JPH10176130A - Water-base ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base ink composition which can give characters and drawn lines not undergoing blurring or erasing when wetted with sweat, having light resistance high enough to prevent characters or drawn lines from being denatured stably for a long time against precipitation by using a fluid obtained by emulsionpolymerizing a vinyl monomer containing a dissolved hydrophobic dye. SOLUTION: This composition contains an aqueous microparticulate colored resin dispersion prepared by emulsion-polymerizing a vinyl monomer containing a dissolved hydrophobic dye in the presence of a polymerizable surfactant. It comprises 3-30wt.% (in terms of the solid component of the resin), based on the total weight of the composition, aqueous microparticulate colored resin dispersion, 10-80wt.% water-soluble organic solvent and 30-90wt.% water. It is desirable that the particle diameter of the colored resin microparticles is 0.5μm or smaller. It can be effectively used in an ink jet recorder or a writing utensil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous ink composition. More specifically, the present invention is an aqueous ink composition for an ink jet recording apparatus that can be used in a commercially available ink jet recording apparatus and an aqueous ink composition for a writing instrument useful for writing instruments such as a felt-tip pen and a ball-point pen that has no bleeding during writing. The present invention relates to an ink composition.

[0002]

2. Description of the Related Art As a conventional ink composition for an ink jet recording apparatus, a water-soluble acid dye or a basic dye is dissolved in an aqueous medium, and additives such as a wetting agent, a pH adjusting agent and a preservative are added. Additive ink compositions and the like are known.

However, in these ink compositions, the printed portion is blurred and the image becomes unclear, the image recorded due to the solubility of the dye in water is blurred or lost by sweat or water, or the color is mixed. There is a disadvantage that the color becomes cloudy. Essentially, water-soluble dyes have poor light fastness, and there is a problem that the quality of an image deteriorates when a printed matter is stored for a long period of time. In addition, these ink compositions can be stored for long periods of time,
There is a drawback in that the physical properties of the ink change or precipitates occur, causing clogging and ejection of nozzles to cause remarkable troubles, resulting in poor printing.

[0004] Dyes and pigments have been known as coloring components of aqueous inks used in writing instruments such as aqueous felt-tip pens and aqueous ball-point pens.

[0005] Inks using dyes have the drawback that letters and lines are blurred or disappeared by sweat or water because the dyes are soluble in water, and the written characters and lines are blurred, resulting in poor water resistance. . Also, since the dye itself has poor light resistance,
There is a problem that characters and drawing lines change over time.

On the other hand, inks using pigments have no problem in terms of water fastness and light fastness, but suffer from problems such as clogging of the pen tip and poor writing due to aggregation or settling of the pigments over a long period of time. Occur. Further, since the ink for writing implements is required to have a finely dispersed pigment, it is difficult to increase the number of colors of the ink by dispersing various organic pigments.

[0007]

An object of the present invention is to solve the above-mentioned drawbacks and problems of the conventional ink composition for an ink jet recording apparatus.
Another object of the present invention is to provide a water-based ink composition which has a sufficient density for ink jet recording and gives a clear image in which printed portions do not bleed. Another object of the present invention is to provide an aqueous ink composition in which an image recorded by water or sweat does not bleed or disappear. Third, it is to provide an aqueous ink composition in which the color is not turbid due to color mixture. Fourth, it is an object of the present invention to provide a water-based ink composition having excellent light fastness in which an image is not deteriorated even when a printed matter is stored for a long period of time. Fifth, it is an object of the present invention to provide a stable aqueous ink composition that does not cause a change in physical properties or a precipitate.

Another object of the present invention is to solve the above-mentioned drawbacks and problems of the conventional water-based ink for writing implements, in which letters and drawn lines are blurred or lost by water or sweat. An object of the present invention is to provide a stable water-based ink composition which gives clear character / drawing lines without any problem, has excellent light fastness in which the character / drawing lines are not deteriorated for a long time, and has no precipitate.

[0009]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a liquid obtained by emulsion-polymerizing a vinyl monomer in which a hydrophobic dye is dissolved is used. The inventors have succeeded in obtaining an aqueous ink composition that has solved the above problems, and have completed the present invention.

[0010] The aqueous ink composition of the present invention contains an aqueous dispersion of colored resin fine particles prepared by emulsion polymerization of a vinyl monomer in which a hydrophobic dye is dissolved using a polymerizable surfactant.

Further, the aqueous ink composition of the present invention contains an aqueous dispersion of colored resin fine particles prepared by emulsion polymerization of a vinyl monomer in which a hydrophobic dye is dissolved using a polymerizable surfactant. Based on the total amount of the composition, the content of the aqueous dispersion of the colored resin fine particles is 3 to 30% by weight (in terms of resin solid content), the content of the water-soluble organic solvent is 10 to 80% by weight, and the content of water is 30. ~ 90% by weight.

It is preferable that the particle diameter of the colored resin fine particles is 0.5 or less. Further, the aqueous ink composition of the present invention is effective when used in an ink jet recording apparatus or a writing instrument.

The aqueous dispersion of the colored resin fine particles is a colored emulsion polymerization solution obtained by emulsion polymerization of a vinyl monomer in which a hydrophobic dye is dissolved using a polymerizable surfactant.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION An aqueous dispersion of colored resin fine particles having a particle diameter of 0.5 μm or less according to the aqueous ink composition of the present invention comprises a vinyl monomer in which a hydrophobic dye is dissolved, ammonium persulfate, potassium persulfate, It is prepared by emulsion polymerization using a polymerizable surfactant, using hydrogen oxide or the like as a polymerization initiator or, if necessary, using a reducing agent in combination.

The aqueous dispersion of the colored resin fine particles obtained as described above (generally obtained as a concentrated liquid having a resin solid content of 20 to 50% by weight) is mixed with an aqueous ink composition for an ink jet recording apparatus or a writing instrument. For this purpose, the resin solid content (polymer fine particles) is adjusted to 3 to 30% by weight in the aqueous ink composition by diluting with water and a water-soluble organic solvent.

The aqueous dispersion of the colored resin fine particles according to the aqueous ink composition of the present invention does not usually agglomerate or precipitate, but is used for an ink jet recording apparatus or writing implement which requires a higher degree of stability. When used as an ink composition for coloring, the particle diameter of the colored resin fine particles is desirably 0.5 μm or less. In order to prevent clogging when the ink composition passes through a fine nozzle such as a fine nozzle or a felt pen, the particle diameter of the colored resin fine particles is desirably 0.5 μm or less.

The vinyl monomer used for preparing the aqueous dispersion of the colored resin fine particles according to the aqueous ink composition of the present invention is not particularly limited. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, Acrylic esters such as n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylic acid
Propyl, methacrylates such as n-butyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl esters such as vinyl salicylate, butadiene, isoprene, olefins such as propylene, styrene, One or more kinds are selected from hydrophobic monomers such as styrenes such as methyl styrene, and are used for emulsion polymerization. In addition, a hydrophilic monomer having a hydrophilic functional group such as an amino group, a carboxyl group, a sulfone group, an amide group, or a hydroxyl group is preferably added within a range that does not impair emulsion polymerization, preferably within 50% by weight (based on the total amount of the vinyl monomer). )). Further, as a cross-linking agent, a monomer having a reactive cross-linking group such as an epoxy group, a hydroxymethylamide group, an isocyanate group, or a polyfunctional monomer having two or more vinyl groups may be blended.

The polymerizable surfactant used for preparing the aqueous dispersion of the colored resin fine particles according to the aqueous ink composition of the present invention is a compound having a vinyl group and a surface (interfacial) activity. There is no particular limitation, and there is no particular limitation on the ionicity of the anion, cation and nonion. For example, "Adekaria Soap NE-10" manufactured by Asahi Denka Kogyo Co., Ltd.
“NE-20”, “NE-30”, “NE-4”
0 "," SE-10N "," Latemul S-180 "," S-180A "," S-120 "manufactured by Kao Corporation.
A "and the like, and one or more of them are used in combination. The amount of the polymerizable surfactant to be used is preferably 0.1 to 50% by weight based on the vinyl monomer.

The hydrophobic dye used for preparing the aqueous dispersion of the colored resin fine particles according to the aqueous ink composition of the present invention is a monoazo type, anthraquinone type, metal complex salt type monoazo type soluble in many organic solvents other than water. Diazo, phthalocyanine and triallylmethane hydrophobic dyes are preferred. For example, “DIARESINY” manufactured by Mitsubishi Chemical Corporation
ELLOW C "[CI Solvent Yellow
w 103], "DIARESIN YELLOW
A ”,“ ORIENT ”manufactured by Orient Chemical Industries, Ltd.
OIL SCARLET # 308 "[CI Solv
ent Red 18], “A” manufactured by Hodogaya Chemical Industry Co., Ltd.
IZEN SPILON BLUE2BNH "[CI
Solvent blue 117], “AIZEN
SPILON BLUE GNH "manufactured by Orient Chemical Industry Co., Ltd." VALI FAST BLACK # 38 "
40 "[CI Solvent Black 27],
“VALI FAST BLACK # 1802” and the like. The amount of the dye during the emulsion polymerization is in the range of 0.2 to 50% by weight based on the total amount of the monomers.

The water-soluble organic solvent used in the aqueous ink composition of the present invention includes ethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, , 2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,5-hexanediol, 3- Methyl 1,3-butanediol, 2-methylpentane-2,4-
Diols, alkylene glycols such as 3-methylpentane-1,3,5 triol, 1,2,3-hexanetriol, glycerin, polyethylene glycol,
Polyalkylene glycols such as polypropylene glycol, glycerols such as glycerol, diglycerol and triglycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycols such as diethylene glycol mono-n-butyl ether Lower alkyl ether, thiodiethanol, N-methyl-2
-Pyrrolidone, 1,3-dimethyl-2-imidaridinone and the like. Its content is preferably from 10 to 80% by weight, more preferably from 10 to 80% by weight based on the total amount of the ink composition.
60% by weight.

In addition, for example, methyl alcohol,
Ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol,
A water-soluble solvent such as alcohols such as nonyl alcohol, decyl alcohol and benzyl alcohol, amides such as dimethylformamide and diethylacetamide, and ketones such as acetone can also be mixed.

The content of water is preferably 30 to 90% by weight, more preferably 40 to 90% by weight based on the total amount of the ink composition.
~ 80% by weight. In addition, if necessary, preservatives, p
An H adjuster, an activator, a lubricant, an antifoaming agent, a rust inhibitor and the like can be appropriately selected and used.

For example, as a pH adjuster, ammonia,
Examples include urea, monoethanolamine, diethanolamine, triethanolamine, alkali metal salts of carbonic acid and phosphoric acid such as sodium tripolynate and sodium carbonate, and hydroxides of alkali metals such as sodium hydroxide.

As preservatives or fungicides, phenol, sodium omazine, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one,
Examples thereof include 3,5,6-tetrachloro-4 (methylphonyl) pyridine, alkali metal salts of benzoic acid, sorbic acid, and dehydroacetic acid, and benzimidazole compounds.

As a lubricant, a polyalkylene glycol derivative such as polyoxyethylene lauryl ether, a fatty acid alkali salt, a nonionic surfactant, a fluorine surfactant such as a perfluoroalkylphosphate ester, or dimethylpolysiloxane added with polyethylene glycol Products, such as polyether-modified silicone.

Since the aqueous dispersion of the colored resin fine particles according to the aqueous ink composition of the present invention is obtained from an emulsion polymerization solution obtained by emulsion polymerization in the presence of a polymerizable surfactant, a conventional surfactant is used. As compared with those obtained by the above method, the surface tension is high (usually 40 dyn / cm or more) because there is almost no surface active substance in the aqueous medium. Therefore, when the aqueous dispersion of the colored resin fine particles of the present invention is used as an ink composition for an ink jet recording apparatus, it is possible to obtain a clear image in which the printed portion does not bleed, and the image bleeds with water or sweat. It is possible to obtain a water-resistant film that does not disappear or disappear. On the other hand, when the aqueous dispersion of the colored resin fine particles of the present invention was used as a writing instrument ink, characters and drawing lines were clear,
It does not bleed or disappear due to water or sweat, and forms a water-resistant drawing film.

The coloring of the resin fine particles is carried out by previously dissolving a hydrophobic dye in a vinyl monomer, followed by emulsion polymerization, whereby the resin fine particles exhibit a vivid color. When the aqueous dispersion of the colored resin fine particles thus obtained is used as an aqueous ink composition for an ink jet recording apparatus, a clear image in which a printed portion does not bleed is obtained, and the image bleeds with water or sweat. It is possible to provide an excellent ink that does not disappear or disappear due to color mixing. Further, it is possible to provide an ink having excellent light fastness in which an image is not deteriorated even when a printed matter is stored for a long period of time. Also, when used as a writing implement ink, the characters and drawing lines are clear and do not bleed or disappear due to water or sweat, making it possible to provide an excellent ink. The amount of the dye used is usually 0.2 to
It is in the range of 50% by weight.

The colored resin fine particles relating to the aqueous ink composition of the present invention are substantially insoluble in water. The aqueous ink composition of the present invention is characterized in that the colored resin fine particles are prepared by emulsion polymerization of a vinyl monomer in which a hydrophobic dye is dissolved using a polymerizable surfactant.

[0029]

EXAMPLES Hereinafter, the aqueous ink composition of the present invention will be described in more detail with reference to Examples and Comparative Examples when the aqueous ink composition of the present invention is used in an ink jet recording apparatus.

The performance test in each example was performed according to the following method. Bleeding: The degree of bleeding of characters printed on PPC copy paper was visually determined. ：: No bleeding Δ: Slight bleeding X: Bleeding Water resistance: The character printed on PPC copy paper was immersed in water for 1 hour, and the degree of bleeding was visually determined. ：: No bleeding Δ: Slight bleeding X: Bleeding Lightfastness: A character printed on PPC copy paper was irradiated with a fade meter for 20 hours to determine whether fading was observed. Storage stability: 5 cartridges filled with ink composition
The sample was placed in a thermostat at 0 ° C., and the number of days until printing became impossible was measured.

The particle diameter, viscosity and surface tension were measured by the following methods. Particle size: The particle size of the colored resin fine particles can be measured using a laser scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Coulter Counter,
(Model N4SD). Viscosity: The viscosity of the aqueous dispersion of colored resin fine particles was measured using a cone plate type rotational viscometer (ELD type, manufactured by Tokyo Keiki Co., Ltd.), and the measurement temperature was 25 ° C. Surface tension: The surface tension of the aqueous dispersion of colored resin fine particles is
It was measured by the hanging plate method. The measurement temperature was 25 ° C.

Example 1 A 2 liter flask was equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a 500 ml separatory funnel for charging monomers, set in a hot water tank, and charged with 500 g of distilled water. The internal temperature was raised to 80 ° C. while introducing nitrogen gas. On the other hand, a vinyl monomer mixture composed of 250 g of methyl methacrylate, 200 g of n-butyl methacrylate and 50 g of methacrylic acid, an oil-soluble red dye [“ORIENT OIL SC manufactured by Orient Chemical Industries, Ltd.”
ARLET # 308 "], 10 g, distilled water 250 g, and 20 g of a polymerizable surfactant [Adekaria Soap SE-10N, manufactured by Asahi Denka Kogyo Co., Ltd.] are mixed, stirred and dispersed, and 1 g of ammonium persulfate is further dissolved. The mixed liquid was prepared and the mixture was poured from the separating funnel to a temperature of 80 ° C.
The mixture was added to the flask maintained at around 0 ° C. with stirring over 3 hours, and the polymerization was terminated at the 5th hour to obtain an aqueous dispersion of red resin fine particles. To this aqueous dispersion, distilled water 3000
g, 1000 g of propylene glycol, and the mixture is stirred uniformly.
m of a red ink composition was obtained. The particle diameter of the colored resin fine particles in the red ink composition was 0.20 μm. Further, the red ink composition had excellent properties of water resistance and light resistance, and exhibited a clear red color without bleeding and clogging.

Example 2 A 2 liter flask was equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a 500 ml separatory funnel for charging monomers, set in a hot water tank, and charged with 500 g of distilled water. The internal temperature was raised to 80 ° C. while introducing nitrogen gas. On the other hand, styrene 200g, methacrylic acid n-
Monomer mixture of 200 g of butyl and 100 g of acrylic acid, oil-soluble blue dye [“AIZEN SPILON BLUE 2BN manufactured by Hodogaya Chemical Industry Co., Ltd.”
H "], 250 g of distilled water and 10 g of a polymerizable surfactant (" Latemul S-180 "manufactured by Kao Corporation) were stirred and dispersed, and a mixed solution in which 2 g of ammonium persulfate was further dissolved was prepared. The mixed solution was placed in a flask maintained at a temperature of about 80 ° C. from the separatory funnel under stirring with stirring.
It was added over a period of time, and the polymerization was terminated at the 5th hour to obtain an aqueous dispersion of blue resin fine particles. To this aqueous dispersion, 3000 g of distilled water and 1000 g of propylene glycol were added, and the mixture was stirred uniformly, and had a viscosity of 3.2 cp and a surface tension of 52 g.
A blue ink composition of dyn / cm was obtained. The particle diameter of the colored resin fine particles in the blue ink composition was 0.24 μm. Further, the blue ink composition had excellent properties of water resistance and light resistance, and exhibited a clear blue color without bleeding and clogging.

Comparative Example 1 Water-soluble acrylic resin ["JONCRYL 61J" (solid content: 30%) manufactured by Johnson Polymer Co., Ltd.] 25
g, water-soluble red dye [“AI manufactured by Hodogaya Chemical Industry Co., Ltd.”
ZEN CATHILON PINK FGH "] 2
g, propylene glycol 10 g, and distilled water 63 g
And mixed for 1 hour with stirring to obtain a red ink composition.

Comparative Example 2 Water-soluble blue dye ["AIZE" manufactured by Hodogaya Chemical Industry Co., Ltd.
N VICTORIAPURE BLUE BOH "]
1 g, propylene glycol 10 g, and distilled water 89
g was mixed and dissolved for 1 hour with stirring to obtain a blue ink composition.

Comparative Example 3 20 g of a polymerizable surfactant ("ADEKAREASOAP SE-10N" manufactured by Asahi Denka Kogyo Co., Ltd.) was added to 5 g of sodium dodecylbenzenesulfonate and 5 g of polyoxyethylene nonylphenyl ether. A red ink composition was produced under the same conditions as in Example 1 except that the composition was changed to. This red ink composition had a viscosity of 3.1 cp and a surface tension of 37 dyn / cm. The particle diameter of the colored resin fine particles in the ink composition was 0.25 μm.

Comparative Example 4 Emulsion polymerization was carried out under the same conditions without dissolving the oil-soluble dye in the monomer mixture of Example 1 to obtain an aqueous dispersion of uncolored resin fine particles. Thereafter, a water-soluble red dye [AIZEN manufactured by Hodogaya Chemical Industry Co., Ltd.] is added to the aqueous dispersion.
CATHILON PINK FGH "], 3,000 g of distilled water, and 1000 g of propylene glycol were added and uniformly stirred to obtain a red ink composition.

Table 1 shows the results obtained in each of the examples and comparative examples.

[0039]

[Table 1]

Hereinafter, the aqueous ink composition of the present invention will be described in more detail with reference to Examples and Comparative Examples when the aqueous ink composition of the present invention is used for a writing instrument.

The performance test in each example was performed according to the following method. Bleeding: The degree of bleeding of the characters drawn on the writing paper was visually determined. ：: Does not bleed. Δ: Slight bleeding. X: Bleed. Water resistance: The characters drawn on the writing paper were immersed in water for one hour, and the degree of bleeding was visually determined. ：: Does not bleed. Δ: Slight bleeding. X: Bleed. Lightfastness: Text drawn on writing paper is used for fade meter 2
Irradiation was performed for 0 hour, and it was determined whether fading was observed. Storage stability: The ink composition was filled in an aqueous felt-tip pen container, placed in a thermostat at 50 ° C., and the number of days until writing became impossible was measured.

Particle size: The particle size of the colored resin fine particles was measured using a laser scattering type particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Coulter Model N4SD). Viscosity: The viscosity of the ink composition was measured using a cone-plate type rotary viscometer (Tokyo Keiki Co., Ltd., ELD type).
The measurement temperature was 25 ° C. Surface tension: The surface tension of the ink composition was measured by a hanging plate method. The measurement temperature was 25 ° C.

Example 3 A 2 liter flask was charged with a stirrer, reflux condenser, thermometer,
A nitrogen gas inlet tube and a 500 ml separatory funnel for charging monomers were attached, the flask was set in a hot water tank, 500 g of distilled water was charged, and the internal temperature was raised to 80 ° C. while introducing nitrogen gas. On the other hand, 250 g of methyl methacrylate and 20 styrene
Oil soluble red dye [ORIENT OIL SCALELET manufactured by Orient Chemical Industry Co., Ltd.] was added to 500 g of a monomer mixture comprising 0 g and 50 g of methacrylic acid.
# 308 "] 8 g, distilled water 250 g and a polymerizable surfactant [Adecaria Soap SE- manufactured by Asahi Denka Kogyo KK
10N ″], stirred and dispersed, and further prepared a mixed solution in which 1 g of ammonium persulfate was dissolved. The mixed solution was placed in the flask maintained at a temperature of about 80 ° C. from the separating funnel for 3 hours under stirring. After 5 hours, polymerization was completed, and an aqueous dispersion of colored resin fine particles was obtained.To the obtained aqueous dispersion of colored resin fine particles, 3000 g of distilled water and 1000 g of propylene glycol were added, and the mixture was stirred uniformly. , Viscosity 2.8 cP, surface tension 54 dyn / cm
Red ink composition was obtained. The pen using the obtained red ink composition did not cause clogging, and the written characters were excellent in water resistance and light resistance, and exhibited clear red without bleeding. The particle diameter of the colored resin fine particles in the composition is 0.15 μm
Met.

Example 4 A 2-liter flask was equipped with a stirrer, a reflux condenser, a thermometer,
A nitrogen gas inlet tube and a 500 ml separatory funnel for charging monomers were attached, the flask was set in a hot water tank, 500 g of distilled water was charged, and the internal temperature was raised to 80 ° C. while introducing nitrogen gas. On the other hand, a monomer mixture 500 composed of 200 g of styrene, 200 g of n-methyl methacrylate, 50 g of acrylic acid and 50 g of 2-hydroxyethyl methacrylate
g, an oil-soluble blue dye [“AI manufactured by Hodogaya Chemical Industry Co., Ltd.”
8 g of ZEN SPILONBLUE GNH ”, 250 g of distilled water and 10 g of a polymerizable surfactant [“ Latemul S-180 ”manufactured by Kao Corporation] are mixed and stirred and dispersed, and 2 g of ammonium persulfate is dissolved to prepare a mixed solution. The mixture was poured into the separatory funnel at a temperature of 80 ° C.
The mixture was added to the flask maintained at about ° C over 3 hours with stirring, and the polymerization was terminated at the 5th hour to obtain an aqueous dispersion of colored resin fine particles. 3000 g of distilled water and 10 g of propylene glycol were added to the obtained aqueous dispersion of colored resin fine particles.
The resulting mixture was uniformly stirred to obtain a blue ink composition having a viscosity of 3.2 cP and a surface tension of 52 dyn / cm. The pen using the obtained blue ink composition did not cause clogging, and the written character was excellent in water resistance and light resistance, and exhibited a clear blue color without bleeding. The particle diameter of the colored resin fine particles in the ink composition was 0.16 μm.

Comparative Example 5 Styrene-maleic acid resin ["A"
MA-1440H "(solid content 26%)], 25 g of a water-soluble red dye [" AIZEN C "manufactured by Hodogaya Chemical Industry Co., Ltd.
ATHILON PINK FGH "], 20 g of propylene glycol and 53 g of distilled water were mixed and stirred and dissolved for 1 hour to obtain a red ink composition.

Comparative Example 6 Water-soluble blue dye ["Aize" manufactured by Hodogaya Chemical Industry Co., Ltd.
N VICTORIAPURE BLUE BOH "]
1 g, propylene glycol 20 g and distilled water 79 g
And mixed for 1 hour with stirring to obtain a blue ink composition.

Comparative Example 7 20 g of a polymerizable surfactant [Adecaria Soap SE-10N manufactured by Asahi Denka Kogyo KK] was added to a surfactant [5 g of sodium dodecylbenzenesulfonate and 5 g of polyoxyethylene nonylphenyl ether]. ], Except for
A red ink composition was obtained under the same conditions as in Example 3. The obtained ink composition had a viscosity of 3.1 cP and a surface tension of 37 d.
yn / cm. The particle diameter of the colored resin fine particles in the ink composition was 0.14 μm.

Comparative Example 8 Emulsion polymerization was carried out under the same conditions without dissolving the oil-soluble dye in the monomer mixture of Example 3 to obtain an aqueous dispersion of uncolored resin fine particles. Then, a water-soluble red dye [“AIZEN CATHILON manufactured by Hodogaya Chemical Industry Co., Ltd.”
PINK FGH "], 3,000 g of distilled water and 1000 g of propylene glycol, and the mixture was stirred uniformly to obtain a red ink composition.

Table 2 shows the results obtained in each of the examples and comparative examples.

[0050]

[Table 2]

[0051]

As described in detail above, the aqueous ink composition of the present invention has excellent storage stability. Further, the ink jet recording obtained by using the aqueous ink composition of the present invention in an ink jet recording apparatus, the printed portion does not bleed,
Gives clear images and is excellent in water resistance and light resistance. The written characters and drawn lines obtained by using the aqueous ink composition of the present invention for a writing instrument are clear and do not bleed, without bleeding or disappearing due to water or sweat, and without turbidity due to color mixing. Further, it is excellent in water resistance and light resistance which does not deteriorate even if written characters and drawing lines are left for a long period of time.

Since the aqueous dispersion of the colored resin fine particles of the present invention is a colored emulsion polymerization solution obtained by emulsion polymerization of a vinyl monomer in which a hydrophobic dye has been previously dissolved, it exhibits a vivid color, Pigment does not aggregate or settle.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Seiwa Sakurai 1091 Tateishi, Fujioka City, Gunma Prefecture Mitsubishi Pencil Co., Ltd. R & D Center

Claims (5)

[Claims] 1. An aqueous ink composition comprising an aqueous dispersion of colored resin fine particles prepared by emulsion polymerization of a vinyl monomer in which a hydrophobic dye is dissolved using a polymerizable surfactant. 2. An aqueous ink composition comprising an aqueous dispersion of colored resin fine particles prepared by emulsion polymerization of a vinyl monomer in which a hydrophobic dye is dissolved using a polymerizable surfactant, The content of the aqueous dispersion of the colored resin fine particles is 3 to 30% by weight (in terms of resin solid content), and the content of the water-soluble organic solvent is 1 based on the total amount of the aqueous ink composition.
An aqueous ink composition having 0 to 80% by weight and a water content of 30 to 90% by weight. 3. The colored resin fine particles have a particle size of 0.5 μm.
3. The aqueous ink composition according to claim 2, wherein m is equal to or less than m. 4. The aqueous ink composition for an ink jet recording apparatus according to claim 1, wherein: 5. The aqueous ink composition for a writing instrument according to claim 1, wherein