JP2980091B2 - Manufacturing method of inkjet ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing an ink jet ink having excellent water resistance and continuous dischargeability.

[0002]

2. Description of the Related Art Conventionally, ink jet recording liquids are disclosed in JP-A-53-61412 and JP-A-54-89.
As disclosed in JP-A-811 and JP-A-55-65269, those obtained by dissolving a water-soluble dye such as an acid dye, a direct dye or a basic dye in a glycol-based solvent and water are often used. However, as the water-soluble dyes, those having high solubility in water are generally used in order to obtain the stability of the recording liquid. There has been a problem that the dye of the recording portion is blurred.

In order to improve such poor water resistance,
As disclosed in JP-A-56-57862, attempts have been made to change the structure of the dye or to prepare a recording solution having a strong basicity. Also, Japanese Patent Application Laid-Open Nos. 50-49004, 57-36692, and 59-2
As disclosed in Japanese Patent Application Laid-Open No. 0696 and Japanese Patent Application Laid-Open No. Sho 59-146889, water resistance is also improved by utilizing the reaction between a recording paper and a recording liquid. These methods have a remarkable effect on certain types of recording paper. However, since various recording papers are used in the ink jet method, sufficient water resistance of the recorded matter can be obtained with a recording liquid using a water-soluble dye. Often not.

As recording liquids having good water resistance, there are those in which an oil-soluble dye is dispersed or dissolved in a high boiling point solvent, and those in which an oil-soluble dye is dissolved in a volatile solvent. Environmentally disliked the emission of
Depending on the case where a large amount of data is recorded or where the apparatus is installed, the necessity of solvent recovery may be a problem. Therefore, in order to improve the water resistance of the recorded matter, a recording liquid in which a pigment is dispersed in an aqueous medium has been developed. However, pigments, unlike dyes, are insoluble in a recording medium, and it is very difficult to disperse them as fine particles and to maintain a stable dispersion state. In addition, while exhibiting the characteristics of pigments with excellent water and light resistance, adjustment of recording liquid ejection conditions, long-term storage stability, fixing to recording media such as paper, image color, bleeding, etc. At present, further improvement is required in order to obtain properties comparable to or better than dyes.

[0005] Further, in the recording liquid for ink jet, as the nozzle diameter becomes smaller due to the higher resolution of the printer, it is necessary to make the particle diameter of the colorant finer. Furthermore, the recording liquid in which the pigment is dispersed is required to have the opposite properties of resolubility at the head after the recording liquid is concentrated or solidified and water resistance on the paper surface. If used, the resin will remain around the nozzle and the viscosity of the recording liquid will increase when the water in the recording liquid evaporates. doing.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink-jet ink which has sufficient water repellency on paper, excellent re-dissolution of ink at a head, and good ejection stability at a nozzle. It is an object of the present invention to provide a method for efficiently manufacturing by a simple operation.

[0007]

Means for Solving the Problems The present inventors have found that in an ink-jet ink obtained by dispersing or dissolving a resin and carbon black having the resin adsorbed in an aqueous liquid, the ink is adsorbed on the carbon black in the ink. If the concentration of no resin is too high, it will adversely affect the ejection stability at the head, resolubility, etc., tend to shorten the life of the head, and the resin not adsorbed to the carbon black in the ink, The inventors have found that ultrafiltration enables efficient removal with a simple operation, leading to the present invention. That is, the present invention provides a concentrated dispersion by dispersing or dissolving carbon black and a resin in an aqueous liquid .
And the dispersion obtained in the step A is heated to 50 to 80 ° C.
A step B of Ru adsorbed the resin to the carbon black was heated to a temperature of the water to the dispersion obtained in the step B
It was diluted by adding engineering to further remove at least a portion of the resin that is not adsorbed on the carbon black to ultrafiltration
C. A method for producing an ink jet ink, comprising:

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing an ink-jet ink of the present invention, carbon black and a resin are dispersed or dissolved in an aqueous liquid to obtain a carbon black concentration of 1%.
After preparing a concentrated dispersion having a concentration of 0 to 40% by weight and a resin concentration of 5 to 30% by weight, and sufficiently adsorbing the resin to the carbon black, at least a part of the resin not adsorbed to the carbon black is subjected to ultrafiltration. To produce an inkjet ink. The manufacture of concentrated dispersions containing carbon black and resin consists of carbon black, resin, water, and, if necessary, dispersants, surfactants, aqueous solvents,
The neutralizing agent is mixed and dispersed by a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like. The concentrated dispersion is heated at a temperature of 50 to 80 ° C.
It is preferable to perform the treatment for 3 to 72 hours because the resin is well adsorbed to the carbon black.

As the carbon black, basic, neutral and acidic carbon blacks can be used. Specific examples of the basic carbon black include # 2300, # 950, # 900, # 850, and # 4 manufactured by Mitsubishi Chemical Corporation.
4, # 40, MCF88, Printex manufactured by Degussa
85, 80, 75, 60, 55, 45, BlackPearls 700 manufactured by Cabot Corporation, MONARCH
800 and the like. Specific examples of neutral carbon black include MA600 manufactured by Mitsubishi Chemical Corporation, Black PEARLS1100 manufactured by Cabot Corporation, and VALCAN.
9A32, REGAL 660, Raven 2500 ULTRA, 88 manufactured by Colombian Industries
Toka Black # 8200, # 7700, # 7550, # 745 manufactured by Tokai Carbon Co., Ltd.
0, # 7400, # 7350, # 4550, and the like.

Specific examples of acidic carbon black include # 2400B, # 2350 and # 22 manufactured by Mitsubishi Chemical Corporation.
00B, # 1000, MA100, MA7, MA8, M
A11, COLOUR BLACK FW manufactured by Degussa
200, FW2, S170, SPECIAL BRAC
K 6,550, MONARCH 1 from Cabot
400, 1300, BLACK PEALS-L, RE
GAL 400, R, manufactured by Colombian Industries
AVEN 7000, 5750, 5250, 3500,
1500, 1200, 1170, 1035, 1255
Toka Black # 8600, # 85 manufactured by Tokai Carbon Co., Ltd.
00, # 8300 and the like.

An acrylic copolymer can be used as the resin. Examples of the acrylic copolymer include copolymers of acrylic monomers such as (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide, and styrene-based polymers such as styrene and α-methylstyrene. Copolymers with monomers are mentioned.
Above all, terpolymers composed of acrylic acid, styrene and α-methylstyrene, and terpolymers composed of acrylic acid and styrene are preferred because of their high dispersibility and water resistance due to adsorption to carbon black. Used.
The weight average molecular weight of the resin is preferably 2,000 to 13,000 from the viewpoints of stable dispersibility, ink resolubility, and ejection stability. Further, the acid value of the resin is preferably 90 to 250, since the acid value can be harmonized from the viewpoints of re-solubility of the ink, ejection stability, and water resistance.

The neutralizing agent is used for stably dissolving the resin in the liquid component of the ink. As a neutralizer,
Hydroxides of alkali metals such as sodium and potassium, aliphatic amines, ethanolamine, propanolamine,
Examples thereof include alcoholamines such as methylethanolamine, morpholine, N-methylmorpholine, dimethylaminoethanol, and diethylaminoethanol. When the neutralizing agent is used in an equimolar amount or an excess amount with respect to the resin, the maintenance of solubility, the maintenance of water resistance, and the maintenance of resolubility can be performed well.

The aqueous liquid used in the method for producing an ink-jet ink of the present invention comprises water and, if necessary, an aqueous solvent. As the water, ion-exchanged water or distilled water from which metal ions and the like have been removed is suitably used. The aqueous solvent prevents drying and solidification of the ink at the nozzle, prevents stable ink ejection and drying of the nozzle over time,
It also works as a humectant.

As the aqueous solvent, ethylene glycol,
Diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether,
Ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-xantriol, tetrafurfuryl alcohol, 4-methoxy-4-methyl petanone and the like are used. Further, alcohols such as methanol, ethanol and isopropyl alcohol can be used for the purpose of speeding up the drying of the ink on paper.

The dispersant and the surfactant are used for the purpose of dispersing carbon black and improving the quality of an image. As the surfactant, anionic, nonionic, cationic, amphoteric surfactants and the like can be used.
Examples of the anionic activator include fatty acid salts, alkyl sulfate salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyphosphates. Oxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like can be exemplified.

Examples of the nonionic activator include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Examples thereof include glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based, and silicon-based nonionic activators. Examples of the cationic activator include an alkylamine salt, a quaternary ammonium salt, an alkylpyridinium salt, and an alkylimidazolium salt. Examples of amphoteric surfactants include alkyl betaines, alkylamine oxides, phosphadylcholines, and the like.

In the concentrated dispersion containing the carbon black and the resin, a part of the resin is adsorbed by the carbon black, and the remaining resin is present in the aqueous liquid as a resin not adsorbed by the carbon black. I have. The resin is
It is preferable that the carbon black is adsorbed in the range of 0.05 to 0.5 part by weight per part by weight of carbon black. When the amount of resin adsorbed is less than 0.05 parts by weight, it is difficult to stably disperse carbon black in an aqueous liquid, and it is not possible to lower the conductivity of carbon black. This may cause frequent short-circuits in the charger section and the deflecting section in a continuous type printer. On the other hand, if the amount of the resin adsorbed exceeds 0.5 parts by weight, the resin is in an excessively adsorbed state, and a stable adsorption state cannot be substantially maintained.

In the method for producing an ink-jet ink of the present invention, at least a part, that is, a part or all of the resin not adsorbed on the carbon black in the concentrated dispersion is removed by ultrafiltration. The ultrafiltration uses an ultrafiltration membrane with a molecular weight cutoff of 50,000 to 400,000 and a molecular weight of 1.5 to 7 kg.
It is preferably carried out at a temperature of 20 to 45 ° C. under a pressure of / cm ² . In order to reduce the amount of resin not adsorbed on carbon black as much as possible, the number of dilutions and dilution ratio may be increased. It is preferable to perform ultrafiltration after diluting up to 6 times.

The dispersion obtained by removing at least a part of the resin not adsorbed on the carbon black by ultrafiltration is
An inkjet ink is prepared which is dispersed together with water and, if necessary, an aqueous solvent, a dispersant, a neutralizing agent, a dye, a penetrant, a fungicide, etc., and has a low concentration of resin not adsorbed on carbon black. The concentration of the resin not adsorbed on the carbon black in the ink is preferably adjusted to be 0.001 to 1.0% by weight. When the concentration of the resin is less than 0.001% by weight, the fixing property and the water resistance of the ink become low. On the other hand, if the content exceeds 1.0% by weight, the excess resin adversely affects the ejection stability and re-dissolvability of the ink head and lowers the surface resistance of the printed matter. Is also less suitable.

The ink-jet ink produced by the method of the present invention generally contains 1 to 8% by weight of carbon black,
0.1-5% by weight of resin adsorbed on carbon black and resin not adsorbed on carbon black, 0-1% by weight of dye,
It is composed of 0.03 to 1.0% by weight of an antifungal agent, 0 to 45% by weight of an aqueous solvent, and 50 to 98.87% by weight of water. The concentration of carbon black in the ink is preferably in the range of 1 to 8% by weight. If the density is lower than this, the density and color reproduction of the image become insufficient. On the other hand, if it is higher than this, the stability of the discharge is remarkably reduced, and clogging at the nozzle is likely to occur frequently. Also, it may be difficult to adjust the viscosity of the ink.

The total amount of the resin adsorbed on the carbon black and the resin not adsorbed on the carbon black in the ink is preferably in the range of 0.1 to 5% by weight of the ink. If the amount of the resin is smaller than this, sufficient adhesion cannot be obtained.
On the other hand, if it is larger than this, it is difficult to obtain long-term ejection stability. When preparing an ink-jet ink, a dye can be used in combination with a water-resistant and light-fast ink for the purpose of adjusting the hue, imparting the density, and adjusting the characteristics of the ink. However, the use of a dye may degrade the dispersion stability of carbon black.
Preferably, it must be kept at 25% by weight or less. As the dye, an acid dye, a basic dye, a direct dye, a reactive dye, a disperse dye, a metal-containing dye and the like are used. The dye is preferably a purified dye from which inorganic salts have been removed.

As a dye, CI Direct Black 1
7, 19, 32, 51, 71, 108, 146, 15
4,166, CI Acid Black 2,7,24,2
6, 31, 52, 63, 112, 118, CI Basic Black 2, CI Direct Blue 6, 22, 25,
71, 90, 106, Food Blacks 1, 2 and their lithium or potassium substitutes, CI Acid Blue 9, 22, 40, 59, 93, 102, 104, 11
3,117,120,167,229,234, CI Basic Blue 1,3,5,7,9,24,25,2
6, 28, 29 and the like.

The antifungal agent prevents fungi and microorganisms from forming on the ink. Sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethion-1-oxide, 1,1,
For example, amine salts of 2-benzisothiazolin-3-one and 1-benzisothiazolin-3-one are used. These are used in the range of about 0.03 to 0.5% by weight of the ink.

When the printing medium of the ink is a permeable material such as paper, a penetrant can be added in order to stop the penetration of the ink into the paper and speed up the apparent dryness. As the penetrant, use may be made of glycol ethers such as diethylene glycol monobutyl ether exemplified as aqueous solvents, alkylene glycol, polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium dioctylsulfosuccinate and the like. it can. These have sufficient effects when used in an amount of 5% by weight or less of the ink. If the amount is more than 5% by weight, bleeding of the print and paper loss (print through) occur, which is not preferable.

Further, in order to block metal ions in the ink and prevent deposition of metal at the nozzle portion and precipitation of insoluble matter in the ink, a range of 0 to 0.5% by weight of the ink is used. And a chelating agent can be added. Examples of the chelating agent include ethylenediaminetetraacetic acid, sodium salts of ethylenediaminetetraacetic acid, diammonium salts of ethylenediaminetetraacetic acid, and tetraammonium salts of ethylenediaminetetraacetic acid.

Further, in order to adjust the pH of the ink and obtain the stability of the ink or the stability with the ink piping in the recording apparatus, a pH adjuster such as an amine, an inorganic salt or ammonia, or a buffer solution such as phosphoric acid is used. be able to. Further, an antifoaming agent can be added in order to prevent the circulation and movement of the ink or the generation of bubbles during the production of the ink. In addition, urea,
Additives such as dimethyl urea and other conventionally known various solvents, additives, salts, synthetic resins, natural resins and the like can be used in combination.

The particle size of the carbon black to which the resin in the ink-jet ink is adsorbed is 0.01 to 0.2 μm as an average particle size by a laser scattering method, and more preferably 0.1 to 0.2 μm.
It is preferably from 01 to 0.1 μm. With such a particle diameter, the ejection of ink during recording is stabilized. The ink has a viscosity of 0.8 to 15 cp, depending on the type of recording device.
s (25 ° C.) and a liquid having a surface tension of 25 to 60 dyn / cm. Further, the pH is not particularly limited, but is preferably adjusted to a range of 7 to 12, particularly preferably a weak alkalinity of 7 to 10. The ink produced by the method of the present invention can be used for both a continuous type printer and an on-demand type printer. In a continuous type printer, the conductivity of the ink is adjusted so that the droplets are appropriately charged.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
In the examples, parts and% represent parts by weight and% by weight, respectively. [Example 1] The following materials were put into a sand mill and dispersed,
A concentrated dispersion was prepared. Carbon black ("MA7" manufactured by Mitsubishi Chemical Corporation) 20.0 parts Resin solution 40.0 parts (acrylic acid / styrene / α-methylstyrene terpolymer (acid value 105, weight average molecular weight 3500) 13.0 parts dimethyl Aminoethanol 1.0 part Purified water 26.0 parts) Purified water 40.0 parts After heating the obtained dispersion at 70 ° C for 12 hours, add 100 parts of purified water, dilute and dilute. The resin was filtered to remove the resin not adsorbed on the carbon black (hereinafter referred to as non-adsorbed resin). Carbon black adsorbs 0.38 part of resin per part of carbon black, and the concentration of non-adsorbed resin in the dispersion is
0.14%.

The following components were mixed and dispersed, and filtered with a 0.45 μ filter to prepare an ink jet ink. The concentration of the non-adsorbed resin in the ink was 0.04%. Ultrafiltration dispersion of resin-adsorbed carbon black 29.0 parts (carbon black 5.8 parts adsorbing resin 2.2 parts non-adsorbing resin 0.041 part) diethylaminoethanol 0.1 part nonionic surfactant (Kaosha) 0.1 parts Dispersant (Solsperse 27000, manufactured by Zeneca) 0.2 parts Propylene glycol 5.0 parts Antifungal agent ("Sodium Omazine", manufactured by Ohlin) 0.15 parts Ethylenediaminetetraacetic Acid sodium salt 0.02 parts Purified water 65.43 parts

[Examples 2 to 12] In the same manner as in Example 1, the treatment shown in Table 1 was performed to prepare an ultrafiltration dispersion of resin-adsorbed carbon black. Carbon black 1
The resin adsorption amount (part) per part was as shown in Table 1.

[Table 1]

C1 carbon black ("No. 2600" manufactured by Mitsubishi Chemical Corporation) C2 carbon black (MA-MA- manufactured by Mitsubishi Chemical Corporation)
7 ") C3 carbon black (Degussa" Print "
ex55 ") C4 carbon black (Degussa" Print "
ex65 ") R1 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 100, weight average molecular weight 5000) 3
2.5% aqueous solution R2 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 180, weight average molecular weight 9000) 3
2.5% aqueous solution R3 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 95, weight average molecular weight 4500) 3
2.5% aqueous solution R4 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 90, weight average molecular weight 4000) 3
2.5% aqueous solution R5 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 120, weight average molecular weight 3000) 3
2.5% aqueous solution R6 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 200, weight average molecular weight 7,000) 3
2.5% aqueous solution R7 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 180, weight average molecular weight 9000) 3
2.5% aqueous solution R8 acrylic acid / styrene / α-methylstyrene 3
Original copolymer (acid value 100, weight average molecular weight 11000)
32.5% aqueous solution D1 Nonionic surfactant ("Emulgen 420" manufactured by Kao Corporation) D2 Dispersant (Solsperse 2700 manufactured by Zeneca Corporation)
0 ”) D3 dispersant (“ Demol N ”manufactured by Kao Corporation)

25.0 parts of an ultrafiltration dispersion of carbon black adsorbed by the resin was mixed and dispersed with the following components to prepare an ink jet ink in the same manner as in Example 1. Dimethylaminoethanol 0.1 part Nonionic surfactant ("Emulgen 420" manufactured by Kao Corporation) 0.1 part Dispersant ("Solsperse 27000" manufactured by Zeneca) 0.2 part Glycerin 3.0 parts Propylene glycol 2.0 Part Antifungal agent (“Proxel GXL” manufactured by Zeneca) 0.25 part Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Purified water 88.50 parts

Comparative Example 1 The following materials were placed in a sand mill and dispersed to prepare a concentrated dispersion. Carbon black ("MA7" manufactured by Mitsubishi Chemical Corporation) 20.0 parts Resin solution 36.0 parts (Acrylic acid / styrene / α-methylstyrene terpolymer (acid value 150, weight average molecular weight 8500) 12.0 parts Dimethyl Aminoethanol 1.0 part Purified water 23.0 parts) Purified water 44.0 parts Carbon black of the obtained dispersion liquid adsorbed 0.12 part of resin per 1 part of carbon black.

After mixing and dispersing 25.0 parts of the above dispersion with the following components, the mixture was filtered through a 0.45 μ filter to prepare an ink jet ink. Diethylaminoethanol 0.1 part Nonionic surfactant (“Emulgen 420” manufactured by Kao Corporation) 0.1 part Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.2 part Glycerin 5.0 parts Fungicide (Ohlin Corporation) "Sodium Omazine") 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 69.43 parts

Comparative Example 2 The following materials were placed in a sand mill and dispersed to prepare a concentrated dispersion. Carbon black (“MA7” manufactured by Mitsubishi Chemical Corporation) 20.0 parts Resin solution 3.6 parts (acrylic acid / styrene / α-methylstyrene terpolymer (acid value 250, weight average molecular weight 13000) 1.2 parts dimethyl Aminoethanol 0.1 part Purified water 2.3 parts) Purified water 76.4 parts In the obtained dispersion, dispersion did not proceed sufficiently, and there were many coarse particles. The carbon black of this dispersion adsorbed 0.03 parts of resin per part of carbon black.

After mixing and dispersing 25.0 parts of the above dispersion with the following components, an ink-jet ink was prepared. Diethylaminoethanol 0.1 part Nonionic surfactant (“Emulgen 420” manufactured by Kao Corporation) 0.1 part Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.2 part Glycerin 5.0 parts Fungicide (Ohlin Corporation) "Sodium Omazine") 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 69.43 parts

[Comparative Examples 3 to 6] Resins obtained by mixing a sand mill with an acrylic acid / styrene copolymer (resin) having the following acid value and weight average molecular weight, amine and purified water in the amounts shown below. 80 parts of the solution and 20.0 parts of carbon black ("MA7" manufactured by Mitsubishi Chemical Corporation) were added and dispersed to prepare a concentrated dispersion. Carbon black 1
The amount of resin adsorbed per part was as follows. Compounding amount (part) Adsorption amount Comparative example Acid value Molecular weight Resin Amine Purified water (part) 3 150 5800 40.2 75.8 0.03 4 195 11000 8 0.2 73.8 0.04 5 200 6000 201 5.5 58.5 0.22 6 200 9000 20 1.5 58.5 0.23

After mixing and dispersing 25.0 parts of the above dispersion with the following components, the mixture was filtered through a 0.45 μ filter to prepare an ink jet ink. Diethylaminoethanol 0.1 part Nonionic surfactant (“Emulgen 420” manufactured by Kao Corporation) 0.1 part Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.2 part Glycerin 5.0 parts Fungicide (Ohlin Corporation) "Sodium Omazine") 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 69.43 parts

The inks obtained in Examples and Comparative Examples were evaluated for water resistance, resolubility, filterability, viscosity, jetting characteristics, resistance and dispersibility. The results are shown in Tables 2 and 3. Further, regarding the ink obtained in the examples, -4
When naturally thawed after storage at 0 ° C. for one week, the initial viscosity was maintained and stable injection characteristics were exhibited. Also, 60
When stored in a constant temperature bath at ℃ for one month, the initial viscosity was maintained and stable injection characteristics were exhibited. Furthermore, -40 ° C 7
When the cycle of time, room temperature for 7 hours and 60 ° C. for 7 hours was repeated three times, the initial printing characteristics and physical properties of the ink were maintained.

The evaluation was performed as follows. (1) Water resistance The ink was placed in the ink tank of an ink jet printer (“GXII” manufactured by Hitachi, Ltd.), printed on plain paper (“K” manufactured by Xerox Corporation), dried, and immersed in water for 1 minute. The presence or absence of bleeding was visually evaluated (o: no bleed, x: bleed). In addition, the change of the printed portion when the solid printed on the coated paper was rubbed three times with a wet cotton swab was visually evaluated (○: no change, Δ: slight change,
X: change).

(2) Resolubility The ink was dropped on a nickel plate, and after 2 days of drying, the solubility when immersed in the same ink was visually evaluated (（: dissolution, Δ: time required for dissolution, × : Insoluble). (3) Viscosity 25 ° C with vibrating viscometer (“VM-1A” manufactured by Yamaichi Denki Co., Ltd.)
Was measured. (4) Filterability The amount of filtration with a 42 mm diameter membrane filter was examined (O: 100 ml capable of filtration, x: 100
ml that cannot be filtered).

(5) Dischargeability Discharge failure of nozzles during continuous printing was evaluated based on the presence or absence of a defect in the printed matter (物: no defect, x: defective). (6) Resistance value Ink was applied to coated paper (“NPI coated paper” manufactured by Nippon Paper Industries). 6 with a bar coater, and the resistance of the coated surface after drying is measured with a resistivity meter (“MCP-T40” manufactured by Mitsubishi Yuka Co., Ltd.).
0]) (○: 1000Ω or more, ×: 100)
<0Ω). (7) Dispersibility Dispersibility was evaluated from the change in particle size before and after storage of the ink at 50 ° C. for 7 days (（: less than 15 nm, ×: 15 nm or more). (8) Average particle size Laser diffraction particle size distribution meter (“DSL
-700 ").

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

The ink-jet ink of the present invention provides water-resistant recorded matter regardless of the type of the recording medium while using water as a medium.
It can be used in fields such as cardboard marking and numbering. Further, the ink of the present invention is excellent in the ejection stability and re-dissolvability of the ink in the head, and has a high surface resistance of the printed matter, and thus is suitably used for a continuous type printer. The ink-jet ink of the present invention is excellent in re-dissolvability, so that even when the ink adheres to the deflection electrode, troubles due to the adhesion and accumulation of the ink are reduced. Further, in the case of ink using carbon black, in particular, there is a possibility that a current shortage due to the ink at the deflection electrode may be a problem. Trouble can be reduced.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-145335 (JP, A) JP-A 8-253716 (JP, A) (58) Fields investigated (Int.Cl. ⁶ , DB name) C09D 11/00

Claims (8)

(57) [Claims] 1. A dispersed or dissolved carbon black and resin in the aqueous liquid to adjust the dispersion of the concentrated form
Step A and the dispersion obtained in Step A
A step B of Ru adsorbed the resin to the carbon black was heated to a temperature, the water dispersion obtained in the step B
A step of further removing at least a portion of the resin that is not adsorbed on the carbon black to ultrafiltration was diluted with
C. A method for producing an ink-jet ink, comprising: 2. The method according to claim 1, wherein the concentration of the resin not adsorbed on the carbon black in the ink is adjusted to be 0.001 to 1.0% by weight. 3. 0.05 parts by weight of carbon black
The method for producing an ink-jet ink according to claim 1 or 2, wherein the resin is adsorbed in an amount of from 0.5 to 0.5 parts by weight. 4. The method for producing an ink-jet ink according to claim 1, wherein an ultrafiltration membrane having a molecular weight cut-off of 50,000 to 400,000 is used. 5. The method for producing an ink jet ink according to claim 1, wherein the resin is an acrylic copolymer. 6. The method according to claim 5, wherein the acrylic copolymer is a terpolymer comprising acrylic acid, styrene and α-methylstyrene. 7. A resin having a weight average molecular weight of 2,000 to 130.
The method for producing an inkjet ink according to any one of claims 1 to 6, wherein the value is 00. 8. The method for producing an ink-jet ink according to claim 1, wherein the acid value of the resin is from 90 to 250.