JP2003012709A - Aqueous colored fine resin particle dispersion, method for producing the same, colored fine resin particle, method for producing the same, ink, recording unit, ink cartridge, ink-jet recording device and ink-jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain colored resin fine particles having waterproof property, weather resistance and scratch resistance, further giving an image having a high color-developing property, excellent in dispersion stability and useful as a coloring material of an ink. SOLUTION: A method for producing an aqueous colored resin fine particle dispersion is characterized by comprising (i) a process of performing a phase- transition emulsification of a polymerizable unsaturated monomer, a coloring agent, an emulsifying agent and a polymerization initiator in an aqueous medium by using a mixer used for a high viscosity coating material and (ii) a process of polymerizing the above polymerizable unsaturated monomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to water resistance and weather resistance,
The present invention relates to a colored resin fine particle useful as a coloring material for an ink, which gives an image having scratch resistance and is excellent in dispersion stability, an aqueous dispersion thereof, and a method for producing them. The present invention also relates to an ink which gives an image having water resistance, weather resistance, and scratch resistance, is excellent in dispersion stability, and is also excellent in ejection stability from a recording head when used for inkjet recording. .
Further, the present invention relates to a recording unit, an ink cartridge, an inkjet recording device and an inkjet recording method.

[0002]

2. Description of the Related Art An ink jet recording method is one in which recording is performed by ejecting ink and adhering the ink to a recording medium such as paper. For example, Japanese Patent Publication No. 61-59911, Japanese Patent Publication No. 61-59912 and Japanese Patent Publication No. 61-5.
According to the ink jet recording method disclosed in Japanese Patent No. 9914, in which an electrothermal converter is used as the ejection energy supply means and thermal energy is applied to ink to generate bubbles to eject droplets, a recording head is provided. High density multi-orifice can be easily realized, and high resolution and high quality images can be recorded at high speed.

By the way, a water-soluble dye, for example, is used as a coloring material in an ink used in a conventional ink jet recording method, and a recorded image by such an ink is required to have further improved water resistance. ing. Further, water-soluble dyes up to now have insufficient weather resistance, and improvement in weather resistance is also required at the same time.

On the other hand, as a means for improving water resistance and weather resistance, there is a technique of using a pigment as a coloring material and dispersing it in water to prepare an ink. However, it is difficult to achieve both the dispersion stability of the pigment and the ejection stability of inkjet recording, and the recorded image obtained with the pigment ink is
In particular, there is still room for improvement in scratch resistance on plain paper. And many means to improve such a subject have been proposed so far.

For example, many techniques have been proposed for adding a resin to a pigment ink for the purpose of improving scratch resistance.
However, there remains a problem that the viscosity of the ink increases due to the added resin. A technique has been proposed in which resin particles are added to the ink for the purpose of suppressing an increase in the viscosity of the ink, but since the resin particles and the pigment are separately dispersed in the ink, the scratch resistance of the obtained image is improved. Was insufficiently improved.

On the other hand, a technique of coating a pigment with a resin has been proposed. Many techniques have been proposed to increase the adsorptivity to the pigment by controlling the hydrophobic and hydrophilic parts of the resin.However, in this production method, the resin floating without adsorbing to the pigment remains in the system. As a result, the viscosity of the ink may be increased, and the ejectability of the ink may be impaired.

As a production method in which such a free resin does not remain, a technique is proposed in which a pigment is added from the stage of a monomer before the resin is prepared, polymerization is performed in the presence of the pigment, and the pigment is coated with the resin. Has been done.

For example, Japanese Unexamined Patent Publication (Kokai) No. 9-279073 discloses a technique for obtaining colored resin fine particles by adding a colorant having an affinity to the unsaturated monomer and emulsion-polymerizing it.
Further, JP-A-11-12512 discloses a technique of adding a pigment to an ethylenically unsaturated monomer and emulsion-polymerizing it to obtain an inkjet ink.

However, according to the study by the present inventors, it is very difficult to obtain the dispersion stability at the time of emulsifying the unsaturated monomer and the pigment, and at this time, the dispersion stability is If it was insufficient, it was feared that the obtained dispersion would also have low stability.

For example, Japanese Patent Laid-Open No. 9-279073 mentioned above.
According to the description in the specification, the colored resin particles described in the publication can be manufactured according to a conventional emulsion polymerization method, and the monomer and the colorant are also used in Examples. After mixing, it is produced by emulsification in water to which an emulsifier has been added, and emulsion polymerization.

However, according to the study by the present inventors, the polymerization proceeds while the mixed liquid of the monomer and the colorant is sheared, so that the particle size varies due to the difference in shearing, and in this method, it is uniform. It was speculated that it is difficult to obtain colored resin particles having a small particle size. According to the description of the specification, the inkjet ink described in JP-A-11-12512 is a method for producing a monomer oil droplet of 0.5 μm or less by using a pipeline mixer or the like when emulsion polymerization is performed. Is listed. However, according to the study by the present inventors,
It is difficult to narrow the particle size distribution only by mechanical dispersion, and if a strong mechanical shearing force is given,
It was speculated that the temporal stability of the particle size would be impaired.

In the method of the above publication, the mass ratio of the polymerizable unsaturated monomer to the pigment is about 10 as in the embodiment.
It is about / 1, and at such a low pigment concentration, sufficient image density cannot be obtained when the ink is used.

[0013]

As described above, the inventors of the present invention have studied conventional techniques and found that not only water resistance and weather resistance but also scratch resistance and further dispersion stability and ejection stability in ink jet inks. With regard to sex, it was concluded that a new technological development, which is different from the previous one, is necessary to achieve further improvement.

As a result of extensive studies, the present inventors have found that as a technique capable of solving the above-mentioned problems in the conventional method for producing colored resin fine particles, the advantages of using colored resin fine particles as a coloring material can be utilized. In a method of emulsifying at least a polymerizable unsaturated monomer, a colorant, an emulsifier and a polymerization initiator in an aqueous medium, and polymerizing the same to produce colored resin fine particles, use a phase inversion emulsification method in the emulsification step. Found.

In the present invention, in the production of an aqueous dispersion of colored resin fine particles using the phase inversion emulsification method, the particle size distribution of the colored resin fine particles is narrower, and the storage stability and ejection stability of the ink when made into an ink are improved. It was made as a result of repeated studies on technologies that can be made even better. Therefore, an object of the present invention is to provide a colored resin fine particle useful as a coloring material of an ink, which has water resistance, weather resistance, and scratch resistance, provides an image with high color development, and has extremely excellent dispersion stability. Another object is to provide an aqueous dispersion and a method for producing the same. Another object of the present invention is to provide colored resin fine particles which are excellent in colorability, have a small particle size and are uniform, and which are suitable for use as an ink, and a method for producing the same. Another object of the present invention is to provide an ink which gives an image with high color developability, is excellent in dispersion stability, and is also very excellent in ejection stability from a recording head when used for inkjet recording. is there. Another object of the present invention is water resistance, weather resistance,
An object of the present invention is to provide an inkjet recording apparatus that is scratch-resistant and that can more stably form an image with high color development, and a recording unit and an ink cartridge that can be used for the inkjet recording apparatus. Still another object of the present invention is to provide an ink jet recording method having water resistance, weather resistance and scratch resistance and capable of more stably forming an image having high color developability.

[0016]

[Means for Solving the Problems] As a result of repeated studies by the present inventors in order to solve the above problems, as a result of increasing the ratio of the colorant while taking advantage of the advantage of using colored resin fine particles as the colorant. The inventors have found a technique capable of solving the problem of a method for producing colored resin fine particles in a system having a high thixotropic property at the time of phase inversion, which has led to the present invention.

That is, according to one aspect of the present invention, (i) a phase-inversion emulsification of a polymerizable unsaturated monomer, a colorant, an emulsifier and a polymerization initiator is carried out in an aqueous medium by using a mixer for high viscosity paint. Process;
And (ii) a step of polymerizing the polymerizable unsaturated monomer, to provide a method for producing an aqueous dispersion of colored resin fine particles.

In the present invention, the emulsifier is a reactive emulsifier; the colorant is a pigment; the colorant is a pigment previously coated with a water-insoluble resin; the water-insoluble resin is a vinyl resin. At least one resin selected from the group consisting of cellulose resins and acrylic resins; the water-insoluble resin is a vinyl chloride-vinyl acetate copolymer; and the polymerization initiator is a polymerizable unsaturated monomer. It is preferably an oil-soluble polymerization initiator soluble in water and the polymerization method is a suspension polymerization method.

Another embodiment of the present invention provides an aqueous dispersion of colored resin particles, which is obtained by the method for producing an aqueous dispersion of colored resin particles described above. Another aspect of the present invention is (i) a step of phase inversion emulsification of a polymerizable unsaturated monomer, a colorant, an emulsifier and a polymerization initiator in an aqueous medium using a mixer for high viscosity paints; And (ii) a step of polymerizing the polymerizable unsaturated monomer, to provide a method for producing colored resin fine particles. Another aspect of the present invention provides colored resin fine particles obtained by the above method for producing colored resin fine particles. Another aspect of the present invention provides an ink comprising the above-mentioned colored resin fine particle water dispersion. Another aspect of the present invention provides an ink containing the above-mentioned colored resin fine particles and a liquid medium. Further, these inks can be ink jet inks.

Another aspect of the present invention provides a recording unit comprising an ink containing portion containing the above ink jet ink and a head portion for ejecting the ink. To do. Another aspect of the present invention provides an ink cartridge including an ink containing portion containing the above ink. Further, another aspect of the present invention provides an inkjet recording apparatus including an ink containing portion containing the above-described inkjet ink and a recording head for ejecting the ink. To do. Another aspect of the present invention provides an ink jet recording method, which comprises a step of ejecting the above ink jet ink by an ink jet method.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The method for producing colored resin fine particles according to the embodiment of the present invention, at least a polymerizable unsaturated monomer, a colorant, an emulsifier and a polymerization initiator are emulsified in an aqueous medium, and this is polymerized to produce colored resin fine particles. In the above method, one feature is that phase inversion emulsification is performed in the emulsification step by using a mixer for high-viscosity paint or a mixer and a high-speed shearing emulsifier.

As an emulsification method, in general, an emulsifier is added to water, an oil component is added to this, and the mixture is stirred with a disperser (hereinafter referred to as a direct emulsification method), or an emulsifier is added to the oil component. A method in which this is placed in a large amount of water (hereinafter referred to as a natural emulsification method) and a phase inversion emulsification method are included. The direct emulsification method is to apply a strong shearing force using a disperser,
This is a method in which emulsion particles are crushed and emulsified, and an emulsion can be obtained relatively easily.

However, when the emulsion particles are not uniformly subjected to shearing force, the particle size distribution becomes broader, and the stability with time is increased as a strong shearing force is applied in order to obtain particles having a small particle size. It is known to be damaged. In addition, the natural emulsification method emulsifies just by adding it to water, but a high degree of specialized knowledge is required to select an emulsifier, and it cannot be applied to all substances.

On the other hand, the phase inversion emulsification method is a method in which water is added little by little to liquid oils containing an emulsifier while stirring. When water is added to the oil droplets, a W / O type emulsion is created first, and the viscosity increases as the amount of water increases,
Eventually, the phase is changed to an O / W type emulsion. The feature of the phase inversion emulsification method is that it passes through this phase inversion point. That is, by stirring with sufficient shearing force at the phase inversion point at which the particles and the continuous phase in which the particles are dispersed are exchanged, it is possible to obtain an emulsion having a uniform small particle size with a very narrow particle size distribution.
Further, it is known that the emulsion obtained by the phase inversion emulsification method is particularly excellent in stability.

However, as described above, if the viscosity during phase inversion is large and the thixotropy is strong, uniform stirring cannot be performed with ordinary stirring and the like, resulting in uneven particle sizes and agglomerates.
A special stirring mixer is used for this solution.

As the mixer for high-viscosity paint according to the embodiment of the present invention, various commercially available mixers as described below can be used, and those having the same structure and type are used for scale-up. it can. For example, a high-viscosity table kneader (trade name PN series, PNV series, PBV series manufactured by Irie Shosha), a high-viscosity desk type kneader (product name HK manufactured by Fritsche Japan)
D series), Disassembly type kneader for experiment (Miki Co., Ltd. product name SND series), Disassembly type table kneader (Miki Co., Ltd. product name SNT series), Experimental Wagner type kneader (Miki Co., Ltd. product name ND series) ), A kneading machine planetary mixer (trade name PVM series, PVM-D manufactured by Asada Iron Works Co., Ltd.), a kneader (trade name manufactured by Satake Chemical Machinery Co., Ltd.), and the like. Further, an anchor mixer capable of uniformly mixing with an anchor type stirring blade can also be used.

As the high-speed shearing type emulsifying machine according to the embodiment of the present invention, various commercially available ones described below can be used, and those having the same structure and type can be used for scale-up. . For example, a high shear mixer (trade name, manufactured by Silverson, IKA, etc.), a homomixer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd., Mizuho Industry Co., Ltd.), a high flex disperser (trade name, manufactured by SMT), Examples include Claremix (trade name, manufactured by M Technique Co., Ltd.), Cavitron (trade name, manufactured by Daiheiyo Kiko Co., Ltd.) and the like.

When the mixer for high-viscosity paint and the high-speed shearing emulsifying machine are used together, it is desirable to select and use one or more of the above-mentioned devices in combination. In addition, a commercially available device in which both of the following are combined can be used, and examples include a Combi mixer (commercial name Combi Mixer manufactured by Asada Iron Works Co., Ltd.) and Harmotech (manufactured by M Technique Co., Ltd.). it can.

In the method for producing colored resin fine particles according to the embodiment of the present invention, at least a polymerizable unsaturated monomer, a colorant, an emulsifier and a polymerization initiator are used. Each constituent element will be described below.

(Polymerizable unsaturated monomer) As the polymerizable unsaturated monomer, vinyl aromatic hydrocarbon, (meth) acrylic acid ester, (meth) acrylamide, alkyl-substituted (meth) acrylamide, N- Examples thereof include substituted maleimide, maleic anhydride, (meth) acrylonitrile, methyl vinyl ketone, vinyl acetate and vinylidene chloride.

Specific examples of vinyl aromatic hydrocarbons include:
For example, styrene, α-methylstyrene, o, m, p-
Examples thereof include chlorostyrene, p-ethylstyrene, and divinylbenzene, which may be used alone or in combination of two or more, but are not limited thereto. Also (meta)
Specific examples of the acrylic acid ester-based monomer include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, methacrylic acid. Acid-2-ethylhexyl, β-hydroxy acrylate, γ-hydroxy acrylate, δ-hydroxy butyl acrylate, β-hydroxy methacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc. However, the present invention is not limited to these.

These polymerizable unsaturated monomers may be used alone or in combination.
Combinations of more than one species can be used. Of course, a small amount of a water-soluble monomer may be added and polymerized in order to improve the properties of the obtained colored resin fine particles depending on the application.

Examples of the water-soluble monomer include those having an anionic group such as sulfonic acid group, phosphoric acid group and carboxylic acid group. These acids are alkali metal salts such as sodium salt and ammonium salt. , Amine salt, etc., or free acid form. Suitable examples thereof include styrene sulfonic acid, sodium styrene sulfonate, 2-acrylamido-2.
-Methylpropene sulfonic acid, 2-hydroxymethyl methacryloyl phosphate, 3-chloro-2-hydroxypropyl methacryloyl phosphate, acrylic acid,
Methacrylic acid, fumaric acid, crotonic acid, tetrahydroterephthalic acid, itaconic acid, maleic acid and the like.

(Colorant) As the colorant, those which can be dissolved or dispersed in the unsaturated monomer are selected, and examples thereof include dyes, pigments and processed pigments. Here, the processed pigment is a normal pigment such as a self-dispersion pigment in which at least one functional group is bonded to the surface of the pigment directly or through another atomic group, or a pigment coated with a pigment dispersant or a resin. Those to which a process that is expected to have additional functions are added to the manufacturing process will be generically shown. In the present invention, pigments and processed pigments are preferably used because they have excellent weather resistance. When a pigment is used, considering the dispersibility in the unsaturated monomer, a pigment precoated with a water-insoluble resin compatible with the unsaturated monomer used is particularly preferable.

The pigment that can be used in the present invention is not particularly limited, but for example, the pigments described below can be preferably used. First, as the carbon black of the black pigment, carbon black produced by a furnace method or a channel method, having a primary particle size of 15 to 40 mμm, a specific surface area by the BET method of 50 to 300 m ² / g, and a DBP oil absorption of 40 to 40 mμm. 150ml / 100g, volatile content is 0.5-10
Those having a mass% and a pH value of 2 to 9 are preferable.

For example, as No.
2300, No. 900, MCF88, No. 40, N
o. 52, MA7, MA8, No. 2200B (product name and above, manufactured by Mitsubishi Kasei), RAVEN1255 (product name
Made in Colombia), REGAL400R, REGAL66
0R, MOGUL L (trade name or more, manufactured by Kyabot), Color Black FW1, Color
Black FW18, Color Black S1
70, Color Black S150, Print
Commercially available products such as ex 35 and Printex U (trade name or more, manufactured by Degussa) can be used. In addition, a new prototype may be used for the present invention.

Examples of the yellow pigment include C.I. I.
Pigment Yellow 1, C.I. I. Pigm
ent Yellow 2, C.I. I. Pigment
Yellow 3, C.I. I. Pigment Yell
ow 13, C.I. I. Pigment Yellow
16, C.I. I. Pigment Yellow 83 and the like.

Examples of magenta pigments include C.I. I.
Pigment Red 5, C.I. I. Pigment
Red 7, C.I. I. Pigment Red 1
2, C.I. I. Pigment Red 48 (Ca),
C. I. Pigment Red 48 (Mn), C.I.
I. Pigment Red 57 (Ca), C.I. I.
Pigment Red 112, C.I. I. Pigme
nt Red 122, C.I. I. Pigment Vi
olet 19 and the like. A quinacridone pigment is particularly preferable as the magenta pigment.

Examples of cyan pigments include C.I. I. P
igment Blue 1, C.I. I. Pigment
Blue 2, C.I. I. Pigment Blue
3, C.I. I. Pigment Blue 15: 3,
C. I. Pigment Blue 16, C.I. I. P
igment Blue 22, C.I. I. Vat Bl
ue 4, C.I. I. Vat Blue 6 etc. are mentioned. Phthalocyanine pigments are particularly preferable as the cyan pigment. Further, with regard to the coloring materials of any of the above colors, those newly manufactured for the present invention can be used.

The processed pigment that can be used in the present invention is selected to be compatible with the unsaturated monomer to be used, and in particular, it has been subjected to a surface treatment for improving dispersibility in the unsaturated monomer. Is preferred. Furthermore, a pigment whose surface is previously coated with a water-insoluble resin compatible with the unsaturated monomer is preferable. Examples of such a material include, for example, what is called a color chip (trade name: Taihei Chemical Co., Taisei Chemical Co., etc.) obtained by kneading a pigment and a resin under heating with a two-roll machine, or a microlith (trade name). Commercially available processed pigments such as Ciba Specialty Chemicals) can be used. Further, a pigment obtained by any known method such as a simple coacervation method in which a pigment is dispersed in a resin solution and a poor solvent is added thereto to deposit the resin on the surface of the pigment can be used.

The water-insoluble resin for coating the pigment is freely selected from the properties of adsorption to the pigment used and solubility to the polymerizable unsaturated monomer used, but especially vinyl chloride resin and vinyl acetate resin. , Vinyl chloride-vinyl acetate copolymer resin, vinyl resin such as polyvinyl acetal resin, and cellulose resin and acrylic resin are preferable, and among them, vinyl chloride-
Vinyl acetate copolymer resins are most suitable for finely stabilizing pigments in polymerizable unsaturated monomers. If desired, two or more water-insoluble resins may be used in combination.

(Emulsifier) The emulsifier used in the present invention may be nonionic, anionic or both. However, a large amount of emulsifier is often used in the phase inversion emulsification method, which is a feature of the present invention, and there is a high possibility that a free emulsifier will remain in the dispersion of the colored resin fine particles produced. Therefore, it is preferable to use a reactive emulsifier in order to reduce the free emulsifier to control the ink permeability and further improve the water resistance of the recorded image.

The reactive emulsifier is an anionic or nonionic emulsifier having at least one kind of unsaturated double bond in the molecule, for example, a sulfosuccinic acid ester-based emulsifier,
Examples include alkylphenol ether type. Examples of the nonionic reactive emulsifier include those having a polyoxyethylene group in the molecule. Specifically, polyoxyethylene allyl glycidyl nonyl phenyl ether "ADEKA REASOAP NE" (trade name, Asahi Denka Co., Ltd.)
Made), polyoxyethylene nonylpropenyl ether "Aqualon RN" (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Etc.

Examples of the anionic reactive emulsifier include sulfonic acid (salt) type, carboxylic acid (salt) type, phosphoric acid ester type and the like. Specifically, polyoxyethylene allyl glycidyl nonyl phenyl ether sulfate ester salt "Adecaria Soap SE" (trade name, manufactured by Asahi Denka Co., Ltd.), polyoxyethylene nonyl propenyl ether sulfate ester salt "Aqualon HS", "Aqualon BC" (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), etc., and "Eleminol JS-" having other structures.
2 "," Eleminol RS-30 "(trade name, manufactured by Sanyo Chemical Industry Co., Ltd.)," Latemur "(trade name, Kao Corporation)
Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like, but are not limited thereto. These reactive emulsifiers can be used alone or in combination of two or more, or can be used in combination with a usual emulsifier. The amount of such an emulsifier used is preferably 5 to 50% by mass, based on the mass of all the monomers,
More preferably, it is 10 to 40 mass%.

(Polymerization Initiator) As the polymerization initiator, a water-soluble or oil-soluble persulfate, a peroxide, an azo compound, a redox composition in which a reducing agent such as a peroxide and a sulfite is combined is used. Can be used. For example, ammonium persulfate,
Potassium persulfate, sodium persulfate, hydrogen peroxide, t-
Butyl hydroperoxide, t-butyl peroxyl benzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) ) And the like. Among them, the polymerization method is preferably carried out by suspension polymerization in which the monomer does not move, and therefore a polymerization initiator soluble in the monomer is preferably used. The amount of such a polymerization initiator used is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the mass of all the monomers.

The colored resin fine particles according to the embodiment of the present invention include, in addition to the polymerizable unsaturated monomer, the colorant, the emulsifier and the polymerization initiator, an ultraviolet absorber, an antioxidant or a color improving agent. You may add additives, such as.

Next, the step of polymerizing the polymerizable unsaturated monomer constituting the method for producing an aqueous dispersion of colored resin fine particles according to one embodiment of the present invention will be described. In the polymerization step, for example, an emulsion polymerization method using a pre-emulsification method and a suspension polymerization method can be used. The emulsion polymerization method and the suspension polymerization method are similar in that they use water as a medium, but the emulsion polymerization method uses a polymerization initiator insoluble in the monomer as the polymerization initiator, while the suspension polymerization method uses The difference is that a polymerization initiator that is soluble in the monomer is used. As a result, emulsion polymerization and suspension polymerization follow completely different polymerization mechanisms.

That is, in the suspension polymerization method, the polymerization proceeds in each monomer particle, whereas in the emulsion polymerization method, the polymerization initiator is added to the micelle formed by the emulsifier in the system and a small amount of the monomer. Polymerization is initiated by the diffusion of the monomer, and the monomer is supplied to this from the monomer oil droplets to promote the polymerization. In the present invention, it is preferable to obtain colored resin fine particles by forming particles of a monomer containing a colorant by pre-emulsification using a phase inversion method, and polymerizing the particles while keeping the shape as it is. . Therefore, it is preferable to carry out the suspension polymerization method, which is a system in which the migration of the monomer from the monomer particles does not occur.

In the conventional suspension polymerization method, a stabilizer such as polyvinyl alcohol is added in order to keep the monomer in a stable dispersed state, and the polymerization is carried out while vigorously stirring to disperse the monomer. Therefore, it has been generally known that polydisperse particles having a large particle size can be obtained as compared with emulsion polymerization. On the other hand, when the method of the present invention is used, stable and uniform small-sized monomer particles can be formed by pre-emulsification using the phase inversion emulsification method, and also particles obtained by suspension polymerization of the same. Similarly, it is presumed that a uniform and small particle size can be obtained.

The average particle diameter of the colored resin fine particles obtained after polymerization is preferably 500 nm or less, more preferably 200 nm or less. Within such a numerical range, sedimentation does not easily occur even after long-term storage, and excellent dispersion stability is maintained.
Further, in order to form colored resin fine particles having an average particle diameter within the above range, the average particle diameter of the monomer particles after phase inversion emulsification is preferably 500 nm or less, and further 2
It is preferably 00 nm or less. It should be noted that what is obtained directly by the above-mentioned method is precisely that in which the colored resin fine particles are dispersed in an aqueous medium, and in the present invention, this is referred to as an aqueous dispersion of the colored resin fine particles for convenience.
When an ink is produced using the colored resin particles according to the present invention, an aqueous dispersion of the colored resin particles may be used depending on the composition of the ink to be obtained, or an aqueous dispersion of the colored resin particles may be used. Remove water from the body using standard methods (eg distillation, centrifugation, filtration, spray drying, etc.),
After taking out as colored resin fine particles, a suitable liquid medium,
For example, it may be dispersed again in an aqueous medium or an oil medium to form an ink.

The colored resin fine particles produced according to the present invention have good water resistance, good weather resistance and scratch resistance of the ink image obtained using the same, and excellent dispersion stability. It can be suitably used as a coloring material for ink. In particular, since it has good dispersibility in water, it is suitably used as an aqueous inkjet ink.

The ink using the colored resin fine particles of the present invention is constituted by maintaining the dispersed state of the colored resin fine particles in the aqueous medium. And it is preferable that at least water is contained as a constituent component of the aqueous medium. The mass ratio of water to the total mass of the ink is, for example, 20 to 95 mass%, particularly 40 to 95 mass%, and further preferably 60 to 95 mass%.

Further, the aqueous medium may contain a water-soluble organic solvent. The amount of the water-soluble organic solvent in the ink is preferably 2 to 60 mass% of the total amount of the ink. Specific water-soluble organic solvents include, for example, methyl alcohol,
C1-C4 alkyl alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol, amides such as dimethylformamide and dimethylacetamide, acetone and the like. Ketones, tetrahydrofuran, ethers such as dioxane, polyethylene glycol, polyalkylene glycols such as polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol,
Alkylene glycols having an alkylene group of 2 to 6 carbon atoms such as triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol, glycerin, ethylene glycol monomethyl (or ethyl) Ethers, lower alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl (or ethyl) ether, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide,
Examples thereof include cyclic amide compounds such as 2-pyrrolidone and ε-caprolactam, and imide compounds such as succinimide.

The ink according to the present invention is preferably used in an ink jet recording method for recording an image by ejecting ink from a recording head by thermal energy or mechanical energy and adhering it to a recording medium. When the ink according to this aspect is particularly suitable for ink jet recording use, the physical properties of the ink at 25 ° C. include a surface tension of 15 to 60 dyn / cm, and further 2
0 to 50 dyn / cm, viscosity of 15 cP or less, especially 1
It is preferably 0 cP or less. Further, the pH range is preferably 3 to 11, and more preferably 3.5 to
It is 10.

As a specific ink composition that can achieve such characteristics, for example, various inks used in Examples described later can be mentioned. In addition to the colored resin fine particles obtained as described above, various additives such as a surfactant, a pH adjuster, and a mildew proofing agent may be added to the ink according to the embodiment of the present invention. .

Further, the recording medium used in the recording method using the ink according to the embodiment of the present invention is not particularly limited, and it is specially used for plain paper such as copy paper and bond paper and for ink jet recording. Examples include prepared coated paper, glossy paper, OHP film, and the like.

The ink of the present invention is particularly suitable for use in an ink jet recording system in which droplets are ejected by the action of heat energy for recording, but it can also be used as another ink jet recording method or a general writing tool. There is no end.

A recording apparatus suitable for recording using the ink of the present invention is an apparatus for applying thermal energy corresponding to a recording signal to the ink in the chamber of the recording head and generating droplets by the energy. To be

An example of the structure of the recording head, which is the main part, is shown in FIGS. 1, 2 and 3. The head 13 is made of glass, ceramics, a plastic plate, or the like having a groove 14 through which ink passes, and a heating head 15 having a heating resistor used for heat-sensitive recording (a head is shown in the drawing, but is not limited to this. It is not a thing) and is obtained by adhering. The heating head 15 has a protective film 1 formed of silicon oxide or the like.
6, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.

The ink 21 is a discharge orifice (fine hole).
22 is filled, and the meniscus 23 is generated by the pressure P.
Is formed. FIG. 4 shows an example of an ink jet recording apparatus incorporating the head as described above. In FIG. 4, 61 is a blade as a wiping member,
One end thereof is held by the blade holding member to become a fixed end, which is in the form of a cantilever. Blade 61
Is arranged at a position adjacent to the recording area of the recording head, and in the case of the example shown in FIG. 4, is held in a protruding form in the movement path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61, and has a configuration in which it moves in a direction perpendicular to the moving direction of the recording head and comes into contact with the ejection surface to perform capping. Furthermore,
Reference numeral 63 denotes an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the moving path of the recording head.

The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the ejection recovery unit 64 removes water, dust, and dust on the ink ejection port surface by the blade 61 and the absorber 63. Done. Reference numeral 65 denotes a recording head having ejection energy generating means for ejecting ink to a recording material facing the ejection port surface where the ejection ports are arranged to perform recording, and 66 denotes a recording head 65 in which the recording head 65 is mounted. It is a carriage for moving the. The carriage 66 slidably engages with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area.

Reference numeral 51 is a paper feed section for inserting a recording material, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the ejection opening surface of the recording head, and as recording progresses, the recording material is ejected to the ejection unit provided with the ejection roller 53. In the above configuration, when the recording head 65 returns to the home position after recording is completed, the cap 62 of the head recovery unit 64 is retracted from the movement path of the recording head 65, but the blade 61 is projected in the movement path. As a result, the ejection port surface of the recording head 65 is wiped.
When the cap 62 comes into contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to project into the moving path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same positions as the above wiping positions. As a result, even during this movement, the ejection port surface of the recording head 65 is wiped. The above-mentioned movement of the recording head to the home position is performed not only at the end of recording and at the time of ejection recovery, but also at the home position adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. Then, with this movement, the wiping is performed.

FIG. 5 is a cross-sectional view showing an example of an ink cartridge 45 in which the head is provided with an ink supply member, for example, an ink storage portion which stores ink supplied via a tube. Here, reference numeral 40 is an ink containing portion containing the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into this stopper 42, the ink in the ink bag 40 can be supplied to the head. Reference numeral 44 is an ink absorber that receives waste ink.

The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separated as described above, and one in which they are integrated as shown in FIG. 6 is also preferable. Used. In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink containing portion containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a head portion having a plurality of orifices. The ink is ejected from 71 as an ink droplet. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head 65 shown in FIG. 4, and is detachable from the carriage 66.

[0066]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist. still,
In the following description, “part” or “%” is based on mass unless otherwise specified.

[Examples 1 to 7 and Comparative Example 1 Preparation and evaluation results of colored resin fine particle water dispersion] (Preparation of colored resin fine particle water dispersion) <Example 1> Styrene 40 as a polymerizable unsaturated monomer Parts and 2-ethylhexyl acrylate (hereinafter 2-EHA
60 parts, and a processed pigment "Microlith Blue 4G" composed of phthalocyanine blue (CI.PB15: 3) as a colorant and a vinyl chloride-vinyl acetate copolymer.
KP "(trade name: pigment concentration 50%: manufactured by Ciba Specialty Chemicals Co., Ltd.) 25 parts, reactive emulsifier" Aqualon BC-20 "(trade name manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier, and a polymerization initiator As a result, 3.6 parts of 2,2-azobisisobutyronitrile was mixed and stirred by a three-one motor (manufactured by Satake Chemical Machinery Co., Ltd.) until uniform.

Then, the homogeneous mixed solution was put into a high-viscosity table kneader (trade name: PNV-1 manufactured by Irie Shosha Co., Ltd.), and water was gradually added while stirring at a rotation speed of 52 rpm. Thickness began to increase as water was added, and thixotropic properties began to appear from about 100 parts added, but the mixture was uniformly mixed and stirred, and when about 130 parts water was added, the viscosity suddenly decreased and the phase inversion occurred. It was confirmed that it happened. After that, water was added so that the components other than water became 20%. This emulsified dispersion is a polymerization device (a polymerization device equipped with a stirrer, a reflux condenser and a nitrogen gas inflow pipe)
The mixture was heated to 75 ° C. in a nitrogen stream and polymerized for 24 hours to obtain an aqueous dispersion of colored resin fine particles.

Example 2 The homogeneous mixed solution prepared in the same manner as in Example 1 was put into a high-viscosity table kneader (trade name PNV-1 manufactured by Irie Shosha Co., Ltd.). While mixing and stirring at a rotation speed of 52 rpm, a high-flex disperser (trade name: HG-9, manufactured by SMT Corporation) of 10,000 rpm is appropriately added.
Water was added while further mixing and stirring in 2).
As the water was added, the viscosity increased and thixotropic properties were developed, but stirring and mixing were always possible in a uniform state. Since the viscosity began to drop when about 120 parts of water was added, the rotation number of the high flex was increased to 18,000 rpm, and phase inversion emulsification was advanced while gradually adding water. After obtaining a sharp decrease in viscosity, water was added so that the components other than water would be 20%, and Example 1
Polymerization was performed in the same manner as in 1. to obtain a colored resin aqueous dispersion.

Example 3 Processed pigment "Microlith Blue 4GKP" (21 parts of methyl methacrylate and 49 parts of 2-EHA as a polymerizable unsaturated monomer, and a vinyl chloride-vinyl acetate copolymer as a colorant) Product name Pigment concentration 50%: Ciba Specialty Chemicals Co., Ltd.
42 parts, reactive emulsifier "Aqualon H" as an emulsifier
S-10 "(trade name manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 2.5 parts of 2,2-azobisisobutyronitrile as a polymerization initiator three-one motor (trade name manufactured by Satake Chemical Machinery Co., Ltd.) And mixed and stirred until uniform.

After that, the homogeneous mixed solution was put into a kneader for Satake experiment (product name KC-07 manufactured by Satake Chemical Machinery Co., Ltd.), and water was gradually added while stirring at a rotation speed of 90 rpm. The viscosity began to increase with the addition of water, and thixotropic properties began to appear from around the point where about 60 parts were added, but the mixture was uniformly mixed and stirred to give about 90
It was confirmed that the viscosity suddenly decreased at the time when some water was added, and phase inversion occurred. After that, water was added so that the components other than water became 20%. This emulsified dispersion liquid was placed in a polymerization device (a polymerization device equipped with a stirrer, a reflux condenser and a nitrogen gas inflow pipe), heated to 75 ° C. under a nitrogen stream and polymerized for 24 hours to obtain a colored resin fine particle water dispersion liquid. Obtained.

<Example 4> The homogeneous mixture prepared in the same manner as in Example 3 was put into a kneader for Satake experiment (trade name: KC-07 manufactured by Satake Chemical Machinery Co., Ltd.). Rotation speed 90 rp
Clear mix (CLM-0.8S manufactured by M Technic Co., Ltd.) at 10,000 rpm while mixing and stirring at m.
Then, water was added while further mixing and stirring. As the water was added, the viscosity increased and thixotropic properties were developed, but stirring and mixing were always possible in a uniform state. Since the viscosity began to drop when about 120 parts of water was added, the number of revolutions of CLEARMIX was set to 2
The phase inversion emulsification was promoted while increasing the speed to 0000 rpm and gradually adding water. After obtaining a rapid decrease in viscosity, water was added so that the components other than water were 20%, and polymerization was carried out in the same manner as in Example 3 to obtain a colored resin aqueous dispersion.

<Example 5> 200 parts of styrene as a polymerizable unsaturated monomer and n-butyl acrylate (hereinafter referred to as n-
(Abbreviated as BA) 300 parts, phthalocyanine blue (CI.PB15: 3) as a colorant as a colorant, and a processed pigment "Microlith Blue 4GKP" (trade name: pigment concentration) composed of a vinyl chloride-vinyl acetate copolymer. 50%: Ciba Specialty Chemicals Co., Ltd., 350 parts, reactive emulsifier "Aqualon HS-20" (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as an emulsifier, and 2,2-azobis as a polymerization initiator. 72 parts of isobutyronitrile were mixed and stirred by a three-one motor (trade name, manufactured by Satake Chemical Machinery Co., Ltd.) until uniform.

After that, the homogeneous mixed solution was put into a planetary mixer (PVM-5, trade name, manufactured by Asada Iron Works Co., Ltd.), and water was gradually added while stirring at a rotation speed of 162 rpm. The viscosity started to increase with the addition of water, and thixotropic properties began to appear from around the addition of about 300 parts, but the mixture was uniformly mixed and stirred, and when about 450 parts of water was added, the viscosity suddenly decreased and the phase inversion occurred. It was confirmed that it happened. After that, water was added so that the components other than water became 20%. This emulsified dispersion is a polymerization device (a polymerization device equipped with a stirrer, a reflux condenser and a nitrogen gas inflow pipe)
The mixture was heated to 75 ° C. in a nitrogen stream and polymerized for 24 hours to obtain an aqueous dispersion of colored resin fine particles.

<Example 6> The homogeneous mixed solution prepared in the same manner as in Example 5 was put into a planetary mixer (PVM-5, trade name, manufactured by Asada Iron Works Co., Ltd.), and water was gradually added while stirring at a rotation speed of 162 rpm. did. Clear mix (CLM-0.8S manufactured by M Technic Co., Ltd.) at 10,000 rpm as appropriate while mixing and stirring at a rotation speed of 162 rpm.
Then, water was added while further mixing and stirring. As the water was added, the viscosity increased and thixotropic properties were developed, but stirring and mixing were always possible in a uniform state. Since the viscosity began to drop when about 400 parts of water was added, the number of revolutions of CLEARMIX was set to 2
The phase inversion emulsification was promoted while increasing the speed to 0000 rpm and gradually adding water. After obtaining a sharp decrease in viscosity, water was added so that the components other than water were 20%, and polymerization was carried out in the same manner as in Example 5 to obtain a colored resin aqueous dispersion.

Example 7 As a polymerizable unsaturated monomer, 160 parts of methyl methacrylate, 160 parts of styrene, 2-
EHA 160 parts and n-butyl acrylate 320 parts,
Phthalocyanine blue (C.I.
I. PB15: 3) and processed pigment "Microlith Blue 4GKP" consisting of a vinyl chloride-vinyl acetate copolymer
(Brand name: 50% pigment concentration: manufactured by Ciba Specialty Chemicals Co., Ltd.) 480 parts, 160 parts of reactive emulsifier "Adekaria Soap SE-20N" (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) as an emulsifier and 2 as a polymerization initiator. , 2-azobisisobutyronitrile (28 parts) was mixed and stirred by a three-one motor (trade name, manufactured by Satake Chemical Machinery Co., Ltd.) until uniform.

After that, the homogeneous mixed solution was mixed with Harmotech (M.
Technics Co., Ltd. trade name HMT-CA-2.0) was added, and water was gradually added while stirring at a rotation speed of the anchor portion of 65 rpm and a rotation speed of the Clearmix rotor portion of 7,000 rpm. The viscosity started to increase with the addition of water, and thixotropic properties began to appear from around the addition of about 200 parts. When water was added, the rotor was rotated up to 20,000 rpm and mixed and stirred. It was confirmed that when about 750 parts of water was added, the viscosity sharply decreased and phase inversion occurred. After that, water was added so that the components other than water became 20%. This emulsified dispersion liquid was placed in a polymerization device (a polymerization device equipped with a stirrer, a reflux condenser and a nitrogen gas inflow pipe), heated to 75 ° C. under a nitrogen stream and polymerized for 24 hours to obtain a colored resin fine particle water dispersion liquid. Obtained.

Comparative Example 1 A polymer dispersant Di was added to a mixed solution of 4 parts of methyl methacrylate and 6 parts of n-butyl acrylate.
A solution prepared by dissolving 1 part of sperbyk 161 (trade name, manufactured by Big Chem Japan Co., Ltd.) in terms of solid content, 1 part of phthalocyanine blue (CI PB15: 3) and 10 parts of glass beads having a diameter of 0.5 mm are added. , And dispersed in a sand mill for 16 hours.

After removing the glass beads, 0.36 part of 2,2-azobisisobutyronitrile as a polymerization initiator is mixed. Reactive emulsifier "Eleminol J"
S-2 "(trade name, manufactured by Sanyo Chemical Industry Co., Ltd.) 2 parts water 5
The above colorant solution was added to what was dissolved in 3.44 parts, and the mixture was stirred with a homomixer to obtain an emulsion. The obtained emulsion is placed in a polymerization device (a polymerization device equipped with a stirrer, a reflux condenser and a nitrogen gas inflow pipe), heated to 75 ° C. under a nitrogen stream to carry out polymerization for 24 hours, and an aqueous dispersion of colored resin fine particles is obtained. Got

(Evaluation Results of Colored Resin Fine Particle Dispersion) Particle Size The average particle diameter of the colored resin fine particle dispersion is measured by the dynamic light scattering method (trade name ELS-8000; manufactured by Otsuka Electronics Co., Ltd.). did.

Storage stability The dispersion of colored resin fine particles was sealed in a Teflon (registered trademark) container and stored at 60 ° C. for 2 months, and the presence or absence of gelation or sediment was visually evaluated. The evaluation results are classified as follows. A: Almost no gelation or sedimentation. B: A slight gelation or precipitate was observed, but there was no problem in practice. C: Gelation and sediment are severe. The evaluation results are shown in Table 1 below.

[0082]

[Examples 8 to 14 and Comparative Example 2 Preparation and Evaluation of Ink] (Preparation of Ink) Using the colored resin fine particle aqueous dispersions obtained in Examples 1 to 7 and Comparative Example 1, each ink was prepared. Prepared. To 5 parts of glycerin, 5 parts of ethylene glycol, 5 parts of trimethylolpropane and 1 part by mass of acetylenol EH, 50 parts of the obtained colored resin fine particle aqueous dispersion is added and stirred. This was filtered to obtain the inks of Examples 8 to 14 and Comparative Example 2.

(Evaluation Results of Ink) The eight types of inks thus prepared are used in a color BJ printer (trade name: B
JC-420J; made by Canon Inc.) is filled in an ink tank of BJ cartridge BC-21, and this cartridge is set in BJC-420J,
Printing was performed on a recording paper (Pro Photo Photo Paper PR-101; manufactured by Canon Inc.) in HQ mode at 360 × 360 dpi.

Storage stability The ink was sealed in a Teflon container and stored at 60 ° C. for 2 months, and the presence or absence of gelation and sediment was visually evaluated. The evaluation results are classified as follows. A: Almost no gelation or sedimentation. B: A slight gelation or precipitate was observed, but there was no problem in practice. C: Gelation and sediment are severe.

Ejection stability A 1-dot vertical line was printed on a recording paper at the beginning of use of the BC-21 cartridge. Further, the text was printed until the BC-21 cartridge was used up, and a vertical line of 1 dot was printed on another recording paper using the cartridge just before the use. These recording papers were visually observed from a distance of 25 cm, and the printing result by the cartridge at the beginning of use and the printing result by the cartridge at the end of use were evaluated according to the following criteria. A: There is no difference between the two. B: Although a dot landing deviation is recognized in a part of the vertical line printed by the cartridge just before the end of use, it can be recognized as a straight line. C: The dot landing deviation is clearly recognized on the vertical line printed by the cartridge just before the end of use, and the vertical line is misaligned.

Evaluation of color developability After printing a solid image for 12 hours, the image density was measured using a reflection densitometer Macbeth RD-918 (manufactured by Macbeth Co.), and the evaluation results were classified as follows. A: Image density 1.50 or more B: Image density 1.30 or more and less than 1.50 C: Image density less than 1.30 Evaluation results are shown in Table 2 below.

[0088]

[0089]

Industrial Applicability As described above, according to the present invention, an image having high color density having water resistance, weather resistance and scratch resistance is provided, and dispersion stability is excellent, and it is useful as a coloring material for ink. It is possible to provide various colored resin fine particles.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of a head portion of an inkjet recording apparatus.

FIG. 2 is a cross-sectional view of a head portion of an inkjet recording device.

FIG. 3 is an external perspective view of a head portion of the inkjet recording apparatus.

FIG. 4 is a perspective view showing an example of an inkjet recording apparatus.

FIG. 5 is a vertical sectional view of an ink cartridge.

FIG. 6 is a perspective view of a recording unit.

[Explanation of symbols]

13: Head 14: groove 15: Heating head 16: Protective film 17-1, 17-2: Aluminum electrodes 18: Heating resistor layer 19: Heat storage layer 20: substrate 21: Ink 22: Discharge orifice (fine hole) 23: Meniscus 25: Recording material 28: Heating head 40: Ink bag 42: Stopper 44: Ink absorber 45: Ink cartridge 51: Paper feed section 52: Paper feed roller 53: Paper ejection roller 61: Wiping member 62: Cap 63: Ink absorber 64: Head recovery unit 65: recording head 66: Carriage 67: Guide shaft 68: Motor 69: Drive belt 70: Recording unit 71: Head part 72: Air communication port

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 2/18 C08F 2/24 A 2/24 C09D 11/00 C09D 11/00 B41J 3/04 101Y (72 ) Inventor Katsushi Dangami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Junichi Sakai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Makiko Endo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2C056 EA13 FC01 FC02 KC21 2H086 BA02 BA53 BA54 BA55 BA59 4J011 DA01 DA03 DB03 JA06 JB26 KA04 KA06 KA14 KA15 KA21 PB PB PCB 29B25 PC06 PC07 4J039 AB02 AD03 AD04 AD05 AD08 AD09 AD14 BA04 BA12 BC07 BC16 BC19 BC20 BC36 BC39 BC44 BC50 BC51 BC54 BC56 BC60 BE01 BE12 BE22 BE26 CA06 DA02 EA0 3 EA34 EA36 EA38 EA44 GA24

Claims (22)

[Claims] 1. A process of (i) phase inversion emulsification of a polymerizable unsaturated monomer, a colorant, an emulsifier and a polymerization initiator in an aqueous medium using a mixer for high viscosity paints; and (ii) A method for producing an aqueous dispersion of colored resin fine particles, which comprises a step of polymerizing a polymerizable unsaturated monomer. 2. The method for producing an aqueous dispersion of colored resin fine particles according to claim 1, further comprising using a high-speed shearing type emulsifier in the step (i). 3. The method for producing an aqueous dispersion of colored resin fine particles according to claim 1, wherein the emulsifier is a reactive emulsifier. 4. The colorant according to claim 1, which is a pigment.
5. The method for producing an aqueous dispersion of colored resin fine particles according to. 5. The method for producing an aqueous dispersion of colored resin fine particles according to claim 4, wherein the colorant is a pigment previously coated with a water-insoluble resin. 6. The method for producing an aqueous dispersion of colored resin fine particles according to claim 5, wherein the water-insoluble resin is at least one resin selected from the group consisting of vinyl resins, cellulose resins and acrylic resins. 7. The method for producing an aqueous dispersion of colored resin fine particles according to claim 5, wherein the water-insoluble resin is a vinyl chloride-vinyl acetate copolymer. 8. The method according to claim 1, wherein the polymerization initiator is an oil-soluble polymerization initiator soluble in a polymerizable unsaturated monomer, and the polymerization method in the step (ii) is a suspension polymerization method. 8. The method for producing an aqueous dispersion of colored resin fine particles according to any one of 7. 9. An aqueous dispersion of fine colored resin particles, which is obtained by the method according to any one of claims 1 to 8. 10. (i) A polymerizable unsaturated monomer, a colorant,
A step of phase-inversion emulsifying the emulsifier and the polymerization initiator in an aqueous medium using a mixer for high-viscosity paint; and (ii) polymerizing the polymerizable unsaturated monomer. Method for producing colored resin fine particles. 11. The method for producing colored resin fine particles according to claim 10, wherein a high-speed shearing type emulsifying machine is further used in the step (i). 12. The method for producing colored resin fine particles according to claim 10, wherein the step of removing the aqueous medium is performed after the steps (i) and (ii). 13. Colored resin fine particles obtained by the method according to any one of claims 10 to 12. 14. An ink containing the aqueous dispersion of colored resin fine particles according to claim 9. 15. An ink containing the colored resin fine particles according to claim 13 and a liquid medium. 16. The liquid medium is an aqueous medium.
Ink described in. 17. The liquid medium is an oil medium.
Ink described in. 18. The ink according to claim 14, which is for ink jet recording. 19. A recording unit comprising an ink containing portion containing the ink according to claim 18 and a head portion for ejecting the ink. 20. An ink cartridge comprising an ink containing portion containing the ink according to any one of claims 14 to 18. 21. An ink jet recording apparatus comprising: an ink containing portion containing the ink according to claim 18; and a recording head for ejecting the ink. 22. An ink jet recording method comprising a step of ejecting the ink according to claim 16 by an ink jet method.