JPH08143802A - 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 composed of a compound having a specific structure and a pigment dispersion dispersed by using a specific dispersing agent, having excellent storage stability and enabling stable ejection through a nozzle. CONSTITUTION: This water-base dispersed ink contains at least (A) water, (B) a water-soluble organic solvent composed of a compound of the formula (R is H, CH3 , CH2 CH3 or Cl; (n) is an integer of 4-20) and (C) a dispersion of a pigment or a disperse dye produced by dispersing a pigment or a disperse dye with a polymeric dispersing agent having an anionic dissociation group. The addition amount of the component B is 1-30wt.%, preferably 3-20wt.% based on the ink. The polymeric dispersing agent preferably has a weight- average molecular weight of 3,000-1,5000 and the weight ratio of (coloring material) : (dispersing agent) is 10:3 to 10:0.5 for the pigment and 1:3 to 20:1 for the disperse dye.

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 water-based pigment inks according to these inventions are not sufficient as inks that solve the problems of fine particle dispersion of organic pigments and disperse dyes, and their ejection properties in the bubble jet method.

Further, in Japanese Patent Publication No. 62-14188, when a compound consisting of polyethylene glycol phenyl ether and its derivative is used in an ink jet water-based ink, in the ink using a dye, the clogging property is improved and the drying property ( Penetration into paper) and bleeding are both effective. The compound used in the invention is said to have a solubility in water of 2-3% or less at room temperature.

[0006]

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 color forming property is excellent, and the printing property is good. 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.

[0009]

That is, the present invention provides an aqueous dispersion ink containing a pigment dispersion or a disperse dye dispersion in which at least water, a water-soluble organic solvent, a pigment or a disperse dye is dispersed using a dispersant. In the water-based dispersion ink for bubble jet, the dispersant is a polymer dispersant having an anionic dissociative group, and the water-soluble organic solvent is a compound represented by the following general formula (I). is there.

[0010]

Embedded image (In the formula, R is H, CH ₃ , CH ₂ CH ₃ or C
1 is shown and n shows the integer of 4-20. m shows the integer of 0-2. ) Further, the present invention is an inkjet recording method for recording by causing ink droplets formed by an inkjet method to adhere to a recording material, wherein the water-based dispersion ink for bubble jet described above is applied as the ink. And an inkjet recording method.

The present invention is also an ink jet recording method for recording by recording the above-mentioned aqueous dispersion ink for bubble jet from a recording head using film boiling of a thin film heater as a discharge energy generating source.

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 portion containing ink and a head portion for ejecting the ink as an ink droplet, the water-based dispersion ink for bubble jet as the ink described above. Is a recording unit characterized by applying.

Further, according to the present invention, there is provided an ink jet recording apparatus for recording by recording ink droplets formed by an ink jet method on a recording material, the ink jet recording characterized by having the ink cartridge or the recording unit described above. It is a device.

The present invention will be described in detail below. 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.

In the aqueous dispersion ink of the present invention, a pigment or disperse dye is finely dispersed with a polymer dispersant having an alkali-soluble anionic dissociative group to prepare a disperse dye dispersion or a pigment dispersion, and the ejection performance is also improved. A new water-soluble organic solvent is essentially used to give

The water-soluble organic solvent selectively used in the present invention is an ethylene oxide addition compound of phenol or its derivative, and is characterized by comprising a compound represented by the following general formula (I).

[0018]

Embedded image

In the formula, R represents H, CH ₃ , CH ₂ CH ₃ or Cl, and n represents an integer of 4 to 20, preferably 5 to 20, more preferably 10 to 18. Also, m is 0
Indicates an integer of ˜2. That is, the number of added moles of ethylene oxide is 4 or more and 20 or less.

The compounds represented by the above general formula (I) have sufficient water solubility and weak surface activity. Here, the weak surface activity refers to emulsifying and solubilizing power.
When the number of moles of ethylene oxide added is 3 or less, the ink using the dispersion of the organic pigment or the disperse dye is
The long-term ejection sustainability of the bubble jet recording head cannot be obtained. The number of moles of ethylene oxide added is preferably 5 or more. When the number of added moles exceeds 20, the effect of improving discharge durability becomes small again.

The addition mole number m of propylene oxide is 0 to
2, the viscosity of the compound of the general formula (I) is lowered by the addition of a small amount of propylene oxide, and the compound is easy to use. Particularly, when n ≧ 15, m is preferably 1 to 2, and when n <15, m is preferably 0 to 1.

Further, the compound represented by the general formula (I) having a relatively long ethylene oxide chain is similar to the conventionally used glycols, but it is essential that one end thereof is phenol or its derivative. Is important to. A hydrophobic atomic group is required at the terminal and, for example, polyoxyethylene having a similar molecular chain length or glycols such as triethylene glycol does not exhibit the performance of emulsification or solubilization at all. In the case of phenol in which the terminal hydrophobic atom group is alkyl-substituted, the carbon number of the alkyl group is 2 or less, and if it is more than that, the water solubility is lowered, which is not preferable. Phenol substituted with chlorine is also effective. When the substituent is parachlorophenol, the water solubility is low, and therefore the ethylene oxide chain needs to be longer than when it is not substituted, and preferably has 5 or more carbon atoms.

The water-based dispersion ink of the present invention to which these water-soluble organic solvents are added does not adversely affect the stability of the polymer dispersant having an alkali-soluble anionic dissociative group and can be stored in the water-based dispersion ink. The stability is good.
Although the reason why these water-soluble organic solvents enhance the ejection performance is not clear, it is considered that the above-mentioned characteristics act to facilitate the removal of dispersion destruction thermally generated on the heater, that is, particle aggregation and its deposition from the heater surface. To be

The compound represented by the general formula (I) in the present invention has a high solubility of 5 to 50% in water because it is used as a water-soluble solvent.

The amount of the water-soluble organic solvent added to the aqueous dispersion ink of the present invention is usually 1 to 30% by weight, preferably 3 to.
It is 20% by weight. If it is less than 1% by weight, the moisture retention becomes insufficient, and if it exceeds 30% by weight, the viscosity becomes high and the frequency response deteriorates, which is not preferable.

When carbon black is used as the pigment, a dispersion having a small particle size and good dischargeability may be obtained by using only the polymer dispersant. At that time, such a water-soluble organic solvent is not always necessary. do not do. Furthermore, the water-based dispersion ink of the present invention is also useful for printing polyester fiber-containing fabrics, and has the effect of improving even dyeing property.

(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.

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 disperse dye: weight of dispersant.

(Base) In order to use the polymer dispersant used in the ink of the present invention in an aqueous system, a base is required. 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 optimum base species varies depending on the type of pigment and dispersant selected, but is preferably non-volatile, stable and highly water-retaining. 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, C.
I.Vat Blue 4, CIVat Blue 60, and the like.

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, CIDisperse Orange 29, CIDisperse Ora
nge 49, CIDisperse Orange 73,

CI Disperse Red 92, CIDisperse Red
126, CIDisperse Red 145, CIDisperse Red 152,
CIDisperse Red 159, CIDisperse Red 177, CIDi
sperse Red 181, CIDisperse Red 206, CIDisperse
Red 283, CIDisperse Blue 60, CIDisperse Blue 8
7, CIDisperse Blue 128, CIDisperse Blue 154,
CIDisperse Blue 201, CIDisperse Blue 214, CI
Disperse Blue 224, CIDisperse Blue 257, CIDisp
Compounds such as erse 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.

(Solvent) The 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, hard to evaporate, excellent in hydrophilicity, the first group of solvents,
A second group of solvents having a hydrophobic atomic group at the end and having good wettability to a hydrophobic surface and also having evaporative drying properties, and a third group of solvent having a suitable wettability and a low viscosity (monohydric alcohol Type).

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 solvents may be used alone or in combination of two or more. The total amount of the water-soluble 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 adjusting agent 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 solid content of the dispersion in the ink is generally in the range of 1 to 25% by weight, preferably 1.5 to 20% by weight.

The water content 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 dissociative 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) Fine particles of the pigment dispersion or disperse dye dispersion obtained as described above, water, a water-soluble organic solvent containing a compound represented by the general formula (I), and other Predetermined amounts of an organic solvent miscible with water and, if necessary, other additives are mixed and stirred to uniformly disperse the aqueous 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 many 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 arrangement, 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 in 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 or 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 via 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 as described above are provided as separate bodies, 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 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.

[0083]

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 [Black ink B-1] Anionic polymer P-1 (styrene-methacrylic acid-ethyl acrylate: acid value 400,
An aqueous solution having a weight average molecular weight of 6000 and a solid content of 20% by weight,
The following carbon black dispersion B-1 was prepared using a neutralizer: monoethanolamine) as a polymer dispersant.

Dispersion B-1 P-1 aqueous solution (solid content 20% by weight) 40 parts Carbon black MA100 (manufactured by Mitsubishi Kasei Co.) 24 parts Ethylene glycol 20 parts Water 116 parts

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 media, and dispersion treatment was carried out 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. This dispersion was centrifuged to remove coarse particles, and thus a dispersion B-1 having an average particle size of 135 mμ and a solid content of 13% was obtained.

Ink Dispersion B-1 (Solid content 13%) 50 parts Ethylene oxide 5 mol addition compound of phenol 10 parts Glycerin 10 parts Isopropyl alcohol 3 parts Water 27 parts Add sufficient stirring and viscosity 3.2 cps. A black inkjet ink B-1 having a surface tension of 45 dyn / cm and a pH of 10.0 was obtained.

Example 2 [Yellow Ink Y-2] Anionic polymer P-2 (styrene-acrylic acid-methyl methacrylate: acid value 2)
The following yellow dispersion Y-2 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-2 P-2 aqueous solution (solid content 20% by weight) 35 parts Pigment Yellow 74 25 parts Ethylene glycol 15 parts Water 125 parts The following dispersion treatment was carried out in the same manner as in Example 1 to obtain an average particle size of 1
A dispersion Y-2 having a particle size of 25 m and a solid content of 15% was obtained.

Ink Y-2 Dispersion Y-2 (solid content 15%) 50 parts Ethylene oxide 10 mol addition compound of phenol 10 parts Glycerine 10 parts Isopropyl alcohol 3 parts Water 27 parts Thus viscosity 2.8 cps, surface tension 44 dyn
/ Cm, pH 9.5 yellow inkjet ink Y-2 was obtained.

Example 3 [Yellow ink Y-3] Anionic polymer P-3 (styrene-acrylic acid-n-butyl acrylate: acid value 3)
The following yellow dispersion Y-3 was prepared by using 60, an aqueous solution having a weight average molecular weight of 9000 and a solid content of 20% by weight, a neutralizing agent: morpholine) as a dispersant.

Dispersion Y-3 P-3 aqueous solution (solid content: 20% by weight) 35 parts Pigment Yellow 109 24 parts Ethylene glycol 6 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
20 mμ of Dispersion Y-3 was obtained.

Ink Y-3 Dispersion Y-3 (solid content 15%) 50 parts Ethylene oxide 5 mol addition compound of parachlorophenol 10 parts Glycerin 10 parts Diethylene glycol 7 parts Water 23 parts Viscosity 3 by sufficiently stirring the above components. A yellow inkjet ink Y-3 having a surface tension of 46 dyn / cm and a pH of 9.5 was obtained.

Example 4 [Cyan ink C-4] The following cyan color dispersion C-4 was prepared by using the anionic polymer P-1 as a dispersant in the same manner as in Example 1.

Dispersion C-4 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.) Ethanol 11 parts Water 135 parts Dispersion treatment is carried out in the same manner as No. 1, and the average particle size is 1
A dispersion C-4 having 20 mμ and a solid content of 15% was obtained.

Ink C-4 Dispersion C-4 (solid content 15%) 50 parts Ethylene oxide 4 mol addition compound of paramethylphenol 10 parts Glycerin 10 parts Diethylene glycol 7 parts Water 23 parts Viscosity by thoroughly stirring the above materials A cyan inkjet ink C-4 having a surface tension of 47 dyn / cm and a pH of 9.6 was obtained.

Example 5 [Magenta Ink M-5] Pigment Red 122 (manufactured by Dainippon Ink and Chemicals, Inc.) was dispersed in the same manner as in Example 1 by using anionic polymer P-1 as a dispersant to disperse magenta color. Body M-5 was created. The average particle size of this dispersion is 145
It was mμ and the solid content was 18%.

Ink M-5 Dispersion M-5 40 parts Parachlorophenol ethylene oxide 20 mol addition compound 15 parts N-methylpyrrolidone 10 parts Treethylene glycol monomethyl ether 5 parts Water 30 parts The above materials are thoroughly stirred. A magenta inkjet ink M-5 having a viscosity of 3.5 cps, a surface tension of 43 dyn / cm and a pH of 9.4 was obtained.

Example 6 [Disperse dye blue ink BL-6] Anionic polymer P
-2 as a dispersant was dispersed in the same manner as in Example 2 to prepare the following blue color dispersion BL-6.

Dispersion BL-6 P-2 aqueous solution (solid content 20% by weight) 20 parts C.I. I. Desperse Blue 79 wet cake 32 parts (solid content) Diethylene glycol 15 parts Water 141 parts The average particle size of this dispersion was 125 mμ and the solid content was 17%.

Ink BL-6 Dispersion BL-6 (solid content 17%) 50 parts Glycerin 15 parts Phenol ethylene oxide 15 mol addition compound 7 parts Water 28 parts Viscosity 2.5 cps with sufficient stirring of these components A blue inkjet ink BL-6 having a tension of 43 dyn / cm and a pH of 9.7 was obtained.

Example 7 [Disperse dye red ink R-7] Anionic polymer P-
5 (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-7 was prepared.

Dispersion R-7 P-5 aqueous solution (solid content 20% by weight) 20 parts C.I. I. Disperse Red 158 Wet cake 24 parts (solid content) Isopropyl alcohol 10 parts Water 146 parts Dispersing treatment was carried out in the same manner as in Example 1 to obtain an average particle size of 1
A dispersion R-7 having a particle size of 15 m and a solid content of 13.5% was obtained.

Ink R-7 Dispersion R-7 40 parts Thiodiglycol 16 parts Ethylenephenol ethylene oxide 15 mol addition compound 10 parts Ethylene glycol diethyl ether 5 parts Water 29 parts Viscosity 3. A red inkjet ink R-8 having 0 cps, a surface tension of 47 dyn / cm and a pH of 9.6 was obtained. The solid content of the final preparation was about 5% by weight.

Example 8 [Disperse dye yellow ink Y-8] Anionic polymer P
-5 (styrene-maleic acid-n-butyl acrylate: acid value 210, weight average molecular weight 7,000, solid content 20)
Aqueous solution of wt% Neutralizer: triethanolamine) was used as a dispersant to prepare the following Yellow Dispersion Y-8.

Dispersion Y-8 P-5 aqueous solution (solid content 20% by weight) 15 parts C.I. I. Disperse Yellow 64 wet cake 28 parts (solid content) ethylene glycol 20 parts water 137 parts The following dispersion treatment was carried out in the same manner as in Experimental Example 1 to obtain an average particle size of 1
A dispersion Y-8 having a particle size of 36 m and a solid content of 15% was obtained.

Ink Y-8 Dispersion Y-8 45 parts Phenol ethylene oxide 4 mol addition compound 10 parts Thiodiglycol 10 parts Glycerin 5 parts Vigorous stirring of these components gives a viscosity of 2.7 cps and a surface tension of 51 dyn / cm. , A yellow ink Jet Ink Y-8 having a pH of 9.2 was obtained.

Example 9 [Magenta ink M-9] Anionic polymer P-5
The following magenta color dispersion M-9 was prepared using an aqueous solution of a monoethanolamine salt of (styrene-maleic acid-n-butyl acrylate: acid value 210, weight average molecular weight 7,000) as a dispersant.

Dispersion M-9 P-5 aqueous solution (solid content 20% by weight) 15 parts Scarlet F2B-02 paste 30 parts Ethylene glycol 10 parts Water 130 parts The above materials were premixed well and carried out in the same manner as in Example 1. Dispersed, average particle size 128mμ, solid content 9.0
% Dispersion M-9 was obtained.

Ink M-9 Dispersion M-9 60 parts Phenol ethylene oxide 15 mol and propylene oxide 2 mol addition compound (compound having the following structure) 10 parts

[0111]

[Chemical 4]

Glycerin 7 parts Ethylene glycol 10 parts Isopropyl alcohol 4 parts Water 9 parts These components were thoroughly stirred and mixed to give a viscosity of 2.7 cps.
A magenta inkjet ink M-9 having a surface tension of 47 dyn / cm and a pH of 8.8 was obtained.

Ink M-10 Dispersion M-9 60 parts Phenol ethylene oxide 10 mol and propylene oxide 1 mol addition compound (compound of the following structure) 8 parts

[0114]

Embedded image

Thiodiglycol 13 parts Glycerin 10 parts Water 9 parts These components were thoroughly stirred and mixed to give a viscosity of 2.4 cps.
A magenta ink jet ink M-10 having a surface tension of 55 dyn / cm and a pH of 8.9 was obtained.

Comparative Example 1 [Comparative Ink CY-1] In Comparative Example Ink CY-1, an ink was prepared in which diethylene glycol was used in place of the ethylene oxide 10 mol addition compound of phenol in Ink Y-2 of Example 2. did.

Comparative Example 2 [Comparative Ink CY-2] In Comparative Example Ink CY-2, an ink in which ethylene glycol was used in place of the ethylene oxide 5 mol addition compound of parachlorophenol in Ink Y-3 of Example 3 was prepared. -2.

Comparative Example 3 [Comparative Ink CC-3] An ink was prepared in which glycerin was used in place of the ethylene oxide 4 mol addition compound of paramethylphenol in Ink C-4 of Example 4,
Comparative ink CC-3 was used.

Comparative Example 4 [Comparative Ink CBL-4] Ink BL-6 of Example 6
In Comparative Example Ink CBL-4, an ink was prepared in which triethylene glycol was used in place of the phenol ethylene oxide 15 mol addition compound.

Comparative Example 5 [Comparative Ink CY-5] An ink was prepared by using an ink Y-2 of Example 2 in which a phenol ethylene oxide 3 mol addition compound was used in place of the phenol ethylene oxide 10 mol addition compound, and compared. Example Ink CY-5 is used.

Comparative Example 6 [Comparative Ink CY-6] Ink Y-3 of Example 3 was prepared by using an ink containing 3 mol of ethylene oxide-added compound of parachlorophenol in place of 5 mol of ethylene oxide-added compound of parachlorophenol. A comparative ink CY-6 was prepared.

COMPARATIVE EXAMPLE 7 [Comparative Ink CC-7] Ink C-4 of Example 4 was prepared by using 30 mol of ethylene oxide-added compound of paramethylphenol instead of 4 mol of ethylene oxide-added compound of paramethylphenol. Then, Comparative Ink CC-7 was obtained.

Comparative Example 8 [Comparative Ink CBL-8] Ink BL-6 of Example 6
In Comparative Example Ink CB, an ink was prepared in which the ethylene oxide 15 mol addition compound of glycerin was used in place of the phenol ethylene oxide 15 mol addition compound.
It was set to L-8.

Test method [Discharge durability test] An ink jet recording apparatus equipped with a bubble jet recording head having 64 nozzles at 360 dpi was filled with each ink of each of Examples and Comparative Examples 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 1.

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 1.

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.

[Print printing test] Examples 6, 7 and 8
Then, the inks of Comparative Examples 4 and 8 were filled in a color ink jet recording apparatus equipped with a bubble jet recording head having 64 nozzles at 360 dpi, 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 1.

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

[0130]

[Table 1]

[0131]

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

Front page continued (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 Inc. (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 a pigment dispersion or a disperse dye dispersion in which at least water, a water-soluble organic solvent, a pigment or a disperse dye is dispersed with a dispersant, wherein the dispersant is an anionic dissociative group. A water-based dispersion ink for bubble jet, which is a polymer dispersant having: and the water-soluble organic solvent comprises a compound represented by the following general formula (I). Embedded image (In the formula, R represents H, CH ₃ , CH ₂ CH ₃ or Cl, n represents an integer of 4 to 20, and m represents an integer of 0 to 2.) 2. An inkjet recording method for recording by recording ink droplets formed by an inkjet method on a recording medium, wherein the ink according to claim 1 is applied as the ink. . 3. The inkjet recording method according to claim 2, wherein the inkjet method is a method in which thermal energy is applied to the ink. 4. The ink jet recording method according to claim 2, wherein recording is performed by ejecting ink from a recording head using film boiling of a thin film heater as a discharge energy generation source. 5. An ink cartridge having an ink containing portion containing ink, wherein the ink according to claim 1 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 is applied as the ink. And a recording unit. 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.