JP2002285056A - Ink-jet recording liquid and method for recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink-jet recording liquid satisfying both problems of head nozzle clogging and blur after recording and capable of obtaining a stable image, and to provide an ink-jet recording method using the same. SOLUTION: The ink-jet recording liquid used for an ink-jet recording device for recording by injecting ink comprises at least two dihydric alcohols as solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ink jet recording liquid and an ink jet recording method using the same.

[0002]

2. Description of the Related Art Ink jet recording is a technique in which fine droplets of a recording liquid for ink jet are caused to fly according to various operating principles and adhere to a recording material to form images such as images and characters. There is an advantage that low noise, multicoloring, and the like are easy. The ink composition used in inkjet recording has water as a main component, a coloring component,
In general, those containing a water-soluble high-boiling organic solvent such as glycerin for the purpose of preventing clogging and the like. The ink composition does not change its physical properties during long-term storage, does not clog the head nozzle holes, has a high recording image density and good color tone, and has excellent color image fastness such as water resistance and heat resistance. It is required that the recording medium be fixed quickly and not bleed after recording, and be inexpensive.

The ink composition is required to have various performances as described above, but most importantly, clogging of head nozzles during printing, when printing is interrupted, and when printing is not performed for a long period of time. And liquid stability without generation of sediment.

The conventional method of adding a humectant such as glycerin improves clogging, but has a drawback that bleeding occurs after recording. Therefore, an ink composition satisfying both clogging and bleeding is difficult. Not obtained. In addition, clogging may be caused by various impurities contained in the dye used in the ink.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to solve both the problems of clogging of head nozzles and bleeding after recording, thereby obtaining a stable image. An object of the present invention is to provide an inkjet recording liquid and an inkjet recording method using the same. That is,
When printing, when printing is interrupted, even when printing is not performed for a long period of time, clogging of the head nozzle does not occur, and stable images with improved bleeding can be obtained even under high humidity An object of the present invention is to provide a recording liquid and an ink jet recording method using the same.

[0006]

The above objects of the present invention have been attained by the following constitutions.

[0007] 1. An ink jet recording liquid used in an ink jet recording apparatus that performs recording by ejecting ink, comprising two or more dihydric alcohols as a solvent.

[0008] 2. 2. The inkjet recording liquid according to 1, wherein at least one of the dihydric alcohols is ethylene glycol.

3. Wherein the dihydric alcohol is ethylene glycol and propylene glycol.
2. The recording liquid for inkjet according to item 1.

[0010] 4. The ethylene glycol content is 1
The recording liquid for inkjet according to 2 or 3, wherein the amount is from 25 to 25% by mass.

5. The recording liquid for inkjet according to any one of claims 1 to 4, wherein the recording liquid contains 1 to 15% by mass of an ether solvent.

6. The inkjet recording liquid according to any one of claims 1 to 5, wherein the total amount of calcium ions, magnesium ions, and iron ions contained in the inkjet recording liquid is 10 ppm or less.

7. The inkjet recording liquid according to any one of claims 1 to 6, wherein the content of magnesium ions contained in the inkjet recording liquid is 2 ppm or less.

8. 8. The ink jet recording liquid according to any one of 1 to 7, wherein the content of calcium ions contained in the ink jet recording liquid is 3 ppm or less.

9. 9. The ink jet recording liquid according to any one of 1 to 8, wherein the content of iron ions contained in the ink jet recording liquid is 3 ppm or less.

10. The inkjet recording liquid according to any one of claims 1 to 9, further comprising a complexing agent.

The recording liquid for inkjet according to any one of 11.1 to 10 is adhered to an image receiving sheet having a porous ink receiving layer containing fine silica particles and a hydrophilic binder on a support. Characteristic ink jet recording method.

[12] The pore size of the ink receiving layer is 10 to
12. The ink jet recording method according to 11, wherein the thickness is 100 nm.

13. 13. The ink jet recording method according to claim 11, wherein the ink receiving layer contains a cationic fixing agent.

The present inventors have conducted intensive studies to develop an ink jet recording liquid that can achieve both clogging and bleeding. As a result, they have found that it is optimal to use a plurality of dihydric alcohols, and have reached the present invention. It is a thing. In particular, the combination of ethylene glycol and propylene glycol is most suitable. The causes of clogging during recording are magnesium, calcium, and iron, which are impurities in the dye, and the problem of clogging can be solved by using an inkjet recording liquid that does not contain such impurities as much as possible. Found to be.

Hereinafter, the present invention will be described in detail. The ink jet recording liquid of the present invention is used in an ink jet recording apparatus that performs recording by ejecting ink, and is characterized by containing two or more dihydric alcohols as a solvent.

Examples of the dihydric alcohol that can be used in the present invention include known water-soluble organic solvents. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, and 1,2-pentanediol. These dihydric alcohols are used in combination of two or more.

In the present invention, at least one of the dihydric alcohols is preferably ethylene glycol. In particular, when ethylene glycol is used as the dihydric alcohol, it is preferable to use propylene glycol as the other dihydric alcohol.

When the above-mentioned ethylene glycol is used,
The content is preferably 1 to 25% by mass, particularly 5 to 25% by mass.
% By mass, more preferably 7 to 24% by mass.

Other water-soluble organic solvents used in the present invention include alcohols (for example, methanol, ethanol, propanol, butanol, isobutanol, and the like).
Secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (eg, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, hexanetriol, etc.), polyhydric alcohol ethers ( For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether Met Ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc., amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc., amide, etc. For example, formamide, N, N-dimethylformamide ), Heterocyclic compounds such as (e.g., 2-pyrrolidone, N- methyl-2
Examples include pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, and the like, sulfoxides (for example, dimethyl sulfoxide), sulfones (for example, sulfolane), acetonitrile, acetone, and the like.

The ink jet recording liquid of the present invention preferably contains 1 to 15% by mass of an ether solvent, more preferably 5 to 10% by mass. As the ether solvent, for example, any of the above solvents may be used, but triethylene glycol monobutyl ether and diethylene glycol monobutyl ether are preferable.

Examples of the water-soluble dyes usable in the present invention include azo dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes and diphenylmethane dyes. Specific compounds are shown below.
However, the present invention is not limited to these exemplified compounds. [C. I. Acid Yellow] 1, 3, 11, 17, 18, 19, 23, 25, 36,
38, 40, 42, 44, 49, 59, 61, 65, 6
7, 72, 73, 79, 99, 104, 110, 11
4, 116, 118, 121, 127, 129, 13
5, 137, 141, 143, 151, 155, 15
8, 159, 169, 176, 184, 193, 20
0, 204, 207, 215, 219, 220, 23
0, 232, 235, 241, 242, 246 [C. I. Acid Orange] 3, 7, 8, 10, 19, 24, 51, 56, 67, 7
4,80,86,87,88,89,94,95,10
7, 108, 116, 122, 127, 140, 14
2, 144, 149, 152, 156, 162, 16
6, 168 [C. I. Acid Red] 1, 6, 8, 9, 13, 18, 27, 35, 37, 5
2, 54, 57, 73, 82, 88, 97, 106, 1
11, 114, 118, 119, 127, 131, 13
8, 143, 145, 151, 183, 195, 19
8, 211, 215, 217, 225, 226, 24
9, 251, 254, 256, 257, 260, 26
1,265,266,274,276,277,28
9,296,299,315,318,336,33
7, 357, 359, 361, 362, 364, 36
6, 399, 407, 415 [C. I. Acid Violet] 17, 19, 21, 42, 43, 47, 48, 49, 5
4, 66, 78, 90, 97, 102, 109, 126 [C. I. Acid Blue] 1, 7, 9, 15, 23, 25, 40, 62, 72, 7
4, 80, 83, 90, 92, 103, 104, 11
2, 113, 114, 120, 127, 128, 12
9, 138, 140, 142, 156, 158, 17
1,182,185,193,199,201,20
3, 204, 205, 207, 209, 220, 22
1, 224, 225, 229, 230, 239, 24
9, 258, 260, 264, 278, 279, 28
0, 284, 290, 296, 298, 300, 31
7, 324, 333, 335, 338, 342, 350 [C. I. Acid Green] 9, 12, 16, 19, 20, 25, 27, 28, 4
0, 43, 56, 73, 81, 84, 104, 108,
109 [C. I. Acid Brown] 2, 4, 13, 14, 19, 28, 44, 123, 22
4, 226, 227, 248, 282, 283, 28
9, 294, 297, 298, 301, 355, 35
7, 413 [C. I. Acid Black] 1, 2, 3, 24, 26, 31, 50, 52, 58, 6
0, 63, 107, 109, 112, 119, 132,
140, 155, 172, 187, 188, 194, 2
07, 222 [C. I. Direct Yellow] 8, 9, 10, 11, 12, 22, 27, 28, 39,
44, 50, 58, 86, 87, 98, 105, 10
6, 130, 132, 137, 142, 147, 153 [C. I. Direct Orange] 6, 26, 27, 34, 39, 40, 46, 102, 1
05, 107, 118 [C. I. Direct Red] 2, 4, 9, 23, 24, 31, 54, 62, 69, 7
9,80,81,83,84,89,95,212,2
24, 225, 226, 227, 239, 242, 24
3, 254 [C. I. Direct Violet] 9, 35, 51, 66, 94, 95 [C. I. Direct Blue] 1, 15, 71, 76, 77, 78, 80, 86, 8
7, 90, 98, 106, 108, 160, 168, 1
89, 192, 193, 199, 200, 201, 20
2, 203, 218, 225, 229, 237, 24
4,248,251,270,273,274,29
0, 291 [C. I. Direct Green] 26, 28, 59, 80, 85 [C. I. Direct Brown] 44, 106, 115, 195, 209, 210, 22
2, 223 [C. I. Direct Black] 17, 19, 22, 32, 51, 62, 108, 11
2, 113, 117, 118, 132, 146, 15
4, 159, 169 [C. I. Basic Yellow] 1, 2, 11, 13, 15, 19, 21, 28, 29,
32, 36, 40, 41, 45, 51, 63, 67, 7
0, 73, 91 [C. I. Basic Orange] 2, 21, 22 [C. I. Basic Red] 1, 2, 12, 13, 14, 15, 18, 23, 24,
27, 29, 35, 36, 39, 46, 51, 52, 6
9, 70, 73, 82, 109 [C. I. Basic Violet] 1, 3, 7, 10, 11, 15, 16, 21, 27, 3
9 [C. I. Basic Blue] 1, 3, 7, 9, 21, 22, 26, 41, 45, 4
7, 52, 54, 65, 69, 75, 77, 92, 10,
0, 105, 117, 124, 129, 147, 151 [C. I. Basic Green] 1, 4 [C. I. Basic Brown] 1 [C. I. Reactive Yellow] 2, 3, 7, 15, 17, 18, 22, 23, 24, 2
5, 27, 37, 39, 42, 57, 69, 76, 8
1, 84, 85, 86, 87, 92, 95, 102, 1
05, 111, 125, 135, 136, 137, 14
2,143,145,151,160,161,16
5, 167, 168, 175, 176 [C. I. Reactive Orange] 1, 4, 5, 7, 11, 12, 13, 15, 16, 2
0, 30, 35, 56, 64, 67, 69, 70, 7
2, 74, 82, 84, 86, 87, 91, 92, 9
3, 95, 107 [C. I. Reactive Red] 2, 3, 5, 8, 11, 21, 22, 23, 24, 2
8, 29, 31, 33, 35, 43, 45, 49, 5,
5, 56, 58, 65, 66, 78, 83, 84, 10
6, 111, 112, 113, 114, 116, 12
0, 123, 124, 128, 130, 136, 14
1,147,158,159,171,174,18
0, 183, 184, 187, 190, 193, 19
4, 195, 198, 218, 220, 222, 22
3, 228, 235 [C. I. Reactive Violet] 1, 2, 4, 5, 6, 22, 23, 33, 36, 38 [C. I. Reactive Blue] 2, 3, 4, 5, 7, 13, 14, 15, 19, 21,
25, 27, 28, 29, 38, 39, 41, 49, 5
0, 52, 63, 69, 71, 72, 77, 79, 8
9, 104, 109, 112, 113, 114, 11
6, 119, 120, 122, 137, 140, 14
3, 147, 160, 161, 162, 163, 16
8, 171, 176, 182, 184, 191, 19
4, 195, 198, 203, 204, 207, 20
9, 211, 214, 220, 221, 222, 23
1, 235, 236 [C. I. Reactive Green] 8, 12, 15, 19, 21 [C. I. Reactive Brown] 2, 7, 9, 10, 11, 17, 18, 19, 21, 2,
3, 31, 37, 43, 46 [C. I. Reactive Black] 5, 8, 13, 14, 31, 34, 39, etc., and the above-listed dyes are described in “Dyeing Notebook 21st Edition” (published by Shimosensha) and the like. .

The total amount of calcium ions, magnesium ions and iron ions contained in the ink jet recording liquid of the present invention is preferably adjusted to 10 ppm or less.

Particularly, the content of magnesium ion is 2 pp
m or less, the content of calcium ions is 3 ppm or less, and the content of iron ions is 3 ppm or less,
Since such impurities in the dye are not contained as much as possible, the problem of clogging occurring during recording is solved.
The smaller the total amount of these ions contained in the ink jet recording liquid, the more the improvement of clogging can be expected.

Methods for adjusting calcium, magnesium and iron ions are described below.

A dye aqueous solution having a predetermined concentration is measured by ICPAES, and the ion concentration in the state of the ink is calculated by converting into a dye concentration used in the ink. As the water, distilled water or ion-exchanged water is used. Thereby, the ion concentration can be estimated. Next, an ink is prepared by adding other additives and the like, and the ion concentration in the ink is measured by ICPAES. When the desired ion concentration is not reached, the aqueous dye solution can be passed through an ion exchange resin to lower the ion concentration. The ion concentration can be further reduced by performing ion exchange a plurality of times. If the desired ion concentration cannot be attained, the same treatment is carried out for additives other than the dye.

The ink jet recording liquid of the present invention preferably contains a complexing agent (metal chelating agent). That is, it is preferable to use a complexing agent to encapsulate the above various ions, since the problem of clogging can be improved. Examples of the complexing agent include iminodiacetate, ethylenediaminetetraacetate, and propylenediaminetetraacetate, and ethylenediaminetetraacetate is particularly preferable.

A surfactant may be added to the ink jet recording liquid of the present invention to control its surface tension.

As the surfactant, for example, anionic, cationic, amphoteric or nonionic surfactants are used.
Typically, anionic surfactants include fatty acid salts, alkyl sulfates, alkyl sulfates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, alkyl naphthalene sulfones Examples of cationic surfactants such as acid formalin condensates and polyoxyethylene alkyl sulfates include amine salts, tetraalkyl quaternary ammonium salts, trialkyl quaternary ammonium salts, alkylpyridinium salts, and alkylquinolinium salts. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene propylene block polymer, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene. Rubitan fatty acid esters, polyoxyethylene alkyl amines, ethylene oxide adducts of acetylene alcohol.

The addition amount of these surfactants is determined by the type of water-soluble dye used, the water-soluble organic solvent contained in the ink, and the type and amount of other additives.
The range is generally about 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the ink.

The ink jet recording liquid of the present invention has a viscosity adjustment suitable for each purpose for the purpose of improving ejection stability, compatibility with a print head or ink cartridge, storage stability, and other various properties. Agents, specific resistance adjusters, film forming agents, ultraviolet absorbers, antioxidants, preservatives, fungicides, rust inhibitors, pH adjusters, dye dissolution aids, defoamers, etc. You can also.

Preferred examples of the preservative and the fungicide include, for example, sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-benzene Isothiazolidine-3-one (Proxel CRL, Proxel BD, Proxel GXL, Proxel TN, Proxel XL-2 manufactured by Zeneca)
And 4-chloro-3-methylphenol (Priventol CMK manufactured by Bayer AG).

PH adjusters, dye dissolution aids, antioxidants,
Examples of antifoaming agents include, for example, amines such as diethanolamine, triethanolamine, propanolamine, morpholine and the like, and modified products thereof, potassium hydroxide,
Inorganic salts such as sodium hydroxide and lithium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide (eg, tetramethylammonium, etc.), potassium carbonate,
Sodium carbonate, carbonates such as lithium carbonate and other phosphates, or N-methyl-2-pyrrolidone, urea,
Examples include ureas such as thiourea and tetramethylurea, silicone emulsions, and silicone compounds.

In order to carry out ink jet recording, there is a method of adhering the above ink jet recording liquid to an image receiving sheet having a porous ink receiving layer containing fine silica particles and a hydrophilic binder on a support. Hereinafter, the image receiving sheet will be described below. The ink receiving layer has inorganic fine particles and forms voids. Examples of the inorganic fine particles include silica, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, and hydrocarbon. Examples include white inorganic pigments such as talcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, lithopone, zeolite, and magnesium hydroxide. Particularly preferred are silica fine particles.

The pore size in the ink receiving layer is 10 to 10
It is preferably 0 nm. To measure the pore size,
For example, a mercury porosimeter (Shimadzu Poreizer 9220)
(Type) under an initial pressure of 0.1 MPa.

As the hydrophilic binder used in the ink receiving layer, a hydrophilic binder known in conventional recording paper can be used. For example, gelatin, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, Carboxymethylcellulose, hydroxyethylcellulose, agar, dextrin and the like can be mentioned, and polyvinyl alcohol having a good film-forming property is particularly preferable.

The polyvinyl alcohol preferably used has a saponification degree of 70 to 100% and an average polymerization degree of 2000 to 2000.
5000, and most preferably a saponification degree of 80 to 99.
%, Average degree of polymerization is 2200 to 4500. The polyvinyl alcohol includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a cation-modified terminal or anion-modified polyvinyl alcohol having an anionic group.

The amount of the inorganic fine particles contained in the ink receiving layer is 5 to 30 g per m ² of recording paper, preferably 10 to ² g.
5 g. The mass ratio of the hydrophilic binder to the inorganic fine particles is from 1 to 15, and preferably from 1.5 to 8.

The cationic fixing agent that can be used in the ink receiving layer includes a cationic polymer and inorganic fine particles having a cationic surface. As the cationic polymer, those conventionally known as ink jet recording paper can be used, and examples thereof include compounds described in JP-A-9-193532.

Particularly preferred cationic polymers in the present invention are polymers having a quaternary ammonium base in the main chain or side chain of the polymer, such as dimethylamine epihadrin condensate, polydiallyldimethylammonium salt and its copolymer, vinyl It is a homopolymer or copolymer of benzyltrimethylammonium salt, or a homopolymer or copolymer of N, N, N-trimethylaminoethyl (meth) acrylate chloride. Specific examples of the cationic polymer having a quaternary ammonium base are shown below.

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The number average molecular weight of the above cationic polymer is preferably from 2,000 to 100,000, particularly preferably from 3,000 to 80,000. The amount of the cationic polymer to be used is generally 0.1 g to 10 g, preferably 0.2 g to 5 g per 1 m ² of recording paper.

Examples of the inorganic fine particles having a cationic surface include alumina, pseudo-boehmite, cation-modified silica having a surface treated with aluminum, and a surface modified as described in JP-A-8-34160. Silica particles obtained by reacting a compound having a cationic group and a group capable of reacting with the silica particles (such as a trismethoxysilyl group) on the surface of the anionic silica particles are exemplified.

In the ink receiving layer, an organic or inorganic crosslinking agent of a hydrophilic binder can be used for the purpose of improving the film forming property of the film and increasing the water resistance and strength of the film.

Preferred examples of the crosslinking agent include boric acid, and it is preferable to use a combination of boric acid and a crosslinking agent other than boric acid in that the gradation can be stabilized early.

In the present invention, the ink jet head used in the ink jet recording method may be of an on-demand type or a continuous type. In addition, as a discharge method, an electric-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shared mode type, a shared wall type, etc.) and an electric-thermal conversion method (for example, thermal Specific examples include an inkjet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.), and a discharge type (for example, a spark jet type). However, any discharge method may be used.

[0059]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited thereto.
In the following, “parts” means “parts by mass”.

Example 1 (Preparation of Image Receiving Sheet 1) A high-density polyethylene (HD) containing titanium oxide on the front and back of a paper substrate having a basis weight of 200 g / m ² was used.
(PE) and a polyethylene (PE) comprising a mixture of low-density polyethylene (LDPE) by a melt extrusion method so that the applied film thickness becomes 31 μm. The surface was subjected to corona discharge treatment to provide a gelatin subbing layer.

On a gelatin undercoat layer, a coating solution having the following composition was applied by a slide hopper method so that the wet film thickness became 180 μm, and an ink receiving layer having a dry film thickness of 40 μm was provided. Obtained. Coating liquid composition (per liter) Silica synthesized by gas phase method (QS-20 manufactured by Tokuyama) 90 g Cationic polymer P-138 8 g Polyvinyl alcohol (average degree of polymerization 3500, saponification degree 88%) 10 g polyvinyl alcohol (average polymerization Degree 4500, saponification degree 88%) 5 g boric acid 0.8 g borax 0.4 g saponin 0.10 g betaine-type fluorinated surfactant FS-1 0.02 g

[0062]

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The coating solution was prepared by dispersing silica powder in pure water, then adding an aqueous solution of a cationic polymer, an aqueous solution of a mixture of boric acid and borax, and polyvinyl alcohol, and sequentially adding saponin and FS-1. This was mixed to give a coating solution.

The coating was performed at 40 ° C. After the coating, the coating was once cooled to 5 ° C. for 10 seconds, and then was blown at 20 ° C. for 20 seconds, 65 ° C. for 1 minute, 50 ° C. for 1 minute, and 40 ° C. for 1 minute. Dry in the air for 1 minute. Further, a MEK solution of an isocyanate curing agent was applied and dried.

The average pore diameter was determined using a mercury porosimeter (Shimadzu Poreizer 9220) at an initial pressure of 0.1 MPa.
It measured on condition of. As a result, the average of the pore diameter was 20 nm.
Met. (Preparation of Image Receiving Sheet 2) A sheet was prepared in the same manner as the image receiving sheet 1 except that the cationic polymer P-13 was not used. (Preparation of inkjet recording liquid) I. Direct Yellow 86 (10% aqueous solution) 50 parts Propylene glycol 22 parts Diethylene glycol 24 parts Olfin E1010 (Nissin Chemical) 0.1 part Proxel GXL (Zeneca) 0.2 parts Priventol CMK (Bayer) 0.2 parts Ion 3.5 parts of exchanged water All of the above components were thoroughly mixed and dissolved in a container, and the pore size was adjusted to 0.
1 kg / c using a membrane filter having 45 μm
After filtration under pressure at a pressure of m ² , deaeration treatment was performed using a vacuum pump to prepare Yellow Ink 1.

Further, based on the yellow ink 1, the solvents (propylene glycol, diethylene glycol, ethylene glycol, etc.) were changed as shown in Table 1, and the yellow inks 2, 3, the magenta inks 1-4, the cyan inks 1-4,
Black inks 1 to 3 were prepared.

[0067]

[Table 1]

Next, an ink was prepared in which the concentration of metal ions was adjusted. Yellow ink 4 Yellow ink 1 “CI Direct Yellow”
ow86 (10% aqueous solution) "was passed through activated carbon, and then passed through an ion exchange resin three times. Further, a yellow ink 4 was obtained in the same manner except that ultrafiltration was performed and the reduced water was replenished with ion-exchanged water. The measurement of metal ions in the ink was performed by ICP-AES (SPS-40 manufactured by Seiko Denshi Kogyo Kogyo).
00).

The measurement of the metal ions was also performed before the yellow ink 1 was treated. The results obtained are shown below. The unit of the concentration of the metal ion is ppm.

[0070] Magenta Ink 5 and 6 “CI Acid Red 52” of Magenta Ink 1
(10% aqueous solution) ", magenta ink 5 was obtained in the same manner as above except that activated carbon was passed through, and then an ion exchange resin was passed once.

The “CI Acid” of magenta ink 1
Red 52 (10% aqueous solution) "
The ion exchange resin was passed three times. Magenta ink 6 was obtained in the same manner except that ultrafiltration was performed and the reduced water was replenished with ion-exchanged water.

The measurement of metal ions in the ink was performed by ICP-AES in the same manner. The measurement of the metal ions was also performed before the magenta ink 1 was treated.
The results obtained are shown below. The magenta ink 5 is shown as 1 after processing, and the magenta ink 6 is shown as 2 after processing. The unit of the concentration of the metal ion is ppm.

Before treatment After treatment 1 After treatment 2 Ca + Mg + Fe = 42 115 Ca = 292 2 Mg = 193 3 1.5 Cyan ink 5, 6 “CI Acid Blue 9” of cyan ink 1
(10% aqueous solution) "was passed through activated carbon, and then an ion exchange resin was passed once, to thereby obtain a cyan ink 5.

The “CI Acid B” of the cyan ink 1
"lue 9 (10% aqueous solution)" was passed through activated carbon, and then passed through an ion exchange resin three times. Cyan ink 6 was prepared in the same manner except that ultrafiltration was performed and the reduced water was replaced with ion-exchanged water.

The measurement of metal ions in the ink was performed by ICP-AES in the same manner. The measurement of the metal ions was also performed before the processing of the cyan ink 1. The results obtained are shown below. Cyan ink 5 is 1 after processing,
Cyan ink 6 is shown as 2 after processing. The unit of the concentration of the metal ion is ppm.

Before treatment After treatment 1 After treatment 2 Ca + Mg + Fe = 25 125 Ca = 164 2.5 Mg = 6.5 2 1.5 “CI Acid Red 24” of Black Ink 4 and 5 Black Ink 3
9 (10% aqueous solution) "," CI Direct Ye
low86 (10% aqueous solution) "," CI Direc
t Blue 199 (10% aqueous solution) "was passed through activated carbon, and then an ion exchange resin was passed once to obtain black ink 4.

The “CI Acid” of the black ink 3
Red 249 (10% aqueous solution) "," CI Dir "
ect Yellow 86 (10% water soluble) "," C.
I. Direct Blue 199 (10% aqueous solution) "was passed through activated carbon, and then passed through an ion exchange resin three times. Further, a black ink 5 was prepared in the same manner except that ultrafiltration was performed and the reduced water was replenished with ion-exchanged water.

The measurement of metal ions in the ink was performed by ICP-AES in the same manner. The measurement of the metal ions was also performed before the black ink 1 was treated.
The results obtained are shown below. The black ink 4 is shown as 1 after processing, and the black ink 5 is shown as 2 after processing. The unit of the concentration of the metal ion is ppm.

Before treatment After treatment 1 After treatment 2 Ca + Mg + Fe = 16 11 3.5 Ca = 65 1 Mg = 4.5 3.5 1 Table 2 shows the ion concentration of the obtained metal ion concentration adjusted ink. Shown in

[0080]

[Table 2]

An ink was prepared in which the metal ion concentration was adjusted using a complexing agent. Yellow ink 5 Yellow ink 5 was obtained in the same manner except that 0.3 part of EDTA-4Na was added to yellow ink 1. (Preparation of ink jet recording liquid for comparison) I. Direct Yellow 86 (10% aqueous solution) 50 parts Propylene glycol 22 parts Glycerin 24 parts Orphin E1010 (Nissin Chemical) 0.1 part Proxel GXL (Zeneca) 0.2 parts Priventol CMK (Bayer) 0.2 parts Ion Exchange water 3.5 parts Solvent (propylene glycol, diethylene glycol, ethylene glycol, etc.) based on yellow ink 1
Was changed as shown in Table 3 to prepare Comparative Yellow Ink 1. Similarly, comparative yellow inks 2 and 3, comparative magenta inks 1 to 3, comparative cyan inks 1 and 2, and comparative black inks 1 to 5 shown in Table 3 were prepared.

[0082]

[Table 3]

[Inkjet image recording]
Each of the obtained inkjet recording liquids was ejected by an inkjet head using a piezoelectric ceramic described in No. 99644 under the following ejection conditions, and an image was recorded on the image receiving sheet 1 or the image receiving sheet 2. The combinations of each ink and the image receiving sheet are shown in Table 4 as Samples 1 to 36, and the following evaluation was performed for each sample. (Ejection conditions) Driving frequency: 30 kHz Droplet amount: 7 pl Recording density: 720 dpi (dpi: represents the number of dots per inch) Image recording: An image having a gradation was produced by changing the dot density per fixed area. (Evaluation of bleeding) The recorded image was allowed to stand for one day in an environment of 20 ° C. and 50% RH, and then for one week in an environment of 20 ° C. and 80% RH. After a week, it was visually evaluated according to the following evaluation criteria.

◎: No bleeding after standing for one week ・ ・ ・: No bleeding on the fifth day, slight bleeding after one week △: No bleeding on the third day, slightly on the fifth day Bleed △: Slight bleed on day 3 ×: Severe bleed on day 3 (head clogging of ink) The ink prepared above was evaluated by the following method. Discharge nozzle diameter 20μ as evaluation machine
m, a piezoelectric element drive voltage of 80 V, a drive frequency of 3 kHz, a resolution of 720 dpi, and a 48 nozzle prototype inkjet head adjusted to an ink ejection amount of 0.08 μg were used. Each of the above inks was converted to 6
Emission was performed for 0 minutes, and it was confirmed whether ink droplets were normally ejected from the nozzles. This evaluation is shown in the table as continuous emission.

◎ ・ ・ ・ Discharge is normal ◎ △ ・ Bend and direction instability are observed, but recovers spontaneously ○ ・ ・ ・ Bend and direction are not constant and unstable, but head is wiped Recovered by cleaning △: Recovered by cleaning that sucks ink due to lack of ink ×: Recovered by cleaning that sucked ink but not recovered × 25% RH, 20% RH without capping the head Was left for 1 hour in the above environment, ejected again for 5 minutes, and the ejection state of the ink droplets was checked visually and with a 20 × magnification stereomicroscope, and evaluated as follows. This evaluation is shown in the table as decap.

◎: Normal discharge ・ ・ ・: The bend and direction are not constant and unstable, but recovered by cleaning by wiping the head △: Recovery occurred by cleaning that sucks ink due to lack of ink X: There is a defect, and the ink is not recovered by cleaning by sucking out the ink. The obtained results are shown below.

[0087]

[Table 4]

As is apparent from Table 4, since the ink jet recording liquid of the present invention contains two or more types of dihydric alcohols as solvents, both clogging of the head nozzle and bleeding after recording are improved. It can be seen that a stable image can be obtained.

[0089]

According to the present invention, both the clogging of the head nozzles and the bleeding after recording are improved, and a remarkably excellent effect that a stable image is obtained can be obtained.

Continued on the front page F term (reference) 2C056 EA05 FC02 2H086 BA01 BA02 BA15 BA19 BA21 BA33 BA35 BA53 BA55 BA59 BA62 4J039 BA30 BA37 BC09 BC10 BC12 BC13 BC15 BC59 BE12 BE22 BE33 EA14 EA15 EA16 EA17 EA19 EA20 EA41 EA44 EA44 EA44

Claims (13)

[Claims] 1. An ink jet recording liquid for use in an ink jet recording apparatus for performing recording by ejecting ink, comprising two or more dihydric alcohols as a solvent. 2. The ink jet recording liquid according to claim 1, wherein at least one of the dihydric alcohols is ethylene glycol. 3. The ink jet recording liquid according to claim 1, wherein the dihydric alcohol is ethylene glycol and propylene glycol. 4. The content of the ethylene glycol is 1 to 4.
The inkjet recording liquid according to claim 2, wherein the content is 25% by mass. 5. The inkjet recording liquid according to claim 1, wherein the recording liquid contains 1 to 15% by mass of an ether solvent. 6. The method according to claim 1, wherein the total amount of calcium ions, magnesium ions and iron ions contained in the recording liquid for inkjet is 10 ppm or less.
6. The ink jet recording liquid according to any one of 5. 7. The ink jet recording liquid according to claim 1, wherein the content of magnesium ions contained in the ink jet recording liquid is 2 ppm or less. 8. The ink jet recording liquid according to claim 1, wherein the content of calcium ions contained in the ink jet recording liquid is 3 ppm or less. 9. The ink jet recording liquid according to claim 1, wherein the content of iron ions contained in the ink jet recording liquid is 3 ppm or less. 10. The ink jet recording liquid according to claim 1, further comprising a complexing agent. 11. The ink jet recording liquid according to claim 1, which is adhered to an image receiving sheet having a porous ink receiving layer containing silica fine particles and a hydrophilic binder on a support. An ink-jet recording method, characterized in that: 12. The ink receiving layer having a void diameter of 10 to 1
The inkjet recording method according to claim 11, wherein the thickness is 00 nm. 13. The ink receiving layer according to claim 11, wherein the ink receiving layer contains a cationic fixing agent.
3. The ink jet recording method according to item 1.