WO1998011170A1 - Encre pour impression par jets et procede de preparation d'une dispersion de fines particules colorees pour cette encre - Google Patents
Encre pour impression par jets et procede de preparation d'une dispersion de fines particules colorees pour cette encre Download PDFInfo
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- WO1998011170A1 WO1998011170A1 PCT/JP1997/003211 JP9703211W WO9811170A1 WO 1998011170 A1 WO1998011170 A1 WO 1998011170A1 JP 9703211 W JP9703211 W JP 9703211W WO 9811170 A1 WO9811170 A1 WO 9811170A1
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- ink
- resin
- film
- pigment
- fine particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0009—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives
- C09B67/001—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives containing resinic acid derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0091—Process features in the making of dispersions, e.g. ultrasonics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
-
- 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 jet ink and a dispersion of colored fine particles for the jet ink.
- the present invention relates to a method for producing a jet ink and a dispersion of colored fine particles for the jet ink.
- the present invention relates to a colored microcapsule-dispersed aqueous jet ink.
- Ink jet recording inks can be broadly classified into oil-based inks and water-based inks.
- Oil-based inks have problems in terms of odor and toxicity, and water-based inks are becoming mainstream.
- many of the conventional water-based inks have a drawback of poor water resistance and light resistance because a water-soluble dye is used as a coloring agent.
- a water-soluble dye is used as a coloring agent.
- printing on so-called plain paper such as copy paper commonly used in offices causes bleeding called whisker-like feathering, which causes a significant decrease in print quality.
- a pigment and a polymer dispersant are charged into a 2-roll mill; ) Milling to obtain a dispersion of pigment and polymer dispersant: and (3) having improved properties, comprising dispersing the pigment dispersion in an aqueous carrier medium
- Adjustment method pigmented Inkujietsuto inks aqueous, in JP-3- 1 5 3 7 7 5 discloses, a) pigment and force Rupokishiru group-containing polyacrylate
- B) a water-dilutable organic solvent c) a wetting agent d) an aqueous ink composition for ink jet printing containing water.
- the resin-dispersed water-based ink has the advantages that the viscosity rise due to evaporation of the ink is relatively small, and that the ink is excellent in water resistance.
- JP-A-58-45272 discloses an ink composition containing a urethane polymer latex containing a dye
- JP-A-62-295366 discloses a water-insoluble organic solvent.
- An ink containing a dye encapsulated in polymer particles has been proposed by dissolving a polymer and an oily dye therein, further mixing and emulsifying with an aqueous solution containing a surfactant, and evaporating the solvent.
- Japanese Patent Application Laid-Open No. 11770672 proposes a recording liquid containing a dye similarly macro-encapsulated, but the dispersion stability of the colored resin dispersion obtained with them is not always sufficient. Also, foaming is large due to the effect of the surfactant used at the time of encapsulation. Injection characteristics of the di-Etsu I was not necessarily sufficient.
- Japanese Patent Application Laid-Open No. 3-240586 proposes an image forming material characterized in that the surface of particles dispersed in a dispersion medium is covered with a resin swelling in the dispersion medium.
- the phase transition of the sol-gel was apt to occur near room temperature, and the dispersion stability of the particles was not always good.
- Japanese Patent Application Laid-Open No. 5-247370 discloses an image recording coloring composition containing a pigment and a resin, wherein the pigment is substantially insoluble in a dispersing medium and is a cured polymer having a polar group.
- a coloring composition for image recording which is characterized by being a pigment coated with a thin film, has been proposed.
- the pigment itself has insufficient self-dispersibility and a fixing ability to recording paper, it is difficult to disperse the pigment.
- Indispensable to use a resin as an agent and a fixing agent the dispersion stability is better than pigments not coated with the cured polymer, but the shortcomings of jetting stability as inkjet and poor water resistance was not improved.
- Japanese Patent Application Laid-Open No. 225585/1990 discloses that in a water-based ink for ink jet recording containing a pigment, a water-soluble resin, a water-soluble organic solvent and water, the water-soluble resin is coated on the surface of the pigment.
- the “fat-adsorbed pigment particles” fixed by a relatively weak force are dispersed in an aqueous medium, and the water-soluble resin is not adsorbed by the pigment in the aqueous medium and the water-soluble resin is 2% by weight or less in the ink. What is dissolved is described.
- the degree of fixation between the pigment surface and the adsorbed resin is still insufficient. Cannot be expected to have stable dispersion.
- the problem to be solved by the present invention is to provide a water-dispersed aqueous dispersion ink of a liquid-dispersed microphone mouth having excellent fine particle diameter, excellent dispersion stability, and excellent ink jetting properties and fixation of capsule particles to a recording medium. Is to do. Disclosure of the invention
- the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, it has been found that the dispersion stability in the ink is further improved by coating the pigment fine particles instead of adsorbing the resin.
- the colored fine particles (hereinafter sometimes referred to as a colored microcapsule) in which the fine particles are coated with a resin have a specific particle diameter in the ink, and the liquid of the ink in which the colored fine particles are dispersed. It is found to be effective if the particle diameter of the colored fine particles dispersed in the liquid medium before and after drying after removing the medium and then re-dispersing in the same liquid medium again is effective.
- a colored microcapsule in which the fine particles are coated with a resin have a specific particle diameter in the ink, and the liquid of the ink in which the colored fine particles are dispersed. It is found to be effective if the particle diameter of the colored fine particles dispersed in the liquid medium before and after drying after removing the medium and then
- the present inventors have proposed that a free-dissolved, film-forming resin component that is not coated with a pigment in the ink does not affect the ejection stability, and that the recording
- the above-mentioned problem has been solved by setting the quantitative range to contribute to the fixation of the capsule particles to the medium. More specifically, instead of using ⁇ resin-adsorbed pigment particles '' in which a water-soluble resin is fixed to the surface of the pigment with relatively weak force as described above, the pigment is coated with a self-dispersible film-forming resin.
- aqueous jet ink in which the “colored microcapsules” are dispersed in an aqueous medium, if the amount of the water-soluble resin dissolved in the ink without adsorbing on the pigment is set to 2% by mass or less, The present inventors have found out that the ink jetting characteristics and the sticking property to a recording medium can be more excellent than the case where “pigment particles” are used, and have completed the present invention.
- the present invention provides the following inventions.
- pigment fine particles (a) are coated with a film-forming resin (b) having a carboxyl group, and colored fine particles (d) are dispersed in an aqueous medium.
- the colored fine particles (d) have a quaternized carboxyl group on the surface and have a volume average particle size of 0.5 im or less.
- a rate of increase in the volume average particle diameter of the colored fine particles (d) in the liquid dispersion is 50 percent or less.
- the standard deviation value in the “frequency distribution of the particle diameter of the colored fine particles in the redispersion liquid of the dried ink” is 0.15 or less.
- the film-forming resin (b) having a carboxyl group has an acid value of 50 to 180, and a part or all of the acid is an organic amine compound and is a quaternary ammonium salt. Jet ink.
- a method for producing a dispersion of colored fine particles for a jet ink wherein the poor solvent for the film-forming resin (b) is added to the dispersion (X) of colored fine particles.
- Depositing the film-forming resin (b) dissolved in the aqueous medium of the dispersion (X) on the surface of the colored fine particles (d), and then removing the organic solvent (e) from the dispersion (X) A method for producing a dispersion of colored fine particles for jet ink, which is characterized by the following.
- S2 and S1 are as follows, respectively. That is, a slide glass with a hole (14 to 16 mm in diameter, 0.4 to 0.8 mm in the deepest part) on the surface, or a mini petri dish (14 to 16 mm in diameter and 10 to 15 mm in height)
- the ink is dried by placing the jet ink 101 in a cylindrical shape) at a temperature of 25 and in an atmosphere of a relative humidity of 20% for 7 days, and then drying the ink in the hole. Is redispersed in 10 ml of pure water (diluted 1 000 times).
- the volume average particle diameter of the colored fine particles (d) contained in the diluted redispersion (hereinafter, simply referred to as “redispersion of dry ink”) is measured, and the measured value is S2.
- the same ink 10/1 as the above-mentioned jet ink is diluted with 1 Om 1 of pure water (diluted 1000 times).
- the volume average particle diameter of the colored fine particles (d) contained in the diluent is measured, and the measured value is defined as S1.
- known ones can be used for the measurement of the particle diameter of these colored fine particles (d).
- frequency distribution of the particle diameter of the colored fine particles (d) in the re-dispersion liquid of the dry ink used in this specification is used to refer to the fine particles in the “re-dispersion liquid of the dry ink” as defined above.
- a frequency distribution of the volume particle size is used.
- the colored fine particles (d) may be called microcapsule particles, colored microcapsules, or simply microcapsules.
- the SI unit system is adopted as the unit system, and the weight is described as mass.
- FIG. 1 is a frequency distribution diagram of the volume particle size of the colored fine particles in the ink of Example 1.
- FIG. 2 is a frequency distribution diagram of the volume particle diameter of the coloring fine particles in the re-dispersion liquid of the dry ink using the jet ink of Example 1.
- FIG. 3 is a frequency distribution diagram of the volume particle diameter of the colored fine particles in the ink of Example 4.
- FIG. 4 is a frequency distribution diagram of the volume particle diameter of the coloring fine particles in the re-dispersion liquid of the dry ink using the jet ink of Example 4.
- FIG. 5 is a frequency distribution diagram of the volume particle size of the colored fine particles in the ink of Example 6.
- FIG. 6 is a frequency distribution diagram of the volume particle size of the coloring fine particles in the re-dispersion liquid of the dry ink using the jet ink of Example 6.
- FIG. 7 is a frequency distribution diagram of the volume particle size of the colored fine particles in the ink of Example 7.
- FIG. 8 is a frequency distribution diagram of the volume particle diameter of the colored fine particles in the re-dispersion liquid of the dry ink using the jet ink of Example 7.
- Ink obtained by a conventional method of using a water-soluble resin as a pigment dispersant to stably disperse pigment fine particles by adsorption tends to cause aggregation of the pigment fine particles with evaporation of water.
- the pigment fine particles Once the pigment fine particles are agglomerated, they cannot be re-dispersed again even if they are wetted by adding water or the same ink again, resulting in nozzle clogging.
- the pigment fine particles or colored fine particles have the same level as the original ink. Whether or not the particles are dispersed can be a measure of the difficulty of nozzle clogging.
- the increase in the particle size over time can be examined. , Median (50% particle size), increase in coarse particles (eg 90% particle size), etc.
- the average particle size, especially the volume average particle size is the most accurate correlation with nozzle clogging. The present inventors have found that this is reflected in the above.
- the jet ink according to the present invention is characterized in that the pigment fine particles (a) are present in a dispersed state in an aqueous medium as a dispersion medium, and the pigment fine particles (a) are coated with a film-forming resin (b) having a carboxyl group.
- (D) "has a volume average particle diameter of 0.5 wm or less, but preferably has a volume average particle diameter in the range of 0.01 to 0.3 zm.
- the jet ink of the present invention means that the “increase rate of the volume average particle diameter of the colored fine particles (d) in the re-dispersed liquid of the dried ink” is 50% or less.
- the rate of increase is preferably 40% or less, and particularly preferably 20% or less, in terms of effects.
- each ink is sampled from the same container to perform the two tests.
- the volume average particle diameter of the colored fine particles (d) of the ink measured immediately after opening the container for the first time when the ink is used can be, for example, the blank S1.
- the volume average particle size is preferably not more than 0.3 m in both cases of S2 and S1.
- the standard deviation (sd) of the volume particle diameter is 0.15 or less, especially 0.1 or less. It is preferable to do so. It is needless to say that it is preferably within this range even under the condition of S1.
- the ink is not limited to the ink of the present invention.
- examples of the ink include “colored microcapsules j in which a pigment is coated with a film-forming resin that does not dissolve in a dispersion medium, and ink that does not dissolve in a dispersion medium that is not coated with a film-forming resin.
- Free pigment particles "free film-forming resin-dispersed particles that are not coated with a pigment and do not dissolve in a dispersion medium”
- films dissolved in a dispersion medium And a dispersion medium, and, if necessary, a drying inhibitor, a penetrant, and the like.
- the present invention provides a jet ink comprising pigment fine particles (a) coated with a film-forming resin (b) having a carboxyl group and colored fine particles (d) dispersed in an aqueous medium.
- the colored fine particles (d) have a quaternized carboxyl group on the surface thereof and have a volume average particle diameter of 0.5 m or less;
- the rate of increase in the volume average particle diameter of the colored fine particles (d) in the redispersion must be 50% or less.
- the present invention is effective to make the dissolved film-forming resin non-existent or to be within an allowable range in the aqueous medium serving as the dispersion medium in the ink composition. .
- the amount of the dissolved film-forming resin is as small as possible in the aqueous medium as the dispersion medium, and the amount is preferably 2% by mass or less based on the weight of the ink.
- the film-forming resin is more susceptible to clogging due to water evaporation at the nozzle end surface than the water-soluble resin such as a polymer dispersant, resulting in poor inkjet ejection stability. Tends to occur.
- the ink is printed on the recording paper by making the resin component soluble in the ink of the film-forming resin into, for example, 0.1 to 2% by mass, and more preferably 0.1 to 1% by mass.
- the ability of the microcapsule particles in the ink layer formed on the recording paper surface to adhere to the recording paper and the bonding force between the microcapsule particles are increased, and the durability of the printed matter, such as friction, is improved. Clogging due to moisture evaporation at the nozzle end face is also eliminated, and ink jet ejection stability is greatly improved.
- the content of the film-forming resin component dissolved in the ink is represented by the absolute content contained in the ink (hereinafter, sometimes referred to as the absolute content).
- the aqueous medium refers to a medium containing only water or water as a main component and optionally containing an organic solvent and other additives.
- the film-forming resin may be any resin capable of forming a film, and is not limited to a natural resin or a synthetic resin, and various film-forming resins can be used.
- a styrene resin an acrylic resin
- a polyester resin And polyurethane resins.
- the resin may be cross-linked at room temperature, but may have a reversible cross-linking property which becomes a non-cross-linked state by heat.
- a film-forming resin which is linear and substantially exhibits thermoplasticity is preferable, and a resin which is not heat-dependent and is permanently crosslinked is not preferable.
- the film-forming resin needs to have a high hydrophilic property, and thus often a large amount of the film-forming resin is contained in the ink. Will be dissolved.
- the dissolved resin may promote aggregation of the microcapsules due to long-term storage due to bridging between the particles caused by entanglement with the resin layer covering the microcapsules.
- jetting abnormalities are likely to occur due to an increase in ink viscosity due to evaporation of water at the nozzle end surface and the adhesion of ink concentrate around the nozzle.
- abnormal injection examples include abnormal ink discharge and clogged nozzles.
- the hydrophilicity of the film-forming resin is low, the dispersion stability of the pigmented microcapsules coated with the film-forming resin in an aqueous medium becomes lower. Therefore, it is preferable to minimize the dissolution of the film-forming resin in the aqueous medium and to enable stable dispersion in the aqueous medium.
- a surfactant or a dispersant may be used, and a film-forming resin having no or little hydrophilicity may be used.
- a film-forming resin having no or little hydrophilicity may be used.
- Examples of a method for preparing the composition so as not to include a surfactant or a dispersant include, for example, using a film-forming resin obtained by neutralizing a resin which can be neutralized and dispersed in an aqueous medium with a neutralizing agent. Good to do.
- the film-forming resin obtained by neutralizing a resin dispersible in an aqueous medium by neutralization with a neutralizing agent typically includes a resin dispersible in an aqueous medium by neutralization with a base.
- a film-forming resin obtained by neutralization with a base is exemplified.
- this resin which can be stably dispersed in an aqueous medium by itself without the aid of a surfactant, a dispersant, or the like may be referred to as a self-water dispersible resin.
- a self-water dispersible resin obtained by neutralizing a resin having an acid value with a base, for example.
- a typical example of the film-forming resin having an acid group is a film-forming resin (b) having a carboxyl group.
- the colored fine particles (d) in which the pigment fine particles (a) are coated with the film-forming resin (b) having a carboxyl group are the aqueous medium of the film-forming resin (b) covering the pigment fine particles (a).
- the carboxyl group on the surface in contact with is mainly quaternized to form a salt, so that it is stably dispersed in an aqueous medium.
- the film-forming resin (b) having a carboxyl group can be a water-soluble resin or a self-water-dispersible resin depending on the degree of quaternization of the carboxyl group content determined by the acid value.
- the effect of the present invention is unique when the film-forming resin (b) existing on the surface of the pigment fine particles (a) does not substantially dissolve in the aqueous medium, that is, when the resin is a self-water-dispersible resin. is there.
- the acid value of the preferred resin is from 10 to 280.
- the acid value is the number of milliliters of potassium hydroxide (K OH) required to neutralize 1 g of resin.
- the gram (mg) number is expressed in mg ⁇ KOHZ g (the unit is abbreviated below).
- Such a resin can be obtained, for example, by neutralizing all or a part of the acid value of the resin having the specific acid value.
- the pH of the ink is 7.5 to 9.0. If the acid value is less than 50, the surface hydrophilicity of the microcapsule particles is poor, and the dispersion stability tends to be insufficient. If the acid value is more than 180, the hydrophilicity of the resin is significantly increased, and the pigment by the resin is used. Is not suitable because it tends to become insufficient due to swelling and the like, and tends to cause aggregation of microcapsule particles and clogging of nozzles. On the other hand, when the pH of the ink is lower than 7.5, the dispersion stability of the colored microcapsule particles tends to decrease, and when the pH is higher than 9.0, the pigment of the colored microphone capsule particles is covered with the pigment. It is not suitable because it tends to be insufficient due to swelling and the like, and the microcapsule particles tend to aggregate or clog the nozzle.
- a resin having an acid value of 50 to 180 is neutralized with a base.
- the use of a self-water-dispersible resin as the film-forming resin and the ink having a pH of 7.5 to 9.0 exhibit a remarkable effect in the present invention.
- the molecular weight range of the film-forming resin is not particularly limited, but is preferably in the range of 100 to 100,000 in terms of weight average molecular weight. If the molecular weight of the film-forming resin is less than 10,000, a sufficient film cannot be formed in many cases, and it is not suitable because the nozzles are easily clogged due to aggregation of the microcapsule particles.
- the resin in order to sufficiently coat the pigment with the film-forming resin, the resin preferably has a molecular weight of 10,000 to 100,000.
- styrene resin or an acrylic resin those having a molecular weight of 100000 or more and 100,000 or less are more preferable.
- the weight average molecular weight of the resin is preferably from 10,000 to 100,000, and particularly preferably from 30,000 to 100,000 in order to obtain more excellent water resistance.
- a preferred film-forming resin is a styrene resin or a (meth) acrylic resin.
- the resin having an acid value of 12 is, for example, a copolymer of at least one monomer selected from the group consisting of styrene and substituted styrene ′ (meth) acrylate and (meth) acrylic acid. Is mentioned.
- the film-forming resin composed of a self-water dispersible resin obtained by using a resin having an acid value and neutralizing the resin with a base is preferably, for example, styrene, substituted styrene, (meth) acrylic, and the like.
- a self-water dispersible resin obtained by at least partially neutralizing a copolymer of at least one monomer selected from the group consisting of acid esters and (meth) acrylic acid with a base is exemplified.
- (Meth) acrylic acid is a general term for acrylic acid and methacrylic acid. In the present invention, either one may be essential, but more preferable film-forming resins are both acrylic acid and methacrylic acid. It has a structure derived from it.
- the ratio of acrylic acid to the monomer components having all carboxyl groups is determined. And the ratio of acrylic acid should be increased.
- the self-water-dispersible resin as the optimum film-forming resin is mainly composed of at least one monomer selected from the group consisting of styrene, substituted styrene, and (meth) acrylic acid ester, and is composed of acrylic acid and methacrylic acid.
- a base is used in the suspension step in a more preferable aqueous jet ink production method (this will be described in detail later).
- Examples of the base include, for example, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and basic substances such as ammonium, triethylamine and morpholine.
- alcoholamines such as triamine, genamine, and N-methylgenamine can be used.
- the base it is preferable to use a volatile base that easily volatilizes at a high temperature at which the film-forming resin does not decompose.
- the higher the neutralization rate with a base the higher the solubility of the resin in the suspension.
- the amount of the base used depends on the degree of dissolution in the liquid medium and the amount of the final aqueous dispersion. It is appropriately adjusted based on the intended size of the dispersed particles.
- the solubility of the resin in water is increased.
- the resin is not sufficiently deposited on the surface of the colorant. Therefore, it is preferable to adjust the strength of the base and the amount (neutralization ratio) of the base in the suspension so that the amount of the water-soluble resin component does not increase.
- aqueous ink for ink jet recording it is preferable to minimize the amount of the water-soluble resin component because nozzle clogging, dispersion stability during storage, and water resistance of printed matter are adversely affected.
- Alcoholamines particularly triethanolamine, are weak bases and generate less of the water-soluble resin component, and are optimal bases for preparing aqueous inks for inkjet recording.
- alcohol bases which are weak bases, especially triethanolamine, are the most suitable bases because the clogging of nozzles, dispersion stability during storage, and water resistance of printed matter are extremely small.
- the neutralization ratio with a base in the suspension step may be not less than the degree to which the resin having an acid value in the resin coloring step is self-emulsified in the suspension. Is at least 10 mol%.
- the neutralization ratio with respect to the acid groups of the film-forming resin is set to 100 mol% or less, preferably 60 mol% or less. It is particularly preferable to use alcohol-amine as a base so that the neutralization ratio of the film-forming resin with respect to the acid groups is 60 mol% or less.
- the film-forming resin having an acid value is a film-forming resin having an acid value of 50 to 18 Omg.KOH / g, and a neutralization ratio of the film-forming resin to an acid group. It is preferable to use a self-water-dispersible resin in which the amount is 60 mol% or less.
- the film-forming resin (b) having a carboxyl group and having an acid value of 50 to 180 is used as the colored fine particles (d), a part or the whole thereof is an organic amine compound. Those which are quaternary ammonium salts are preferred.
- a more preferable method for producing the aqueous jet ink in the present invention is not particularly limited, and any known and commonly used colorant can be used.
- the use of a pigment makes it easier to obtain a colored resin film having excellent water resistance than the use of a dye.
- the colored microcapsules of the present invention using a pigment can obtain a colored resin film having better water resistance and light resistance than colored resin particles using a dye.
- the pigment used in the colored microcapsule-dispersed aqueous jet ink of the present invention is not particularly limited, and any of known pigments can be used. This pigment is present as pigment fine particles (a) in the colored fine particles (d) in the present invention.
- pigments examples include inorganic pigments such as Ribon Black, titanium black, titanium white, zinc sulfide, and red iron oxide, phthalocyanine pigments, azo pigments such as monoazo and disazo pigments, phthalocyanine pigments, and quinacridone pigments. Organic pigments and the like are used.
- the pigment used to obtain the ink is one of carbon black, phthalocyanine pigment, halogenated phthalocyanine pigment, quinacridone pigment, benzimidazolone pigment, perinone pigment, and isoindolinone pigment. Is preferred.
- achromatic colored resin particles especially black colored resin particles
- a chromatic pigment In order to obtain a color image, it is preferable to use a chromatic pigment.
- the color tone of the pigment used must be at least a combination of three colors: cyan (blue), magenta (red), and yellow.
- an image can be formed using four colors of ink combined with black, or an image can be formed by adding a complementary color in addition to the three or four colors.
- the cyan pigment is preferably a phthalocyanine pigment from the viewpoint of color tone and weather resistance.
- Specific examples of the phthalocyanine pigment include gold-free phthalocyanine, copper phthalocyanine or chlorinated copper phthalocyanine, and various other metal phthalocyanines. Among these, copper phthalocyanine is preferred, and C.I. Pigment Blue 15: 4 is more preferred in view of color tone and dispersibility when combined with other color pigments.
- the magenta evening pigment is preferably a quinacridone pigment from the viewpoint of color tone and weather resistance.
- the quinacridone pigment include dimethylquinacridone and dichloroquinacridone.
- C.I. Pigment Red 122 is preferred in view of color tone and dispersibility when combined with other color pigments.
- the yellow color pigment is preferably a benzimidazolone pigment in terms of color tone and weather resistance.
- benzimidazolone pigments include C.I. Pigment Yellow 120, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Yellow 1 156, C.I.
- CI Pigment Yellow 151 is most preferable in terms of color tone, dispersibility and light fastness when combined with other color pigments.
- the black pigment is not particularly limited, but carbon black is preferred from the viewpoint of color tone and weather resistance.
- the image obtained by forming a color image using a combination of ink using color black as a colorant and at least three inks each composed of a fluorinated cyanine pigment, a quinacridone pigment, and a benzimidazolone pigment is an optical image. Extremely high image quality stability with little change in color tone due to fading.
- phthalocyanine pigments such as C.I. Pigmentable 15: 4, quinacridone pigments C.I. Pigment Red 122 and Benzimidazolone pigments are used.
- the image obtained by performing color image formation by combining with CI Yellow 1501 and, if necessary, by combining it with bonbon black is particularly preferable in terms of image quality stability.
- Each of the above color pigments can be used alone or in combination. If necessary, other types of pigments may be used in combination to form a color image.
- each aqueous jet ink of a neutral color in addition to each aqueous ink using the above-mentioned four suitable pigments.
- a halogenated phthalocyanine pigment an imidazolone pigment, a perinone pigment, or an isoindolinone pigment
- the intermediate color aqueous ink using such a high pigment a colored microcapsule may be used. Some are not of the dispersion type, but the following are preferred.
- a microcapsule-dispersed orange aqueous jet containing, in an aqueous medium, a colored microforce pigment coated with fine particles of one of pigments selected from imidazolone pigments, perinone pigments, and isoindolinone pigments, with a film-forming resin. ink.
- the resin component soluble in the ink in the range of 0.01 to 2% by mass among the film-forming resins is the same as the aqueous ink described above. It is preferable in combination.
- the amount of the pigment to be used is not particularly limited as long as the effects of the present invention can be achieved. However, the amount is usually adjusted to be 0.5 to 20% by mass in the finally obtained ink. preferable.
- the ratio varies depending on the specific surface area of the pigment and the thickness of the coating resin. 5 to 2 parts by mass are preferred.
- the amount of free pigment that is not resin-coated in the ink is extremely small, almost all the pigments used can be approximated by the above content as colored microcapsules only.
- both the pigment and the film-forming resin having an acid value are used so that they have almost the same mass, more preferable results can be obtained in a method for producing a preferred ink jet recording ink described later. Examples of the range include a case where both are the same mass or a case where the pigment is within a range of ⁇ 15% of the mass of the resin.
- the ink may contain an organic solvent that does not dissolve or hardly dissolves the film-forming resin.
- the organic solvent used in the ink is used as an anti-drying agent or a penetrant, for example.
- the anti-drying agent has an effect of preventing the ink from drying at the ejection nozzle port of the ink jet, and usually has a boiling point higher than that of water.
- any of the conventionally known and commonly used ones can be used. Examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polypropylene glycol.
- polyhydric alcohols such as glycerin.
- glycerin When glycerin is the anti-drying agent, it shows the best anti-drying effect.
- glycerin enhances the dispersion stability of the microcapsule particles by binding to the film-forming resin on the surface of the microforce particles by strong hydrogen bonding, and at the same time, even if a small amount of the film-forming resin is dissolved in the ink.
- the penetrant penetrates the ink into the recording medium and adjusts the dot diameter on the recording medium.
- the penetrant include lower alcohols such as ethanol and isopropyl alcohol, and ethylene glycol hexyl ether and diethylene glycol.
- Examples include an ethylene oxide adduct of an alkyl alcohol such as tyl ether and a propylene oxide adduct of an alkyl alcohol such as propylene glycol propyl ether.
- Organic solvents with good permeability to recording media often break microcapsules and impair the stability of the ink.
- mono-alcohol propylene oxide adduct (k) of 1 mol alone has a particularly large number of carbon atoms.
- To 6 mono alcohol propyle At least one member selected from the group consisting of 10 to 40 mol homoaddition polymer (1), and 1 mol monooxide ethylene oxide monoadduct ( m ) having 4 to 8 carbon atoms. It is possible to maintain the stability of the microcapsule by using an appropriate amount of in the ink. In particular, it is preferable to select and use two substances in each of the groups (k), (1) and (m).
- a silicone-based emulsified dispersion type antifoaming agent can be added to suppress bleeding on the recording medium, suppress foaming, and further improve ink ejection stability. It is particularly effective to use each substance of each of the above groups in place of the silicone-based emulsified dispersion type antifoaming agent.
- Examples of the 1-mol monopropylene propylene oxide adduct (k) include, for example, propylene oxide (1 mol) monoadduct of propanol.
- Examples of the homo-addition polymer (1) of mono-alcohol propylene oxide having 1 to 6 carbon atoms of 10 to 40 moles include propylene oxide (17.7 mol) addition polymer of bushanol. No.
- Examples of the monoalcohol ethylene oxide single adduct (m) include, for example, ethylene oxide (1 mol) monoadduct of hexanol, and the ethylene oxide (1 mol) monoadduct of hexanol.
- the contents of (k), (1) and (m) in the ink are preferably added so as to minimize bubbling of the ink, and the addition amount may be controlled to a level that does not cause layer separation on the ink surface. Although not particularly limited, it is generally in the range of 0.01 to 10% by mass.
- the amount of the organic solvent to be added is preferably 1 to 80% by mass when used as a drying inhibitor in the ink, and 0.01 to 10% by mass when used as a penetrant.
- the organic solvent dissolves the resin coated on the pigment in excess of 2% by mass and sprays it. Therefore, the pH range of the ink was considered so that the content in the ink was 2% by mass or less, and more preferably 1% by mass or less, depending on the type of the organic solvent. Above, it is necessary to control the addition amount.
- the dispersion medium of the finally obtained ink is an organic solvent (e) that dissolves the film-forming resin.
- the resin (b) having a quaternized salt structure on the surface of the dispersed colored fine particles (d) may be used. It is preferable to keep the content of the ink low so that the ink does not dissolve.
- the present invention provides a dispersion stability without losing the characteristics of the resin dispersion type water-based ink excellent in print quality, water resistance, and light resistance. It has excellent ink jetting characteristics and does not cause nozzle clogging, and enables stable ink jetting characteristics.
- the method of measuring the components dissolved in the ink of the film-forming resin of the present invention is as follows.If there are few solid components other than the resin, for example, sediment the microcapsule particles with an ultracentrifuge, The supernatant can be dried sufficiently and measured directly as non-volatile components. If a large amount of solids other than the resin and high-boiling organic solvents are present in the ink, the centrifuged sediment is sufficiently dried, and then analyzed by a thermal analyzer based on the difference in thermal decomposition temperature. Then, the ratio of the resin and the pigment is measured, and the amount of the resin component dissolved in the ink can be obtained by converting the ratio of the resin and the pigment charged in the ink.
- a dispersion in an aqueous medium is composed of only colored microcapsules, and free pigment particles that are not coated with a film-forming resin or “particles of only a film-forming resin containing no pigment” are used. If not included, measurement can be made with particularly high accuracy. If the ink contains additives such as anti-drying agents and penetrants, it is necessary to dry and remove the former at a temperature at which the pigment and the film-forming resin do not decompose. Thus, the measurement accuracy can be further increased.
- the following method is particularly preferable when the pigment is coated using a film-forming resin having an acid value.
- a resin and a component derived from a pigment dispersed in an aqueous medium consist of only colored microcapsules, and “free pigment particles not coated with a film-forming resin” or “a pigment-free film”. It is possible to easily obtain an extremely small amount of ink even if it does not contain any of the particles containing only the forming resin or the dissolved film-forming resin.
- the following method involves dispersing pigment fine particles in an organic solvent solution of a self-water dispersible resin.
- particles of only the film-forming resin containing no pigment or the dissolved film-forming resin It is possible to more easily obtain an ink which does not contain or contains a very small amount.
- At least water, an organic solvent that dissolves the film-forming resin, a base, and the solid coloring compound obtained in the resin coloring step are mixed, and dispersed by dispersion to at least partially dissolve the resin.
- a colorant is dispersed in a film-forming resin having an acid value to obtain a solid colored compound. (Kneading process)
- the colorant is uniformly dispersed in the resin in a solution or a heated and molten state. (Solid colored compound).
- a dispersing means capable of forming a state where a relatively high shearing force is applied, among conventionally known dispersing methods, Specifically, it is preferable to perform dispersion under high shearing force using two rolls.
- the organic solvent that dissolves the resin functions as a good solvent for the resin, and can be appropriately selected for the resin.
- ketones such as acetone, dimethyl ketone, and methyl ethyl ketone are used.
- Solvent, methanol, ethanol, isop Alcohol solvents such as pill alcohol, chlorinated solvents such as chloroform, methylene chloride, etc .; aromatic solvents such as benzene and toluene; ester solvents such as ethyl acetate; ethylene glycol monomethyl ether; ethylene glycol dimethylene Any solvent can be used as long as it can dissolve resins such as glycol ether solvents such as ter and amides.
- the dispersion medium used in this step is mainly water that functions as a poor solvent for the film-forming resin, and since it is used as an aqueous ink for inkjet recording, it preferably has a purity of ion exchange water or higher.
- the mixed solution of water and the organic solvent is uniform. If not, if necessary, use a surfactant or mechanically emulsify it into an O / W type. It is preferable to use a co-solvent together to make it uniform.
- the organic solvent and co-solvent that dissolve the resin may be used alone or in combination of two or more.
- the resin is selected from the group consisting of, for example, styrene, substituted styrene, and (meth) acrylate.
- a ketone solvent such as methyl ethyl ketone is mainly used, and an auxiliary solvent is selected from alcohol solvents such as isopropyl alcohol. At least one combination is better.
- the ratio between the water and the organic solvent is not particularly limited as long as the effects of the present invention are achieved, but is preferably an amount such that the weight ratio of the water Z organic solvent is 10/1 to 1/1.
- any known and commonly used method can be employed.
- a stirring blade or a stirring vessel having a desired shape can be easily used. It can be suspended in
- the reprecipitation step of ⁇ 3> can be immediately performed.
- the suspension step of ⁇ 2> and the ⁇ In order to increase the dispersion stability of the suspension obtained from the former compound and to reduce the particle size of the colorant particles in the colorant suspension obtained from the latter compound, between the reprecipitation step and 3). Therefore, it is preferable to provide a step of exposing and dispersing the suspension under high shear.
- the film-forming resin component dissolved in the pigment suspension is deposited on the surface of the pigment to obtain microcapsules.
- This step is a step of depositing the dissolved resin component present in the suspension on the surface of the colorant in the colorant suspension obtained in the suspension step.
- the term “reprecipitation” in this step does not mean that particles in a semi-capsule state in which the colorant or the dissolved resin is adsorbed on the surface of the colorant are separated and settled from the liquid medium of the suspension. Therefore, what is obtained in this step is not a simple mixture in which the solid component and the liquid component are clearly separated, but the colorant that has absorbed the dissolved resin on the colorant surface is stable in the liquid medium of the suspension. This is an aqueous dispersion of colored resin particles, which is specifically dispersed.
- this step includes dissolving the pigment present in the suspension on the surface of the pigment in the pigment suspension obtained in the suspension step.
- This is a step of depositing a resin component and a dispersed resin component.
- the “re-precipitation” in this step does not mean that the pigment or the particles in a semi-capsule state in which the dissolved resin is adsorbed on the pigment surface is separated and settled from the liquid medium of the suspension. Therefore, what is obtained in this step is not a mere mixture in which the solid component and the liquid component are clearly separated, and the microcapsules in which the soluble resin-dispersed resin is coated on the pigment surface are stable in the liquid medium of the suspension.
- Colored resin particles are aqueous dispersions. That is, the deposition of the dissolved resin on the surface of the free colorant in the colorant suspension and on the surface of the colorant particles coated with Z or the self-water dispersible resin is caused by the free colorant and Z or self-water dispersion.
- the process is performed in a state in which the colorant particles whose surfaces are coated with a hydrophilic resin are dispersed in an aqueous medium.
- the deposition of the dissolved resin on the surface of the free colorant in the colorant suspension in this suspension step and on the surface of the colorant particles coated with Z or self-water-dispersible resin is carried out by dissolving the dissolved resin component into the aqueous medium. Can be carried out by lowering the solubility of the resin component.
- a necessary amount of the poor solvent for the resin is added to the aqueous medium in which the resin component is dissolved, or the resin component is contained in the aqueous medium. ⁇
- chemical components that dissolve fat components are removed from the system in required amounts.
- the dissolved resin preferentially approaches the surface of the free colorant particles dispersed in the system and / or the surface of the colorant particles whose surface is coated with the self-water dispersible resin. It deposits on each surface, and is pressed down on it.
- the deposition of the dissolved resin on the surface of the colorant in the colorant suspension in the suspension step includes, for example, (1) at least partly adding the resin to the colorant suspension in which the film-forming resin is dissolved.
- the method can be easily carried out by adding an aqueous medium functioning as a poor solvent, and / or (2) removing the organic solvent from the colorant suspension.
- the deposition of the resin on the surface of the microcapsule includes, for example, (1) at least a part of the film-forming resin dissolved and / or Easily by adding to the dispersed pigment suspension an aqueous medium that functions as a poor solvent for the resin, and / or by removing the organic solvent from the pigment suspension. You can do it.
- an aqueous medium that functions as a poor solvent for the resin is added to the colorant suspension is preferable because it causes less aggregates.
- the aqueous medium is dropped while the suspension is gently stirred, so that the resin can be surely deposited (reprecipitated) on the surface of the colorant while preventing the generation of aggregates.
- the anti-drying agent is previously present in the aqueous medium or added after reprecipitation.
- the finally obtained colored resin particle dispersion is used as a jet ink
- a jet ink is used to realize stable ejection without clogging.
- the average particle diameter is on the order of submicrons (less than 101).
- the aqueous dispersion of colored resin particles having a sub-micron opening obtained by the method for producing an aqueous dispersion of colored resin particles of the present invention when used as an aqueous ink for ink jet recording, has excellent dispersion stability and excellent jetting properties. Is shown.
- the suspension in the suspension step (2) contains an anti-drying agent, thereby achieving extremely high dispersion stability. Excellent suspensions and aqueous dispersions as well as aqueous inks are obtained.
- the colored resin particles having a desired particle diameter can be obtained by the above ⁇ 1> kneading step ⁇ 2> suspension step ⁇ 3> reprecipitation step, and the average particle diameter range is usually 0.0. 1 or more and less than 1 / m.
- the aqueous dispersion of colored resin particles obtained in the reprecipitation step can be used as it is.
- the colored resin particles are often swollen due to the coexisting organic solvent, so the solvent must be removed to further improve the storage stability and to enhance the safety against fire and pollution. Is preferred.
- the organic solvent removed in this manner can be recycled and reused in a closed system without incineration, for example, for the purpose of continuous production.
- the aqueous dispersion of colored resin particles (colored microcapsules) obtained through the steps ⁇ 1> to ⁇ 4> is made up entirely of “colored microcapsules” derived from the resin and pigment used in the preparation.
- This is an aqueous dispersion composed of only “capsules” and substantially does not include the three components of "free pigment particles", “particles of film-forming resin only", and "dissolved film-forming resins".
- it is extremely difficult to reduce the amount of the dissolved film-forming resin component to zero its content is generally at least 0.01% by mass of all components constituting the dispersion.
- the dispersion thus obtained usually consists essentially of a pigmented microcapsule capsule coated with a film-forming resin and a dispersion medium.
- the content of the colored microcapsules in the dispersion is usually from 10 to 40% by mass based on the total of the dispersion and the dispersion medium.
- various additives are included in the steps up to this point, they are also included in the dispersion.
- a jet ink comprising pigment fine particles (a) coated with a film-forming resin (b) having a carboxyl group and colored fine particles (d) dispersed in an aqueous medium.
- the fine particles (d) have a quaternized carboxyl group on the surface thereof and have a volume average particle size of 0.5 xm or less.
- the jet ink is characterized in that the “increase rate of the volume average particle size of the fine particles (d)” is 50 percent or less, but the ink having such excellent characteristics can be easily obtained. Therefore, it is preferable to adopt the following manufacturing method.
- a coloring compound (V) formed by kneading a pigment and a film-forming resin (b) having a carboxyl group, (ii) water, and the film-forming resin (b) can be dissolved.
- aqueous medium (W) comprising the organic solvent (e) and (iii) the basic compound (c)
- the pigment fine particles (a) are coated with a film-forming resin (b) having lipoxyl groups.
- the step (3) is carried out in the case where the dispersion-forming liquid (X) contains no quaternized carboxyl group (that is, a salt structure) dissolved film-forming resin,
- the dispersion stability of the colored fine particles (d) dispersed in the liquid (X) is good, there is no need to add a poor solvent for the film-forming resin (b), and the organic solvent (e) is removed. You can just do it.
- the aqueous dispersion of colored resin particles on the order of submicron, which contains no or almost no liquid medium other than water, obtained by the step ⁇ 4>, is basically an aqueous ink for ink jet recording. Can be used as It is preferable to adjust the ink of the obtained dispersion liquid in consideration of dispersion stability and jetting characteristics.
- the ink is passed through a filter having a desired particle diameter and filtered, and the ink jet recording apparatus is an aqueous ink for ink jet recording in which only particles having a small nozzle diameter are dispersed in a liquid medium. Served as use.
- the adjustment of the ink is performed, for example, by adding the above-mentioned anti-drying agent or permeable organic solvent, adjusting the concentration, adjusting the viscosity, adjusting the pH, dispersing the surfactant, dispersing the ink into the paper, and preserving the ink.
- Agents, chelating agents, plasticizers, antioxidants, ultraviolet absorbers and the like can be added as necessary.
- various additives those which do not dissolve the film-forming resin present on the surface of the colored microcapsules are selected and only those having such properties are used, or the same additives can be dissolved. It is necessary to take measures such as minimizing the amount of use to a concentration that does not substantially dissolve the substance.
- the recording medium is something other than impervious recording medium such as glass 'metal' film (permeable recording medium), it differs from the film-forming resin to the extent that it does not affect the jetting stability. However, other water-soluble resins can also be added.
- the colored microcapsule-dispersed aqueous jet ink of the present invention can be used in any conventional ink jet recording system such as a piezo system or an on-demand system.
- the ink can be used to form an image on a known and commonly used recording material, for example, paper, resin-coated paper, ink-jet recording paper, glass, metal, film, ceramic, and the like.
- the colored microcapsule-dispersed aqueous jet ink of the present invention is excellent in transparency, color-developing property and dispersion stability, and can be applied to other inks, paints, and color filters in addition to inkjet recording. is there.
- a stable jet without clogging of the nozzle is realized by using the aqueous dispersion of colored resin particles smaller than the nozzle diameter of the inkjet recording device obtained in the following process, and the dispersion stability during storage and printed matter An aqueous jet ink having excellent water resistance and a colored resin particle dispersion type.
- At least water, an organic solvent that dissolves the film-forming resin, an amount of a base that minimizes the amount of the water-soluble resin component, and the solid coloring compound obtained in the resin coloring step are mixed to form a film-forming resin.
- a colored microcapsule-dispersed aqueous jet ink characterized in that:
- At least water, an organic solvent dissolving the film-forming resin, a base, and the solid coloring compound obtained in the resin coloring step are mixed, and the film-forming resin is self-dispersed in water and at least a part of the resin is dispersed. Suspension process to obtain a pigment suspension adjusted to dissolve
- At least water, an organic solvent dissolving the film-forming resin, a base, and the solid coloring compound obtained in the resin coloring step are mixed, and the film-forming resin is self-dispersed in water and at least a part of the resin is dispersed. Suspension process to obtain a pigment suspension adjusted to dissolve
- a reprecipitation step in which the solubility of the resin component in the aqueous medium of the dissolved resin component is reduced on the surface of the pigment in the pigment suspension obtained in the suspension step to deposit the dissolved resin component.
- a resin coloring step in which at least a pigment is dispersed in a film-forming resin having an acid value to obtain a solid coloring compound.
- At least water, an organic solvent that dissolves the film-forming resin, a base, and the solid coloring compound obtained in the resin coloring step are mixed, and the film-forming resin is self-dispersed in water and at least a part of the resin is dispersed. Suspension process to obtain a pigment suspension adjusted to dissolve
- aqueous medium that functions as a poor solvent for the dissolved resin is added to the surface of the pigment in the pigment suspension obtained in the suspension step, and the organic solvent is removed from the suspension.
- a resin coloring step in which at least a pigment is dispersed in a film-forming resin having an acid value to obtain a solid coloring compound.
- At least water, an organic solvent that dissolves the film-forming resin, a base, and the solid coloring compound obtained in the resin coloring step are mixed, and the film-forming resin is self-dispersed in water.
- aqueous medium that functions as a poor solvent for the dissolved resin is added to the surface of the pigment in the pigment suspension obtained in the suspension step to form a film, and then an organic solvent that dissolves the resin is formed.
- the solvent is removed from the suspension, and the solubility of the resin component in the aqueous medium is reduced by reducing the solubility of the resin component in the aqueous medium on the pigment surface in the pigment suspension obtained in the suspension step.
- the pigment and the film-forming resin having an acid value are the same, or both are used such that the pigment has a mass of ⁇ 15% of the mass of the resin. 1, 2, 3, 4, 5 above , 6, 7, 8, 9, 10, and 11.
- the self-water-dispersible film-forming resin is neutralized with a neutralization rate of not more than 60 mol% of the acid group of the resin having an acid value of 5 ( ⁇ to 18 Omg ⁇ KOHZg). 2.
- the film-forming resin having an acid value is a resin having an acid value of 50 to 180 mg * KOH / g, and a base having a neutralization ratio of not more than 60 mol% of the acid group.
- a jet ink in which pigment fine particles (a) are coated with a film-forming resin (b) having a carboxyl group and colored fine particles (d) are dispersed in an aqueous medium, (1)
- the colored fine particles (d) have a quaternized carboxyl group on the surface thereof and have a volume average particle diameter of 0.5 im or less.
- a jet ink characterized in that the “increase rate of the volume average particle diameter of the colored fine particles (d)” is 50% or less.
- the film-forming resin (b) having a lipoxyl group has an acid value of 50 to 180, and a part or all of the resin is an organic amine compound which is converted into a quaternary ammonium salt. Jet ink described in 15, 16, 17 above.
- Pigment fine particles (a) coated with a film-forming resin (b) having a carboxyl group, and colored fine particles having a quaternized carboxyl group on the coated surface
- a method for producing a dispersion of colored fine particles for jet-ink comprising removing the organic solvent (e) from the dispersion (X).
- An ink adjusting agent is added to the ink base to adjust the concentration and physical properties, followed by filtration.
- the colored microcapsules are 0.5 to 20% by mass in terms of pigment, pH 7.5 to 7.5%.
- the water-based ink for ink-jet recording of 11 was used.
- the content of the film-forming resin component dissolved in the ink is also set to 0.1 to 1% by mass.
- parts means “parts by mass”.
- particle diameter of the colored fine particles was measured using the above-mentioned “Microtrac particle size analyzer manufactured by Leeds and No. Slap Co., Ltd.” In each case of measuring the particle size S2, a slide glass provided with a hole defined in the specification on the surface was used.
- a roll kneaded mixture is a mixed solution of 210 parts of water, 35 parts of glycerin, 8 parts of triethanolamine (equivalent to 50 mol% of acid groups), 90 parts of methylethyl ketone, and 40 parts of isopropyl alcohol. And stirred at room temperature for 3 hours to obtain a colorant suspension.
- This aqueous dispersion was filtered using a 1-m filter to obtain an aqueous ink for ink jet recording.
- the microcapsules in the obtained aqueous ink have an average particle size of 0.09 jum, show stable dispersion for a long time without agglomerates, and print using a piezo inkjet printer stably.
- the obtained printed matter showed high blackness without bleeding, and was excellent in water and light resistance.
- Water-based inks are collected using an ultracentrifuge Acceleration 9. 8 km / s 2 - precipitated microcapsules particles by centrifugation conditions for 3 hours, allowed to resulting sediment 140 more hours drying at 1 0 5 oven, film-forming ⁇ pigment only After that, the ratio of the resin to the pigment was determined by a thermal analyzer, and only the film-forming resin dissolved in the ink was determined to be 0.3% by mass. Even after storage at room temperature for one year, the print on the pudding was stable without agglomerates, and the printed matter was excellent in water and light resistance.
- Example 1 Except for excluding methyl ethyl ketone (a good organic solvent that dissolves the film-forming resin), the two-roll kneaded material was stirred in the same manner as in Example 1 except that the suspension composition of Example 1 was used. The substance did not dissolve, a suspension was not obtained, and no ink could be formed.
- methyl ethyl ketone a good organic solvent that dissolves the film-forming resin
- Example 2 (Example 1 for magenta ink)
- a mixture of 22 parts of glycerin and 250 parts of water was added dropwise to the obtained suspension at a rate of 5 ml / min with stirring to obtain a magenta colored resin particle dispersion.
- Methyl ethyl ketone and isopropyl alcohol were distilled off from the obtained capsule solution using a rotary evaporator to obtain a final aqueous dispersion of magenta colored resin particles.
- This aqueous dispersion was filtered using a 1 tm filter and used as an ink jet recording aqueous ink.
- the colored resin particles in the obtained aqueous ink have an average particle diameter of 0.12 / m, exhibit stable dispersion for a long time without aggregation, and are printed using a piezo-type inkjet printer.
- the obtained printed matter had no bleeding, showed a very vivid magenta evening color with high transparency, and was excellent in water resistance and light resistance.
- the capsule particles are allowed to settle, and the obtained precipitate is dried in an oven at 105: for 140 hours to obtain only the film-forming resin and the pigment, and then the ratio of the resin to the pigment is determined by a thermal analyzer.
- the film-forming resin component dissolved in the ink was determined, it was 0.3% by mass. Even after storage at room temperature for one year, printing on the printer was stable without agglomerates, and the printed matter was excellent in water and light resistance.
- Example 3 (Example 2 of magenta evening ink)
- the microcapsules in the obtained aqueous ink had an average particle size of 0.15 / m, and had a pH of 8.4. Acceleration 9
- the ratio of resin to pigment was determined by a thermal analyzer, and only the film-forming resin dissolved in the ink was determined. It was 4% by mass.
- This ink shows stable dispersion without aggregation after storage for 1 year at room temperature.
- Printing using the ZO-type ink pudding Yuichi is stable, and the obtained printed matter shows a vivid magenta evening color (print density 1.30) without bleeding.
- the print density after immersion in purified water for 24 hours was 1.30, which was no change from that before printing.
- Example 4 (Example 3 of mazen evening ink)
- Example 3 To 100 parts of the ink of Example 3 was added 0.1 part of a propylene oxide addition polymer of vinyl alcohol (average number of moles of added propylene oxide 17.7), and the mixture was sufficiently stirred to obtain an ink.
- a propylene oxide addition polymer of vinyl alcohol average number of moles of added propylene oxide 17.7
- the microcapsules in the obtained aqueous ink had an average particle diameter of 0.15 m, and had a pH of 8.4.
- the content of the film-forming resin dissolved in the ink in the same manner as in Example 3 was found to be 0.4% by mass.
- This ink shows stable dispersion without aggregation after storage at room temperature for one year, and printing using a piezo ink jet printer is more stable than that of Example 3; Shows a vivid magenta evening color (print density 1.30) without bleeding, and the print density immediately after printing is immersed in purified water for 24 hours and the print density is 1.30, which is completely the same as before printing. No change.
- Example 5 Magnetic ink example 4.
- the microcapsules in the obtained aqueous ink had an average particle size of 0.15 jLtm, and had a pH of 8.4.
- the content of the film-forming resin dissolved in the ink was determined in the same manner as in Example 3, and was found to be 0.6% by mass.
- This ink shows stable dispersion without aggregation after storage at room temperature for one year, and printing using a piezo ink jet printing is more stable than in Example 4, and the recording paper
- the drying immediately after printing was remarkably fast and instantaneous as compared with Examples 3 and 4.
- the obtained printed matter showed moderate bleeding, was superior in the smoothness of the printed portion in comparison with Examples 3 and 4, and exhibited a vivid magenta evening color (print density 1.35).
- the recording paper was immersed in purified water for 24 hours, the print density was 1.35, which was no change from that before printing.
- Example 6 Example of cyan ink
- the microcapsules in the obtained aqueous ink had an average particle size of 0.17 // m, and had a pH of 8.6.
- the content of the film-forming resin dissolved in the ink was determined in the same manner as in Example 3, and was found to be 0.2% by mass.
- This ink shows stable dispersion without aggregation after storage at room temperature for one year, and printing using the piezo-type ink jet printing is stable. It showed a cyan color (print density 1.30), and the print density after immersing the recording paper immediately after printing in purified water for 24 hours was 1.30, which was no change from that before printing.
- the obtained ink has good dispersibility and no agglomerates even when left in a glass container at room temperature for one year.As a result of a jet test using a piezo ink jet pudding, there is no nozzle clogging. Stable jetting was possible, and the resulting plain paper print was clear and excellent in water resistance.
- Example 7 (Example of yellow ink)
- Example 3 In the same manner as in Example 3, except that the pigment used in Example 3 was replaced with CI Yellow Yellow 151, an aqueous dispersion of yellowish-colored resin particles was similarly obtained.
- aqueous dispersion To 2 parts of the aqueous dispersion, 3 parts of glycerin as an anti-drying agent and 5 parts of propylene glycol propyl ether as a penetrant were added, and the concentration was 3.3 mass in terms of pigment of the colored microcapsules in the ink. %, Stirred, and then filtered using a l / m filter to obtain an aqueous ink for ink jet recording.
- the microcapsules in the obtained aqueous ink had an average particle size of 0.18 and its pH was 8.4.
- the content of the film-forming resin dissolved in the ink was determined in the same manner as in Example 3, and was found to be 0.5% by mass.
- This ink shows stable dispersion without aggregation after storage at room temperature for one year, and printing using a piezo-type ink jet printer is stable.
- the obtained printed matter has no bleeding and bright yellow ( The print density was 1.17), and the print density after immersing the recording paper immediately after printing in purified water for 24 hours was 1.17, which was no change from that before printing.
- the obtained ink had good dispersibility and no agglomeration even when left in a glass container at room temperature for one year.As a result of a jet test using a piezo-type ink jet pudding, there was no nozzle clogging. Stable jetting was possible, and the obtained plain paper print was clear and excellent in water resistance.
- Example 8 (example of black ink)
- the microcapsules in the obtained aqueous ink had an average particle size of 0.09 m and the pH was 8.5.
- the content of the film-forming resin dissolved in the ink was determined in the same manner as in Example 3, and was found to be 0.6% by mass.
- This ink shows stable dispersion without aggregation after storage at room temperature for one year, and printing using a piezo-type ink jet printer is stable. It shows a near black color (print density 1.32), and the print density immediately after printing was immersed in purified water for 24 hours, and the print density was 1.35. .
- each of the inks in the above examples had no change in the volume average particle diameter even when the inks immediately after preparation and those immediately after preparation were filled in containers, sealed and left at room temperature for one year.
- the colored resin particles in the aqueous colored resin particle dispersion obtained by the method for producing an aqueous dispersion of colored resin particles of the present invention have a fine particle diameter and are extremely excellent in dispersion stability.
- it does not destroy the features of resin-dispersed water-based inks with excellent print quality, water resistance, and light fastness, has excellent dispersion stability, and does not cause nozzle clogging, and enables stable ink jetting characteristics.
- the amount of the film-forming resin component dissolved in the ink is adjusted to 2% by mass or less.
- the rate of increase of the volume average particle size of the colored fine particles in the ink redispersion liquid is 50% or less, and the dispersion stability with time is excellent, and the ejection characteristics and the image sticking property to the recording medium are particularly remarkable. It produces various technical effects.
- the stable ink jetting characteristics that are excellent in dispersion stability, without nozzle clogging, without losing the characteristics of the resin dispersion type water-based ink having excellent print quality, water resistance, and light resistance. enable.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/068,340 US6074467A (en) | 1996-09-13 | 1997-09-11 | Jet ink and process for preparing dispersion of colored fine particles for jet ink |
EP97940350A EP0861880B1 (en) | 1996-09-13 | 1997-09-11 | Jet ink and process for preparing dispersion of colored fine particles for jet ink |
DE69736547T DE69736547T2 (de) | 1996-09-13 | 1997-09-11 | Tintenstrahltinte und verfahren zur herstellung einer dispersion von gefärbten feinpartikeln für diese tinte |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24316196A JPH1088042A (ja) | 1996-09-13 | 1996-09-13 | 着色樹脂粒子水分散液製造方法 |
JP8/243161 | 1996-09-13 | ||
JP9/103145 | 1997-04-21 | ||
JP10314597A JP3882956B2 (ja) | 1997-04-21 | 1997-04-21 | 着色マイクロカプセル分散型水性ジェットインク |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998011170A1 true WO1998011170A1 (fr) | 1998-03-19 |
Family
ID=26443802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1997/003211 WO1998011170A1 (fr) | 1996-09-13 | 1997-09-11 | Encre pour impression par jets et procede de preparation d'une dispersion de fines particules colorees pour cette encre |
Country Status (6)
Country | Link |
---|---|
US (1) | US6074467A (ja) |
EP (1) | EP0861880B1 (ja) |
KR (1) | KR100517535B1 (ja) |
CN (2) | CN1222584C (ja) |
DE (1) | DE69736547T2 (ja) |
WO (1) | WO1998011170A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0953615A2 (en) * | 1998-04-30 | 1999-11-03 | Hewlett-Packard Company | Homogenization process for ink-jet inks containing fine dispersions of pigments |
KR100463082B1 (ko) * | 1999-02-16 | 2004-12-23 | 다이니치 세이카 고교 가부시키가이샤 | 안료분산액, 필기구용 잉크 및 프린터용 잉크 |
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1997
- 1997-09-11 DE DE69736547T patent/DE69736547T2/de not_active Expired - Lifetime
- 1997-09-11 WO PCT/JP1997/003211 patent/WO1998011170A1/ja active IP Right Grant
- 1997-09-11 EP EP97940350A patent/EP0861880B1/en not_active Expired - Lifetime
- 1997-09-11 KR KR1019980703586A patent/KR100517535B1/ko not_active IP Right Cessation
- 1997-09-11 CN CNB031017614A patent/CN1222584C/zh not_active Expired - Fee Related
- 1997-09-11 US US09/068,340 patent/US6074467A/en not_active Expired - Lifetime
- 1997-09-11 CN CN97191250A patent/CN1130433C/zh not_active Expired - Fee Related
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JPS50122528A (ja) * | 1974-03-13 | 1975-09-26 | ||
JPH05247370A (ja) * | 1992-03-10 | 1993-09-24 | Dainichiseika Color & Chem Mfg Co Ltd | 画像記録用着色組成物 |
JPH08183920A (ja) * | 1994-10-31 | 1996-07-16 | Dainippon Ink & Chem Inc | インクジェット記録用水性インク及びその製造方法 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0953615A2 (en) * | 1998-04-30 | 1999-11-03 | Hewlett-Packard Company | Homogenization process for ink-jet inks containing fine dispersions of pigments |
EP0953615A3 (en) * | 1998-04-30 | 2000-01-26 | Hewlett-Packard Company | Homogenization process for ink-jet inks containing fine dispersions of pigments |
KR100463082B1 (ko) * | 1999-02-16 | 2004-12-23 | 다이니치 세이카 고교 가부시키가이샤 | 안료분산액, 필기구용 잉크 및 프린터용 잉크 |
Also Published As
Publication number | Publication date |
---|---|
EP0861880A1 (en) | 1998-09-02 |
EP0861880A4 (en) | 2001-12-19 |
CN1130433C (zh) | 2003-12-10 |
US6074467A (en) | 2000-06-13 |
CN1205025A (zh) | 1999-01-13 |
KR100517535B1 (ko) | 2006-05-09 |
DE69736547T2 (de) | 2007-09-13 |
DE69736547D1 (de) | 2006-10-05 |
CN1473889A (zh) | 2004-02-11 |
EP0861880B1 (en) | 2006-08-23 |
CN1222584C (zh) | 2005-10-12 |
KR19990067563A (ko) | 1999-08-25 |
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