WO2006001513A1 - 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
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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- WO2006001513A1 WO2006001513A1 PCT/JP2005/012157 JP2005012157W WO2006001513A1 WO 2006001513 A1 WO2006001513 A1 WO 2006001513A1 JP 2005012157 W JP2005012157 W JP 2005012157W WO 2006001513 A1 WO2006001513 A1 WO 2006001513A1
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- water
- ink
- fine particles
- resin
- color material
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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
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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
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
Definitions
- the present invention relates to an aqueous ink, an ink jet recording apparatus, an ink jet recording method, and an ink jet recorded image using a dispersible colorant and a water-soluble nonionic resin or emulsion particles.
- the ink jet method is a method for recording images, characters, etc. by causing a small droplet of ink to fly from a nozzle to reach a recording medium (paper, etc.) according to various operating principles. It has features such as easy multi-coloring, high flexibility in recording patterns, and no need for development and fixing operations, and is rapidly spreading in various applications.
- full-color water-based inkjet recording technology has made remarkable progress, and it can form multicolor images that are comparable to multicolor printing by conventional plate making methods and printing by color photography methods.
- printed matter can be obtained at a lower cost than ordinary multi-color printing or printing, so that it is being widely applied to the field of full-color image recording.
- water-based ink jet recording apparatuses and recording methods have been improved.
- the performance required for water-based inks used in ink jet recording devices is as follows: (1) A uniform image with high resolution and high density without blurring or fogging can be obtained on paper (2) Clogging due to ink drying at the nozzle tip No misalignment, always good discharge response and good discharge stability, (3) good fixability of ink on paper, (4) good weather resistance of images, (5) long-term storage The stability is good.
- Color materials used in water-based 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 coloring material for water-based inkjet recording inks that can achieve high weather resistance of images, the development of coloring materials that are essentially insoluble in water, especially inks that use pigments, has been energetically advanced.
- a color material insoluble in water, particularly a pigment as a water-based ink jet recording ink, it is necessary to stably disperse the color material in water.
- a method of stabilizing the dispersion using a surfactant or a polymer dispersant (hereinafter also referred to as a dispersion resin) has been used.
- a method for chemically modifying the surface of a water-insoluble colorant has been proposed (for example, Japanese Patent Laid-Open No. Hei 10-1953).
- microcapsule type pigments in which the pigment is coated with a resin have been proposed (for example, Japanese Patent Laid-Open Nos. 8-1 8 3 9 2 0 and 2 0 3 3 4
- the colored fine particle dispersion contains a water-insoluble colorant in the presence of the dispersant. And then polymerized by adding a vinyl monomer after dispersion in an aqueous medium, and when the dispersant is dispersed with a water-insoluble colorant, it exhibits dispersion stability, and in the presence of the dispersant alone.
- a dispersion of water-based colored fine particles which is characterized by poor stability of the latex produced when the monomer is polymerized, is described as "a vinyl monomer when emulsion-polymerized into a water-insoluble colorant dispersion”.
- the affinity of the dispersant for the resulting polymer is not so high, so it is difficult for the dispersant to desorb from the pigment surface, and the dispersant is adsorbed. Because the polymerization progressed on the surface of the pigment ”, it was stated that“ it can be obtained in high yield without agglomerating the fine particle dispersion coated with the pigment surface ”. It is said that water-based inks that give an image excellent in water resistance, light resistance, and scratch resistance are obtained. Disclosure of the invention
- the object of the present invention is to solve these problems of the prior art, and to achieve a high image quality with glossiness, which is made of a dispersible color material that has sufficiently high dispersion stability and does not cause the resin component to be detached from the color material.
- the object is to provide a water-based ink capable of recording.
- another object of the present invention is to provide an ink tank, an ink jet recording apparatus, an ink jet recording method, and an ink jet recording image using such aqueous ink.
- the present inventors have intensively studied the means for solving the above-mentioned problems, and as a result, by using a dispersible color material having a novel shape, high dispersion stability is maintained and the resin component is colored.
- the present invention relates to a dispersible color material having a color material and chargeable resin pseudo fine particles smaller than the color material, wherein the color material and the chargeable resin pseudo fine particles are fixed to each other. And at least one of a water-soluble nonionic resin and emulsion particles.
- the present invention is an ink tank comprising the above water-based ink.
- an ink jet recording apparatus wherein an ink jet recording image is formed using the water-based ink.
- an ink jet recording method wherein an image is formed by an ink jet recording apparatus using the water-based ink.
- the present invention is also an ink jet recording image formed by an ink jet recording apparatus using the water-based ink.
- an aqueous ink that is excellent in gloss of a recorded image recorded on a glossy recording medium and excellent in dispersion stability.
- an ink tank, an ink jet recording apparatus, an ink jet recording method, and an ink jet recorded image using an aqueous ink that gives an image having excellent glossiness are provided.
- FIGS. 1A and 1B are schematic diagrams showing the basic structure of a dispersible colorant fused with flat chargeable resin pseudo fine particles according to the present invention.
- 2A, 2B, 2C, and 2D are schematic views of typical steps in the production method of the present invention.
- FIG. 3 is a schematic diagram for explaining the process of refining flat chargeable resin pseudo fine particles and the process of fusing them to a color material in the production method of the present invention.
- FIG. 4 is an enlarged schematic view of the charged resin pseudo fine particles of the present invention as seen from the interface side fused with the coloring material.
- FIG. 5 is an enlarged schematic view of the interface where the chargeable resin pseudo fine particles of the present invention and the color material are fused.
- FIGS. 6A and 6B illustrate a pigment peeling phenomenon that occurs in the technique of directly modifying an organic pigment with a hydrophilic group, which is typically disclosed in the above-mentioned Japanese Patent Application Laid-Open No. Hei 10-195 5 3 60. It is a schematic diagram.
- FIGS. 7A and 7B are schematic views showing a state in which a water-soluble nonionic resin forms a film in a gap between dispersible color materials on a recording medium.
- 8A, 8B, 8C, and 8D are schematic diagrams showing how emulsion particles are formed in the gaps of the dispersible color material on the recording medium.
- reference numeral 1 is a color material
- la is a color material molecule
- 2 is a charged resin pseudo fine particle
- 3 is a dispersed resin
- 4 is a monomer
- 5 is an aqueous polymerization initiator solution
- 6 is a dispersible color material
- 7 is a monomer.
- 1 is a polymerized oligomer
- 8 is a precipitate in which the oligomer is insolubilized in water
- 9 1 1 is a hydrophilic monomer part in a flat chargeable resin pseudo fine particle
- 9-2 is a flat chargeability Hydrophobic monomer unit in the resin pseudo fine particles
- 1 0 is the binding site with the color material
- 1 1 is the interface part of the flat chargeable resin pseudo fine particle with the color material
- 1 2 is the hydrophilicity directly modified to the color material
- 3 is a hydrophilic coloring material molecule
- 14 is a recording medium
- 15-1 is a water-soluble nonionic resin
- 15-4 is a water-soluble nonionic resin.
- 1 6 1 1 is a particulate emulsion
- 1 6-2 is a collapsed particle emulsion
- 1 6-3 is a fluidized emulsion
- 1 6-4 is formed by emulsion
- the term “dispersible colorant” means essentially in the presence of water or aqueous ink media without the need for addition of surfactants or polymeric dispersants.
- a color material that is dispersible in color that is, a color neo that has self-dispersibility.
- the dispersible color material used in the ink according to the present invention is a dispersible color material having a color material and chargeable resin pseudo fine particles smaller than the color material, wherein the color material and the above-mentioned charge material are charged.
- the adhesive resin pseudo fine particles are fixed.
- the coloring material is a material in which a plurality of the charged resin pseudo fine particles are scattered and fixed to the coloring material.
- the first feature of the dispersible color material used in the present invention is a dispersible color material comprising a color material and a chargeable resin pseudo fine particle, wherein the color material comprises the chargeable resin pseudo fine particle. It is in the point where it adheres.
- 1A and 1B are schematic diagrams of a dispersible color material in which the chargeable resin pseudo fine particles 2 are fixed to the color material 1, which explains the characteristics of the present invention.
- the portion 2 ′ in FIG. 1B is a portion schematically showing a state in which a part of the chargeable resin pseudo fine particles 2 fixed on the surface of the color material 1 is fused.
- the charge of the charge resin pseudo fine particles is imparted 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 adhesion to the recording medium due to the presence of the resin component adhering to the surface.
- the dispersion used in the present invention is not a simple physical adsorption state of the resin component. Dispersibility used in the present invention is because the chargeable resin pseudo fine particles, which are characteristic of the colorant, are fixed to the colorant, and the chargeable resin pseudo fine particles are not detached from the colorant surface. Color materials are also excellent in long-term storage stability.
- the chargeable resin pseudo fine particles in the present invention are resin aggregates in which the resin component is strongly aggregated, and preferably have many physical crosslinks formed therein (resin aggregate) Means that the resin component has a fine particle form or a stable form as a micro-aggregate close to it). Details of the chargeable resin pseudo fine particles will be described later.
- the state in which the charged resin pseudo fine particles are fixed to the color material in the present invention is caused by a strong interaction between the color material surface and the charge resin pseudo fine particles, and is achieved in the following state.
- Conceivable. Fig. 4 shows an enlarged schematic diagram of the interface of the chargeable resin pseudo fine particles in contact with the coloring material.
- the chargeable resin pseudo fine particles 2 are formed by intertwining polymers composed of various monomer unit compositions (indicated by 9-1 and 9_2 in the figure). Since the polymer has various structures locally at the interface with the colorant 1, its local surface energy also has 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 in good agreement locally. (The part indicated by a black circle in the figure). Further, at the interface where one chargeable resin pseudo fine particle is in contact with the colorant 1, there are a plurality of points where the surface energies of both coincide locally as shown in FIG. It is expected that the fixed state of the present application is realized by the strong interaction between these plural places. In the present invention, as indicated by 2 'in FIG. 1B, for example, a state where 30% or more of the surface area of the chargeable pseudo fine particles is in contact with the coloring material 1 is referred to as "fused" for convenience.
- the dispersible color material used in the present invention has the charged resin pseudo fine particles fixed to the color material
- such a form increases the specific surface area of the dispersible color material, and the color material surface
- the charge possessed on the surface of the chargeable resin pseudo fine particles can be distributed in many parts.
- the dispersible colorant has a high specific surface area
- the charge of the chargeable resin pseudo fine particles can be converted to the surface charge of the dispersible colorant with extremely high efficiency.
- the form of the dispersible 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 actual acid value or amine concentration of the resin component is smaller as compared with the form in which the color material is coated with the resin, as representatively shown in the No. 0 publication.
- organic pigments are insolubilized (pigmented) by crystallizing coloring material molecules by strong interaction.
- a dispersible color material in which the color material used in the present invention is an organic pigment as described above, a plurality of interaction points are distributed at the interface between the chargeable resin pseudo fine particles and the color material.
- the charged resin pseudo fine particles 11 adheres to several colorant molecules 1a in the pigment particles (see FIG. 5).
- the local colorant molecule la illustrated in FIGS. 6A and 6B,
- “pigment peeling” due to hydrophilicity by the hydrophilic group 12 does not occur in the present invention.
- 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 color material molecule.
- An organic pigment dispersible colorant imparted with high dispersibility can be obtained without breaking the crystal structure of the pigment.
- the state in which the coloring material “fixes” the chargeable resin pseudo fine particles can be easily confirmed by a technique involving the following three stages of separation. First, the color material to be confirmed is separated from the other water-soluble component (including the water-soluble resin component) contained in the ink or water dispersion by the first separation, and then the second separation. To separate the color material and the water-insoluble resin component contained in the precipitate in the first separation.
- the third separation separates the weakly adsorbed resin component from the dispersible colorant to which the charged resin pseudo fine particles are fixed, and the resin component contained in the supernatant obtained by the third separation.
- the fixation of the coloring material and the chargeable resin pseudo fine particles is confirmed by quantifying and comparing the precipitate obtained in the second separation with the precipitate obtained in the third separation.
- the ink or water dispersion in which the coloring material is dispersed Take 20 g of the ink or water dispersion in which the coloring material is dispersed, adjust the total solid content to about 10%, and use a centrifuge to 1 2, 0 0 0 Rotate at 60 minutes for the first separation.
- the lower layer sediment containing the coloring material is redispersed in pure water approximately three times the amount of the sediment, followed by conditions of 8 0, 0 0 0 rotation, 90 minutes
- the second separation is done with.
- the bottom 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, 00 rotation and 90 minutes. Remove the sediment in the lower layer.
- the sediment in the second separation and the sediment in the third separation were each taken to have a solid content of about 0.5 g and dried under reduced pressure at 30 ° C for 18 hours. Observe at 50,000 times with a scanning electron microscope. The observed dispersible colorant has a fine particle-like substance on its surface or a fine particle equivalent thereto. If it is confirmed that a plurality of small aggregates are adhered and the respective precipitates from the second separation and the third separation have the same form, this coloring material is a resin pseudo fine particle. Is determined to be fixed. Furthermore, the upper layer supernatant in the third separation is gently taken from the top so that the volume is reduced to about half, and the solid content mass is calculated from the mass change before and after heating when dried at 60 ° C for 8 hours. Calculate and the change is 1? If it is less than this, it is considered that the resin pseudo fine particles are not detached from the dispersible color material, and it can be determined that the dispersible color material has the resin pseudo fine particles fixed thereto.
- the separation conditions described above is merely a preferable example, and any other separation method or separation condition can be used as long as it 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 present invention.
- the first separation is intended to separate the coloring material contained in the ink and water dispersion and the resin component adsorbed thereto, and the water-soluble component
- the second separation is a color separation.
- the purpose is to separate the resin component adhering to the color material and the color material from the other resin component adsorbed to the color material.
- the third separation is intended to confirm that the resin component adhering to the colorant is not detached.
- the water-insoluble color material 1 is a dispersible color material that can be dispersed alone in an aqueous medium in a state where the chargeable resin pseudo fine particles 2 are fixed. It is in.
- the dispersible colorant used in the present invention is essentially self-dispersible, which can be stably dispersed in water and water-based inks without the aid of other surfactants or polymer dispersants. It is a sex color material.
- the dispersible colorant used in the present invention the dispersion of the colorant is stabilized with a polymer dispersant or other resin component or surfactant component that may be released for a long time. It is not necessary to add for the purpose. That As a result, when the dispersible color material used in the present invention is used as a water-based ink, the degree of freedom in designing with respect to components other than the dispersible color material is increased. For example, the permeability of ink such as plain paper is high. It is also possible to obtain a water-based ink that can obtain a sufficiently high printing density even on a recording medium.
- 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-fold with pure water, and concentrated to the original concentration using an ultrafiltration filter with a molecular weight cut off of 50,00.
- This concentrated solution is separated using a centrifugal separator under the conditions of 1 2, 0 0 0 rotation and 2 hours, and the sediment is taken out and redispersed in pure water. At this time, it is judged that the one in which the sediment can be redispersed well has self-dispersibility.
- the dispersible colorant used in the present invention has 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.
- the chargeable resin pseudo fine particles are scattered in large numbers and fixed to the color material.
- Such a form can be 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 resin pseudo fine particles fixed to the color material surface are fixed at a certain distance, or the color material surface is exposed between the fixed charged resin pseudo fine particles.
- the chargeable resin pseudo fine particles are sometimes partly close, In some cases, fusion can be observed, but even in this case, there is a distance between the charged resin pseudo fine particles as a whole, or there is a portion where the color material surface is exposed, and
- these states are distributed, it is obvious to those skilled in the art that the charged resin pseudo fine particles are regarded as being scattered and fixed to the coloring material.
- the water-based ink containing the dispersible colorant having the above-described characteristics used in the present invention exhibits excellent quick drying on the recording medium.
- the dispersible color material is dispersed in the ink in a form in which charged resin pseudo fine particles are fixed to the color material surface.
- the aqueous solvent in the ink (hereinafter referred to as “ink solvent”) is a pore on the recording medium (capacity between cellulose fibers in the case of plain paper) due to capillary action. In the case of paper or glossy paper, it is absorbed into the pores of the receiving layer.
- the dispersible colorant used in the present invention due to its morphological characteristics, charged 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, capillary action acts on the ink solvent existing between the color materials, and it is quickly absorbed into the recording medium.
- the use of the dispersible colorant in the form in which charged resin pseudo fine particles are scattered on the surface shows more preferable quick drying. Expected to be achieved.
- the surface functional group density of the dispersible colorant according to the present invention is preferably 2 5 0 mo 1 / g or more and less than 1, 0 0 0 ⁇ mo 1 ./g, and 2 90 mol Z g or more 9 0 More preferably, it is less than 0 xmo 1.
- the surface functional group density is lower than 2 5 0 mo 1 Z g, the long-term storage stability of the dispersible colorant may be deteriorated.
- the surface functional group density is considerably larger than 1, 0 0 0; mo 1 Z g, the dispersion stability becomes too high, and it becomes easy to permeate on the recording medium to ensure a high print density. Can be difficult.
- the surface functional group density is obtained, for example, as follows.
- aqueous hydrochloric acid (HC 1) solution is added to an aqueous dispersion or ink containing a dispersible colorant to be measured, and a centrifugal separator is used at 20 and 00 rpm for 1 hour. Allow to settle. Collect the sediment and re-disperse it in pure water, then measure the solid content by the drying method. Weigh the re-dispersed sediment, add a known amount of sodium hydrogen carbonate, and stir the dispersion further using a centrifuge at 80, 00 rpm for 2 hours. Weigh the supernatant and subtract the known amount of sodium bicarbonate from the neutralization amount obtained by neutralization titration with 0.1 N hydrochloric acid to obtain the surface functional group density as the number of mo per lg of colorant. It is done.
- HC 1 aqueous hydrochloric acid
- the color material which is a constituent component of the dispersible color material used in the present invention will be described below.
- the coloring material used in the present invention it is desirable to use a known coloring material or a newly developed coloring material that is insoluble in water and that can be stably dispersed in water together with a dispersing agent.
- examples of such substances include hydrophobic dyes, inorganic pigments, organic pigments, metal colloids, and colored resin particles.
- the dispersed particle size is in the range of 0.001 to 0.5 m (10 to 500 nm), particularly preferably 0.03 to 0.3 (30 to 300 nm). Use color materials within the range of).
- a dispersible color material using a color material having a dispersed particle diameter within this range is a preferred dispersible color material that gives an image having high coloring power and high weather resistance when used as an aqueous ink.
- Such a dispersed particle diameter is the cumulant average value of the particle diameter measured by the 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 molybdate range. , Yellow lead, chrome yellow, cadmium yellow, yellow iron oxide, titanium Erotic, chromium oxide, pyridian, cobalt green, titanium cobalt gallium, cobalt chrome green, ultramarine blue, ultramarine blue, bitumen, cobalt blue, cerulean blue, manganese violet, cobalt violet, my strength and so on.
- 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. And other hydrophobic dyes. Of these, disperse dyes are particularly preferable.
- the charged resin pseudo fine particles which are another constituent of the dispersible color material used in the present invention, are substantially insoluble in water, and the color material to be fixed is 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 (charged resin pseudo fine particles) are arranged within a certain range.
- the resin components constituting the charged resin pseudo fine particles are desirably physically or chemically cross-linked with each other, and whether or not the resin components constituting the rechargeable resin pseudo fine particles are cross-linked with each other.
- 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 chargeable resin pseudo fine particles and the polymer are immersed in an organic solvent that is a good solvent, and their solubility is compared, 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 charge resin pseudo fine particles is crosslinked.
- the average value of the cumulant dispersed particle diameter is preferably It is desirable to be in the range of 1 O nm or more and 200 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. When the center value of the dispersed particle diameter is larger than 20 O nm or the polydispersity index is larger than 0.2, the original purpose of finely dispersing and stabilizing the coloring material may not be sufficiently achieved. .
- the average value of the dispersed particle diameter is smaller than 10 nm, the form as the charged resin simulated fine particles cannot be sufficiently maintained, and the resin is easily dissolved in water. May not be obtained.
- the particle diameter is in the range of 10 nm or more and 200 nm or less, the particle diameter is smaller than that of the color material particles themselves. Is effectively expressed.
- the above preferred embodiment is the same when the dispersion particle size of the charged resin pseudo fine particles is not measurable. In that case, for example, the average diameter of the charge resin pseudo fine particles in the electron microscopic observation is It is considered to be within the preferred range described above or within the range equivalent thereto.
- the color material is an organic pigment
- the charged resin pseudo fine particles are smaller than the dispersed particle diameter of the pigment and larger than the color material molecule as described above. By doing so, a dispersible colorant having a structurally extremely stable and high dispersibility can be obtained, which is particularly desirable.
- the chargeability in the present invention refers to a state in which a functional group that is ionized in some form in an aqueous medium itself is retained, and is desirably self-dispersible by the chargeability. Therefore, whether or not it is a chargeable resin pseudo fine particle is determined by a publicly known and arbitrary method, for example, the surface of the charge resin pseudo fine particle.
- the resin component constituting the chargeable resin pseudo fine particles is not limited to any resin component such as any commonly used natural or synthetic polymer, or a polymer newly developed for the present invention. It can be used without.
- resin components that can be used include acrylic resins, styrene / acrylic resins, polyester resins, polyurethane resins, polyurea resins, polysaccharides, and polypeptides.
- the weight of the monomer component having a radically polymerizable unsaturated bond represented by acrylic resin or styrene / acrylic resin is used.
- a polymer or copolymer can be preferably used.
- monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, etc., and salts thereof, styrene sulfonate
- Anionic hydrophilic monomers having a sulfonic acid group such as acid, sulfonic acid -2-propylacrylamide, acrylic acid-2-sulfonic acid ethyl, methacrylic acid 2-ethyl sulfonic acid, butylacrylamide sulfonic acid, and the like, and salts thereof
- anionic hydrophilic monomers having a phosphonic acid group such as methacrylic acid mono-2-phosphonate, acrylic acid_2-phosphonate, and the like.
- the chargeable resin pseudo fine particles preferably used in the present invention preferably have a glass transition temperature of 40 ° C. (: ⁇ 60 ° C.) By being within this range, the chargeable resin The pseudo fine particles are imparted with a high film-forming property (film-forming ability), and adjacent color materials on the recording paper can be formed to form a strong colored film. By using a dispersible color material having such a configuration, high scratch resistance can be imparted to the printed matter obtained.
- 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 soxle-extracting the precipitate with an organic solvent such as THT (terahydrofuran) 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 (trade name) manufactured by MET LER may be used.
- aqueous dispersion in which a dispersible colorant and a water-soluble nonionic resin coexist, it can be separated using a centrifuge.
- a centrifuge For example, when separation is performed under a centrifugal separation condition of 1 2 0 00 0 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-described conditions. Further functions can be imparted to the charged resin pseudo fine particles fixed to the coloring material.
- Specific examples of the monomer include a hydrophobic monomer, an anionic hydrophilic monomer as described above, and a nonionic hydrophilic monomer.
- hydrophobic monomers examples include methyl acrylate, acrylate acrylate, isopropyl acrylate, 1-propyl acrylate, _n_propyl acrylate, 1-t-butyl acrylate, benzyl acrylate, and methacrylate.
- Styrene monomers such as benzyl itaconate; maleate esters such as dimethyl maleate; fumarate esters such as dimethyl fumarate; acrylonitrile, methacrylonitrile, vinyl acetate and the like.
- hydrophilic monomer having an anionic group examples include those described above.
- nonionic hydrophilic monomer there are a radical polymerizable unsaturated bond and a strong hydrophilicity in a structure such as (meth) hydroxylethyl acrylate and (meth) hydroxylpropyl acrylate.
- a radical polymerizable unsaturated bond and a strong hydrophilicity in a structure such as (meth) hydroxylethyl acrylate and (meth) hydroxylpropyl acrylate.
- Monomers containing an alkylene oxide group other known or new various oligomers, macromonomers, etc. can also be used without limitation.
- the alkylene oxide group-containing monomer is excellent in copolymerizability with the hydrophobic monomer component, and provides uniform surface properties of the chargeable resin pseudo fine particles, and uniform adhesion to the colorant and fusion. From this viewpoint, a favorable result is given.
- the chargeable resin pseudo fine particles are composed of a copolymer of monomer components including at least one hydrophobic monomer and at least one hydrophilic monomer among the monomers listed above. That is a desirable mode.
- the chargeable resin pseudo fine particles are composed of a copolymer of monomer components including at least one hydrophobic monomer and at least one hydrophilic monomer among the monomers listed above. That is a desirable mode.
- at least one type of hydrophobic monomer good adhesion to the colorant and thermal stability can be achieved by using at least one type of hydrophilic monomer.
- Shape control and dispersion stability can be imparted respectively. Therefore, By using these monomers at the same time, it is possible to obtain chargeable resin pseudo fine particles that can always adhere well to the colorant and can impart good dispersion stability.
- the synthesis of the chargeable resin pseudo fine particles and the fixing to the color material can be carried out by following the procedure of a known method for synthesizing the charge resin pseudo fine particles or a method for combining the charge resin pseudo fine particles and the color material.
- the present inventors as a result of intensive studies, are a dispersible color material having a color material and charged resin pseudo fine particles 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 color material.
- a suitable method for producing a dispersible color material that can easily obtain the dispersible color material used in the present invention will be described.
- the dispersible colorant used in the present invention having the above-described characteristics can be manufactured very simply by applying the aqueous precipitation polymerization method under the following conditions. It became.
- a dispersed aqueous solution of the water-insoluble colorant is prepared by dispersing the water-insoluble colorant using a dispersant.
- the chargeable resin pseudo fine particles are fixed to the coloring material by a step of aqueous precipitation polymerization of the radical polymerizable monomer using an aqueous radical polymerization initiator.
- 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 firmly fixed to the colorant in a uniform and scattered state. 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. And the chargeable resin pseudo fine particles are satisfactorily achieved.
- preferred embodiments of the above manufacturing method will be described in more detail.
- a water-insoluble colorant preferably used in the present invention as described above is dispersed with a dispersing agent to obtain an aqueous dispersion.
- a dispersing agent 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.
- a hydrophobic portion that exhibits sufficient water solubility and serves as an adsorption site for the surface of the colorant fine particles and the radical polymerizable monomer added in the polymerization step, particularly the hydrophobic monomer to the oil droplet interface.
- a hydrophobic portion that exhibits sufficient water solubility and serves as an adsorption site for the surface of the colorant fine particles and the radical polymerizable monomer added in the polymerization step, particularly the hydrophobic monomer to the oil droplet interface.
- the hydrophobic monomers used in the subsequent polymerization step be present as a unit constituting the dispersing agent. From the viewpoint of easily inducing fixation to the color material, it is preferable.
- 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.
- the polymer can be polymerized with a monomer having an ionic group. It can be produced by reacting a monomer with a monomer in a non-reactive solvent in the presence or absence of a catalyst.
- a styrene-acrylic polymer compound obtained by polymerizing a monomer having an ionic group as described above and a styrene monomer as essential components, or a monomer having an ionic group, and the number of carbon atoms It is clear that good results are obtained when a dispersant selected from ionic group-containing acryl-based polymer compounds obtained by polymerizing a (meth) acrylic acid ester monomer of 5 or more as an essential component is used. It has become. In this case, when the obtained dispersible colorant is intended to have an anionic group in particular, an 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.
- a cationic dispersion having an acid value of not less than 100 and not more than 2500 from the viewpoint of both maintaining the dispersion stability of the coloring material during the polymerization process In the case of using an agent, it is also desirable to use those having an amine number of 1500 or more and 300 or less. When the acid value and amine value are smaller than these lower limits, 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.
- the dispersing agent Before the pseudo fine particles adhere to the coloring material, the dispersing agent may be detached from the coloring material surface, and the dispersed state may not be maintained. In addition, when the acid value and amine value are larger than these upper limit values, 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 it is preferable to select a dispersant having a carboxyl group as an anionic group from the viewpoint of not inhibiting the adhesion of the resin fine particles to the coloring material.
- the colorant preferably has a dispersed particle diameter of from 0.0 Ol m to 0.5 m (10 nm to 500 nm or less). ), Particularly preferably within the range of 0.03 zm 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 viewpoints of the above-described coloring power, weather resistance of the image, and dispersion stability. .
- the dispersed 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 becomes 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 aqueous dispersion.
- it is important to narrow the particle size distribution of the coloring material in order to surely induce fixing due to heteroaggregation of the coloring material and the charged resin pseudo fine particles.
- the polydispersity index of the color material is in the range of 0.25 or less, the dispersible color material obtained has excellent dispersion stability. Become.
- 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. Based on the dynamic light scattering method according to 0 (trade name), the average particle size and polydispersity index determined by 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 coloring material used in the present invention include a disperser such as a paint shaker, a sand mill, an agitator mill, a three-neck one-mill, a high-pressure homogenizer such as a microfluidizer, a nanomizer, and an optimizer. Any dispersion method that is generally used for each color material, such as an ultrasonic disperser, is not limited.
- aqueous precipitation polymerization which is a step of synthesizing the chargeable resin pseudo fine particles, which is a feature of the present invention, and fixing it to a coloring material.
- the present invention is not limited at all by the embodiments described below.
- 2A, 2B, 2C and 2D are process diagrams schematically illustrating the process flow of the manufacturing method. The process up to obtaining a dispersible colorant by this step is considered as follows. First, as shown in FIG. 2A, a dispersed aqueous solution in which the coloring material 1 is dispersed in the aqueous solution by the dispersant 3 is prepared.
- coloring material 1 is dispersed and stabilized by adsorption of dispersant 3, and this adsorption is in a thermal equilibrium state.
- FIG. 2A The aqueous dispersion prepared in step 1 is heated while being stirred, and the monomer component 4 is added to the dispersion together with, for example, the aqueous radical polymerization initiator 5 (see FIG. 2B).
- the added aqueous radical polymerization initiator 5 generates radicals by cleaving when the temperature is raised.
- a small amount of the 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 step by step the process shown in FIG. 2C until the monomer 4 is polymerized to produce a dispersible colorant.
- the oligomer 7 formed by the polymerization reaction of the monomer components becomes insoluble in water, and precipitates from the aqueous phase to form a precipitate 8.
- the charged resin pseudo fine particles 2 are formed together.
- the charged resin pseudo fine particles 2 further cause hetero-aggregation using the hydrophobic surface of the color material 1 in the dispersion aqueous solution as a nucleus, and the resin component constituting the surface of the color material 1 and the charge resin pseudo fine particles 2 is hydrophobic. Strongly adsorbed by interaction. At this time, the polymerization reaction continues to proceed inside the chargeable resin pseudo fine particles 2, and changes to a more energy-stable form while increasing the adsorption point with the color material 1. At the same time, since the physical crosslinks are highly formed inside the chargeable resin pseudo fine particles 2, the form that adsorbs the color material 1 most stably is fixed and fixed. On the other hand, the coloring material 1 is stabilized by fixing the plurality of chargeable resin pseudo fine particles 2, and the dispersing agent 3 in an equilibrium state is detached from the surface of the coloring material 1.
- 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 chargeable resin pseudo fine particles which are aggregates of resin components, have hydrophilic monomer units 9-11, hydrophobic monomer units 9-12, etc. distributed in an arbitrary manner. There is a distribution of local surface energy, and there are many adsorption points 10 that coincide with the surface energy of the coloring material.
- FIG. 5 shows an enlarged schematic view of the adhesion interface between a part of the charged resin pseudo fine particles 11 and a part of the molecules 1a of the colorant particles.
- the field of charged resin pseudo fine particles The surface 11 adheres stably to the surface according to the surface shape of some of the molecules 1 a of the coloring material while adsorbing the adsorption point 10 shown in FIG.
- fixation to the coloring material is achieved by fixing in a form in which adsorption is stabilized.
- the dispersible colorant having the above-described configuration is easily formed (see FIG. 2D).
- the charge resin pseudo fine particles are between By the electrostatic repulsive force acting on each other, the charged resin pseudo fine particles are scattered and fixed to the coloring material, and the preferred form described above is obtained.
- the polymerization reaction conditions vary depending on the properties of the polymerization initiator, dispersant, and monomer used.
- the reaction temperature is 100 ° C. or lower, preferably 40 ° C. or higher and 80 ° C. or lower. is there.
- 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 containing at least one kind of hydrophobic monomer and at least one kind of hydrophilic monomer is polymerized to obtain the charged resin pseudo fine particles
- the monomer is used. It is desirable to add the components dropwise to an aqueous dispersion of a water-insoluble colorant that already contains an aqueous radical polymerization initiator. 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 different properties is always kept constant. It is desirable. If the monomer mixture is added to the polymerization system in excess of the amount of monomer consumed in the polymerization reaction within a certain period of time, only the specific monomer species are polymerized in advance, and the remaining monomers are preceded. There is a tendency for the polymerized monomer to be polymerized after being consumed, and in this case, A large nonuniformity occurs in the properties of the fat pseudo fine particles. Among the charged resin simulated fine particles thus produced, those having a particularly large hydrophilic monomer component content may not be able to adhere to the surface of the color material.
- an anionic monomer such as acrylic acid or methacrylic acid as a hydrophilic monomer
- it may partially depend on the characteristics of the polymer dispersant in which the coloring material is dispersed. May become unstable and cause agglomeration.
- 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 to the surface of the color material is obtained by controlling many control factors. Can do.
- the dispersible colorant having undergone the process of the present invention can obtain a large surface functional group density even if the amount of anionic monomer used in the above process is relatively small. 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 water-soluble nonionic resin added to the ink which is another feature of the ink according to the present invention, will be described.
- the water-soluble nonionic resin used in the present invention is preferably a copolymer of the nonionic hydrophobic monomer as mentioned above and a nonionic hydrophilic monomer. That is, by using a nonionic hydrophobic monomer as a resin component, high fixability of the dispersible colorant on the recording paper can be obtained, while a nonionic hydrophilic monomer is used as a resin component.
- the water-soluble nonionic resin 15 5-1 can penetrate well between the color material on the recording paper (see Fig.
- the water-soluble nonionic resin that penetrates between the coloring material and the coloring material forms a resin film 15-2 (see FIG. 7B), and makes it possible to give the recorded image smoothness. That is, the water-soluble nonionic resin having such a structure contained in the ink is used for the coloring material on the recording paper. By filling the gap, forming a film, and smoothing the recorded image surface, the glossiness of the image can be improved.
- water-soluble nonionic resin examples include polymers of monomers containing an alkylene oxide group, or monomers or vinyl alcohols containing an alkylene oxide group, and styrene or methyl methacrylate. And a copolymer thereof.
- Styrene / CH 2 C (R,) COOR 2 40 ⁇ 70.Z60 ⁇ 30 copolymer.
- R, H or CH 3
- R 3 H or CH 3
- the ink contains a water-soluble chargeable resin copolymerized with an anionic or cationic monomer instead of the nonionic hydrophilic monomer, it is not preferable from the following points.
- the chargeable resin pseudo fine particles of the dispersible colorant and the water-soluble chargeable resin are electrically contradictory, that is, when the chargeable fine particles are anionic and the water-soluble chargeable resin is cationic.
- the charged fine particles are cationic and the water-soluble chargeable resin is anionic, the ions of the dispersible colorant and the ions of the water-soluble chargeable resin are ion-bonded and aggregated.
- the chargeable resin pseudo fine particles of the dispersible colorant and the water-soluble chargeable resin are electrically homogeneous, the water-soluble chargeable resin will remain in the gap between the dispersible colorant and the dispersible colorant. It is more preferable to use a nonionic hydrophilic monomer because the effect of improving the glossiness of the recorded image may be reduced.
- the water-soluble nonionic resin used in the present invention preferably has a weight average molecular weight Mw of 1,000,000 to 100,000, and more preferably 2,000 to 30,000. Furthermore, it is preferably 2,000 to 10,000. Within this range, fluidity for imparting smoothness to the recorded image can be obtained. Furthermore, the content of the water-soluble nonionic resin is as follows. By adding 1% by mass or more, smoothness can be imparted to the recorded image. Further, although there is no particular limitation, since the viscosity of the ink is increased and the fluidity for imparting smoothness to the recorded image may be lost, the content in the ink may be 10% by mass or less. preferable.
- the charged fine particles of the dispersible coloring material can be used. It is preferable that it is electrically homogeneous or nonionic. That is, if the charged fine particles are anionic, the emulsion particles are preferably anionic, and if the charged fine particles are cationic, the emulsion particles are preferably cationic. If the electrical properties conflict, ions of the dispersible colorant and ions of the emulsion particles may be ion-bonded and agglomerated, thereby losing dispersibility. Therefore, it is necessary that the emulsion particles are electrically homogeneous with the chargeable fine particles of the dispersible colorant or nonionic.
- the emulsion particles have an average particle diameter of 10 nm to 80 nm in the aqueous ink. If the average particle size is larger than 1 O nm, the image stays on the recording medium without penetrating the recording medium, and the smoothness can be given to the image by filling the gap between the dispersible colorant and the dispersible colorant. Improved glossiness can be obtained. On the other hand, if the average particle size of the emulsion particles exceeds 80 nm, the gap between the dispersible colorant and the dispersible colorant will be filled rather than the effect of filling the gap between the dispersible colorant. Smoothness may be lost.
- the glass transition temperature (T g) of the emulsion particles is from ⁇ 40 ° C. to 60 ° C. By being within this range, a film is formed in the gap between the dispersible colorant and the dispersible colorant, and smoothness and film strength are imparted to the recorded image surface, and either glossiness or scratching of the recorded image is provided. An improvement can be obtained.
- T g glass transition temperature
- the following three effects are typical. Fruits. However, composite systems with these effects can also be selected by adding emulsion particles with different Tg.
- the emulsion particles 1 6 _ 1 dispersed in the form of particles in the water-based ink are stacked while maintaining the state of the particles during recording image formation, and fills the gap between the dispersible colorant and the dispersible colorant.
- First effect (see Fig. 8A): Emulsion particles that were dispersed in the form of particles in the aqueous ink were crushed during recording image formation, and piled up while maintaining the state of particles 16-2
- the second effect is to form a film by filling the gap between the emulsion particles and emulsion particles (see Fig. 8B); and the emulsion particles dispersed in the form of particles in the aqueous ink are in the state of the particles when the recorded image is formed.
- Emulsion 1 6-3 that has lost its fluidity and flows into the remaining gap, fills the gap, and can obtain the third effect of forming the film 1 6-4 (Fig. 8 C). And 8D).
- Tg any one of the first, second and third effects
- the gloss of the recorded image can be improved by the action of the emulsion particles as described above.
- Such emulsion particles are commercially available as a glaze (matting agent) used to improve the glossiness of water-based adhesive compositions or printed materials.
- Japanese Patent Nos. 3 3 5 0 5 1 8 and 3 3 3 9 6 2 9 describe a water-based emulsion composed of urethane resin. These aqueous emulsions exhibit a certain amount of solubility in water (most preferably methylethyl ketone, etc.) by synthesizing a urethane resin in a solvent, neutralizing the aqueous system, and then distilling off the organic solvent while stirring. Can be produced.
- Japanese Patent Laid-Open No. 10-2 7 9 8 7 9 discloses that two or more monomer components are supplied to an aqueous system all at once or continuously. A method for supplying a water-based emulsion is disclosed.
- aqueous emulsions it is necessary to incorporate a monomer having a ionic functional group such as a hydroxyl group or a sulfone group in the resin in order to stably disperse in the aqueous system. Therefore, in general emulsion polymerization or suspension polymerization, monomers having these ionic functional groups may not be sufficiently contained in the emulsion particles.
- a polymer having an ionic functional group is polymerized in advance, and then the polymerization solvent is distilled off, or a monomer having an ionic functional group and a hydrophobic monomer in an aqueous phase system are mixed with an aqueous system.
- a method of producing water-based emulsion by precipitation polymerization is adopted.
- the emulsion suitable for the present invention may be produced by any one of the above two methods, and the polymer constituting the emulsion may be any resin.
- the content of emulsion particles by adding 0.1% by mass or more in the ink, smoothness can be imparted to the recorded image. Further, although there is no particular limitation, it is more preferable to set the content to 10% by mass or less in the ink. This is because if the content is more than 10% by mass, the viscosity of the ink becomes high and the fluidity for imparting smoothness to the recorded image may be lost.
- the water-based ink according to the present invention includes the dispersible colorant described above and at least one of a water-soluble nonionic resin and emulsion particles.
- the colorant used is a pigment
- the pigment content is 0.1 mass relative to the total mass of the ink? It is set to not less than 20% by mass and not more than 20% by mass, preferably not less than 0.3% by mass and not more than 15% by mass.
- the aqueous medium water or a mixed medium containing a water-soluble organic solvent as necessary is also preferable. Further, it may further contain a penetrating agent, an antiseptic agent, an antifungal agent and the like for helping to penetrate the recording medium.
- the dispersible colorant 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 colorant 1 as shown in FIGS.
- the ink according to the present invention can be suitably used for recording using an ink jet recording apparatus as described later.
- a recording medium used at this time any medium capable of ink jet recording can be used without limitation.
- the dispersible color material used in the present invention and the water-based ink containing the color material are used in an inkjet discharge head, and also as an ink tank containing the ink, or as a filling ink Can also be used effectively.
- the present invention provides excellent effects in a bubble jet type recording head and recording apparatus among ink jet recording types.
- the basic configurations disclosed in US Pat. Nos. 4, 7 2 3, 1 2 9 and 4, 7 4 0, 7 96 It is preferable to use the principle.
- This method can be applied to both the so-called on-demand type and the continuous type.
- the on-demand type it is arranged corresponding to the sheet or liquid channel holding the ink.
- At least one of the selected electrothermal transducers to give a rapid temperature rise exceeding nucleate boiling corresponding to the recorded information The Therefore, the coloring material 1 is bonded to the recording medium and the adjacent coloring material on the recording medium via the chargeable resin pseudo fine particles 2 fixed to the surface. Accordingly, the printed matter obtained using the water-based ink of the present invention has excellent scratch resistance.
- B / P ratio By setting the B / P ratio to 0.3 or more, the adhesion between the coloring materials and between the coloring material and the recording medium can be improved, and excellent scratch resistance can be imparted to the printed matter.
- a dispersible color material formed by fixing charged resin pseudo fine particles composed of a resin component having a glass transition temperature of 40 ° C. or more and 60 ° C.
- the film property can be expressed more effectively, and the result is that the scratch resistance of glossy paper is further increased.
- BZP is significantly larger than 4.0, the ink becomes highly viscous as a whole, and when used in an ink jet recording device, ejection stability may be impaired.
- the amount of resin relative to the color material is extremely large, the coloring property of the color material on the recording medium may be hindered and the print density may not be sufficiently obtained.
- the water-based ink has excellent scratch resistance and is compatible with ejection stability in the ink jet recording apparatus. Can do.
- the resin mass as used herein refers to the total mass of the chargeable resin pseudo fine particles contained in the ink according to the present invention, and may include other resin components that are clearly strongly adsorbed on the pigment surface. is there. However, water-soluble resin components that can be easily separated from pigments are not included.
- the above-mentioned B.ZP value can be generally obtained by differential thermogravimetry, but in the present invention, TGAZSDTA851 (trade) manufactured by METTLER
- TGAZSDTA851 trade
- METTLER METTLER
- the configuration of the recording head in addition to the combined configuration of the discharge port, the waveguide, and the electrothermal transducer as disclosed in each of the above patent specifications (the linear liquid channel is a right angle liquid channel), US Pat. No. 4, 5 5 8, 33 3 3 and US Pat. No. 4, 4 5 9, 600 which disclose a configuration in which the heat acting portion is bent are arranged.
- the present invention is also effective for other configurations.
- a configuration in which a common discharge hole is used as an electrothermal converter discharge part Japanese Patent Laid-Open No. 59-1300. The present invention is effective.
- 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-mentioned patent specification is used. Any of the configuration satisfying the length and the configuration as a single integrally formed recording head can be applied, but the present invention can exhibit the above-described effects more effectively.
- a recording head cleaning means for example, 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 by a combination thereof, recording and Is a preliminary discharge mode in which another discharge is performed.
- a recording sink 1-1 according to Example 1-11 was prepared as follows. First, a mixed liquid composed of 10 parts of carbon black, 6 parts of glycerin, 10 parts of styrene-acrylic acid resin dispersant, and 74 parts of water was subjected to 1,500 rpm by using a sand mill manufactured by Kanada Rika Kogyo Co., Ltd. For 5 hours to obtain Pigment Dispersion Liquid 1. For sand mill, zirconia beads with a diameter of 0.6 mm were used, and the filling rate in the pot was 70%.
- the carbon black used in this example is B lack Pearls 880 (trade name; hereinafter abbreviated as BP 880) promoted by Cabot, USA.
- the obtained pigment dispersion liquid 1-11 was stably dispersed with an average dispersion particle diameter of 98 nm, and the polydispersity index was 0.16.
- 100 parts of the pigment dispersion 1 and 1 obtained above were heated to 70 ° C in a nitrogen atmosphere, and the following three liquids were charged into the dropping device respectively while stirring with a motor.
- the liquids were: (1) 5.5 parts of methyl methacrylate, (2) 0.5 parts of acrylic acid, 0.25 parts of potassium hydroxide and 20 parts of water, (3) potassium persulfate 0.05. And 20 parts of water.
- the obtained dispersion was diluted 10-fold with water and subjected to centrifugal separation at 5,000 rpm for 10 minutes to remove aggregated components. Thereafter, the mixture was further purified by centrifuging at 12,500 rpm for 2 hours to obtain a dispersible colorant 11 as a sediment.
- This dispersible colorant 1 1 1 is dispersed in water, centrifuged at 12,000 rpm for 60 minutes, and the precipitate re-dispersed in water is dried, and the scanning electron microscope JS M-6700 (Product name; manufactured by JEOL Hi-Tech Co., Ltd.) and observed at a magnification of 50,000 times, it was found that the charged resin pseudo fine particles smaller than the force of the color material, Bonn Black, were fixed on the surface of the carbon black. Observed. In this example, the form of the dispersible colorant was also confirmed for the other colorant described later by the same method as described above.
- Dispersible colorant obtained as described above 1 1 1 Power To be contained in the ink at a concentration of 4%, the following component composition is mixed with this, and a membrane having a pore size of 2.5 microns The pressure was filtered through a filter 1 to prepare the recording ink 1 1 1 of this example. The total amount of ink was adjusted with water so as to be 100 parts.
- Example 1 1 1 Using 100 parts of the pigment dispersion 1 1 obtained in 1 and heating to 70 ° C in a nitrogen atmosphere, the following three liquids were respectively added to the dropping device while stirring with a motor. Filled and added dropwise in 6 hours to carry out polymerization. (1) Benzyl methacrylate 4.5, butyl acrylate 1.2 parts, (2) acrylic acid 3 parts, potassium hydroxide 0.15 parts and water 20 parts, (3) potassium persulfate 0. 05 parts and 20 parts of water.
- the dispersible colorant 1-2 obtained above is contained in the ink at a concentration of 4%, and the following component composition is mixed with it, and further added with a membrane filter having a pore size of 2.5 microns.
- recording ink 1-2 of this example was prepared. The total amount of ink was adjusted with water so as to be 100 parts.
- Recording ink 1 to 13 was prepared as follows. First, with the color material Pigment Red (PR) 122 (Ciba Specialty 'CROMOPHTAL MAZENTA DMQ (trade name) manufactured by Chemicals) 10 parts, Glycerin 6 parts, Styrene monoacrylic dispersant 10 parts, Water 74 parts The mixed liquid having composition was dispersed with a sand mill manufactured by Kaneda Rika Kogyo Co., Ltd. for 1,500 rpm for 5 hours to obtain Pigment Dispersion Liquid 5. In the sand mill, 0.6 mm diameter zirconia beads were used, and the filling rate in the pot was 70%.
- PR Color material
- 122 Ciba Specialty 'CROMOPHTAL MAZENTA DMQ (trade name) manufactured by Chemicals
- Glycerin 6 parts Glycerin 6 parts
- Styrene monoacrylic dispersant 10 parts Water 74 parts
- the mixed liquid having composition was dispersed with a sand
- the obtained pigment dispersions 1 to 13 were stably dispersed with an average dispersion particle size of 88 nm, and the polydispersity index was 0.13.
- the dispersible colorant 1 to 3 obtained above is contained at a concentration of 4% in the ink, and the following component composition is mixed with this. Further, a membrane filter having a pore size of 2.5 microns is prepared. And recording ink 1 to 3 of this example was prepared. The total amount of ink was adjusted with water so as to be 100 parts.
- Recording links 1 to 4 were produced in the following manner.
- a composition consisting of 10 parts of FAST YELLOW7413 (trade name) (Vigment Yellow 74; manufactured by Sanyo Dye Co., Ltd.), 6 parts of glycerin, 10 parts of styrene-dimethylaminoethyl acetate dispersant, and 74 parts of water as a coloring material.
- FAST YELLOW7413 trade name
- glycerin 10 parts of styrene-dimethylaminoethyl acetate dispersant
- 74 parts of water a coloring material.
- water and an acetic acid slightly larger than the amine value were added in advance, and the mixture was stirred at 80 ° C. to obtain an aqueous solution.
- the obtained pigment dispersion liquid 1-4 was stably dispersed with an average dispersion particle diameter of 111 nm, and the polydispersity index was 0.16.
- the solution consists of (1) 4.2 parts benzyl methacrylate, (2) dimethylaminoethyl acrylate 1.8 parts and water 20 parts, (3) potassium persulfate 0.05 parts and water 20 parts. .
- the resulting dispersion was diluted 10-fold with water, centrifuged at 5,000 rpm for 10 minutes to remove the agglomerated components, and then further subjected to conditions of 12,500 rpm for 2 hours. By centrifuging, dispersible colorant 1-14 which is a sediment was obtained.
- the dispersible colorant 1 to 4 obtained above is contained in the ink at a concentration of 4%, and the following component composition is mixed with this, and the pore size is 2.'5 microns.
- the ink was subjected to pressure filtration with a plain filter 1 to prepare a recording ink 1-4 of this example.
- the total amount of ink was adjusted with water so as to be 100 parts.
- the dispersible colorant 1 1 1 obtained above is contained at a concentration of 4% in the ink, and the following component composition is mixed with this. Further, a membrane filter having a pore size of 2.5 microns is prepared. The ink for recording 11 of this comparative example was prepared. The total amount of ink was adjusted with water so as to be 100 parts.
- the dispersible colorant obtained above was added to the ink at a concentration of 4%, and the following composition was mixed with it.
- a membrane fill with a pore size of 2.5 microns was prepared.
- the ink for recording 1 and 2 of this comparative example containing a water-soluble anionic resin was prepared by filtration under pressure. The total amount of ink was adjusted to 100 parts with water. .
- the dispersible colorant 1 to 3 obtained above is contained in the ink at a concentration of 4%, and the following component composition is mixed with this, and a membrane filter having a pore size of 2.5 microns is further mixed. Then, the ink for recording 1 to 13 of this comparative example was prepared. The total amount of ink was adjusted with water so as to be 100 parts.
- the glass transition temperature (Tg) of the charged resin pseudo fine particles was measured by the following procedure.
- the dispersible colorant was acidified with hydrochloric acid, and the solid content obtained after acid praying was subjected to Soxhlet extraction using THF (tetrahydrofuran), and THF was distilled off to obtain a charged resin pseudo fine particle component.
- THF tetrahydrofuran
- ME differential scanning calorimetry
- Each dispersible colorant is dispersed in water and dried, and observed with a scanning electron microscope JSM-6700 (trade name; manufactured by JEOL Hi-Tech Co., Ltd.) at a magnification of 50,000 times.
- JSM-6700 (trade name; manufactured by JEOL Hi-Tech Co., Ltd.) at a magnification of 50,000 times.
- the state in which the fat fine particles are fixed and the properties of the fixed resin fine particles were evaluated as follows.
- Dilute 50-dispersion of each dispersible colorant 10 times with pure water concentrate to the original concentration using an ultrafiltration filter with a molecular weight cut off of 50, 00, and concentrate was separated using a centrifugal separator under the conditions of 1 2, ..0 0 0 rotation, 2 hours.
- the separated sediment is taken out and redispersed in pure water, and is visually dispersed uniformly, and the average particle size measured by the dynamic light scattering method described later is the particle size before the operation.
- each dispersible colorant was placed in a glass sample bottle in the form of a dispersed aqueous solution, and after standing at 60 ° C for 1 month in a sealed 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-8000 (trade name) manufactured by Otsuka Electronics Co., Ltd., and the cumulant average value was defined as the average particle size.
- the surface functional group density of each dispersible colorant was determined as follows. Add a large excess of hydrochloric acid (HC 1) to the aqueous dispersion of the coloring material, and use a centrifuge to re-disperse the sediment that has settled at 20,000 rpm for 1 hour in pure water. The sediment was weighed to determine the rate, and a dispersion obtained by adding a known amount of sodium bicarbonate and stirring was further sedimented using a centrifuge at 80,000 rpm for 2 hours. Weigh the supernatant and subtract the known amount of sodium hydrogen carbonate and the blank value obtained by measuring pure water from the neutralization amount obtained by neutralization titration with 0.1 HC 1 aqueous solution to calculate the surface functional group density. did.
- HC 1 hydrochloric acid
- the gloss of printed matter was measured using maicrohazemater (trade name; BYK Gardner) and evaluated according to the following criteria.
- G L O S S value (20 ° gloss) is 50 or more
- G L O S S value (20 ° gloss) is 40 or more and less than 50
- G L ⁇ S S value (20 ° gloss) is 30 or more and less than 40
- G L O S S value (20 glossiness) is 20 or more and less than 30
- the scratch resistance of the printed matter was evaluated by the following criteria by rubbing the printed portion with 40 g of sylbon paper with a weight of '' cm 2 three times, and visually observing the degree of shaving of the image portion.
- Table 1-12 Main composition of each ink and evaluation result of formed image
- Pigment Blue (PB) 15 3 (Ciba 'Speciality' Chemicals IRI GAL I TE BLUE 8700 (trade name)), glycerin 6 parts, styrene monoacrylic acid resin dispersant 10 parts, and A mixture of 74 parts of water was dispersed for 5 hours at 1,500 rpm using a sand mill manufactured by Kanada Rika Kogyo Co., to obtain Pigment Dispersion 2-1. In the sand mill, 0.6 mm diameter zirconia beads were used, and the filling rate in the pot was 70% '.
- As the styrene-acrylic acid resin dispersant water and potassium hydroxide equivalent to the acid value described above were added in advance and stirred at 80 ° C. to obtain an aqueous solution.
- the obtained pigment dispersion 2-1 was stably dispersed with an average dispersion particle size of 11 nm, and the polydispersity index was 0.16.
- the obtained dispersion was diluted 10-fold with water and subjected to centrifugal separation at 5,000 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 dispersible colorant 2-1 as a precipitate.
- This dispersible colorant 2 _ 1 is dispersed in water, centrifuged at 12,000 rpm for 60 minutes, the precipitate is redispersed in water, dried, and scanned by electron microscope JS M-6700 (Product name: manufactured by JEOL Hitec Co., Ltd.) As a result, it was observed that the chargeable resin pseudo fine particles smaller than the carbon material Bragg, which is the coloring material, were fixed on the surface of the bonbon black. For other color materials described later in this example, the form of the color material was confirmed by the same method as described above.
- the resulting dispersion is diluted 10-fold with water, centrifuged at 5,000 rpm for 10 minutes to remove the agglomerated components, and then centrifuged at 12,500 rpm for 2 hours.
- dispersible colorant 2-2 which was a precipitate, was obtained.
- the resulting dispersion is diluted 10-fold with water, centrifuged at 5,000 rpm for 10 minutes to remove aggregated components, and then centrifuged under conditions of 12,500 rpm for 2 hours. By separating, dispersible colorant 2-3 as a sediment was obtained.
- the liquid consists of (1) butyl acrylate. 5.7 parts, (2) dimethylaminoethyl acrylate 1.8 parts and water 20 parts, (3) potassium persulfate 0.05 parts and water 20 parts.
- Emulsion particles 1 were prepared as follows. In a nitrogen atmosphere, 100 parts of the 2% aqueous solution of styrene-acrylic acid resin dispersant described above was heated to 70 ° C. Then, it was added dropwise over 6 hours to carry out polymerization. (1) 5.5 parts of methyl methacrylate, (2) 0.5 parts of acrylic acid, 0.25 parts of potassium hydroxide and 20 parts of water, (3) 0.05 parts of potassium persulfate and water It consists of 20 parts.
- the resulting dispersion is centrifuged at 80,000 rpm for 2 hours. Further refinement gave the emulsion particles 1 as sediment.
- the emulsion particles 1 had an average dispersed particle size of 20 nm.
- Emulsion particles 2 were obtained in the same manner as in the preparation of emulsion particles 1 except that 4.5 parts of benzyl methacrylate and 1.0 parts of butyl acrylate were used instead of 5.5 parts of methyl methacrylate. .
- Emulsion particles 3 were obtained in the same manner as in Emulsion 1 except that 0.7 parts of methyl methacrylate and 4.8 parts of butyl acrylate were used instead of 5.5 parts of methyl methacrylate. .
- Emulsion particles 4 were obtained in the same manner as in Preparation 1 except that 5.0 parts of benzyl methacrylate and 0.5 parts of butyl acrylate were used instead of 5.5 parts of methyl methacrylate.
- Emulsion particles 5 were obtained in the same manner as in the preparation of emulsion 1, except that 5.5 parts of butyl acrylate was used instead of 5.5 parts of methyl methacrylate.
- Emulsion particles 8 were prepared as follows. In a nitrogen atmosphere, 100 parts of a 2% aqueous solution of styrene-acrylic acid dimethylaminoethyl acid-based resin dispersant described above was used, and 7 (each of the following three liquids were stirred while being stirred in The liquid was charged in a dropping device and polymerized by adding dropwise in 6 hours. The liquid was (1) butyl acrylate, 4.5 parts, benzyl methacrylate, 1.2 parts, and (2) dimethylamino acrylate. Ethyl 1. 8 parts and 20 parts of water (3) Consists of 0.05 parts of persulfuric acid rhodium and 20 parts of water
- the obtained dispersion was purified by centrifuging at 80,000 rpm for 2 hours to obtain emulsion particles 8 as a precipitate.
- the emulsion particles 8 had an average dispersed particle size of 60 nm.
- Example 2 Recording ink 2-1 according to 1 was produced in the following manner. Dispersible colorant 2_2 was included in the ink at a concentration of 43 ⁇ 4, and the following composition of ingredients was mixed with it, and pressure filtered through a membrane filter with a pore size of 2.5 microns. Recording ink 2-1 of this example was prepared.
- Glycerin 7 parts Diethylene glycol 5 parts Trimethylolpropane 5 parts Acetylenol EH (trade name: manufactured by Kawaken Fine Chemicals Co., Ltd.) 0.25 parts Emulsion particles 1 4 parts Ion-exchanged water balance (total amount to 100 parts)
- a recording ink 2-2 was prepared in the same manner as in Example 1 except that the emulsion particles 2 were used instead of the emulsion particles 1.
- Example 2-3 Recording inks 2-3 were prepared in the same manner as in Example 1 except that emulsion particles 3 were used instead of emulsion particles 1.
- a recording ink 2-4 was prepared in the same manner as in Example 1 except that the emulsion particles 4 were used instead of the emulsion particles 1.
- Recording inks 2-5 were adjusted in the same manner as in Example 1 except that the emulsion particles 5 were used instead of the emulsion particles 1.
- a recording ink 26 was prepared in the same manner as in Example 1 except that 0.2 part of emulsion particles 2 was used instead of 4 parts of emulsion particles 1.
- Recording inks 2-7 were prepared in the same manner as in Example 1 except that 0.2 parts of emulsion particles 6 were used instead of 4 parts of emulsion particles 1.
- Recording inks 2-8 were obtained in the same manner as in Example 1 except that 0.2 parts of emulsion particles 7 were used instead of 4 parts of emulsion particles 1.
- a recording ink 2-9 was obtained in the same manner as in Example 1 except that the colorant 2-5 was used instead of the dispersible colorant 2-2, and the emulsion particle 8 was used instead of the emulsion particle 1. .
- the recording ink 2-10 was adjusted in the same manner as in Example 2-6 except that the dispersible colorant 2-1 was used instead of the dispersible colorant 2-2.
- Example 2 except that dispersible colorant 2-3 was used instead of dispersible colorant 2-2 Same as 6 and adjusted recording sync 2-1 1.
- Recording ink 2-12 was adjusted in the same manner as in Example 2-6, except that dispersible colorant 2-4 was used instead of dispersible colorant 2-2.
- Dispersible colorant 2-1 is contained in the ink at a concentration of 4%, and the following component composition is mixed with this, and pressure filtration is performed with a membrane filter having a pore size of 2.5 microns.
- a recording ink of this comparative example was prepared.
- Glycerin 7 parts Diethylene glycol 5 parts Trimethylolpropane 5 parts Acetylenol EH (trade name: Kawaken Fine Chemicals Co., Ltd.) 0.25 parts Ion-exchanged water balance (total amount to 100 parts),
- the glass transition temperature (Tg) of the chargeable resin pseudo fine particles was measured laterally as follows. .
- the dispersible colorant was acidified with hydrochloric acid, and the solid content obtained after acid praying was subjected to Soxhlet extraction with THF (tetrahydrofuran), and THF was distilled off to obtain a charged resin pseudo fine particle component. Further, Tg of the obtained charged resin pseudo fine particle component was measured by a differential scanning calorimetry (manufactured by METTLER, DSC82 2 e) apparatus. In the case of an aqueous dispersion in which a dispersible colorant and a water-soluble nonionic resin are coexistent, they can be separated using a centrifuge. The results obtained are shown in Table 2-1.
- Each dispersible colorant is dispersed in water and dried, and observed with a scanning electron microscope J SM-6700 (trade name; manufactured by JEOL Hi-Tech Co., Ltd.) at a magnification of 50,000 times.
- J SM-6700 (trade name; manufactured by JEOL Hi-Tech Co., Ltd.) at a magnification of 50,000 times.
- the state in which the fat fine particles are fixed and the properties of the fixed resin fine particles were evaluated as follows.
- the solution was concentrated to the original concentration using a 100 ultrafiltration filter, and the concentrated solution was separated using a centrifuge at 1 2, 0 0 0 rotations for 2 hours.
- the separated sediment is taken out and redispersed in pure water, and is visually dispersed uniformly, and the average particle size measured by the dynamic light scattering method described later is the particle size before the operation.
- each dispersible colorant was placed in a glass sample bottle in the form of a dispersed aqueous solution, and after standing at 60 ° C for 1 month in a sealed state, the dispersion state was visually determined.
- the evaluation criteria are as follows. .
- Each dispersible colorant and emulsion particles were measured by a dynamic light scattering method using ELS-8100 (trade name) manufactured by Otsuka Electronics Co., Ltd., and the average value of the cumulant was taken as the average particle diameter.
- HC 1 hydrochloric acid
- the average particle size was measured by FPAR 1 0 0 0 (trade name)). Further, the glass transition temperature of the emulsion particles was measured by differential scanning calorimetry (DSC 8 2 2 e (trade name) manufactured by MET LERR Co., Ltd.) obtained by evaporating and drying the obtained emulsion dispersion. The results are shown in Table 2_2.
- the gloss of the printed matter was measured using maicrohazemater (trade name; BYK Gardner) and evaluated according to the following criteria.
- GLOS S value (20 ° glossiness) is 50 or more.
- GLOS S value (20 ° glossiness) is 40 or more and less than 50.
- GLOS S value (20 ° glossiness) is 30 or more and less than 40.
- the scratch resistance of the printed matter was evaluated by the following criteria by rubbing the printed portion with a Silbon paper having a weight of 40 g / 'cm 2 and observing the degree of shaving of the image portion visually.
- Example 2-Example 2 Example 2 Example 2 Example 2 Example 2 Example 2-1 1 2-3-4 5 Color Material No 2-2 2 -2 2-2 '? J — 0 2-2 Emmarjon
- Quantity parts 4 4 4 4 4 4 Particle size (nm) 35 30 30 40 45
- an image having high dispersion stability, excellent long-term dispersion stability, and excellent fastness such as scratch resistance can be obtained.
- a suitable water-based ink is provided.
- an ink tank, an ink jet recording apparatus, an ink jet recording method, and an ink jet recording image using such an excellent aqueous ink are provided.
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- Inks, Pencil-Leads, Or Crayons (AREA)
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US7291211B2 (en) | 2007-11-06 |
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