JPH08143804A - Water-base dispersed ink for bubble-jet recording and ink-jet recording and apparatus using the ink - Google Patents

Abstract

PURPOSE: To obtain the subject ink containing water, a water-soluble organic solvent, a dispersion of a pigment or a disperse dye treated with a specific dispersing agent and a specific surfactant and exhibiting excellent storage stability, fixability, color development, etc. CONSTITUTION: This ink contains at least (A) water, (B) a water-soluble organic solvent, (C) a dispersion of a pigment or a disperse dye produced by dispersing (i) a pigment or a disperse dye with (ii) a polymeric dispersing agent having anionic dissociation group and (D) a surfactant having an HLB of >=14 and consisting of a block copolymer of ethylene oxide and propylene oxide expressed e.g. by the formula ((m) is an integer of 5-50; (n) is an integer of 7-160; (k) is an integer of 7-160). The addition amount of the component D is 0.1-1.5wt.%, preferably 0.3-1.0wt.% based on the ink. The component (ii) preferably has a weight-average molecular weight of 3,000-15,000 and is composed of a copolymer of a hydrophobic monomer and a hydrophilic monomer or its salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion ink for bubble jet using a pigment or a disperse dye, an ink jet recording method and a recording apparatus using the same. More specifically, it has excellent ejection performance in a bubble jet type ink jet recording apparatus, and has recording ability to absorb water-based ink, that is, ink jet paper, high quality paper,
So-called plain paper such as copy paper, letter paper, thermal transfer paper, business form paper for wire dot printers,
And an ink jet which gives a recorded image having high color quality and fastness to a recording medium having absorbability of an aqueous ink, specifically, an inkjet paper, a film, a cloth, an under-treated metal, a plastic, etc. TECHNICAL FIELD The present invention relates to a recording ink, an inkjet recording method and a recording apparatus using the same.

[0002]

2. Description of the Related Art In recent years, aqueous pigment dispersions have come to be used as inks in writing instruments. The purpose is that it is the best material system that provides robustness such as water resistance and light resistance. Behind this is the development of aqueous fine particle dispersion technology for pigments, oil dyes, and disperse dyes. Attempts have also been made to apply such a pigment dispersion technique that can secure long-term storage stability with low viscosity to inkjet.

However, in a method such as the bubble jet method, in which a high heat is applied directly to the ink momentarily to boil the ink itself to form droplets and discharge energy, the recording principle is obtained. There was great difficulty in using the obtained dispersion as an ink for bubble jet by itself. The reason is simply that the dispersion agglomerates on the heating elements of the recording head. Therefore, there has been a need for a material, means, or device that can suppress the aggregation by some means or can maintain the ejection even after the aggregation. In particular, it is difficult to disperse fine particles having an average particle diameter of 0.2 μ or less with organic pigments and disperse dyes, and there is a limit to the particle size that can be achieved in an industrial sense. It was necessary to impart discharge sustainability underneath.

On the other hand, water-based pigment inks for ink jet are disclosed in JP-A-2-255875 and JP-A-4-255875.
Inventions such as 334870, JP-A-4-57859, and JP-A-4-57860 are disclosed.
However, the aqueous pigment inks according to these inventions do not disclose the problem of fine particle dispersion of organic pigments and disperse dyes, and the problem of their ejection properties in the bubble jet method.

[0005]

SUMMARY OF THE INVENTION The present invention has been achieved in view of the above-mentioned prior art, is an ink using a pigment dispersion or a disperse dye dispersion, and has excellent storage stability and bubble jet recording. It is an object of the present invention to provide an aqueous dispersion ink for bubble jet which can perform stable ejection in an apparatus.

Further, according to the present invention, when color recording is performed on plain paper or cloth, bleeding or feathering does not occur, the fixing property is excellent, the coloring property is excellent, and the printing is good with fastness. It is an object of the present invention to provide an aqueous dispersion ink for bubble jet, which gives a product.

Another object of the present invention is to provide an ink jet recording method, apparatus and recording apparatus using the above water-based dispersion ink for bubble jet.

[0008]

That is, the present invention contains at least water, a water-soluble organic solvent, a pigment dispersion or a disperse dye dispersion prepared by dispersing a pigment or a disperse dye with a dispersant, and a surfactant. In the water-based dispersion ink, the dispersant is a polymer dispersant having an anionic dissociative group, and the surfactant is a block copolymer of ethylene oxide and propylene oxide having HLB of 14 or more. A water-based dispersion ink for bubble jet.

Further, according to the present invention, in the ink jet recording method in which ink droplets formed by an ink jet method are adhered to a recording material to perform recording, the above-mentioned aqueous dispersion ink for bubble jet is applied as the ink. It is a characteristic inkjet recording method.

Further, the present invention is an ink cartridge having an ink containing portion for containing ink, wherein the water-based dispersed ink for bubble jet described above is applied as the ink.

Further, according to the present invention, in a recording unit having both an ink containing section for containing ink and a head section for ejecting the ink as ink droplets, the water-based dispersion ink for bubble jet as the ink described above. Is a recording unit characterized by applying.

In addition, the present invention is an ink jet recording apparatus for recording by recording ink droplets formed by an ink jet method on a recording material, wherein the ink cartridge or the recording unit described above is provided. It is a device.

Hereinafter, the present invention will be described in detail. The water-based dispersion ink for bubble jet of the present invention (hereinafter referred to as “water-based dispersion ink”) has the ejection performance in the bubble jet method, which has been difficult in the above-mentioned conventional technology, to be a pigment or a disperse dye which is difficult to be made into fine particles. It is characterized in that it can be given to the other.

The aqueous dispersion ink of the present invention is obtained by dispersing fine particles of a pigment or disperse dye with a polymer dispersant having an alkali-soluble anionic dissociation group to obtain a pigment dispersion or disperse dye dispersion, and at the same time, ejection performance. Certain surfactants are used to provide

The surfactant selected and used in the present invention is H
It is a block copolymer of ethylene oxide and propylene oxide having LB of 14 or more, and its own solubility in water is relatively high, and it is known as a group of nonionic surfactants. The compounds effective in the present invention are HLB (H
hydrophobic-Liophobic Bala
nce), that is, it is essential that the index value of the balance between hydrophobicity and hydrophilicity is 14 or more. When the HLB is less than 14, the long-term ejection sustainability deteriorates and the storage stability of the ink also deteriorates, resulting in loss of practicality. HLB is 14
The above is effective. The HLB of 14 or more means increasing the mole fraction of ethylene oxide in the copolymer. The preferred range of HLB is 1
4-18.

Of these surfactants, those having an average molecular weight of usually 1,500 or more are used, and the dischargeability and the storage stability are good. However, when the average molecular weight is 10,000 or more, the dischargeability and the storage stability are further improved. , Give better results. A more preferable average molecular weight range is 1000.
It is 0 to 25,000.

Such a surfactant has a relatively high surface tension of its own aqueous solution (45 dy at 0.1 to 0.5%).
n / cm or more), large emulsifying / solubilizing action but wettability,
It is a substance that is not high in surface activity such as permeability but rather high in solubility in an aqueous solution. It is not clear why these substances enhance the ejection performance, but it is considered that the above-mentioned characteristics act to facilitate the removal of the dispersion destruction thermally generated on the heater, that is, the particle aggregation and the deposition from the heater surface. Further, the water-based dispersion ink of the present invention is useful in printing on polyester fiber-containing fabrics, and particularly has the effect of improving the levelness.

(Surfactant) The surfactant used in the present invention can be easily synthesized by block copolymerization of ethylene oxide and propylene oxide, and is selected from industrially manufactured and commercially available products. It is possible to

The block structure of the block copolymer of ethylene oxide and propylene oxide used as a surfactant is represented by the formula A-B-A, which is represented by the following general formula (I).

[0020]

Embedded image (In the formula, m is an integer of 5 to 50, n is an integer of 7 to 160,
k represents an integer of 7 to 160. )

Specific examples of these copolymers are shown below.

[0022]

Embedded image

Further, examples of commercial products as ethylene oxide / propylene oxide block copolymer type surfactants are shown in Table 1 below.

[0024]

[Table 1]

Note 1) The products (11) to (16) are products of NOF Corporation. Note 2) (11) is a compound that can be used in the present invention, (12)
~ (16) are compounds that do not give the performance of the present invention. Note 3) Average molecular weight indicates number average molecular weight. The measurement method is
This is a GPC method using polyethylene glycol as a standard substance.

The ethylene oxide / propylene oxide block copolymer type surfactant used in the present invention can be selected from the products industrially manufactured and marketed by other companies.

The amount of the surfactant added is 0.1 to 1.5% by weight, preferably 0.3 to 1.0% by weight, based on the ink. The optimum amount for each formulation is determined experimentally. When carbon black is used as the pigment, a dispersion having a small particle size and good ejection properties may be obtained using only the polymer dispersant, and in that case, the surfactant is not always necessary.

(Polymer Dispersant) The polymer dispersant used in the aqueous dispersion ink of the present invention is an alkali-soluble water-soluble resin and has a weight average molecular weight of 1,000 to 30,000, preferably 3,000 to 3,000. The range is 15,000.
Specifically, hydrophobic monomers such as styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, alkyl esters of acrylic acid and alkyl esters of methacrylic acid, and α, β-ethylenically unsaturated carboxylic acids and their aliphatic alcohols. The copolymers and their salts are composed of hydrophilic monomers such as esters, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and their derivatives.

As the base forming a salt, alkali metal ions, monoethanolamine, diethanolamine,
Alcohol amines such as triethanolamine. The copolymer may have any structure such as random, block or graft. Acid value is 100-450,
It is preferably in the range of 130 to 400.

As the polymer dispersant used in the present invention, water-soluble polymers such as polyvinyl alcohol and carboxymethyl cellulose, water-soluble resins such as naphthalene sulfonic acid formaldehyde condensate and polystyrene sulfonic acid can also be used. is there.

In the present invention, a pigment dispersion or a disperse dye dispersion is formed by dispersing a pigment or a disperse dye with a polymer dispersant. In the case of a pigment dispersion, the amount of the polymer dispersant used is 1 by weight of pigment: weight of dispersant.
The range is from 0: 3 to 10: 0.5. The suitable ratio is experimentally determined from the viewpoint of average particle size, viscosity, stability, dispersion efficiency, etc. which can be reached by using the selected pigment and the polymeric dispersant. In the aqueous dispersion ink of the present invention used in a bubble jet recording apparatus, the amount of the polymer dispersant which is not adsorbed by the pigment and is dissolved is preferably 2% by weight or less in the ink.

Further, in the case of the disperse dye dispersion, the amount of the polymer dispersant used is in the range of 1: 3 to 20: 1 by weight of the disperse dye: weight of the dispersant.

(Base) In order to use the polymer dispersant used in the ink of the present invention in an aqueous system, a base is necessary. Suitable bases therefor include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethyldiethanolamine, 2-
Amino-2-methylpropanol, 2-ethyl-2-amino-1,3-propanediol, 2- (2-aminoethyl) ethanolamine, tris (hydroxymethyl)
Organic bases such as aminomethane, ammonia, piperidine, morpholine and β-dihydroxyethylurea, and inorganic bases such as sodium hydroxide, potassium hydroxide and lithium hydroxide are used. The most suitable base species is the selected pigment,
Although it depends on the type of dispersant, a non-volatile, stable and highly water-retaining agent is preferable. The amount of the base used is basically an amount calculated from the acid value of the polymer dispersant, and is used as the amount of the base necessary for neutralizing it. In some cases, more than the equivalent amount of acid may be used. It is carried out for the purpose of improving dispersibility, adjusting pH of ink, adjusting recording performance, and improving moisturizing property.

(Pigment) The amount of the pigment contained in the aqueous dispersion ink used in the present invention is preferably in the range of 1 to 20% by weight, preferably 2 to 12% by weight, based on the whole ink.

The carbon black used in the black ink is a carbon black produced by the furnace method or the channel method, the primary particle size is 15 to 40 mμ, the specific surface area by the BET method is 50 to 300 m ² / g, and the DBP oil absorption. Volume is 40-150ml / 100g, volatile content is 0.5 to 1
Those having 0% and a pH value of 2 to 9 are preferable.

Those carbon black pigments (C.I.
Pigment Black 7) No. 2300, N
o.900, MCF-88, No.33, No.40, No.45, No.52, MA7, MA
8, MA100, No.2200B (Made by Mitsubishi Kasei), Raven 700,
Raven 5750, Raven 5250, Raven 5000, Raven 3500, Ra
ven 1255 (Made by Colombia),

Regal 400R, Regal 330R, Regal 660R, Mo
gul L, Monarch 700, Monarch 800, Monarch 880, Monar
ch 900, Monarch 1000, Monarch 1100, Monarch 1300,
Monarch 1400 (above made by Cabot),

Color Black FW1, Color Black FW2, Colo
r Black FW2V, Color Black FW18, Color Black FW200,
Color Black S150, Color Black S160, Color Black S1
70, Printex 35, Printex U, Printex V, Printex 140U,
Printex 140V, Special Black 6, Special Black 5, S
Pecial Black 4A, Special Black 4 (above made by Degussa) or the like can be used.

As the pigment used in the yellow ink, CIPigment Yellow 12, CIPigment Yellow 13,
CIPigment Yellow 14, CIPigment Yellow 16, CIP
igment Yellow 17, CIPigment Yellow 73, CIPigme
nt Yellow 74, CIPigment Yellow 75, CIPigment Ye
llow 83, CIPigment Yellow 108, CIPigment Yello
w 109, CIPigment Yellow 110, CIPigment Yellow 18
0, CIPigment Yellow 182,

Pigments used as magenta ink include CIPigment Red 5, CIPigment Red 7, CIPi
gment Red 12, CIPigmentRed 112, CIPigment Red
122, CIPigment Red 123, CIPigment Red 168, CI
Pigment Red 184, CIPigment Red 202,

Pigments used as cyan ink include CIPigment Blue 1, CIPigment Blue 2, CIPi
gment Blue 3, CIPigment Blue 15: 3, CIPigment B
lue 16, CIPigment Blue 22, CIPigment Blue60,
CIVat Blue 4, CIVat Blue 60, etc. are mentioned.

In addition to the above, when red, green, blue and intermediate colors are required, the following pigments are preferably used alone or in combination. CIPigment Red 209, C.
I.Pigment Red 224, CIPigment Red 177, CIPigmen
t Red 194, CIPigment Orange 43, CIVat Violet 3,
CIPigment Violet 19, CIPigment Green 36, CIP
igment Green 7, CIPigment Violet 23, CIPigment
Violet 37, CIPigment Blue 15: 6,

(Disperse Dye) The amount of the disperse dye contained in the aqueous dispersion ink used in the present invention is 1 with respect to the total amount of the ink.
It is preferably used in the range of -25 wt%, preferably 1.5-20 wt%. The disperse dyes used are the following compounds.

<Disperse Yellow Dye> CIDisperse Y
ellow 5, CIDisperse Yellow 42, CIDisperse Yell
ow 54, CIDisperse Yellow 64, CIDisperse Yellow
79, CIDisperse Yellow82, CIDisperse Yellow 83,
CIDisperse Yellow 93, CIDisperse Yellow 99, C.
I. Disperse Yellow 100, CIDisperse Yellow 119, C.
I. Disperse Yellow 122, CIDisperse Yellow 124, C.
I. Disperse Yellow 126, CIDisperse Yellow160, C.
I. Disperse Yellow 184: 1, CIDisperse Yellow 186,
CIDisperse Yellow 198, CIDisperse Yellow 199,
CIDisperseYellow 204, CIDisperseYellow 224, C.
I. Disperse Yellow 237,

<Disperse Orange Dye> CIDisperse O
range 13, CIDisperse Orange 29, CIDisperse Ora
nge 31: 1, CIDisperse Orange 33, CIDisperse Ora
nge 49, CIDisperse Orange54, CIDisperse Orange
55, CIDisperse Orange 66, CIDisperse Orange7
3, CIDisperse Orange 118, CIDisperse Orange 11
9, CIDisperse Orange 163,

<Disperse Red Dye> CI Disperse Red 5
4, CIDisperse Red 72, CIDisperse Red 73, CID
isperse Red 86, CIDisperse Red 88, CIDisperse
Red 91, CIDisperse Red 92, CIDisperse Red 93,
CIDisperse Red 111, CIDisperse Red 126, CIDi
sperse Red 127, CIDisperse Red 134, CIDisperse
Red 135, CIDisperse Red 143, CIDisperse Red 1
45, CIDisperse Red 152, CIDisperse Red 153, C.
I.Disperse Red 154, CIDisperse Red 159, CIDisp
erse Red 164, CIDisperse Red 167: 1, CIDisperse
Red 177, CIDisperse Red 181, CIDisperse Red 2
04, CIDisperse Red 206, CIDisperse Red 207, C.
I.Disperse Red 221, CIDisperse Red239, CIDispe
rse Red 240, CIDisperse Red 258, CIDisperse Re
d 277, CIDisperse Red 278, CIDisperse Red 283,
CIDisperse Red 311, CIDisperse Red 323, CIDi
sperse Red 343, CIDisperse Red 348, CIDisperse
Red 356, CIDisperse Red 362,

<Disperse Violet Dye> CIDisper
se Violet 33,

<Disperse Blue Dye> CIDisperse Blu
e 56, CIDisperse Blue 60, CIDisperse Blue 73,
CIDisperse Blue 87, CIDisperse Blue 113, CID
isperse Blue 128, CIDisperse Blue 143, CIDispe
rse Blue 148, CIDisperse Blue 154, CIDisperse
Blue 158, CIDisperse Blue 165, CIDisperse Blue
165: 1, CIDisperseBlue 165: 2, CIDisperse Blue
176, CIDisperse Blue 183, CIDisperseBlue 185,
CIDisperse Blue 197, CIDisperse Blue 198, CI
Disperse Blue 201, CIDisperse Blue 214, CIDisp
erse Blue 224, CIDisperse Blue 225, CIDisperse
Blue 257, CIDisperse Blue 266, CIDisperse Blu
e 267, CIDisperse Blue 287, CIDisperseBlue 354,
CIDisperse Blue 358, CIDisperse Blue 365, C.
I. Disperse Blue 368,

<Disperse Green Dye> CIDisperse Gre
en 6: 1, CIDisperse Green 9, and so on.

Of these dyes, CIDisp is preferred.
erse Yellow 5, CIDisperse Yellow 42, CIDispers
e Yellow 83, CIDisperse Yellow 93, CIDisperse
Yellow 99, CIDisperse Yellow 198, CIDisperse Y
ellow 224,

CI Disperse Orange 29, CIDisperse O
range 49, CIDisperse Orange 73, CIDisperse Red
92, CIDisperse Red 126, CIDisperse Red 145, C.
I.Disperse Red 152, CIDisperse Red 159, CIDisp
erse Red 177, CIDisperse Red 181, CIDisperse R
ed 206, CIDisperse Red 283,

[0052] CI Disperse Blue 60, CIDisperse Blu
e 87, CIDisperse Blue 128, CIDisperse Blue 15
4, CIDisperse Blue 201, CIDisperse Blue 214,
CIDisperse Blue 224, CIDisperse Blue 257, CI
Compounds such as Disperse Blue 287 and CIDisperse Blue 368. Further, these dyes are preferable examples, and the dyes are not limited to these and may be newly synthesized ones.

(Water-Soluble Organic Solvent) The water-soluble organic solvent used in the present invention is an organic solvent miscible with water. If these solvents are classified, they can be divided into the following three groups. Highly moisturizing, highly evaporative and hydrophilic solvent of the first group, solvent of the second group having hydrophobic atomic groups at the end and good wettability to the hydrophobic surface, and also evaporative drying, moderate It is a solvent (monohydric alcohols) of the third group having low wettability and low viscosity.

As the solvent belonging to the first group, ethylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, glycerin,
1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5-pentanetriol, 1,2
-Butanediol, 1,3-butanediol, 1,4-
Butanediol, dimethyl sulfoxide, diacetone alcohol, glycerin monoallyl ether, propylene glycol, butylene glycol, polyethylene glycol 300, thiodiglycol, N-methyl 2-pyrrolidone, 2-pyrrolidone, γ-butyrolactone, 1,
3-dimethyl-2-imidazolidinone, sulfolane,
Trimethylolpropane, trimethylolethane, neopentyl glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether ,
Examples include triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, β-dihydroxyethyl urea, urea, acetonylacetone, pentaerythritol, and 1,4-cyclohexanediol.

Solvents belonging to the second group include hexylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl. Ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl Ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, glycerin monoacetate, glycerin diacetate, glycerin triacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, cyclohexanol, 1,2-cyclohexanediol, 1-butanol, 3-methyl-1,5-pentanediol, 3-
Examples are hexene-2,5-diol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, and 2,5-hexanediol.

Examples of the solvent belonging to the third group include ethanol, n-propanol, 2-propanol, 1-methoxy-2-propanol, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like. The above water-soluble organic solvents can be used alone or in combination of two or more.

The total amount of the water-soluble organic solvent is about 5 to 40% by weight based on the whole ink.

(Other Additives) The aqueous dispersion ink of the present invention may contain other additives such as a pH adjuster and a preservative. Proxel (Zeneca) is a stable and effective commercial preservative in the basic range.
(UK) is typical.

The basic physical properties of the ink composed of the above materials are summarized as follows: viscosity: 2-6 cps, surface tension: 35-55 dyn / cm, pH: 7.0-10.
0, average particle size 80 to 200 nm, preferably 80 to 15
It is 0 nm, and more preferably in the range of 80 to 120 nm.

The content of water in the ink is usually 10
˜93 wt%, preferably 25-87 wt%.

Next, a method for preparing the aqueous dispersion ink of the present invention will be described. (Particulation of pigment dispersion or disperse dye dispersion) First, a water-soluble organic solvent, pigment or disperse dye is dispersed using a polymer dispersant to obtain a pigment dispersion or a disperse dye dispersion. . The following method is used to obtain a fine particle dispersion using the material of the present invention.

In order to remove coarse particles, a wet cake of pigment or disperse dye is subjected to premixing treatment in a solution of an anionic polymer dispersant having an anionic dissociation group and then milled by a disperser having a high shear rate. Centrifuge process. At this time, it is also effective to use several kinds of dispersers in combination when the desired particle size cannot be obtained with a high yield by one kind of disperser. 10,0 without using beads
It is effective to use a bead mill with a method of using a mixing device rotating at a high speed exceeding 00 rpm, a method of jetting a dispersant solution into contact with a pigment at a high speed, or ultrasonic dispersion.

After that, materials for a desired ink formulation are added, and in some cases, the temperature is raised to 35 to 50 ° C. to perform aging treatment. After that, finally, centrifugal separation treatment, pressure filtration and the like are performed to obtain a desired average particle diameter. However, in the case of organic pigments and disperse dyes where it is difficult to reduce the particle size, a method in which a polymer dispersant or a surfactant coexists during the colorant synthesis to suppress the crystal growth and keep the particle size small or It is effective to use a wet cake raw material with a small particle size and improved wettability by contacting with a polymer dispersant or a surfactant to suppress crystal growth at the stage of completing the reaction and precipitating crystals. is there.

(Preparation of Aqueous Dispersion Ink) The fine particles of the pigment dispersion or disperse dye dispersion obtained as described above are dispersed in water, and a surfactant and, if necessary, other additives are added in predetermined amounts. Is mixed and stirred to obtain a water-based dispersion ink of the present invention.

The aqueous dispersion ink of the present invention is an ink using the above disperse dye dispersion or organic pigment dispersion.
It is a water-based dispersion ink for bubble jet that can perform stable ejection in a bubble jet recording apparatus, that is, can respond to a driving frequency of 3 KHz to 6 KHz.

Further, the aqueous dispersion ink of the present invention can be used for designing for any application using a disperse dye or pigment for recording by using the bubble jet method. Specific examples include stationery, color printers, color plotters, poster printing, sign printing, light printing, textile printing, and color filters for liquid crystal displays.

As a method and an apparatus suitable for recording using the ink of the present invention, a thermal energy corresponding to a recording signal is applied to the ink in the chamber of the recording head, and a droplet is generated by the thermal energy. And devices.

An example of the head structure, which is the main part of the apparatus, is shown in FIGS. 1, 2 and 3. The head 13 closely adheres a glass, a ceramics or a plastic plate having a groove 14 through which an ink is passed, and a heating head 15 (a head is shown in the drawing, but not limited to this) used for thermal recording. Obtained. The heating head 15 includes a protective film 16 for forming silicon oxide or the like and an aluminum electrode 17
-1 and 17-2, a heat-generating resistor layer 18 formed of nichrome or the like, a heat storage layer 19, a substrate 2 having good heat dissipation such as alumina.
It consists of zero.

The ink 21 has a discharge orifice (fine hole) 2
2, the meniscus 23 is formed by a pressure (not shown). Now, when an electric signal is applied to the electrodes 17-1 and 17-2, a region indicated by n of the heating head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact therewith,
The meniscus 23 is projected by the pressure, the ink 21 is ejected, becomes a recording droplet 24 from the orifice 22, and is ejected toward the recording material 25.

FIG. 3 shows an external view of a multi-head in which a large number of the heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG. FIG.
2 is a cross-sectional view of the head 13 taken along the ink flow path, and FIG. 2 is a cross section taken along the line AB of FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head.

Further, in the case of this example, the recording head is held in a protruding form in the moving path. 62 is a cap,
It is arranged at the home position adjacent to the blade 61,
The recording head is moved in a direction perpendicular to the moving direction to come into contact with the ejection port surface to perform capping. 6 more
Reference numeral 3 denotes an ink absorber arranged 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 blade 61 and the absorber 63 remove water, dust, and the like on the ink ejection port surface.

Reference numeral 65 denotes a recording head which has an ejection energy generating means and ejects ink to a recording material facing the ejection port surface where the ejection ports are arranged to perform recording, and 66 is equipped with this recording head 65. And a carriage for moving the recording head 65. The carriage 66 slidably engages with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor 68.
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 port surface of the recording head, and is ejected to a paper ejection unit provided with a paper ejection roller 53 as the recording progresses.

In the above configuration, when the recording head 65 returns to the home position after recording is completed, the head recovery unit 6
The fourth cap 62 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 movement 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 position as the above-mentioned position at the time of wiping. 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 adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. The wiper is moved to the position, and the wiping is performed along with the move.

FIG. 5 is a diagram showing an example of an ink cartridge in which the ink is supplied to the head through an ink supply member, for example, 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. An ink absorber 44 receives the waste ink. It is preferable for the present invention that the liquid contact surface of the ink containing portion is made of polyolefin, particularly polyethylene.

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 separately provided as described above, but is also suitable for the one in which they are integrated as shown in FIG. Used.

In FIG. 6, reference numeral 70 denotes a recording unit in which an ink containing portion for containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a plurality of orifices. Head portion 71
It is configured to be ejected as an ink droplet from. For the present invention, it is preferable to use polyurethane as the material of the ink absorber.

Reference numeral 72 is an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. This recording unit 70 is
It is used in place of the recording head shown in FIG. 4, and is detachable from the carriage 66.

[0082]

EXAMPLES Next, the present invention will be specifically described with reference to examples. In the following description, parts represent weight ratios,
GPC with styrene polymer as the weight average molecular weight
The value measured by the method and the average particle size are the values measured by the dynamic light scattering method.

Example 1 [Yellow ink Y-1] Anionic polymer P-1 (styrene-acrylic acid-methyl methacrylate: acid value 2)
The following yellow dispersion Y-1 was prepared by using 80, an aqueous solution having a weight average molecular weight of 11,000 and a solid content of 20% by weight, a neutralizing agent: diethanolamine) as a dispersant.

Dispersion Y-1 P-1 aqueous solution (solid content 20% by weight) 35 parts Pigment Yellow 86 24 parts Triethylene glycol 10 parts Diethylene glycol 10 parts Ethylene glycol monobutyl ether 1.0 part Isopropyl alcohol 0.5 parts Water 135 Department

These materials were placed in a batch type vertical sand mill (manufactured by IMEX Co., Ltd.), glass beads having a diameter of 1 mm were filled as a medium, and dispersion treatment was performed for 3 hours while cooling with water. The viscosity of the liquid after dispersion is 9 cps and the pH is 1.
It was 0.0. The dispersion liquid was centrifuged to remove coarse particles, and thus a dispersion Y-1 having an average particle diameter of 100 mμ was obtained.

Liquid 10 prepared by diluting 100 parts of Ink Y-1 Dispersion Y-1 with 80 parts of water.
0.3 part of surfactant No. Add (7), stir well, viscosity 2.3 cps, surface tension 48 d
A yellow inkjet ink Y-1 having a yn / cm and a pH of 9.5 was obtained. The solid content of the final preparation was about 8% by weight.

Example 2 [Cyan ink C-2] The following cyan color dispersion C-2 was prepared by using the anionic polymer P-1 as a dispersant in the same manner as in Example 1.

Dispersion C-2 P-1 aqueous solution (solid content 20% by weight) 30 parts Pigment Blue 15: 3 24 parts (Fastgen Blue FGF, Dainippon Ink and Chemicals, Inc.) Glycerin 15 parts Diethylene glycol monobutyl ether 0.5 Parts Isopropyl alcohol 3 parts Water 135 parts The following dispersion treatment was performed in the same manner as in Example 1 to obtain an average particle size of 1
20 mμ of dispersion C-2 was obtained.

Liquid 10 prepared by diluting 100 parts of Ink C-2 Dispersion C-2 with 85 parts of water.
0.5 parts of surfactant No. 0 to 0 parts. Add (8), stir well, viscosity 3.1 cps, surface tension 45d
A cyan inkjet ink C-2 having a yn / cm and a pH of 9.2 was obtained. Solid content of final preparation is about 7.6% by weight
Met.

Example 3 [Magenta Ink M-3] The following magenta color dispersion M-3 was prepared by using the anionic polymer P-1 as a dispersant in the same manner as in Example 1.

Dispersion M-3 P-1 aqueous solution (solid content 20% by weight) 20 parts Pigment Red 122 (manufactured by Dainippon Ink & Chemicals, Inc.) 24 parts Glycerin 15 parts Isopropyl alcohol 3 parts Water 135 parts The same as Example 1 below. And perform dispersion treatment, average particle size 1
15 mμ of dispersion M-3 was obtained.

Liquid 10 prepared by diluting 100 parts of Ink M-3 Dispersion M-3 with 50 parts of water.
1.0 part of surfactant No. to 0 part. Add (9), stir well, viscosity 3.5 cps, surface tension 45d
A magenta inkjet ink M-3 having a yn / cm and a pH of 9.4 was obtained. The solid content of the final preparation was about 9.2% by weight.

Example 4 [Disperse dye blue ink BL-4] Anionic polymer P
-1 (styrene-acrylic acid-methyl methacrylate: acid value 280, weight average molecular weight 11,000, solid content 2
The following blue dispersion BL-4 was prepared using a 0 wt% aqueous solution and a neutralizing agent: diethanolamine) as a dispersant.

Dispersion BL-4 P-1 aqueous solution (solid content 20% by weight) 20 parts C.I. I. Disperse Blue 79 Wet cake 24 parts (solid content) 1,2,4-butanetriol 15 parts Triethylene glycol monobutyl ether 2.0 parts Ethyl alcohol 4 parts Water 135 parts Dispersion treatment is carried out in the same manner as in Example 1 below. , Average particle size 1
25 mμ of dispersion BL-4 was obtained.

Ink BL-4 Dispersion BL-4 Liquid 1 prepared by diluting 100 parts with 60 parts water.
0.7 parts of surfactant No. Add (10), stir well, viscosity 2.5 cps, surface tension 4
A blue inkjet ink BL-4 having 3 dyn / cm and a pH of 9.7 was obtained. The solid content of the final preparation is about 8.5.
% By weight.

Example 5 [Disperse dye red ink R-5] Anionic polymer P-
2 (styrene-acrylic acid-ethyl acrylate: acid value 250, weight average molecular weight 13000, solid content 20% by weight)
Was used as a dispersant, and the following red color dispersion R-5 was prepared.

Dispersion R-5 P-2 aqueous solution (solid content 20% by weight) 20 parts C.I. I. Disperse Red 158 Wet cake 24 parts (solid content) Diethylene glycol 20 parts Ethylene glycol monobutyl ether 1.0 part Isopropyl alcohol 5.0 parts Water 135 parts Dispersion treatment was carried out in the same manner as in Example 1 to obtain an average particle size of 1
15 mμ of dispersion R-5 was obtained.

Liquid 10 prepared by diluting 100 parts of Ink R-5 Dispersion R-5 with 25 parts of water.
0.5 parts of surfactant No. 0 to 0 parts. Add (11) and stir well to obtain a viscosity of 3.0 cps and a surface tension of 47.
A red inkjet ink R-5 having a dyn / cm and a pH of 9.6 was obtained. Solid content of final preparation is about 11% by weight
Met.

Example 6 [Disperse dye yellow ink Y-6] Anionic polymer P
-3 (styrene-maleic acid-n-butyl acrylate: acid value 210, weight average molecular weight 7,000, solid content 20)
The following yellow dispersion Y-6 was prepared using a wt% aqueous solution neutralizing agent: triethanolamine) as a dispersant.

Dispersion Y-6 P-3 aqueous solution (solid content 20% by weight) 20 parts C.I. I. Disperse Yellow 64 Wet cake 24 parts (solid content) Glycerin 15 parts Ethylene glycol 5 parts Isopropyl alcohol 3 parts Water 135 parts Dispersion treatment was carried out in the same manner as in Experimental Example 1 to obtain an average particle size of 9
A dispersion Y-6 of 5 mμ was obtained.

Ink Y-6 Dispersion Y-6 Liquid 10 prepared by diluting 100 parts of water with 60 parts of water.
0.5 parts of surfactant No. 0 to 0 parts. Add (6), stir well and have a viscosity of 2.7 cps and a surface tension of 51 d.
A yellow inkjet ink Y-6 having a yn / cm and a pH of 9.2 was obtained. The solid content of the final preparation was about 8.5% by weight.

Example 7 [Blue Ink BL-7] Anionic polymer P-3 (styrene-maleic acid-n-butyl acrylate: acid value 2)
The following blue color dispersion BL-7 was prepared by using an aqueous solution having a weight average molecular weight of 7,000 and a solid content of 20% by weight as a dispersant.

Dispersion BL-7 P-3 aqueous solution (solid content 20% by weight) 22 parts C.I. I. Pigment Violet 37 (Chromoftal Violet B, manufactured by Ciba-Geigy Co., Ltd.) 24 parts Ethylene glycol 5 parts Glycerin 15 parts Isopropyl alcohol 3 parts Water 135 parts Dispersion treatment was carried out in the same manner as in Example 1 to obtain an average particle size of 1
18 mμ of dispersion BL-7 was obtained.

Ink BL-7 Dispersion BL-7 Liquid 1 prepared by diluting 100 parts with water 50 parts
0.7 parts of surfactant No. Add (5), stir well and have a viscosity of 2.8 cps and a surface tension of 44.
A blue inkjet ink BL-7 having a dyn / cm and a pH of 9.0 was obtained. The solid content of the final preparation was about 9.3% by weight.

Example 8 [Red ink R-8] Anionic polymer P-3 (styrene-maleic acid-n-butyl acrylate: acid value 21)
The following red color dispersion R-8 was prepared by using an aqueous solution of 0, a weight average molecular weight of 7,000, and a solid content of 20% by weight as a dispersant.

Dispersion R-8 P-3 aqueous solution (solid content 20% by weight) 27 parts C.I. I. Pigment Red 177 (Chromoftal Red A2B, manufactured by Ciba-Geigy Co., Ltd.) 24 parts Ethylene glycol 5 parts Glycerin 15 parts Isopropyl alcohol 3 parts Water 135 parts The following dispersion treatment was carried out in the same manner as in Example 1 to obtain an average particle size of 9
A dispersion R-8 of 5 mμ was obtained.

Liquid 10 prepared by diluting 100 parts of Ink R-8 Dispersion R-8 with 45 parts of water.
0.5 parts of surfactant No. 0 to 0 parts. Add (4), stir well, viscosity 3.3 cps, surface tension 43d
A red inkjet ink R-8 having a yn / cm and pH of 9.6 was obtained. Solid content of final preparation is about 9.5% by weight
Met.

Example 9 [Green ink G-9] Anionic polymer P-3 (styrene-maleic acid-n-butyl acrylate: acid value 2)
The following green color dispersion G-9 was prepared by using an aqueous solution having a weight average molecular weight of 7,000 and a solid content of 20% by weight as a dispersant.

Dispersion G-9 P-3 aqueous solution (solid content 20% by weight) 20 parts C.I. I. Pigment Green 7 (Heliogen Green D8730, manufactured by BASF) 24 parts Ethylene glycol 5 parts Glycerin 15 parts Isopropyl alcohol 3 parts Water 135 parts Dispersion treatment was carried out in the same manner as in Example 1 to obtain an average particle size of 1
A 30 mμ dispersion G-9 was obtained.

Liquid 10 prepared by diluting 100 parts of Ink G-9 Dispersion G-9 with 45 parts of water.
0.5 parts of surfactant No. 0 to 0 parts. Add (3), stir well, viscosity 3.3 cps, surface tension 44d
A green inkjet ink G-9 having a yn / cm and a pH of 9.8 was obtained. The solid content of the final preparation was about 9.5% by weight.

Comparative Example 1 [Comparative Ink CY-1] In the ink Y-6 of Example 6, the surfactant No. CY-1 was used. A liquid in which (6) was not added was prepared and designated as Comparative Ink CY-1.

Comparative Example 2 [Comparative Ink CR-2] In the ink R-5 of Example 5, the surfactant No. A liquid not containing (11) was prepared and designated as Comparative Ink CR-2.

Comparative Example 3 [Comparative Ink CBL-3] Ink BL-4 of Example 4
In the surfactant No. A liquid in which (10) was not added was prepared and designated as Comparative Ink CBL-3.

Comparative Example 4 [Comparative Ink CG-4] In the ink G-9 of Example 9, the surfactant No. A liquid not containing (3) was prepared and designated as Comparative Ink CG-4.

Comparative Example 5 [Comparative Ink CY-5] In the ink Y-6 of Example 6, the surfactant No. Instead of (6), the surfactant No. 1 which is a compound unsuitable for the present invention. A liquid to which (12) was added was prepared as a comparative ink CY-5.

Comparative Example 6 [Comparative Ink CR-6] In the ink R-5 of Example 5, the surfactant No. Instead of (11), surfactant No. 1 which is a compound unsuitable for the present invention. A liquid to which (13) was added was prepared and designated as Comparative Ink CR-6.

Comparative Example 7 [Comparative Ink CBL-7] Ink BL-4 of Example 4
In the surfactant No. Instead of (10), the surfactant No. 1 which is a compound unsuitable for the present invention. A liquid to which (14) was added was prepared and designated as Comparative Ink CBL-7.

Comparative Example 8 [Comparative Ink CG-8] In the ink G-9 of Example 9, the surfactant No. Instead of (3), the surfactant No. 3, which is a compound unsuitable for the present invention. A liquid to which (15) was added was prepared as a comparative ink CG-8.

Test Method [Discharge Durability Test] An ink jet recording apparatus equipped with a bubble jet recording head having 360 nozzles at 360 dpi was filled with each ink of each Example and each Comparative Example through an ink supply tube. The drive frequency of the recording apparatus is 4 KHz, and the amount of droplets of a single dot is 80 ng.
Under this condition, every other 32 nozzles were used, 5 × 10 ⁸
A continuous discharge test of the pulse was carried out. Judgment is initial 5 × 10
A test document including a document, a solid pattern, and ruled lines was printed after each ejection of ⁸ pulses, and the deterioration of printability was evaluated.
The results are shown in Table 2.

Evaluation ○: Vivid characters, uniform bright solid printing, ruled line printing without blurring △… Slightly faint characters, solid printing with a decrease in density, ruled line printing with blurring ×… Distorted ruled line printing ○ is a level that is not a problem in practical use.

[Storage Stability Test] 50 ml of each ink of each Example and each Comparative Example was filled in a shot heat-resistant bottle having an internal volume of 100 ml, sealed tightly, and subjected to an accelerated storage test at 60 ° C. for 3 months. For the determination, the viscosity was measured after storage and the quality of the storage stability was determined. The results are shown in Table 2.

Evaluation ⊚: Almost no increase in viscosity and no increase in average particle size. ◯: The increase in viscosity is within 10% of the initial level, and the amount of precipitate is small. Δ: The change in viscosity was 10 to 50% of the initial value, and precipitation occurred. X: Gelled. Or it is a hard precipitate. ◯ and ◎ are levels at which there is no problem in actual use.

[Printing Printing Test] Examples 4, 5, 6
And the inks of Comparative Examples 5, 6 and 7 at 6 at 360 dpi.
The color ink jet recording device equipped with a bubble jet recording head having four nozzles was filled and color recording was performed on the polyester cloth. After recording, it was heated in steam at 180 ° C. for 8 minutes and washed in a usual manner to obtain a printed material. The level dyeing property of the obtained print was visually evaluated and evaluated. The results are shown in Table 2.

Evaluation ◯: Vivid and clear with no coloring unevenness in the printed portion Δ: Slightly uneven coloring, causing blurring or blurring ×: Conspicuous coloring unevenness, blurring or blurring, and darkness

[0125]

[Table 2]

[0126]

As described above, the aqueous dispersion ink of the present invention is a bubble jet ink using a disperse dye dispersion or an organic pigment dispersion, and has excellent storage stability.
Stable ejection can be performed in the bubble jet recording apparatus.

Further, according to the aqueous dispersion ink of the present invention, and the ink jet recording method and recording apparatus using the same, no bleeding or feathering occurs when color recording is performed on plain paper or cloth. A printed matter having excellent fixability, excellent color development, and good fastness can be obtained.

[Brief description of drawings]

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

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

FIG. 3 is an external perspective view of a head in which the heads shown in FIGS. 1 and 2 are multi-headed.

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]

 61 Wiping Member 62 Cap 63 Ink Absorber 64 Ejection Recovery Section 65 Recording Head 66 Carriage 71 Orifice Tip (Head) 72 Atmosphere Communication Port

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Shoji Koike 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Masahiro Haruta 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Tomoya Yamamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Mariko Suzuki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (8)

[Claims] 1. An aqueous dispersion ink containing at least water, a water-soluble organic solvent, a pigment or a disperse dye dispersed with a dispersant, or an aqueous dispersion ink containing a surfactant, wherein the dispersant is A polymer dispersant having an anionic dissociative group, wherein the surfactant is HLB.
Is a block copolymer of 14 or more ethylene oxide and propylene oxide, and is an aqueous dispersion ink for bubble jet. 2. The average molecular weight of the surfactant is 1000.
The water-based dispersion ink for bubble jet according to claim 1, which is 0 or more. 3. An inkjet recording method for recording by recording ink droplets formed by an inkjet method on a recording material, wherein the ink according to claim 1 or 2 is applied as the ink. Recording method. 4. The inkjet recording method according to claim 3, wherein the inkjet method is a method in which thermal energy is applied to the ink. 5. An ink cartridge having an ink containing portion containing ink, wherein the ink according to claim 1 or 2 is applied as the ink. 6. A recording unit having both an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets, wherein the ink according to claim 1 or 2 is applied as the ink. Recording unit characterized by. 7. The recording unit according to claim 6, wherein thermal energy is applied to the ink to eject the ink in the head portion. 8. An inkjet recording apparatus for recording by recording ink droplets formed by an inkjet method on a recording material, comprising the ink cartridge or the recording unit according to any one of claims 5 to 7. Inkjet recording device.