JPH1095941A - Pigment-containing ink composition capable of forming image having little bleeding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink for inkjet recording having a high color density and capable of forming water-proofing records having no bleeding on regenerated paper. SOLUTION: This ink composition containing a pigment dispersible or soluble in water in the absence of a dispersant and a glycol ether of one kind or more selected from the group consisting of diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether and dipropylene glycol mono-n-butyl ether, which can produce print having extremely little bleeding. Further, this composition can produce high quality images little in bleeding by an inkjet recording method in which the composition is brought to contact with a reaction liquid containing a reactant capable of breaking a state of dispersion or solution of the pigment in the ink composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording ink capable of obtaining high quality printing with little bleeding on plain paper, recycled paper or coated paper.

2. Description of the Related Art Ink jet recording is a method of recording characters and graphics on the surface of a recording medium by ejecting ink from fine nozzles as small droplets. Inks used for such ink-jet recording are required to have characteristics such as good recording dryness, no recording bleeding, and uniform recording on all surfaces of the recording medium.

[0003] A particular problem here is that when paper is used as a recording medium, bleeding is likely to occur due to fibers having different permeability. Further, in the case where recycled paper that is frequently used in recent years due to environmental problems or the like is used, bleeding becomes a further problem. This is because recycled paper contains various paper components and has a different permeation rate but is an aggregate, and therefore easily bleeds due to the difference in permeation rate.

Conventionally, various ink compositions for preventing bleeding have been proposed.

For example, Japanese Patent Publication No. 2-2907 discloses the use of a glycol ether as a wetting agent.
Japanese Patent Publication No. 5542 proposes use of a water-soluble organic solvent, and Japanese Patent Publication No. 2-3837 proposes use of a dye dissolution promoter.

In US Pat. No. 5,156,675, addition of diethylene glycol monobutyl ether to improve permeability is disclosed in US Pat. No. 5,183,502.
In this specification, the addition of Surfynol 465, which is an acetylene glycol-based surfactant, is proposed, and in U.S. Pat. No. 5,196,056, the addition of both diethylene glycol monobutyl ether and Surfynol 465 is proposed. Here, diethylene glycol mono-
n-Butyl ether is also called butyl carbitol,
For example, it is described in U.S. Pat. No. 3,291,580. Alternatively, U.S. Pat. No. 2,083,372 discusses the use of ethers of diethylene glycol. Furthermore, Japanese Patent Application Laid-Open No. 56-147661 proposes a combined use of a pigment and triethylene glycol monomethyl ether.

[0007] In order to reduce bleeding, heating the recording paper has been studied. However, if the recording paper is heated during recording, it takes a long time to start up the heating unit in the apparatus to a predetermined temperature, the power consumption of the apparatus main body increases, or recording paper or other recording material may be damaged. There is a problem of doing damage.

In inks using pigments, glycol ethers are disclosed in JP-A-56-1 in order to suppress permeability.
Methyl ethers such as those used in 47861 are often used.

However, it can be said that there is still a need for an ink composition capable of realizing a high quality image with little bleeding.

To the knowledge of the present inventors, there has been no proposal of an ink composition in which a pigment is combined with a butyl ether of a glycol such as diethylene glycol monobutyl ether.

[0011]

SUMMARY OF THE INVENTION The present inventors have now realized that an ink composition comprising a pigment and a butyl ether of a specific glycol such as diethylene glycol monobutyl ether can effectively suppress bleeding and realize high quality images. I got the knowledge. Further, in a recording method using a so-called two-liquid printing by attaching a reaction liquid and an ink composition,
It has been found that use of such an ink composition can provide a better image. The present invention is based on this finding.

Accordingly, an object of the present invention is to provide an ink composition capable of realizing good-quality images with little bleeding even on plain paper and even recycled paper.

Another object of the present invention is to provide a recording method capable of realizing good-quality images with little bleeding even on plain paper and further on recycled paper.

The ink composition according to the present invention contains at least a pigment, a glycol ether, and water, and the pigment is a pigment that can be dispersed and / or dissolved in water without a dispersant. One or more of the glycol ethers selected from the group consisting of diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether Which is a mixture of

Further, the recording method according to the present invention is a recording method for performing printing by adhering a reaction liquid containing a reactant and an ink composition to a recording medium, wherein printing is performed. A method using the ink composition according to the present invention, wherein the reactant is capable of destroying the dispersed and / or dissolved state of the pigment.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Ink Composition The ink composition is used in a recording system using the ink composition according to the present invention. Examples of the recording method using the ink composition include an ink jet recording method, a recording method using a writing instrument such as a pen, and various other printing methods. In particular, the ink composition according to the present invention is preferably used for an ink jet recording method.

[0017] The ink composition according to the present invention comprises at least a pigment, a glycol ether, and water.
Further, in the present invention, the pigment can be dispersed and / or dissolved in water without a dispersant. In the present invention, the glycol ethers are selected from the group consisting of diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether. Or a mixture of two or more.

The pigment preferably used in the present invention is a pigment which is dispersed by a surface treatment such that at least one functional group of a carbonyl group, a carboxyl group, a hydroxyl group, or a sulfone group or a salt thereof is bonded. It can be dispersed and / or dissolved in water without an agent. Specifically, it can be obtained by grafting a functional group or a molecule containing a functional group to the surface of carbon black by a physical treatment such as vacuum plasma or a chemical treatment. In the present invention, the functional groups grafted to one carbon black particle may be single or plural. The type and the degree of the functional group to be grafted may be appropriately determined in consideration of the dispersion stability in the ink, the color density, the drying property on the front surface of the inkjet head, and the like.

In the present invention, the state where the pigment is stably present in water without a dispersant is referred to as "dispersion and / or dissolution". In many cases, it is difficult to clearly distinguish whether a substance is dissolved or dispersed.
In the present invention, as long as the pigment can be stably present in water without a dispersant, such a pigment can be used irrespective of whether the pigment is dispersed or dissolved. Therefore, in this specification, a pigment that can be stably present in water without a dispersant is sometimes referred to as a water-soluble pigment, but this does not mean that a pigment in a dispersed state is excluded.

The pigment preferably used in the present invention can be obtained, for example, by the method described in JP-A-8-3498. A commercially available product can be used as the pigment. Preferred examples include MicroJet CW1 or 2 manufactured by Orient Chemical Industries, Ltd.

The amount of the pigment added to the ink composition is 2 to 1
It is preferably 5% by weight, more preferably about 4 to 10% by weight.

The glycol ethers to be added to the ink composition according to the present invention in combination with the pigment described above include diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether or diethylene glycol mono-n-butyl ether. It is selected from propylene glycol mono-n-butyl ether.

Generally, in a pigment-based ink composition, the pigment is dispersed by a dispersant. According to experiments performed by the present inventors, when a glycol ether is added to a pigment-based ink using these dispersants to improve ink permeability, stable dispersion is destroyed, and aggregation or thickening occurs. Was observed.

The present inventors have attempted to add glycol ethers in order to improve the permeability of an ink composition containing a pigment that disperses and / or dissolves in water without the above-mentioned dispersant. As a result, it has been found that bleeding is effectively prevented by the above four types of addition. The result is
Considering that the degree of improvement was not or only slightly improved for some glycol ethers other than the above four types, the results were unexpected.

The amount of the glycol ether added to the ink composition according to the present invention is preferably about 3 to 30% by weight, more preferably about 5 to 10% by weight.

According to a preferred embodiment of the present invention, since a part of the glycol ethers has low water solubility, it is preferable to improve the solubility by adding the following components. Components that can be added include other highly water-soluble glycol ethers, thiodiglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, dipropylene glycol, Alternatively, diols and glycols such as tripropylene glycol, and a surfactant may be used.

According to a preferred embodiment of the present invention, the ink composition according to the present invention preferably contains an acetylene glycol-based surfactant. Examples of the acetylene glycol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, An acetylene glycol-based surfactant such as 5-dimethyl-1-hexyne-3ol, for example, Surfynol 104, 82, 465, 485 or TG manufactured by Nissin Chemical Co., Ltd. can be used. Especially Surfynol 104 and TG
Shows good recording quality.

The addition amount of these acetylene glycol surfactants is preferably about 0.1 to 5% by weight of the ink composition, more preferably about 0.5 to 1.5% by weight. Acetylene glycol in the above range further reduces bleeding.

Some acetylene glycol-based surfactants, such as Surfynol 104 and TG,
Low solubility in water due to low LB. This solubility can be improved by adding components such as glycol ethers, glycols, and surfactants to the ink composition.

According to a preferred embodiment of the present invention, the ink composition according to the present invention preferably contains a glycol in order to prevent clogging of a nozzle of an ink jet recording head. As the glycols, water-soluble glycols are preferable, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 600 or less, and 1,3-propylene. Glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, mesoerythritol, pentaerythritol and the like.

Further, thiodiglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, dipropylene glycol can be used as a component for more effectively preventing clogging of other nozzles. , Tripropylene glycol, neopentyl glycol, 2-methyl-2,4 pentanediol, trimethylolpropane, trimethylolethane and the like.

The amount of the component for preventing clogging may be appropriately determined within the range of preventing clogging. In the case of glycols, it is preferably about 3 to 25% by weight.

According to a preferred embodiment of the present invention, the ink composition according to the present invention improves the solubility of glycol ethers having low solubility in water, and further improves the permeability to a recording medium such as paper. Alternatively, it preferably contains a water-soluble organic solvent in order to prevent nozzle clogging. Preferred examples of the water-soluble organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol and isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol monomethyl. Ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t -Butyl ether, diethylene glycol mono-t-butyl acrylate 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene Glycol ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin , Triacetin, sulfolane and the like. The addition amount is preferably about 5 to 60% by weight based on the total amount of the ink composition.

According to a preferred embodiment of the present invention, the ink composition according to the present invention may comprise another surfactant for controlling its permeability. The surfactant preferably has good compatibility with the ink composition, and among the surfactants, those having high permeability and high stability are preferable.
Preferred specific examples thereof include amphoteric surfactants and nonionic surfactants. Examples of the amphoteric surfactant include lauryl dimethylamino acetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amide propyldimethylamino acetate betaine, polyoctyl polyaminoethyl glycine, and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether Ethers such as ethylene alkyl ether and polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiate Esters such as oleate, polyoxyethylene monooleate, and polyoxyethylene stearate; Alkyl esters, such as fluorine-containing surfactants such as perfluoroalkyl carboxylate are exemplified.

According to a preferred embodiment of the present invention, the ink composition according to the present invention may comprise a saccharide. Addition of sugar effectively prevents nozzle clogging of the ink jet recording head. The saccharide may be any of a monosaccharide and a polysaccharide, and specific examples thereof include glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitolose, maltose, cellobiose, sucrose, trehalose, In addition to maltotriose and the like, alginic acid and its salts, cyclodextrins, and celluloses may be mentioned. The addition amount is preferably about 1% to 10%, more preferably 3 to 7%.

Further, according to a preferred embodiment of the present invention, the ink composition according to the present invention comprises a preservative, a fungicide, a pH adjuster, a dye dissolution aid, or an antioxidant for improving its properties. , A conductivity adjuster, a pH adjuster, a surface tension adjuster, an oxygen absorber and the like.

Preferred examples of preservatives and fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenziso. Thiazolin-3-one (ICI
Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel TN).

Examples of pH adjusters, dye dissolution aids, and antioxidants include amines such as diethanolamine, triethanolamine, propanolamine, and morpholine, and modified products thereof, potassium hydroxide, sodium hydroxide, Inorganic salts such as lithium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide (such as tetramethylammonium), carbonates such as potassium carbonate, sodium carbonate, and lithium carbonate, and other phosphates; and N-methyl-2-pyrrolidone L-ascorbic acid and salts thereof, such as ureas such as urea, thiourea, and tetramethylurea; allohanates such as allohanate and methyl allohanate; burettes such as burette, dimethyl buret, and tetramethyl buret; Is mentioned.

Further, the ink composition according to the present invention may comprise an antioxidant and an ultraviolet absorber. Examples of those commercial products include Tinu from Ciba Geigy.
Vin 328, 900, 1130, 384, 292, 1
23, 144, 622, 770, 292, Irgaco
r252, 153, Irganox 1010, 107
6, 1035 and MD1024.

Further, the ink composition according to the present invention may comprise a viscosity modifier. Specific examples thereof include rosins, alginic acids, polyvinyl alcohol,
Examples include hydroxypropylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, polyacrylate, polyvinylpyrrolidone, gum arabic and the like.

According to a preferred embodiment of the present invention, the ink composition according to the present invention improves the coloring property of a pigment,
Alternatively, a dye can be included to improve the color density. Examples of dyes include direct dyes, acid dyes, basic dyes, reactive dyes, food colorants, and the like.

Specific examples of the dye usable in the present invention include C.I. I. Direct Black 2, 4, 9, 11, 14, 17, 19, 22, 27, 3
2, 36, 41, 48, 51, 56, 62, 71, 7
4, 75, 77, 78, 80, 105, 106, 10
7, 108, 112, 113, 117, 132, 14
6, 154, 168, 171, 194, C.I. I. Direct Yellow 1, 2, 4, 8, 11, 12, 24, 2
6, 27, 28, 33, 34, 39, 41, 42, 4
4, 48, 50, 51, 58, 72, 85, 86, 8
7, 88, 98, 100, 110, 127, 135, 1
41, 142, 144, C.I. I. Direct Orange 6, 8, 10, 26, 29, 39, 41, 49, 51,
62, 102, C.I. I. Direct Red 1, 2, 4,
8, 9, 11, 13, 15, 17, 20, 23, 24,
28, 31, 33, 37, 39, 44, 46, 47, 4
8, 51, 59, 62, 63, 73, 75, 77, 7
9, 80, 81, 83, 84, 85, 87, 89, 9
0, 94, 95, 99, 101, 108, 110, 14
5, 189, 197, 224, 225, 226, 22
7, 230, 250, 256, 257, C.I. I. Direct violet 1, 7, 9, 12, 35, 48, 5
1, 90, 94, C.I. I. Direct Blue 1, 2,
6, 8, 12, 15, 22, 25, 34, 69, 70,
71, 72, 75, 76, 78, 80, 81, 82, 8
3, 86, 87, 90, 98, 106, 108, 11
0, 120, 123, 158, 163, 165, 19
2,193,194,195,196,199,20
0, 201, 202, 203, 207, 218, 23
6, 237, 239, 246, 258, 287, C.I.
I. Direct Green 1, 6, 8, 28, 33, 3
7, 63, 64, C.I. I. Direct Brown 1A,
2, 6, 25, 27, 44, 58, 95, 100, 10,
1, 106, 112, 173, 194, 195, 20
9, 210, 211, C.I. I. Acid Black 1, 2, 7, 16, 17, 24, 26, 28,
31, 41, 48, 52, 58, 60, 63, 94, 1
07, 109, 112, 118, 119, 121, 12
2, 131, 155, 156, C.I. I. Acid Yellow 1, 3, 4, 7, 11, 12, 13, 14, 17, 1
8, 19, 23, 25, 29, 34, 36, 38, 4
0, 41, 42, 44, 49, 53, 55, 59, 6
1, 71, 72, 76, 78, 79, 99, 111, 1
14, 116, 122, 135, 142, 161, 17
2, C.I. I. Acid orange 7, 8, 10, 19, 2
0, 24, 28, 33, 41, 45, 51, 56, 6
4, C.I. I. Acid Red 1, 4, 6, 8, 13, 1
4, 15, 18, 19, 21, 26, 27, 30, 3,
2, 34, 35, 37, 40, 42, 44, 51, 5,
2, 54, 57, 80, 82, 83, 85, 87, 8
8, 89, 92, 94, 97, 106, 108, 11
0, 111, 114, 115, 119, 129, 13
1, 134, 135, 143, 144, 152, 15
4, 155, 172, 176, 180, 184, 18
6,187,249,254,256,289,31
7, 318, C.I. I. Acid Violet 7, 11,
15, 34, 35, 41, 43, 49, 51, 75,
C. I. Acid Blue 1, 7, 9, 15, 22, 2
3, 25, 27, 29, 40, 41, 43, 45, 5,
1, 53, 55, 56, 59, 62, 78, 80, 8
1, 83, 90, 92, 93, 102, 104, 11
1, 113, 117, 120, 124, 126, 13
8, 145, 167, 171, 175, 183, 22
9, 234, 236, 249, C.I. I. Acid Green 3, 9, 12, 16, 19, 20, 25, 27, 4
1, 44, C.I. I. Acid Brown 4, 14, basic dye C.I. I. Basic Black 2, 8, C.I.
I. Basic Yellow 1, 2, 11, 14, 21, 3
2, 36, C.I. I. Basic Orange 2, 15, 2
1, 22, C.I. I. Basic Red 1, 2, 9, 1
2, 13, 37, C.I. I. Basic violet 1,
3, 7, 10, 14, C.I. I. Basic Blue 1,
3, 5, 7, 9, 24, 25, 26, 28, 29, C.I.
I. Basic Green 1, 4, C.I. I. Basic Brown 1, 12, C.I. I. Reactive black 1, 3, 5, 6, 8, 12, 14, C.I. I.
Reactive yellow 1, 2, 3, 12, 13, 14,
15, 17, C.I. I. Reactive Orange 2, 5,
7, 16, 20, 24, C.I. I. Reactive Red 6, 7, 11, 12, 15, 17, 21, 23, 24,
35, 36, 42, 63, 66, 84, 184, C.I.
I. Reactive Violet 2, 4, 5, 8, 9,
C. I. Reactive Blue 2, 5, 7, 12, 13,
14, 15, 17, 18, 19, 20, 21, 25, 2,
7, 28, 37, 38, 40, 41, C.I. I. Reactive Green 5, 7, C.I. I. Reactive Brown 1, 7, 16 and C.I. I. Fudo Black 1, 2, C.I. I. Fudo Yellow 3, 4, 5, C.I.
I. Fludred 2, 3, 7, 9, 14, 52, 87,
92, 94, 102, 104, 105, 106, C.I.
I. Fudo Violet 2, C.I. I. Fudo blue 1,
2, C.I. I. Fudo Green 2, 3 and the like.

Other dyes usable in the present invention include Kayaset Black 009A, Direct Deep Black XA, and Direct Special Black AXN (all manufactured by Nippon Kayaku Co., Ltd.), Biscript Black SP Liquid, Rebasel Turquois Blue KS -6
GLL and pyranine (above, manufactured by Bayer), J
I. BK-2, JI. BK-3 (all manufactured by Sumitomo Chemical Co., Ltd.), JPK-81L, JPX-127L, JPK-1
39, C.I. I. Flowcent Brightening Agents 14, 22, 24, 32, 84, 85, 86, 87,
90, 134, 166, 167, 169, 175, 17
6, 177 (all manufactured by Orient Chemical Co., Ltd.) and the like.

According to a preferred embodiment of the present invention, a dye preferably added is a water-soluble dye represented by the following formula (I) or (II).

[0045]

Embedded image (In the formula, A represents POOM or COOM, X and Y each independently represent an alkoxy group or an alkyl group, and M represents an alkali metal, H, or NH ₄ or an organic amine.)

[0046]

Embedded image (In the formula, M represents an alkali metal, H, or NH ₄ or an organic amine, m represents 1 or 2, and n represents 0 or 1.) By adding these dyes, the print density is further improved. Is advantageous. Further, even with a pigment capable of obtaining red, blue, or yellowish black, a better black color can be produced by using the pigment together with a dye.

The amount of the water-soluble dye represented by the formula (I) or (II) is preferably from 50% by weight to less than 200% by weight based on the pigment.

Preferred specific examples of the water-soluble dye represented by the above formula (I) or (II) include the following dye (1)
To (23).

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image According to a preferred embodiment of the present invention, the ink composition according to the present invention may further comprise a surfactant and / or a regulated polymerization type water-soluble resin. These surfactants and regulated polymerization type water-soluble resins further promote or stabilize the dispersion of the pigment in the ink composition according to the present invention. Another advantage is that the printed color density can be improved, and the ejection stability at high temperatures can be improved in the ink jet recording method.

Examples of the surfactant that can be used in the present invention include the surfactants described above.

In the present invention, the regulated polymerization type water-soluble resin has a portion having a functional group capable of forming a hydrogen bond or a covalent bond with a pigment functional group at the terminal or middle of the molecule, and a hydrophilic group at the molecular terminal. However, it has a structure in which molecules are regularly arranged, and includes alternating copolymerization and block copolymerization. Specific examples of this regulated polymerization type resin include Solsperse S3000, S5000, S5000 manufactured by Zeneca Corporation (Osaka, Osaka).
9000, S12000, S13240, S1394
0, S22000, S24000GR, S26000,
S27000 and S28000 can be exemplified.

Inkjet using reaction liquid and two liquids
Recording Method The ink composition according to the present invention may form an image by an ink jet recording method, but a better image can be formed by being combined with a so-called two-liquid ink jet recording method. Specifically, a good image with little bleeding is realized even on plain paper. In addition, compared to the case of an image formed alone, by being combined with the inkjet recording method using two liquids,
The print density can be improved.

The ink jet recording method according to the present invention comprises:
Adhering a reaction liquid containing a reactant and the ink composition to a recording medium. Here, the reactant destroys the dispersed and / or dissolved state of the pigment,
It can be agglomerated.

In a recording method using two liquids such as the ink jet recording method according to the present invention, good printing can be realized by contact between the reaction liquid and the ink composition. That is, when the reaction liquid comes into contact with the ink composition, the reactant in the reaction liquid destroys the dispersed state of the pigment and other components in the ink composition, and aggregates them. It is considered that this aggregate adheres to the recording medium and realizes printing with high color density, bleeding and unevenness. Further, in a color image, uneven color mixing in a boundary region of different colors,
That is, there is an advantage that color bleed can be effectively prevented.

Therefore, even in the present invention, the reaction liquid is brought into contact with the ink composition. At that time, the step of recording an image by discharging droplets of the ink composition onto the recording medium may be before or after the step of attaching the reaction liquid to the recording medium, but is performed later. Is preferred.

The reaction liquid can be attached to the recording medium by either a method in which the reaction liquid is selectively applied only to a place where the ink composition is applied, or a method in which the reaction liquid is applied to the entire surface of the paper. Is also good. The former is economical because it can minimize the consumption of the reaction liquid, but requires a certain degree of accuracy in the position where both the reaction liquid and the ink composition are adhered. On the other hand, in the latter, the requirement for the accuracy of the adhesion position of the reaction liquid and the ink composition is relaxed as compared with the former, but a large amount of the reaction liquid adheres to the entire surface of the paper, and the paper is easily curled during drying. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the reaction liquid. When the former method is adopted, the reaction liquid can be attached by an ink jet recording method.

The reaction liquid used in the present invention contains a reaction agent having a property of destroying the dispersion state of the colorant and the like in the ink composition and aggregating the colorant components and the like.

The reactant used in the present invention includes a cationic substance such as a primary, secondary, tertiary or quaternary amine, or a compound having ammonium, phosphorus or phosphonium in the molecule. No. Also, salts of polyallylamine, polyethyleneimine, polyvinylpyrrolidone, polyvinylimidazole, polyvinylpyridine, ionene, and polydialkylallylammonium can be used. In addition, alkali metals such as lithium, sodium, and potassium, alkaline earth metals such as magnesium and calcium, and metal ions such as aluminum, zinc, chromium, copper, nickel, and iron are used as cations. Acid, succinic acid, aspartic acid, ascorbic acid, gluconic acid, glutaric acid, glutamic acid, lactic acid, butyric acid, isobutyric acid, benzoic acid,
Oleic acid, glyceric acid, molybdic acid, palmitic acid, phosphonic acid, patetonic acid, phosphinic acid, phthalic acid, formic acid, acetic acid, sulfurous acid, nitrous acid, nitric acid, phosphoric acid, phosphorous acid, pyrophosphoric acid, salicylic acid, silicic acid, borosilicate, Caproic acid, capric acid, caprylic acid, lauric acid, malonic acid, maleic acid, metabisulfite, myristic acid, stearic acid, tartaric acid, bitartrate, aluminate, boric acid, hydrochloric acid,
It is also possible to use salts such as sulfuric acid.

Further, it is also possible to use a commercial product as the above-mentioned reactant, and specific examples thereof include Sunfix (manufactured by Sanyo Chemical), Protex, Fix (manufactured by Kuroda Kako), Moulin Fixconk (manufactured by Morin Chemical). ), Amigen (Daiichi Kogyo), Epomin (Nippon Shokubai), Fix Oil (Meisei Chemical), Neofix (Nichika Chemical), Polyamine Sulfone (Nitto Boseki), Polyfix (Showa Kogaku) ), Nicafix (manufactured by Nippon Carbide), Rebogen (manufactured by Bayer), sponge (manufactured by Dick Hercules) and the like.

In the present invention, the amount of the reactant added is 0.5
About 40% by weight, more preferably 1 to 10% by weight.
% By weight. When the reactant contains a metal ion, the content of the metal ion is 0.01 mol / mol.
It is preferably about kg to 1 mol / kg, more preferably 0.03 to 0.3 mol / kg.

The reaction liquid used in the ink jet recording method according to the present invention is a glycol ether such as diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether or dipropylene glycol mono-ether. It preferably contains one or a mixture of two or more selected from n-butyl ether. The addition amount of these glycol ethers is 3 to 30.
% By weight, more preferably 5 to 10% by weight.
It is about. By adding the glycol ethers, the permeability of the reaction solution to paper is improved, and bleeding can be reduced. Further, since the glycol ether has a low vapor pressure, drying of the ink at the tip of the nozzle of the ink jet recording head can be suppressed. Further, when the ink composition is recorded in a state where the reaction liquid has penetrated the paper to some extent, there is an advantage that the recording quality is improved by compatibility with glycol ethers which are components of the ink composition.

According to a preferred embodiment of the present invention, the reaction liquid used in the ink jet recording method according to the present invention can appropriately contain a component which can be added to the above ink composition. Further, the amount of addition may be the same as that of the ink composition.

The reaction solution used in the present invention is preferably colorless or light-colored so as not to affect printed characters or images and to be usually invisible to human eyes. In this case, the reaction liquid is black ink and / or
Alternatively, it is preferable that the ink be attached to the recording medium before printing of the color ink.

On the other hand, it is also possible to add a colorant component to the reaction liquid to have the function of the color ink composition. When the colorant also functions as a color ink composition, it is necessary to select a dye that does not coagulate or thicken with the above-described reactants. Generally, dyes having a polar group such as a carboxyl group tend to be easily aggregated by metal ions. The present inventors have confirmed that aggregation of such dyes can be suppressed by introducing a hydrophilic group such as a sulfone group. Therefore, by introducing a functional group while taking into consideration the water resistance of the dye, etc., there are cases where a dye that cannot be used as it is can be used in the present invention. Specific examples of the dye that can be used or can be used by introducing a functional group include the dyes listed in the above ink composition.

In order to prevent bleeding of the color mixture between the black ink and the color ink, that is, bleeding, it is preferable that the color ink contains a reactive component.

According to a preferred embodiment of the present invention, the amount of the ink composition is preferably from 50 to 200% of the amount of the reaction liquid, and more preferably from 75 to 150%.

According to a preferred embodiment of the present invention, it is preferable that the time from when the reaction liquid is attached to the recording medium to when the recording is performed with the ink composition is 3 seconds or less,
The time is more preferably 1 second or less, even more preferably 0.1 second or less. When the time interval is short, the aggregation reaction of the pigment in the ink composition by the reaction liquid is more likely to occur, and the color density is increased to improve the recording quality.

Further, according to the recording method of the present invention, when the reaction liquid also serves as the color ink composition, the number of times of adhesion to the recording medium is one or more than one single color, or a mixture of plural colors. Can be performed once or multiple times. As a result, the color of the base can be changed, and the final color density after recording the ink composition can be made desired. For example, blue mixed with cyan and magenta, green mixed with cyan and yellow, red mixed with magenta and yellow, cyan, magenta, and a color obtained by mixing all of yellow are used as a base. By doing so, the final color density can be improved.

An ink jet recording apparatus for carrying out the ink jet recording method using two liquids according to the present invention will be described below with reference to the drawings.

The ink jet recording apparatus shown in FIG. 1 is an embodiment in which an ink composition and a reaction liquid are stored in a tank, and the ink composition and the reaction liquid are supplied to a recording head via an ink tube. That is, the recording head 1 and the ink tank 2 are connected by the ink tube 3. Here, the inside of the ink tank 2 is partitioned, and a room for the ink composition, and in some cases, a plurality of color ink compositions, and a room for the reaction liquid are provided.

The recording head 1 is moved along a carriage 4 by a timing belt 6 driven by a motor 5. On the other hand, the paper 7 as a recording medium is placed at a position facing the recording head 1 by the platen 8 and the guide 9.
In this embodiment, a cap 10 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is stored in a waste ink tank 13 via a tube 12.

FIG. 2 is an enlarged view of the nozzle surface of the recording head 1. The portion indicated by 1b is the nozzle surface of the reaction liquid, and the nozzle 21 for discharging the reaction liquid is provided in the vertical direction. On the other hand, the portion indicated by 1c is the nozzle surface of the ink composition, and from the nozzles 22, 23, 24, and 25, the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition are respectively provided. Discharged.

Further, an ink jet recording method using the recording head shown in FIG. 2 will be described with reference to FIG.
The recording head 1 moves in the direction of arrow A. During this movement, the reaction liquid is ejected from the nozzle surface 1 to form a strip-like reaction liquid attachment region 31 on the recording medium 7. Next, the recording medium 7
Is transported by a predetermined amount in the paper feed direction arrow B. During that time, the recording head 1 moves in the direction opposite to the arrow A in the figure, and returns to the position on the left end of the recording medium 7. Then, the ink composition is printed on the reaction liquid adhering area where the reaction liquid has already adhered, and a printing area 32 is formed.

Further, as shown in FIG. 4, in the recording head 1, all the nozzles can be arranged in the horizontal direction. In the figure, 41a and 41b are discharge nozzles of the reaction liquid, and the nozzles 42, 43, 44, and 45 discharge yellow ink composition, magenta ink composition, cyan ink composition, and black ink composition, respectively. You. In the recording head of such an aspect, the recording head 1 can perform printing both in the forward path and the return path in which the recording head 1 reciprocates on the carriage, so that the recording head 1 has a higher speed than the case of using the recording head shown in FIG. Printing can be expected.

Further, in some ink jet recording apparatuses of the present invention, replenishment of the ink composition is performed by replacing a cartridge which is an ink tank. This ink tank may be integrated with the recording head.

FIG. 5 shows a preferred example of an ink jet recording apparatus using such an ink tank. In the figure, the same members as those of the apparatus of FIG. 1 are denoted by the same reference numerals. In the embodiment of FIG. 5, the recording heads 1a and 1b
Are integrated with the ink tanks 2a and 2b.
The recording head 1a or 1b discharges the ink composition and the reaction liquid, respectively. The printing method may be basically the same as that of the apparatus shown in FIG. In this embodiment, the recording head 1a, the ink tank 2a, and the recording heads 1a and 2b move on the carriage 4.

In the ink jet recording apparatus of the present invention, with an ink having a relatively large amount of a solid such as a pigment as in the present invention, a nozzle which does not discharge for a long time dries the ink on the front surface of the nozzle and easily thickens, so that printing can be performed. Disturbance is easy to occur.
Then, by slightly moving the ink so as not to be ejected on the front surface of the nozzle, the ink is stirred and the ink can be ejected stably. The fine movement method can be generated by controlling the pressure of the pressurizing means for discharging the ink so that the ink is not discharged. When such control is performed, it is preferable to use an electrostrictive element as the pressurizing means because of easy control. Also, by using this mechanism,
Since the pigment concentration in the ink can be increased, it is possible to discharge the ink stably with a high color concentration using the pigment ink.

When the above-mentioned fine movement is performed on the nozzle surface in the ink jet recording apparatus, it is effective for an ink composition having a pigment content of about 5% to 15% by weight, more preferably 7% to 10% by weight. % Of the ink composition.

Next, the ink jet recording apparatus according to the present invention is characterized in that an ink cartridge containing black and color inks is filled with polyurethane foam, and the ink and urethane foam are in contact with each other. In this case, a glycol ether or an acetylene glycol-based surfactant which is preferably used in the present invention is adsorbed on the urethane foam. Therefore, it is preferable to add excessively in consideration of the amount to be adsorbed. Further, the urethane foam can secure a negative pressure by using an ink which is preferably used in the present invention,
In addition, it is unlikely that the ink used in the present invention is decomposed by the components of the ink or generates foreign matter, thereby causing clogging. As the curing catalyst for this urethane foam, a catalyst containing a metal salt or a cationic system is not used, and polyfunctional isocyanates such as tolylene diisocyanate and meta-xylylene diisocyanate and glycols such as polypropylene glycol and polyethylene glycol having an average molecular weight of about 300 to 3000 are used. Urethane foam comprising a substance having a plurality of hydroxy groups such as glycerin, pentaerythritol, dipentaerythritol, neopentyl glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. It is preferable to use them from the viewpoints of ensuring negative pressure due to the stability of the foam shape and chemical stability.

[0086]

The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto.

The following abbreviations are used in the examples. PGmBE: propylene glycol mono-n-butyl ether DEGmBE: diethylene glycol mono-n-butyl ether DPGmBE: dipropylene glycol mono-n-butyl ether, TEGmBE: triethylene glycol mono-n-butyl ether, PGmME: propylene glycol monomethyl ether DMI: 1,3 -Dimethyl-2-imidazolidinone DPGmME: dipropylene glycol monomethyl ether MPD: 2-methyl-2,4-pentanediol DEGmtBE: diethylene glycol-mono-t-butyl ether TEGmME: triethylene glycol monomethyl ether Indicates% by weight.

Example A In Example A, the average particle size of the water-soluble pigment was 60 to 1
A carbon black having a surface of 50 μm carboxylated by chemical treatment was used. In addition, Proxel XL-2 was added to the remaining water to prevent corrosion of the ink.
Benzotriazole was added in an amount of 0.001 to 0.05% to prevent corrosion of the inkjet head member.

The following ink composition was prepared. Example A1 Water-soluble pigment (average particle size: 90 μm) 5.0% PGmBE 5.0% DEGmBE 7.0% Glycerin 6.0% 1,4-butanediol 5.0% Surfynol 104 1.0% Ion exchange Water Amount Example A2 Water-soluble pigment 4.5% DPGmBE 5.0% TEGmBE 10.0% Dipropylene glycol 5.0% Urea 5.0% Surfynol TG 1.2% Fluorinated surfactant 0.1 % Amount of ion-exchanged water Example A3 Water-soluble pigment 5.5% PGmBE 5.0% DEGmBE 10.0% Propylene glycol 7.0% Triethylene glycol 3.0% 1,5-pentanediol 5.0% Surfy Nord TG 1.4% ion exchanged water Balance example A4 soluble pigment 5.0% DEGmBE 10.0% 1,6- hexanediol .0% tripropylene glycol 2.0% DMI 2.0% Surfynol 104 0.8% Surfynol 465 0.4% Ion exchanged water Balance

The following reaction mixture was prepared. Reaction liquid A1 Direct Blue 199 3.0% PGmBE 5.0% DPGmME 10.0% MPD 3.0% Trimethylolpropane 3.0% Magnesium nitrate 3.0% Surfynol TG 1.2% Triethanolamine 0.0% 9% Deionized water Residual amount of reaction solution A2 Acid Red 289 3.5% PGmBE 5.0% DPGmBE 2.0% DEGmBE 10.0% Neopentyl glycol 5.0% Calcium L-ascorbate 3.0% Surfynol TG 0.5% Cyfinol 104 0.5% Ion-exchanged water Residual reaction liquid A3 Direct Yellow 132 5.0% TEGmBE 10.0% Glycerin 5.0% Trimethylolpropane 5.0% Trimethylolethane 5.0% Magnesium acetate 2.0% Calcium acetate 1.0 % Surfynol 465 1.0% Surfinol TG 0.6% Triethanolamine 0.1% Ion-exchanged water Residual reaction liquid A4 Bonjet Black 817 5.5% DPGmBE 5.0% DEGmtBE 5.0% DEGmBE 5 0.0% Diethylene glycol 5.0% Tetrapropylene glycol 5.0% Magnesium benzoate 2.5% Surfynol 104 1.0% Ion-exchanged water Residual reaction liquid A5 TEGmBE 10.0% Glycerin 5.0% Trimethylolpropane 5.0% Trimethylolethane 5.0% Magnesium acetate 2.0% Calcium acetate 1.0% Surfynol 465 1.0% Surfynol TG 0.6% Triethanolamine 0.1% Residual ion exchange water

Next, the following ink compositions of comparative examples were prepared. In the ink composition of Comparative Example, a pigment dispersion in which carbon black having an average particle size of 60 to 150 μm was dispersed with a styrene acrylic dispersant was used. Comparative Example A1 Pigment Dispersion 5.0% TEGmME 10.0% Ethylene Glycol 8.0% Dispersant 3.0% DEGmME 7.0% Deionized Water Residue Comparative Example A2 Pigment Dispersion 5.5% Glycerin 10. 0% Diethylene glycol 10.0% Dispersant 5.0% Ion-exchange water balance Comparative Example A3 Pigment dispersion 5.5% Diethylene glycol 10.0% Surfynol 465 1.0% Ion-exchange water balance

Printing Test Using the ink compositions of Examples A1 to A4 and Comparative Examples A1 to A3, an ink jet printer MJ-700V2C manufactured by Seiko Epson Corporation prints on each recording paper in Table 1 below. Was done.

Further, the reaction liquid A5 was solid-printed (100%) on the recording medium before printing with the ink composition using the same head as that of the ink jet printer MJ-700V2C.
% Duty), and then printing was performed in the same manner as described above.

[0094] The "bleeding" and "whisker" of these recorded materials were evaluated. Here, "smearing" indicates a minute non-uniformity of penetration that reduces the roundness of the dot,
The "whisker" refers to a linear permeation non-uniformity that extends in a streak along the paper fibers. They were visually observed to evaluate the effect on the image. The results were evaluated as follows.

No effect on the image-excellent (）) affects the image but no problem in practical use-good (（) affects the image and causes a problem in practical use-(△) does not affect the image Given and unsuitable for practical use-(x) The results were as shown in Table 1 below.

[Table 1] In the table, Ricoy 6200 paper, Yamayuri paper, and Xerox R are recycled paper.

Next, after printing the above-mentioned reaction liquids A1 to A4 on a recording medium, printing was performed with the ink composition of Example A1. Printing was performed using the same printer as described above.

The OD value of the obtained print was measured. The results were as shown in Table 2 below.

[Table 2]

Example B In the following examples, the water-soluble pigment was defined as having an average particle size of 80 to 13
Carbon black having a structure in which functional groups such as a carbonyl group, a carboxyl group, and a hydroxyl group were grafted on the surface of a 0-micron carbon black by a chemical treatment was used. The numerical values in parentheses of the water-soluble pigments 1 to 8 indicate the average particle size (μm) of carbon black. In addition, 0.1-1% of Proxel XL-2 was added to the remaining water to prevent corrosion of the ink, and 0.001-0.05% of benzotriazole was added to prevent corrosion of the ink jet head members.

The following ink composition was prepared. Example B1 Water-soluble pigment 1 (105) 5.0% Food black 2 1.0% PGmBE 5.0% DEGmBE 7.0% Glycerin 6.0% 1,4-butanediol 5.0% Surfynol 104 1 0.0% Triethanolamine 0.8% Deionized water Remaining Example B2 Water-soluble pigment 2 (85) 4.5% Direct black 154 1.0% DPGmBE 5.0% TEGmBE 10.0% Dipropylene glycol 5 0.0% Urea 5.0% Surfynol TG 1.2% Fluorosurfactant 0.1% Ion-exchanged water Remaining Example B3 Water-soluble pigment 3 (120) 5.5% Acid Black 63 0.5% PGmBE 5.0% DEGmBE 10.0% Propylene glycol 7.0% Triethylene glycol 3.0% 1,5-pentanediol .0% Surfynol TG 1.4% 0.1% Potassium hydroxide ion-exchanged water Balance Example B4 soluble pigment 4 (80) 5.0% by script black SPL 1.0% DEGmBE 10.0% 1 5,6-hexanediol 5.0% Tripropylene glycol 2.0% DMI 2.0% Surfynol 104 0.8% Surfynol 465 0.4% Sodium benzoate 0.1% Deionized water Remaining Example B5 Water-soluble pigment 5 (95) 5.0% Direct black 11 1.0% PGmBE 5.0% DPGmME 10.0% MPD 3.0% Trimethylolpropane 3.0% Surfynol TG 1.2 Triethanolamine 0 .9 ion-exchanged water Balance example B6 soluble pigment 6 (100) 5.0% direct black 171 1.0% P mBE 5.0% DPGmBE 2.0% DEGmBE 10.0 % Neopentyl glycol 5.0% Surfynol TG 0.5% Saifinoru 104 0.5% Ion-exchanged water Balance Example B7 soluble pigment 7 (110) 5.0% Acid Black 24 1.0% TEGmBE 10.0% Glycerin 5.0% Trimethylolpropane 5.0% Trimethylolethane 5.0% Surfynol 465 1.0% Surfinol TG 0.6% Tri Ethanolamine 0.1% Deionized water Remaining Example B8 Water-soluble pigment 8 (90) 5.5% Acid black 156 1.0% DPGmBE 5.0% DEGmtBE 5.0% DEGmBE 5.0% Diethylene glycol 5.0 0% tetrapropylene glycol 5.0% Surfynol 104 % Ion exchange water balance

An ink composition of the following comparative example was prepared.
The pigment dispersion in the ink composition of Comparative Example had an average particle size of 90.
What disperse | distributed the carbon black of about 110 micrometers using the styrene acrylic-acid type dispersing agent was used. The numerical value in parentheses of the pigment dispersion indicates the average particle size of the carbon black.

Comparative Example B1 Pigment Dispersion (90) 5.0% TEGmME 10.0% Ethylene Glycol 8.0% Dispersant 3.0% DEGmME 7.0% Deionized Water Remaining Comparative Example B2 Pigment Dispersion ( 100) 5.5% Glycerin 10.0% Diethylene glycol 10.0% Dispersant 5.0% Ion-exchanged water Remaining comparative example B3 Pigment dispersion (110) 5.5% Diethylene glycol 10.0% Surfynol 465 1. 0% ion exchange water

Printing Test Printing with the above ink composition was evaluated in the same manner as in Example A. (Printing with only the ink composition was evaluated without using the reaction liquid together.)

The results were as shown in Table 3 below.

[Table 3]

[0104] In addition, the O
The D value was evaluated in the same manner as in Example A. (Printing with only the ink composition was evaluated without using the reaction liquid together.)

The results were as shown in Table 4 below.

[Table 4]

In Examples B1 to B8, the addition of a saccharide could improve the clogging recovery by about 10 to 30%.

Example C In the following examples, a pigment dispersion was defined as having an average particle size of 10 to 30.
A carbon black having a dispersity of 0 or less at 0 nm and having a functional group such as a carbonyl group, a carboxyl group, or a hydroxyl group grafted on its surface by a chemical treatment to be dispersed and / or dissolved in water without a dispersant. It is one that is dispersed by a surfactant and / or a water-soluble resin that has undergone regulated polymerization. The values in parentheses of the pigment dispersions 1 to 8 indicate the average particle size (nm) of carbon black.

In the remaining amount of water, 0.1-1% of Proxel XL-2 for preventing corrosion of ink, and 0.001-0.05% of benzotriazole for preventing corrosion of ink jet head members. Was added.

Example C1 Pigment Dispersion 1 (105) 5.0% Solsperse 20000 1.0% PGmBE 5.0% DEGmBE 7.0% Glycerin 6.0% 1,4-butanediol 5.0% Surfynol 104 1.0% Triethanolamine 0.8% Deionized water Remaining Example C2 Pigment Dispersion 2 (85) 4.5% Solsperse 27000 1.0% DPGmBE 5.0% TEGmBE 10.0% Dipropylene glycol 5.0% Urea 5.0% Surfynol TG 1.2% Fluorinated surfactant 0.1% Ion-exchanged water Remaining Example C3 Pigment Dispersion 3 (20) 5.5% Solsperse 20000 0.5% Solsperse 27000 0.5% PGmBE 5.0% DEGmBE 10.0% Propylene glycol 7.0% Triethylene Glycol 3.0% 1,5-pentanediol 5.0% Surfynol TG 1.4% potassium hydroxide 0.1% ion-exchanged water remaining amount Example C4 Pigment dispersion 4 (80) 5.0% Regulation Polymerized acrylic resin 1.0% DEGmBE 10.0% 1,6-hexanediol 5.0% Tripropylene glycol 2.0% DMI 2.0% Surfinol 104 0.8% Surfinol 465 0.4% Benzo Sodium acid 0.1% Ion exchange water Remaining example C5 Pigment dispersion 5 (95) 5.0% Regulated polymerization type styrene acrylic resin 1.0% PGmBE 5.0% DPGmME 10.0% MPD 3.0% trimethylolpropane 3.0% Surfynol TG 1.2% 0.9% triethanolamine ion-exchanged water Balance example C6 pigment dispersion 6 ( 00) 5.0% Solsperse 20000 1.0% Regulated polymerization type styrene acrylic resin 1.0% PGmBE 5.0% DPGmBE 2.0% DEGmBE 10.0% Neopentyl glycol 5.0% Surfynol TG 0.5 % Cyfinol 104 0.5% Ion-exchanged water Remaining Example C7 Pigment dispersion 7 (150) 5.0% Regulated polymerization type acrylic resin 1.0% Regulated polymerization type styrene acrylic resin 1.0% TEGmBE 10.0% Glycerin 5.0% Trimethylolpropane 5.0% Trimethylolethane 5.0% Surfynol 465 1.0% Surfynol TG 0.6% Triethanolamine 0.1% Ion-exchanged water Remaining Example C8 Pigment dispersion Liquid 8 (200) 5.5% Solsperse 27000 0.5% Regulated polymerization type acrylic resin 1.0% DPGmBE 5.0% DEGmtBE 5.0% DEGmBE 5.0% Diethylene glycol 5.0% Tetrapropylene glycol 5.0% Surfynol 104 1.0% Deionized water remaining.

An ink composition of the following comparative example was prepared.
The pigment dispersion in the ink composition of Comparative Example had an average particle size of 90.
What disperse | distributed the carbon black of about 110 micrometers using the styrene acrylic-acid type dispersing agent was used. The numerical value in parentheses of the pigment dispersion indicates the average particle size of the carbon black.

Comparative Example C1 Pigment Dispersion 9 (90) 5.0% TEGmME 10.0% Ethylene Glycol 8.0% Dispersant 3.0% DEGmME 7.0% Ion Exchange Water Remaining Comparative Example C2 Pigment Dispersion 10 (100) 5.5% Glycerin 10.0% Diethylene glycol 10.0% Dispersant 5.0% Ion-exchanged water Remaining comparative example C3 Pigment dispersion 11 (110) 5.5% Diethylene glycol 10.0% Surfynol 465 1.0% Remaining amount of ion-exchanged water.

Printing Test Printing with the above ink composition was evaluated in the same manner as in Example A. (Printing with only the ink composition was evaluated without using the reaction liquid together.)

The results were as shown in Table 5 below.

[Table 5]

Example D In the following examples, the pigment dispersion was defined as having an average particle size of 10 to 30.
A carbon black having a dispersity of 0 or less at 0 nm and having a functional group such as a carbonyl group, a carboxyl group, or a hydroxyl group grafted on its surface by a chemical treatment to be dispersed and / or dissolved in water without a dispersant. It is one that is dispersed by a surfactant and / or a water-soluble resin that has undergone regulated polymerization. The values in parentheses of the pigment dispersions 1 to 8 indicate the average particle size (nm) of carbon black.

In the remaining water, 0.1-1% of Proxel XL-2 for preventing corrosion of ink, and 0.001-0.05% of benzotriazole for preventing corrosion of ink jet head members. Was added.

In the following examples, dyes (1) to
(23) is the same as the above-mentioned dye number.

Example D1 Pigment Dispersion 1 (105) 5.0% Mixture of dyes (1) to (23) 3.0% Solsperse 20000 1.0% PGmBE 5.0% DEGmBE 7.0% Glycerin 0% 1,4-butanediol 5.0% Surfynol 104 1.0% Triethanolamine 0.8% Deionized water Remaining Example D2 Pigment dispersion 2 (85) 4.5% Dye (2) 2 0.5% Solsperse 27000 1.0% DPGmBE 5.0% TEGmBE 10.0% Dipropylene glycol 5.0% Urea 5.0% Surfynol TG 1.2% Fluorinated surfactant 0.1% Deionized water mixture 3.0% Solsperse 20000 0.5% of the remaining amount in example D3 pigment dispersion 3 (20) 5.5% dye (1) to (5) Solsperse 2700 0.5% PGmBE 5.0% DEGmBE 10.0% Propylene glycol 7.0% Triethylene glycol 3.0% 1,5-pentanediol 5.0% Surfynol TG 1.4% Potassium hydroxide 0.1 % Ion-exchanged water Remaining Example D4 Pigment dispersion 4 (80) 5.0% Dye (6) 2.0% Dye (7) 2.0% Regulated polymerization type acrylic resin 1.0% DEGmBE 10.0% 2.0% 1,6-hexanediol 5.0% tripropylene glycol DMI 2.0% Surfynol 104 0.8% Surfynol 465 0.4% sodium benzoate 0.1% ion-exchanged water Balance example D5 pigment dispersion 5 (95) 3.0% dye (1) 1.0% 6.0% regulated polymerization type styrene-acrylic resin PGmBE 5.0% DPGmME 10 0% MPD 3.0% Trimethylolpropane 3.0% Surfynol TG 1.2% Triethanolamine 0.9% Ion-exchanged water Balance Example D6 pigment dispersion 6 (100) 5.0% Dye (3 3.5% Solsperse 20000 1.0% Regulated polymerization type styrene acrylic resin 1.0% PGmBE 5.0% DPGmBE 2.0% DEGmBE 10.0% Neopentyl glycol 5.0% Surfinol TG 0.5% Cyfinol 104 0.5% Deionized water Remaining Example D7 Pigment dispersion 7 (150) 5.0% Mixture of dyes (4) to (8) 4.0% Regulated polymerization type acrylic resin 1.0% Regulated polymerization Type styrene acrylic resin 1.0% TEGmBE 10.0% Glycerin 5.0% Trimethylolpropane 5.0% Trimethylolethane .0% Surfynol 465 1.0% Surfynol TG 0.6% Triethanolamine 0.1% Ion-exchanged water Balance Example D8 pigment dispersion 8 (200) 5.5% Dye (3) 1.0 % Dye (5) 2.5% Solsperse 27000 0.5% Regulated polymerization type acrylic resin 1.0% DPGmBE 5.0% DEGmtBE 5.0% DEGmBE 5.0% Diethylene glycol 5.0% Tetrapropylene glycol 5.0 % Surfynol 104 1.0% Deionized water

An ink composition of the following comparative example was prepared.
The pigment dispersion in the ink composition of Comparative Example had an average particle size of 90.
What disperse | distributed the carbon black of about 110 micrometers using the styrene acrylic-acid type dispersing agent was used. The numerical value in parentheses of the pigment dispersion indicates the average particle size of the carbon black.

Comparative Example D1 Pigment Dispersion (90) 5.0% TEGmME 10.0% Ethylene glycol 8.0% Dispersant 3.0% DEGmME 7.0% Ion-exchanged water Remaining Comparative Example D2 Water-soluble dye ( Food black 2) 5.5 Glycerin 10.0% Diethylene glycol 10.0% 2-Pyrrolidone 5.0% Ion-exchanged water Remaining comparative example D3 Pigment dispersion (110) 5.5% Water-soluble dye (Food black 2) 2.5% Diethylene glycol 10.0% Surfynol 465 1.0% Deionized water

Printing Test Printing with the above ink composition was evaluated in the same manner as in Example A. (Printing with only the ink composition was evaluated without using the reaction liquid together.)

The results were as shown in Table 6 below.

[Table 6]

In Example D1, the contents of pigments and dyes were changed as shown in Table 7 below. Perform printing as described above using each ink composition,
The OD value of the obtained printed matter was measured. The results were as shown in Table 7 below.

[Table 7]

Example E In the following examples, the water-soluble pigment is carbon black dispersed by a surface treatment.
Reference numeral 4 denotes MicroJet CW2 manufactured by Orient Chemical Industry Co., Ltd., and water-soluble pigments 5 to 8 are CW1 manufactured by Orient Chemical Industry. These are obtained by oxidizing the surface of carbon black having a particle size of 10 to 300 nm and a degree of dispersion of 10 or less to form a carbonyl group, a carboxyl group, a hydroxyl group, a sulfone group, etc. on the surface.
The values in parentheses of the pigment dispersions 1 to 8 indicate the average particle size (nm) of carbon black. In addition, Proxel XL-2 was added to the remaining water to prevent corrosion of the ink.
Benzotriazole was added in an amount of 0.001 to 0.05% to prevent corrosion of the inkjet head member.

The following black ink composition was prepared. Example E11 Water-soluble pigment 1 (105) 5.0% PGmBE 5.0% DEGmBE 7.0% Glycerin 6.0% 1,5-pentanediol 5.0% Surfynol 104 1.0% Triethanolamine 0 8.8 Deionized water remaining amount Example E12 Water-soluble pigment 2 (85) 4.5 DPGmBE 5.0% TEGmBE 10.0% Dipropylene glycol 5.0% Urea 5.0% Surfynol TG 1.2% Fluorine 0.1% ion-exchanged water Remaining Example E13 Water-soluble pigment 3 (90) 5.5% PGmBE 5.0% DEGmBE 10.0% Propylene glycol 7.0% Triethylene glycol 3.0% 1,6-hexanediol 5.0% Surfynol TG 1.4% potassium hydroxide 0.1% ion-exchanged water Balance example E1 Soluble pigment 4 (80) 5.0% DEGmBE 10.0 % 1,6- hexanediol 5.0% tripropylene glycol 2.0% DMI 2.0% Surfynol 104 0.8% Surfynol 465 0. 4% Sodium benzoate 0.1% Deionized water Remaining Example E15 Water-soluble pigment 5 (95) 3.0% PGmBE 5.0% DPGmME 10.0% MPD 3.0% Trimethylolpropane 3.0% Surfynol TG 1.2% Triethanolamine 0.9% Ion-exchanged water Remaining Example E16 Water-soluble pigment 6 (100) 5.0% PGmBE 5.0% DPGmBE 2.0% DEGmBE 10.0% Neopentyl glycol 5.0% Surfynol TG 0.5% Saifinoru 104 0.5% ion-exchanged water Balance example E17 water Pigment 7 (150) 5.0% TEGmBE 10.0% Glycerin 5.0% Trimethylolpropane 5.0% Trimethylolethane 5.0% Surfynol 465 1.0% Surfinol TG 0.6% Triethanol Amine 0.1% Ion exchange water Remaining Example E18 Water-soluble pigment 8 (200) 5.5% DPGmBE 5.0% DEGmtBE 5.0% DEGmBE 5.0% Diethylene glycol 5.0% Tetrapropylene glycol 5.0 % Surfynol 104 1.0% Deionized water

The following color ink composition was prepared. Example E21 Direct Blue 23 5.0% Magnesium Nitrate 1.0% PGmBE 5.0% DEGmBE 7.0% Glycerin 6.0% 1,5-Pentanediol 5.0% Surfynol 104 1.0% Triethanol Amine 0.8% Deionized water Remaining Example E22 Direct Red 283 4.5% Calcium oxalate 1.5% DPGmBE 5.0% TEGmBE 10.0% Dipropylene glycol 5.0% Urea 5.0% Surf Nol TG 1.2% Fluorinated surfactant 0.1% Ion-exchanged water Remaining Example E23 Direct Yellow 86 5.5% Calcium carbonate 1.0% PGmBE 5.0% DEGmBE 10.0% Propylene glycol 7. 0% triethylene glycol 3.0% 1,6-hexanediol 5. % Surfynol TG 1.4% 0.1% Ion-exchanged water Balance potassium hydroxide Example E24 Acid Blue 9 5.0% magnesium succinate 1.0% DEGmBE 10.0% 1,6-hexanediol 5. 0% Tripropylene glycol 2.0% DMI 2.0% Surfynol 104 0.8% Surfynol 465 0.4% Sodium benzoate 0.1% Deionized water Remaining Example E25 Acid Red 283 3.0% Magnesium ascorbate 1.5% PGmBE 5.0% DPGmME 10.0% MPD 3.0% Trimethylolpropane 3.0% Surfynol TG 1.2% Triethanolamine 0.9% Deionized water Remaining Examples E26 acid yellow 23 5.0% calcium glutarate 1.0% PGmBE 5 0% DPGmBE 2.0% DEGmBE 10.0% Neopentyl glycol 5.0% Surfynol TG 0.5% Saifinoru 104 0.5% Ion-exchanged water Balance Example E27 Direct Blue 86 5.0% glutamic acid calcium 1 0.0% TEGmBE 10.0% Glycerin 5.0% Trimethylolpropane 5.0% Trimethylolethane 5.0% Surfynol 465 1.0% Surfynol TG 0.6% Triethanolamine 0.1% Ion exchange Water Remaining Example E28 Acid Red 35 5.5% Magnesium lactate 1.0% DPGmBE 5.0% DEGmtBE 5.0% DEGmBE 5.0% Diethylene glycol 5.0% Tetrapropylene glycol 5.0% Surfynol 104 1 0.0% ion exchange Water remaining

The following comparative ink compositions were prepared.
The pigment dispersion in the ink composition of Comparative Example had an average particle size of 90.
What disperse | distributed the carbon black of about 110 micrometers using the styrene acrylic-acid type dispersing agent was used. The numerical value in parentheses of the pigment dispersion indicates the average particle size of the carbon black.

Comparative Example E31 Pigment Dispersion (90) 5.0% TEGmME 10.0% Ethylene Glycol 8.0% Dispersant 3.0% DEGmME 7.0% Deionized Water Remaining Comparative Example E32 Pigment Dispersion ( 110) 5.5% Water-soluble dye (food black 2) 2.2% Dispersant 1.0% Diethylene glycol 10.0% Surfynol 465 1.0% Deionized water Remaining comparative example E33 Water-soluble dye (food black) 2) 5.5% glycerin 10.0% diethylene glycol 10.0% 2-pyrrolidone 5.0% ion exchanged water remaining

Printing Test Using the above-described black ink and color ink, black ink dots and color ink dots were formed adjacent to each other, and the color mixture between adjacent dots, that is, the presence or absence of bleed was observed. Printing is performed by an inkjet printer MJ-900 manufactured by Seiko Epson Corporation.
The recording was performed by a printer in which the material of the head portion of C was improved, and the recording paper shown in Table 8 below was used as a recording medium.

The bleed was visually observed to evaluate the effect on the image. The results were evaluated as follows. Has no effect on the image-excellent (◎) has an effect on the image but has no problem in practical use-good (○) has an effect on the image and has a problem in practical use-(△) has an effect on the image and has a practical effect Not suitable-(×)

The results were as shown in Table 8 below.

[Table 8]

Next, from the color ink compositions of Examples E21 to E28, magnesium sulfate, calcium oxalate, calcium carbonate, magnesium succinate, magnesium ascorbate, calcium glutarate, calcium glutamate, and magnesium lactate were respectively removed. A color ink composition was prepared. These were prepared in Example E4.
1 to 48 ink compositions were obtained.

A reaction solution was prepared by removing the water-soluble pigment from Example E11 and adding polyallylamine.

Printing was performed using the above ink composition and the reaction liquid. First, the reaction liquid was applied using MJ-900C manufactured by Seiko Epson before printing with the ink composition. Thereafter, black dots and color dots were formed in the same manner as above, and the presence or absence of bleed between adjacent dots was observed. The results were evaluated as described above. Note that Xerox 4024 paper was used as recording paper.

The results were as shown in Table 9 below.

[Table 9]

[Brief description of the drawings]

FIG. 1 is a view showing an ink jet recording apparatus according to the present invention. In this embodiment, a recording head and an ink tank are independent of each other, and an ink composition and a reaction liquid are supplied to the recording head through an ink tube.

FIG. 2 is an enlarged view of a nozzle surface of a recording head,
Is the nozzle surface of the reaction liquid, and 1c is the nozzle surface of the ink composition.

FIG. 3 is a diagram illustrating inkjet recording using the recording head of FIG. 2; In the drawing, reference numeral 31 denotes a reaction liquid adhering area, and reference numeral 32 denotes a printing area where the ink composition is printed on the reaction liquid adhering thereto.

FIG. 4 is a diagram showing another embodiment of the recording head according to the present invention, in which all the ejection nozzles are arranged in the horizontal direction.

FIG. 5 is a view showing an ink jet recording apparatus according to the present invention. In this embodiment, a recording head and an ink tank are integrated.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Recording head 2 Ink tank 3 Ink tube 21 Reaction liquid discharge nozzle 22, 23, 24, 25 Ink composition discharge nozzle 31 Reaction liquid adhesion area 32 Printing area

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application Hei 8-94568 (32) Priority date Hei 8 (1996) April 16 (33) Priority claim country Japan (JP) (31) Priority Claim No. Japanese Patent Application No. 8-204008 (32) Priority date Hei 8 (1996) August 1 (33) Priority claiming country Japan (JP)

Claims (32)

[Claims] 1. A pigment comprising at least a pigment, a glycol ether and water, wherein the pigment is dispersible and / or dissolvable in water without a dispersant, and the glycol ether is diethylene glycol monoester. An ink composition which is one or a mixture of two or more selected from the group consisting of -n-butyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether . 2. The method according to claim 1, wherein the pigment has a carbonyl group on its surface.
A surface treatment for binding at least one functional group of a carboxyl group, a hydroxyl group, or a sulfone group, or a salt thereof, so as to be dispersible and / or dissolvable in water without a dispersant; The ink composition according to claim 1. 3. The ink composition according to claim 1, comprising 2 to 15% by weight of a pigment. 4. The ink composition according to claim 1, comprising 3 to 30% by weight of the glycol ether. 5. The ink composition according to claim 1, further comprising an acetylene glycol-based surfactant. 6. The ink composition according to claim 5, comprising 0.1 to 5% by weight of the acetylene glycol-based surfactant. 7. The method according to claim 1, further comprising a glycol.
7. The ink composition according to any one of claims 1 to 6. 8. The ink composition according to claim 7, comprising 3 to 25% by weight of the glycol. 9. The ink composition according to claim 1, further comprising a dye. 10. The ink composition according to claim 9, wherein said dye is a water-soluble dye represented by the following general formula (I) or (II). Embedded image (In the formula, A represents POOM or COOM, X and Y each independently represent an alkoxy group or an alkyl group, and M represents an alkali metal, H, or NH ₄ or an organic amine.) (In the formula, M represents an alkali metal, H, or NH ₄ or an organic amine, m represents 1 or 2, and n represents 0 or 1.) 11. The ink composition according to claim 10, wherein the amount of the water-soluble dye is from 50% by weight to less than 200% by weight based on the pigment. 12. The ink composition according to claim 1, further comprising a surfactant and / or a regulated polymerization type water-soluble resin. 13. The ink composition according to claim 12, wherein the surfactant and / or the regulated polymerization-type water-soluble resin further promotes or stabilizes the dispersion of the pigment. 14. A recording method for printing by adhering a reaction liquid containing a reactant and an ink composition to a recording medium, wherein the ink composition is used as the ink composition. The recording method, wherein the reactant is capable of destroying the dispersed and / or dissolved state of the pigment. 15. The recording method according to claim 14, wherein the reactant is a cationic substance or a salt. 16. The method according to claim 16, wherein the cationic substance is primary, secondary,
The recording method according to claim 15, wherein the recording method is selected from a group of compounds having tertiary and quaternary amines and ammonium, phosphorus, and phosphonium in a molecule. 17. The recording method according to claim 15, wherein the salt is a salt of polyallylamine, polyethyleneimine, polyvinylpyrrolidone, polyvinylimidazole, polyvinylpyridine, ionene, or polydialkylallylammonium. (18) the salt is an alkali metal, an alkaline earth metal,
16. The recording method according to claim 15, wherein metal ions of aluminum, zinc, chromium, copper, nickel, and iron are used as cationic species. 19. The reaction liquid according to claim 14, wherein said reaction liquid contains a coloring agent and functions as an ink composition.
9. The recording method according to any one of items 8 to 9. 20. The method according to claim 14, wherein the reaction liquid is adhered to a recording medium, and thereafter, the ink composition is printed on the recording medium.
The recording method according to any one of the above. 21. The recording method according to claim 20, wherein the time from adhering the reaction liquid to the recording medium until printing the ink composition is 3 seconds or less. 22. The method according to claim 14, wherein the ink composition is printed on a recording medium, and then the reaction liquid is applied to the recording medium.
The recording method according to any one of the above. 23. The recording method according to claim 14, wherein printing is performed on the recording medium immediately before or immediately after the reaction liquid and the ink composition are attached to the recording medium. 24. The recording method according to claim 14, wherein said reaction solution further comprises a glycol ether. 25. The reaction solution according to claim 14, wherein the reaction solution further comprises an acetylene glycol-based surfactant.
5. The recording method according to any one of 4. 26. The recording method according to claim 25, wherein said reaction solution contains 0.1 to 5% by weight of an acetylene glycol-based surfactant. 27. The recording method according to claim 14, wherein the reaction liquid and / or the ink composition is discharged as droplets from a fine nozzle, and the droplets are attached to a recording medium. 28. The recording method according to claim 27, wherein the ink composition is finely moved in the fine nozzle to such an extent that the ink composition is not ejected as a droplet while the droplet of the ink composition is not ejected. 29. The recording method according to claim 28, wherein the ink composition contains 5 to 15% by weight of a pigment. 30. The amount of the ink composition used is 50 to 200% by weight based on the amount of the reaction liquid.
The recording method according to any one of claims 14 to 29. 31. Recorded matter printed by the method according to any one of claims 14 to 30. 32. An ink jet recording apparatus for performing the recording method according to any one of claims 14 to 30, wherein: a means for adhering a reaction liquid to a recording medium; And an ink jet recording means for forming and attaching the droplets to the recording medium.
Ink jet recording device.