic monomer units 9_1, hydrophobic monomer units 9_2, etc. distributed in an arbitrary manner.
- the surface energy has a distribution, and there are many adsorption points 10 that match the surface energy of the coloring material.
- Fig. 5 shows an enlarged schematic diagram of the fixing interface between a part of the charged resin pseudo fine particles 1 1 and a part of the colorant particles 1 a. While adsorbing the adsorption point 10 shown in Fig. 4, it adheres stably in a form corresponding to the surface shape of part 1a of the color material.
- the polymerization reaction conditions depend on the properties of the polymerization initiator, dispersant, and monomer used.
- the reaction temperature is 100 and below, preferably in the range of 40 to 80.
- 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 50 rpm or more and 500 rpm or less, more preferably 1550 rpm or more and 400 rpm or less.
- the monomer component is preferably used. It is desirable to drop it into a dispersed aqueous solution of a water-insoluble colorant that contains an aqueous radical polymerization initiator in advance. Alternatively, it is also desirable to add it dropwise to the aqueous dispersion of the water-insoluble coloring material at the same time or separately from the aqueous radical polymerization initiator.
- the resin component has a high content of hydrophilic monomer component, it cannot be precipitated due to its high hydrophilicity, and it may remain in the system as a water-soluble resin component without forming charged resin pseudo fine particles. is there.
- the monomer component by dropping the monomer component into a water-insoluble colorant-dispersed aqueous solution containing an aqueous radical polymerization initiator, the copolymerization ratio between the hydrophobic monomer and the hydrophilic monomer was always kept constant.
- the chargeable resin pseudo fine particles having a desired copolymerization ratio can be obtained uniformly.
- hydrophilic monomer particularly when anionic monomers such as acrylic acid and methacrylic acid are added to the polymerization system, it is partially dependent on the characteristics of the polymer dispersant in which the coloring material is dispersed. May destabilize and cause aggregation. In order to prevent this, it is also a preferred embodiment that the anionic monomer is neutralized in advance and added in the form of sodium salt or potassium salt.
- a dispersible color material in which charged resin pseudo fine particles made of a desired copolymer are fixed on the surface of the color material is obtained.
- the dispersible colorant that has undergone the process of the present invention may have a relatively small amount of anionic monomer used in the above process.
- a large surface functional group density can be obtained, and high dispersion stability can be imparted. As a result, it becomes possible to increase the dispersion stability of the charged resin pseudo fine particles without impairing the long-term storage stability.
- the weight average molecular weight of the obtained resin is not less than 2,00 0 and not more than 2 0, 000.
- the above polymerization reaction may be controlled by using a chain transfer agent as a molecular weight adjusting agent.
- a chain transfer agent a compound having a thiol group such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, or 3-mercaptopropionic acid can be used.
- the method according to the present invention is characterized in that colored resin fine particles are obtained through an ultrafiltration step after the aqueous precipitation polymerization.
- the ultrafiltration step the dispersing agent and emulsion particles used to disperse the coloring material during the dispersing step are formed in the dispersion aqueous solution containing the dispersible coloring material formed by fixing the charged resin pseudo fine particles. Untreated resin can be removed.
- the content of the resin not fixed to the colorant in the 10% by mass aqueous solution of the dispersible colorant obtained after the ultrafiltration step is 0% relative to the dispersible colorant aqueous solution. It is preferable to be 1% by mass or less.
- the pH of the aqueous solution to be filtered is maintained at 9 or more and 13 or less, and ultrafiltration is performed by adding a water-soluble organic solvent. If the pH is lower than this, the resin not fixed to the coloring material in the aqueous solution may precipitate and clog the ultrafiltration membrane, and if the pH is higher than this, the resin will decompose and the pigment Sufficient dispersibility may not be obtained.
- Various organic bases and organic bases can be used to adjust the pH to 9 to 13, but it is desirable to use a base group that is adaptable to inkjet ink. Of these, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like, which are strong inorganic bases that are effective in a small amount, are most preferable.
- Examples of preferable water-soluble organic solvents to be added in the ultrafiltration step include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1, 2 , 6-hexanetriol, thioglycol, to Polyhydric alcohols such as xylene dallicol, glycerin, trimethylolethane, trimethylol puffer; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, jetylene glycol monomethyl ether, diethylene glycol monoethyl Alkyl ethers of polyhydric alcohols such as ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether; 2_pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-1,2-imidazolidinone, triethanolamine and
- the amount of the water-soluble organic solvent added is preferably 5% by mass or more and 40% by mass or less with respect to the aqueous solution containing the dispersible colorant.
- the type of membrane used for the ultrafiltration, the flow rate, the conditions in the flow path, etc. can be appropriately selected according to the substance to be removed.
- the water-based ink according to the present invention includes the dispersible colorant described above, at least one of a water-soluble nonionic resin and emulsion particles.
- the color material to be used is a pigment
- the content of the face is 0.1% by mass or more and 20% by mass or less, preferably 0.3% by mass or more and 15% by mass or less with respect to the ink.
- the aqueous medium water or a mixed medium containing a water-soluble organic solvent as necessary is also preferable. Further, it may contain a penetrant, an antiseptic, an antifungal agent and the like for helping the permeability to the recording medium.
- the dispersible color material used in the present invention is present in the ink in a state where the chargeable resin pseudo fine particles 2 are fixed to the surface of the color material 1. Obedience Therefore, the color material adheres to the recording medium and the adjacent color material on the recording paper via the chargeable resin pseudo fine particles fixed to the surface. Therefore, the printed matter obtained using the aqueous ink of the present invention has excellent scratch resistance.
- the ratio of the pigment and the chargeable resin pseudo fine particles should be in the range of 0.3 or more and 4.0 or less. This is also a desirable embodiment of the present invention in order to increase the scratch resistance of the printed matter formed of the color material.
- B / P ratio By setting the B / P ratio to 0.3 or more, it is possible to impart excellent scratch resistance to the printed matter by improving the adhesion between the coloring materials and between the coloring material and the recording medium.
- the structure can be expressed more effectively, resulting in higher scratch resistance on glossy paper.
- the ink as a whole becomes highly viscous, and particularly when used in an ink jet recording apparatus, the ejection stability may be impaired.
- the amount of resin relative to the color material is extremely large, the colorant of the color material may be hindered on the recording medium, and the print density may not be sufficiently obtained.
- the resin mass as used herein refers to the total amount of the chargeable resin pseudo fine particles contained in the ink according to the present invention.
- the resin mass that is clearly strongly adsorbed on the pigment surface may be included. is there. However, water-soluble resin components that can be easily separated from pigments are not included.
- the above-described BZP value can be generally obtained by differential thermogravimetric analysis, but in the present invention, it is a value measured and calculated by TGAZS D TA 85 1 manufactured by METTLER.
- the dispersible colorant or the colorant according to the present invention is used. Is a sediment obtained by centrifuging the water-based inkjet recording ink containing the coloring material under the conditions of 80,000 rotation, 2 hours, drying, weighing, and raising the temperature in a nitrogen atmosphere or in the air. The mass change before and after the decomposition temperature of the pigment and the resin component was calculated, and BZP was calculated.
- the ink according to the present invention can be suitably used for recording using an ink jet recording apparatus as described later.
- the recording medium used in this case can be used without limitation even if it is a medium such as ink jet recordable.
- the dispersible color material used in the present invention and the water-based ink containing the color material are used for an ink jet discharge type head, and also as an ink tank in which the ink is stored or for filling the ink tank It is also effective as an ink.
- the present invention brings about an excellent effect in a bubble jet type recording head and a recording apparatus among ink jet recording types.
- the basic structure disclosed in US Pat. Nos. 4, 7 2 3 and 1 29, 4 7 4 0 and 7 96 What is performed using the principle is preferable.
- This method can be applied to both the so-called on-demand type and the continuous type.
- the electric heat disposed corresponding to the sheet or waveguide holding the ink is used.
- heat energy is generated in the electrothermal transducer, and the thermal action surface of the recording head This is effective because the film is boiled and, as a result, this drive signal corresponds one-to-one and bubbles in the ink can be formed.
- the drive signal has a pulse shape, since the bubble growth and contraction is immediately and appropriately performed, and ink ejection with particularly excellent response can be achieved.
- the driving signal having the pulse shape 3 those described in US Pat. Nos. 4, 4 6 3, 3 59 and 4, 3 4 5, 2 62 are suitable. ing. Further excellent recording can be performed by employing the conditions described in US Pat. Nos. 4, 3 1 3 and 1 24 which are inventions related to the rate of temperature increase of the heat acting surface.
- the recording head is composed of a combination of a discharge port, a liquid passage, and an electrothermal transducer (linear liquid flow path or right-angle liquid flow path) as disclosed in the above specifications.
- U.S. Pat. No. 4,558,33,3, U.S. Pat. No. 4,459,600 which discloses a configuration in which the action portion is arranged in a bent region
- the present invention is effective.
- a common configuration is such that the discharge hole serves as a discharge portion of the electrothermal transducer (Japanese Patent Laid-Open No. 59-13023, etc.).
- the present invention is effective for a plurality of electrothermal transducers.
- 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 device
- a combination of a plurality of recording heads as disclosed in the above specification is used. Any of a configuration satisfying the length and a configuration as a single recording head formed integrally may be used, but the present invention can exhibit the above-described effects more effectively.
- the present invention is a replaceable chip-type recording head or recording head that can be connected to the main body of the device and can be electrically connected to the main body of the device and supply ink from the main body of the device.
- the present invention is also effective when a cartridge type recording head provided integrally with the head itself is used.
- the present invention is preferably provided as a configuration of a recording apparatus to which the present invention is applied, and it is preferable to add recovery means, preliminary auxiliary means, etc. to the recording head because the effects of the present invention can be further stabilized. It is. Specific examples of these include: a recording head cleaning means, a cleaning means, a pressure or suction means, an electrothermal converter, a heating element other than this, or a preheating means using a combination thereof. Preliminary to perform discharge separately from recording It is a discharge mode.
- each solution was gradually added dropwise for polymerization.
- Each solution consists of (1) 5.7 parts of methyl methacrylate and 1.0 part of octylmerbutane, (2) 0.3 part of acrylic acid, 0.25 part of potassium hydroxide and 20 parts of water, (3) persulfate Potassium 0.04 parts and water 20 parts.
- the obtained dispersion liquid was diluted 3 times with water, and centrifuged at 5,000 rpm for 10 minutes to remove aggregated components.
- diethylene glycol and pure water were added to diethylene glycol so that the amount of diethylene glycol was 40%, diluted 10 times, and the pH was adjusted to 13 using potassium hydroxide.
- the resulting solution was purified a total of 8 times using Fi 1 tron manufactured by Pall 1 and a Centramate ultrafiltration system. Furthermore, after diluting 10 times with pure water, purification was performed twice in total using the ultrafiltration system described above, followed by concentration to obtain dispersible colorant 1.
- the pump output and the pressure in the flow path were adjusted so that the total flow rate was 1 liter and the membrane pressure was 0.05 MPa.
- the resulting dispersible colorant 1 was dispersed in water, centrifuged at 12,000 rpm for 60 minutes, and the precipitate re-dispersed in water was dried, and the scanning electron microscope JS M-6700 When observed at 50,000 times (manufactured by JEOL Hitec Co., Ltd.), it was observed that the chargeable resin pseudo fine particles smaller than the force-pump rack, which is the coloring material, were fixed on the surface of the carbon black. .
- the form of the dispersible color material was confirmed by the same method as described above.
- the content of the resin not fixed to the color material in the aqueous dispersion material was measured by the following method.
- the resulting dispersible colorant 1 was adjusted to an aqueous solution so that the solid content was 10%, centrifuged at 25,500 rpm for 3 hours, and the supernatant aqueous solution was collected.
- the supernatant aqueous solution was dried at 120 for 2 hours, and the remaining solid content was measured. From this and the total solid content, the content of the resin not fixed to the color in the dispersible colorant aqueous solution was 0.05%.
- the weight average molecular weight of the resin was measured by Separatio sModu 1e manufactured by Wantes, the weight average molecular weight Mw in terms of polystyrene was 5,000.
- the dispersible colorant 1 has a concentration of 4%, and filtered under pressure with a membrane filter having a pore size of 2.5 microns. Obtained. The total amount was adjusted to 100 parts with water.
- ink 1 obtained as described above, recording was performed on Canon PPC paper, and ink was evaluated as follows.
- BJS700 was used as an ink jet recording apparatus used for recording.
- a specific B k text was printed on 100 sheets in succession, and the printing of the head face after printing, burnt on the heater board, and ejection stability were evaluated by the following methods and criteria. The results are shown in Table 1.
- the ink in the head is completely replaced with pure water, and then observed with an optical microscope. If no kogation is seen on the heater board, the heater A case where a kogation was found on a part of the surface was evaluated as ⁇ , and a sample showing a kogation on one side was evaluated as X.
- the ejection stability was evaluated according to the following criteria by printing 100 sheets of specific B k texts continuously and comparing the initial printed matter with the last printed matter.
- the pigment dispersion 1 used in Example 1 was set to 100 parts, under a nitrogen atmosphere, 70 While stirring with a motor, the monomer, chain transfer agent, and water-soluble radical polymerization initiator were gradually added dropwise for polymerization.
- Each solution consists of (1) benzyl dimethacrylate 4.28 parts, methoxypolyethylene glycol 1.4 2 parts and octylmel strength 0.1 parts, (2) methacrylic acid 0. 3 parts, 0.2 part of potassium hydroxide and 20 parts of water, (3) 0.04 part of potassium persulfate and 20 parts of water.
- the obtained aqueous solution of the dispersible colorant was diluted 3 times with water, and centrifuged at 5,00 rpm for 10 minutes to remove the agglomerated components. '
- Example 2 In the same manner as in Example 1, the content of the resin not fixed to the colorant in the 10% aqueous solution of the dispersible colorant 2 and the weight average molecular weight Mw of the resin were measured, and 0.0% was obtained for each. 8% and 1 6, 0 0 0.
- ink 2 was obtained in the same manner as in Example 1 except that dispersible colorant 2 was used instead of dispersible colorant 1. Further, using the obtained ink 2, an image was formed in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- the pigment dispersion liquid 1 used in Example 1 was set to 100 parts, heated to 70 in a nitrogen atmosphere, and stirred in a motor with two stages of the first stage and the second stage. Resin was synthesized.
- the first step reaction was as follows: (1) Benzyl methacrylate, 4.28 parts, methoxypolyethylene glycol methacrylate, 1.42 parts and octyl mercabtan, 0.1 part, (2) methacrylic acid, 0. Three types were used: 3 parts, potassium hydroxide 0.2 parts and water 20 parts, (3) potassium persulfate 0.04 parts and water 20 parts. After stirring at 7 Ot for 5 hours to complete the first stage polymerization, the second stage reaction was performed.
- the solution used for the second stage reaction contained 0.6 parts methacrylic acid, 0.2 parts potassium hydroxide and 20 parts water.
- the mixture is stirred at 70 for 5 hours to carry out the polymerization reaction, and the resulting aqueous solution of the dispersible colorant is diluted 10-fold with water and centrifuged at 5,000 rpm for 10 minutes to remove the agglomerated components. Removed.
- diethylene glycol and pure water were added to diethylene glycol so that the diethylene glycol was 20%, diluted 10 times, and the pH was adjusted to 13 using potassium hydroxide.
- the obtained solution was purified 8 times in total using a Fi 1 tron, Centramate ultrafiltration system manufactured by Pal 1. This time, after diluting 10 times with pure water, the above ultrafiltration system is used for purification twice, followed by concentration to color the charged resin pseudo fine particles with small color material. A dispersible colorant 3 adhered to the surface of the material was obtained.
- the pump output and the pressure in the flow path were adjusted so that the total flow rate was 1 liter and the membrane pressure was 0.05 MPa.
- ink 3 was obtained in the same manner as in Example 1 except that dispersible colorant 3 was used instead of dispersible colorant 1. Further, using the obtained ink 3, an image was formed in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 4 (1) Benzyl methacrylate 4.28 parts, methoxypolyethylene glycol methacrylate 1.42 parts and octyl mercabtan 0.1 parts, (2) methacrylic acid 0.3 parts A dispersible colorant was obtained in the same manner as in Example 1 except that 0.2 part of potassium hydroxide and 20 parts of water were used. (3) 0.04 part of potassium sulfate and 20 parts of water were used.
- ink 4 was obtained in the same manner as in Example 1 except that dispersible colorant 4 was used instead of dispersible colorant 1. Further, using the obtained ink 4, an image was formed in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- a dispersible colorant was obtained in the same manner as in Example 2 except that octyl mercabtan as a chain transfer agent was not used.
- Example 2 In the same manner as in Example 1, the content of the resin not fixed to the coloring material in the 10% aqueous solution of the dispersible coloring material 5 and the weight average molecular weight Mw of the resin were measured. 20% and 1 0 0, 0 0 0.
- ink 4 was obtained in the same manner as in Example 1 except that dispersible colorant 5 was used instead of dispersible colorant 1. Furthermore, using the obtained ink 5, an image was formed in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Dispersible colorant 6 was obtained in the same manner as in Example 1 except that the amount of octyl mercabtan used was 0.1 part and no ultrafiltration was performed.
- ink 4 was obtained in the same manner as in Example 1 except that dispersible colorant 6 was used instead of dispersible colorant 1. Further, using the obtained ink 6, an image was formed in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.
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Abstract
Description
Claims
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WO2006001508A1 (ja) * | 2004-06-24 | 2006-01-05 | Canon Kabushiki Kaisha | 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 |
WO2007111384A1 (ja) | 2006-03-24 | 2007-10-04 | Canon Kabushiki Kaisha | 水性インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置 |
US8052271B2 (en) * | 2006-12-08 | 2011-11-08 | Canon Kabushiki Kaisha | Coating liquid, ink jet recording method and ink jet recording apparatus |
US7868060B2 (en) * | 2007-02-05 | 2011-01-11 | Canon Kabushiki Kaisha | Aqueous ink, ink jet recording method, ink cartridge, recording unit, ink jet recording apparatus, and image |
US8382858B2 (en) * | 2008-06-25 | 2013-02-26 | University Of Massachusetts | Nanoparticle-textured surfaces and related methods for selective adhesion, sensing and separation |
JP2011046921A (ja) * | 2009-07-30 | 2011-03-10 | Canon Inc | 着色粒子 |
WO2011121727A1 (ja) * | 2010-03-30 | 2011-10-06 | キヤノン株式会社 | 着色粒子 |
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- 2005-06-28 WO PCT/JP2005/012294 patent/WO2006001546A1/ja active Application Filing
- 2005-12-30 US US11/321,463 patent/US20060167136A1/en not_active Abandoned
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