JPH08113739A - Ink jet recording ink - Google Patents

Abstract

PURPOSE: To obtain an ink composition excellent in various characteristics, esp. capable of realizing low-blur printing. CONSTITUTION: This ink jet recording ink composition contains a dye, propylene glycol mono-n-butyl ether (PGmBE) and/or dipropylene glycol mono-n-butyl ether (DPGmBE) and other water-soluble glycol ether(s). The sum of the PGmBE and DPGmBE accounts for 3-30wt.% of this ink composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to an ink for ink jet recording.

[0002] Background Art Ink jet recording ink, various characteristics are required. For example, ink for inkjet recording is required to realize printing with little bleeding on various recording media. In order to suppress this bleeding, various ink compositions have been proposed (eg, Japanese Patent Publication No. 2-2907, Japanese Patent Publication No. 1-15542, Japanese Patent Publication No. 2-3837).

Further, it has been proposed to improve the penetrability of the ink composition to suppress bleeding. For example, US Pat. No. 5,156,675 discloses an ink composition to which diethylene glycol monobutyl ether is added. US Pat. No. 5,183,502 discloses an ink composition containing a surfactant. Further, US Pat. No. 5,196,056 discloses an ink composition containing diethylene glycol monobutyl ether and a surfactant. Here, diethylene glycol monobutyl ether is called butyl carbitol and is disclosed in, for example, US Pat. No. 3,291,580. Further, US Pat. No. 2,083,372 discloses an ink composition containing diethylene glycol ether.

With these ink compositions, a certain amount of bleeding can be suppressed, but there is a need for an ink composition with less bleeding.

On the other hand, recently, recycled paper is widely used from the viewpoint of environmental protection. These recycled papers are composed of various paper components, and the permeation speed of the ink with respect to the components is different, resulting in bleeding of printing. In order to prevent such bleeding on recycled paper, a method of heating the recording paper during printing has been proposed. However, in this method, it takes a certain amount of time to heat the paper to a predetermined temperature. In addition, it consumes a large amount of power and is not economical. further,
There is concern about deterioration of recording paper and printing due to heating.

Further, the ink composition for ink jet recording is required to have such properties that a good print density can be obtained, that intermittent printing time is long, that it is stable, and that it is less likely to cause nozzle clogging.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an ink composition for ink jet recording excellent in various characteristics. In particular, the present invention has an object to provide an ink composition for ink jet recording capable of realizing printing with less bleeding.

The ink composition for ink jet recording according to the present invention comprises a dye, propylene glycol mono-n-butyl ether (PGmBE) and / or dipropylene glycol mono-n-butyl ether (DPGmB).
An ink composition for ink jet recording comprising E) and a water-soluble glycol ether other than PGmBE and DPGmBE, which comprises PGmBE and DPGmB
The total amount of E is 3 to 30% by weight based on the ink composition.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The ink composition according to the present invention comprises P
GmBE and / or DPGmBE are contained in a total amount of 3 to 30% by weight, preferably 5 to 10% by weight, based on the ink composition. PGmBE and / or DPGmB
When E is in the above range, bleeding on the recording paper can be effectively suppressed.

The ink composition according to the present invention comprises PGmBE
And / or PGmBE in addition to DPGmBE
And water-soluble glycol ethers other than DPGmBE.

Not being bound by the following theory,
It is considered that by combining PGmBE and DPGmBE with a water-soluble glycol ether, the above-mentioned addition amounts of PGmBE and DPGmBE can be realized. P
GmBE and DPGmBE show low solubility in water. For example, the present inventors have confirmed that it is 5 to 6% with respect to water alone and decreases to less than about 2% when other ink composition components such as a dye are present. However, the addition amount of PGmBE and DPGmBE can be realized by adding a water-soluble glycol ether to this system. In addition to that, various properties of the ink composition can be improved. Specifically, for example, it is possible to obtain printing without bleeding.

Preferred examples of the water-soluble glycols include ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, triethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, And alkoxy-substituted aliphatic alcohols, more preferably ethylene glycol mono C _1-6 alkyl ethers, diethylene glycol mono C _1-6 alkyl ethers, triethylene glycol mono C _1-6 alkyl ethers, propylene glycol mono C. _1-6 alkyl ethers, dipropylene glycol mono C _1-6 alkyl ethers, and C _1-6 alkoxy substituted C _1-6 aliphatic alcohols. Be done. Specific examples of these water-soluble glycols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether. Tail, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether,
Ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, etc. Is mentioned.

The amount of the water-soluble glycol ether added is such that the ink permeation rate is sufficient and PGmBE and D
Although PGmBE may be appropriately determined within the range in which phase separation does not occur in the ink composition, it is preferably 5 to 60% by weight, more preferably 5 to 15% by weight based on the ink composition.

According to a preferred embodiment of the present invention, the water-soluble glycol ether is PGmBE and DP.
The amount of GmBE is 0.5 or more, preferably 0.
8 to 3 is added. When the water-soluble glycol ether is in the above range, the dissolution stability of PGmBE and DPGmBE can be improved, and a part of the oil-soluble component in the ink composition exudes around the print on the recording medium. Can be prevented. Furthermore, the glycol ether odor can be reduced.

Furthermore, according to a preferred embodiment of the present invention, the ink composition according to the present invention may contain urea and / or a urea modified product. By adding this urea and / or urea modified product, it was possible to unexpectedly improve the print density and prevent clogging of the ink ejection port. Examples of the urea modified product include ethylene urea, thiourea, biurea, biuret, and tetramethylurea. The amount of urea and / or urea modified product added may be appropriately determined within a range in which the print density of the ink composition is improved or nozzle clogging is effectively prevented, but it is preferably 2 to 5 based on the ink composition. It is about 20% by weight, more preferably about 5 to 10% by weight.

Furthermore, according to a preferred embodiment of the present invention, the ink composition according to the present invention may further contain thiodiglycol. By adding this thiodiglycol, it was possible to unexpectedly extend the intermittent printing time. Here, the intermittent printing time refers to a time during which printing can be performed without causing trouble such as clogging when printing is restarted after ink is not ejected. In an inkjet recording printer, ink is ejected at regular intervals so as to prevent clogging due to drying around the nozzles.
Generally, this operation is called a flushing operation. When the ink composition has a long intermittent printing time, the interval for performing this flushing operation can be set long. As a result, the waste of the ink composition is reduced, and the printing speed can be increased, which is advantageous. Furthermore, the addition of this thiodiglycol is also advantageous in that the stability of the ink composition can be improved.

According to a preferred embodiment of the present invention, the ink composition according to the present invention may further contain a surfactant. The addition of the surfactant can improve the performance of the ink composition such as the improvement of the intermittent printing time. Examples of preferable surfactants include anionic surfactants, amphoteric surfactants, cationic surfactants and nonionic surfactants. Examples of anionic surfactants include alkylsulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-
Acyl amino acid and its salt, N-acyl methyl taurine salt, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, Examples thereof include alkylphenol type phosphoric acid ester, alkyl type phosphoric acid ester, alkylallyl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfo succinate and dioctyl sulfo succinate. Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly-4-vinylpyridine derivative. As the amphoteric surfactant, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-
N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl dimethylamino acetic acid betaine,
Examples include polyoctylpolyaminoethylglycine and other imidazoline derivatives. As a nonionic surfactant,
Polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl Ethers such as ether, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate , Ester systems such as polyoxyethylene stearate, 2,4,7,9-tetramethyl-5-decyl Acetylene glycols such as -4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 3,5-dimethyl-1-hexyne-3-ol (for example, Surfinol manufactured by Nisshin Chemical Co., Ltd.) 10
4, 82, 465, TG, etc.), fluorine-substituted alkyl esters, fluorine-containing surfactants such as perfluoroalkyl carboxylates (eg, Neos Co., Ltd. Futgent series, Ciba-Geigy Rhodine series,
DuPont Zonil series, ICI Montfloor series, Asahi Glass Co., Ltd. Surflon series, Daikin Industries Co., Ltd. Unidyne series, or Sumitomo 3M FC series). Above all, it is preferable to use a fluorosurfactant, particularly an amphoteric or nonionic surfactant. The addition amount of the surfactant may be appropriately determined, but in the case of the fluorine-based surfactant, 1 to 1
About 10,000 ppm is preferable.

Further, according to a preferred embodiment of the present invention, the ink composition according to the present invention may further contain a water-soluble organic solvent. Examples of such a water-soluble organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 600 or less, and propylene. Glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol having a molecular weight of 400 or less, 1,3-butylene glycol, 1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Examples thereof include polyhydric alcohols or glycols such as hexanediol, thiodiglycol, glycerin, mesoerythritol, and pentaerythritol, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, and sulfolane.

The ink composition according to the present invention may also contain various additives in order to improve various properties of the ink composition. Examples of additives include preservatives,
Examples thereof include antifungal agents, pH adjusting agents, viscosity adjusting agents and the like.
Specifically, as an antiseptic / antifungal agent, sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium tehydroacetate, 1,2-dibenzisothiazoline-3- ON (Proxel CRL manufactured by ICI,
Proxel BDN, Proxel GXL, Proxel XL
-2, Proxel TN) and the like can be added.

Further, amines such as diethanolamine, triethanolamine, prohanolamine and morpholine as pH adjusters, inorganic salts such as potassium hydroxide, sodium hydroxide and lithium hydroxide, ammonium hydroxide and quaternary ammonium water. Oxides (tetramethylammonium, etc.), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and other phosphates, or ureas such as N-methyl-2-pyrrolidone, urea, thiourea, tetramethylurea, alohanates, Alohanates such as methyl alohanate, burettes such as burette, dimethyl burette and tetramethyl burette can be added.

Further, as a viscosity modifier, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methylserose, polyacrylic acid salt, polyvinylpyrrolidone,
Gum arabic starch and the like can be added.

The colorant used in the ink composition according to the present invention is not particularly limited, but direct dyes, acid dyes, basic dyes, reactive dyes, food dyes and the like can be used.

A preferred specific example is C.I. I. Direct Black 2, 4, 9, 11, 14,
17, 19, 22, 27, 32, 36, 41, 48, 5
1, 56, 62, 71, 74, 75, 77, 78, 8
0, 105, 106, 107, 108, 112, 11
3, 117, 132, 146, 154, 168, 17
1, 194, C.I. I. Direct Yellow 1, 2, 4,
8, 11, 12, 24, 26, 27, 28, 33, 3
4, 39, 41, 42, 44, 48, 50, 51, 5
8, 72, 85, 86, 87, 88, 98, 100, 1
10, 127, 135, 141, 142, 144, C.I.
I. Direct Orange 6, 8, 10, 26, 29, 3
9, 41, 49, 51, 62, 102, C.I. I. Direct Red 1, 2, 4, 8, 9, 11, 13, 15, 1
7, 20, 23, 24, 28, 31, 33, 37, 3
9, 44, 46, 47, 48, 51, 59, 62, 6
3, 73, 75, 77, 79, 80, 81, 83, 8
4, 85, 87, 89, 90, 94, 95, 99, 10
1, 108, 110, 145, 189, 197, 22
4, 225, 226, 227, 230, 250, 25
6, 257, C.I. I. Direct violet 1,7,
9, 12, 35, 48, 51, 90, 94, C.I. I. Dicleto Blue 1, 2, 6, 8, 12, 15, 22, 2
5, 34, 69, 70, 71, 72, 75, 76, 7
8, 80, 81, 82, 83, 86, 97, 90, 9
8, 106, 108, 110, 120, 123, 15
8, 163, 165, 192, 193, 194, 19
5, 196, 199, 200, 201, 202, 20
3,207,218,236,237,239,24
6, 258, 287, C.I. I. Direct Green 1,
6, 8, 28, 33, 37, 63, 64, C.I. I. Direct Brown 1A, 2, 6, 25, 27, 44, 5
8, 95, 100, 101, 106, 112, 173,
194, 195, 209, 210, 211 and the like.

Further, as an acid dye, 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, 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 and the like can be mentioned.

As the basic dye, C.I. I. Basic Black 2, 8, C.I. I. Basic Yellow 1,
2, 11, 14, 21, 32, 36, C.I. I. Basic orange 2,15,21,22. C. I. Basic Red 1, 2, 9, 12, 13, 37, C.I. I. Basic Violet 1, 3, 7, 10, 14, C.I. I. Basic Blue 1, 3, 5, 7, 9, 24, 25, 2
6, 28, 29, C.I. I. Basic green 1, 4,
C. I. Basic brown 1, 12 and the like can be mentioned.

As the reactive dye, C.I. I. Reactive black 1, 3, 5, 6, 8, 12, 14, C.I.
I. Reactive Yellow 1, 2, 3, 12, 13, 1
4, 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, 2
4, 35, 36, 42, 63, 66, 84, 184,
C. I. Reactive violet 2, 4, 5, 8,
9, C.I. I. Reactive Blue 2, 5, 7, 12, 1
3, 14, 15, 17, 18, 19, 20, 21, 2
5, 27, 28, 37, 38, 40, 41, C.I. I. Reactive Green 5, 7, C.I. I. Reactive Brown 1, 7, 16 and the like can be mentioned.

Further, as a food dye, C.I. I. Fudo Black 1, 2, C.I. I. FOOD YELLOW 3, 4, 5,
C. I. Hooded 2,3,7,9,14,52,8
7, 92, 94, 102, 104, 105, 106,
C. I. Fudo Violet 2, C.I. I. FOOD BLUE 1, 2, C.I. I. Examples include FOOD GREEN 2 and 3.

Kayaset Black 009A manufactured by Nippon Kayaku Co., Direct Tipe Black XA, Direct Special Black AXN, Special Black SP Liquid manufactured by Bayer Co., Biscript Black SP Liquid, Levacell Turquoise Blue KS-6GLL, Pyranin, Sumitomo JI. BK-2, JI. BK-
3, Orient Chemical Co., Ltd. JPK-81L, JPX-12
7L, JPK-139, C.I. I. Flowcent Brightening Agents 14, 22, 24, 32, 84, 8
5,86,87,90,134,166,167,16
9, 175, 176, 177 and the like can be used.

The physical properties of the ink composition according to the present invention may be appropriately determined so as to be compatible with the ink jet recording method. In particular, the foamability, surface tension, and advancing contact angle of the nozzle surface of the ink jet recording head are taken into consideration. Preferably. Specifically, regarding the foaming property, the foaming property at 15 ° C. by the Ross Miles Test is an initial value of 200 mm or less, and the value after 5 minutes is 10 mm.
It is preferably 0 mm or less. Here, the Rossmile method is 200 ml of test liquid from a height of 90 cm to an inner diameter of 29 m.
50 ml of the same test solution through the m pore
It is a method in which the height of bubbles is observed by allowing it to flow down into a graduated mm tube. If the initial value and the value after 5 minutes are in the range of the above value,
Generation of bubbles is suppressed, and the ink composition can be easily filled in the nozzle. As a result, missing dots can be effectively prevented. The surface tension of the ink composition is preferably in the range of 15-40 mN / m. When the surface tension is within the above range, the ink composition can be easily filled in the nozzle, and good quality printing can be obtained. Further, the advancing contact angle of the ink composition on the nozzle surface is preferably in the range of 10 to 50 degrees. When the contact angle of the ink composition is within the above range, the ink composition evenly wets the nozzle surface, and good printing is obtained. Further, it is possible to obtain an advantage that the intermittent printing time can be set longer.

The ink composition according to the present invention can be manufactured by a conventional method. That is, the above components are sufficiently stirred and mixed, and if necessary, filtered to remove solid components to obtain an ink composition.

[0031]

The present invention will be explained in more detail by the following examples, but the present invention is not limited to these examples. In the following examples, printing was performed with an inkjet printer MJ-500 manufactured by Seiko Epson Corporation unless otherwise specified. In addition,% is% by weight unless otherwise specified. Further, Example A
Ink compositions other than Comparative Example A and Proxel XL
-2 (corrosion inhibitor) 0.1 to 1%, benzotriazole (to prevent corrosion of recording head members) 0.001 to 0.
It comprises 005%.

Example A The following ink compositions of Examples A1-8 and Comparative Examples A1-3 were prepared by a conventional method. That is, the following compositions were stirred and mixed, and then filtered with a filter to obtain an ink composition. Example A1 C.I. I. Direct Black 19 2% Propylene glycol mono-n-butyl ether 10% Diethylene glycol monoethyl ether 10% 1,4-Butanediol 5% Sodium dioctyl sulfosuccinate 1.5% Water Remainder Example A2 C.I. I. Food Black 19 2.5% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-n-butyl ether 10% Dipropylene glycol 5% Proxel GXL 0.3% Water Remainder Example A3 C.I. I. Acid Green 9 2.5% Propylene glycol mono-n-butyl ether 10% 1-Methyl-1-methoxybutanol 15% Diethylene glycol 5% Water Remainder Example A4 Special Black SP Liquid 20% Dipropylene glycol mono-n-butyl ether 10 % Propylene glycol monoethyl ether 10% 1,3-Dimethyl-2-imidazolidinone 5% Water Remainder Example A5 Direct Special Black AXN 4% Propylene glycol mono-n-butyl ether 9% Dipropylene glycol monomethyl ether 12% N -Methylpyrrolidone 5% water remaining

Example A6 C.I. I. Reactive Red 6 4% Propylene glycol mono-n-butyl ether 9% Dipropylene glycol mono-n-butyl ether 5% Diethylene glycol mono-n-butyl ether 15% N-acylmethyl taurine sodium 1.5% Water Remainder Example A7 C ． I. Basic Yellow 115% Propylene glycol mono-n-butyl ether 10% Triethylene glycol monobutyl ether 12% Glycerin 10% Surfynol 465 1% Surfynol 104 0.5% Water Remaining Example A8 C.I. I. Direct Green 1 3% C.I. I. Direct Green 28 1% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-t-butyl ether 5% Diethylene glycol mono-n-butyl ether 5% Diethylene glycol 10% Propylene glycol monomethyl ether Remaining amount

Comparative Example A1 C.I. I. Direct Green 1 3% Diethylene glycol mono-n-butyl ether 5% Tetraethylene glycol 15% Potassium hydroxide 0.1% Water Remaining amount comparative example A2 C.I. I. Direct Red 227 2.5% Diethylene glycol mono-n-butyl ether 15% Triethylene glycol 5% Glycerin 10% Water Remaining amount comparative example A3 C.I. I. Acid Red 254 2.5% Diethylene glycol mono-n-butyl ether 7% Diethylene glycol 15% Water Remaining amount

Evaluation Test A1 The above ink compositions were printed on various recording papers shown in Table 1. The print was evaluated as follows. Whether the roundness of the dots was reduced due to uneven penetration of the bleed ink was evaluated according to the following criteria. A: The roundness is extremely good. ◯: The roundness is slightly reduced, but there is no problem in practical use. Δ: A decrease in roundness was observed, and there was a problem in practical use. X: The roundness is remarkably reduced and is not suitable for practical use.

The degree of non-uniform penetration of the ink along the fibers of the mustache paper, ie, beard, was evaluated according to the following criteria. ⊚: Very good with almost no beard. ◯: Some beard is observed, but there is no problem in practical use. Δ: Many whiskers were observed, which was a problem in practical use. X: The beard was remarkably generated and was not suitable for practical use. The above results were as shown in Table 1 below.

[0037]

[Table 1]

The recording paper in the table can be obtained from the following. CONQUEROR Paper: Arjo Wigging FAVORIT X Paper: Favorit MODO COPY Paper: Modo RAPID COPY Paper: Igepa EPSON EPP Paper: Seiko Epson XEROX P Paper: Fuji Xerox XEROX 4024 Paper: Xerox XEROX 10 Paper: Xerox NEENACH BOND Paper: Kimberly-Clark RICOPY 6200 Paper: Ricoh Yamayuri Paper: Honshu Paper XEROX R Paper: Xerox

Evaluation test A2 In the ink composition of Example A1, the organic solvent of diethylene glycol monoethyl ether and 1,4-butanediol was added in an amount of 2 to 35% with the addition ratio being 2: 1. Was changed in the range of (the amount of change was adjusted with water). 1 μl of the ink composition was added to DERSCH
The ER paper was dropped in spots, the drying time was measured paper, and this was used as the penetration time. The result is shown by ● in FIG.

In the ink composition of Example A1, 10% of PGmBE was added to 10% of Surfynol 465.
%, Diethylene glycol monoethyl ether and 1,4-butanediol were added at an addition ratio of 2: 1.
The addition amount was changed as it was. The penetration time of the ink composition was measured in the same manner as above. The result is shown by a circle in FIG. Further, in the ink composition of Example A1, 10% of PGmBE was added to 10% of diethylene glycol mono-n-butyl ether, respectively.
%, And 1% of Surfynol 465, diethylene glycol monoethyl ether and 1,4-butanediol were added in different amounts with the addition ratio kept at 2: 1. The penetration time of the ink composition was measured in the same manner as above. The results are shown as □ and Δ in FIG. 1, respectively.

Evaluation Test A3 In the ink composition of Example A1, the addition amount of PGmBE and diethylene glycol monoethyl ether was changed while keeping the addition ratio of 1: 1. The penetration time of the ink composition was measured in the same manner as in Example A2. The result is shown as □ in FIG. Also, PGmB
The penetration time of the ink composition was measured in the same manner as above except that D was replaced with DPGmBE. The result is shown as a circle in FIG.

Example B The ink compositions of Examples B1-8 and Comparative Examples B1-3 below were prepared according to a conventional method. Example B1 C.I. I. Direct Black 19 2% Propylene glycol mono-n-butyl ether 10% Diethylene glycol monoethyl ether 10% 1,4-Butanediol 5% Urea 5% Dipropylene glycol 5% Water Remainder Example B2 C.I. I. Food Black 2 2.5% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-n-butyl ether 10% Dipropylene glycol 5% Urea 10% Proxel GXL 0.3% Water Remaining Example B3 C.I. I. Acid Green 9 2.5% Propylene glycol mono-n-butyl ether 10% 1-Methyl-1-methoxybutanol 15% Urea 7% Diethylene glycol 5% Water Residual amount Example B4 Special black SP liquid 20% Dipropylene glycol mono-n -Butyl ether 10% Propylene glycol monoethyl ether 10% 1,3-Dimethyl-2-imidazolidinone 5% Thiourea 5% Water Remainder Example B5 Direct Special Black AXN 4% Propylene glycol mono-n-butyl ether 9% Di Propylene glycol monomethyl ether 12% N-methylpyrrolidone 5% Ethylene urea 5% Water remaining amount

Example B6 C.I. I. Reactive Red 6 4% propylene glycol mono -n- butyl ether 9% dipropylene glycol mono -n- butyl ether 5% Diethylene glycol monobutyl -n- butyl ether 15% N-acyl 1.5% methyl taurine sodium biurea 3% water balance carried Example B7 C.I. I. Basic Yellow 115% Propylene glycol mono-n-butyl ether 10% Triethylene glycol monobutyl ether 12% Glycerin 10% Surfynol 465 1% Surfynol 104 0.5% Biuret 3% Water Remaining Example B8 C.I. I. Direct Green 1 3% C.I. I. Direct Green 28 1% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-t-butyl ether 5% Diethylene glycol mono-n-butyl ether 5% Diethylene glycol 10% Tetramethylurea 3.5% Propylene glycol monomethyl ether Remaining amount

Comparative Example B1 C.I. I. Direct Green 8 3% C.I. I. Direct Green 1 1% Diethylene glycol mono-n-butyl ether 5% Tetraethylene glycol 15% Potassium hydroxide 0.1% Water Remaining amount comparative example B2 C.I. I. Direct Red 227 2.5% Diethylene glycol mono-n-butyl ether 15% Triethylene glycol 5% Glycerin 10% Water Remaining amount comparative example B3 C.I. I. Acid Red 254 2.5% Diethylene glycol mono-n-butyl ether 7% Diethylene glycol 15% Water Remaining amount

Evaluation Test B1 The above ink compositions were printed on various recording papers shown in Table 2. The printing was evaluated in the same manner as the evaluation test A. The results are shown in Table 2 below.

[0046]

[Table 2]

Evaluation Test B2 The OD value of the prints made from the ink compositions of Examples B1-8 was measured. Further, ink compositions similar to these ink compositions were prepared except that urea or urea modified product was not added. The OD value of the printed matter with this ink composition was measured. The ratio of OD values was obtained from the following formula. OD value ratio = (A / B) × 100−100 where A is O when urea or a urea modified product is added.
D value and B are OD values when urea or urea modified product was not added. The ratio of OD values was as follows.

Example OD value ratio 1 8.8 2 9.7 3 7.7 4 9.2 5 6.5 6.5 6 2.3 7 3.2 8 1.5

Evaluation Experiment B3 In the ink composition of Example B1, the amount of urea added was changed (the amount of change was adjusted with water). The OD value of the printed matter by the ink composition was measured. The results were met as shown in Figure 3.

Example C The following ink compositions of Examples C1-8 and Comparative Examples C1-3 were prepared according to a conventional method. Example C1 C.I. I. Direct Black 19 2% Propylene glycol mono-n-butyl ether 10% Triethylene glycol monobutyl ether 10% 1,4-Butanediol 2.5% 1,6-Hexanediol 2.5% 2-Pyrrolidone 1.5% Water residue Amount Example C2 C.I. I. Food Black 2 2.5% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-n-butyl ether 10% Dipropylene glycol 3% Tripropylene glycol 3% Urea 5% Water Remainder Example C3 C.I. I. Acid Green 9 2.5% Propylene glycol mono-n-butyl ether 10% 1-Methyl-1-methoxybutanol 15% Propylene glycol 5% Triethylene glycol 5% 1,5-Pentanediol 5% Water Remainder Example C4 Special Black SP Liquid 20% Dipropylene glycol mono-n-butyl ether 10% Propylene glycol monoethyl ether 10% 1,6-hexanediol 2% Tripropylene glycol 3% 1,3-Dimethyl-2-imidazolidinone 5% Water residue Amount Example C5 Direct Special Black AXN 4% Propylene glycol mono-n-butyl ether 9% Dipropylene glycol monomethyl ether 12% 2-Methyl-2,4-pentanediol 5% 1,2-propane Diol 4% N-Methylpyrrolidone 5% Water Remaining amount

Example C6 C.I. I. Reactive Red 6 4% Propylene glycol mono-n-butyl ether 9% Dipropylene glycol mono-n-butyl ether 5% Diethylene glycol mono-n-butyl ether 15% Neopentyl glycol 2% 1,3-Butanediol 2% N-acylmethyl Sodium taurine 1.5% water Remainder Example C7 C.I. I. Basic Yellow 115% Propylene glycol mono-n-butyl ether 10% Triethylene glycol monobutyl ether 12% Glycerin 10% Trimethylolpropane 3% Trimethylolethane 1% Polypropylene glycol with a number average molecular weight of 400 1% Surfynol 465 1% Surfynol 104 0.5% water residual amount Example C8 C.I. I. Direct Green 1 3% C.I. I. Direct Green 28 1% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-t-butyl ether 5% Diethylene glycol mono-n-butyl ether 5% Diethylene glycol 10% Tetrapropylene glycol 2% 1,3-Propanediol 5% Water remaining amount

Comparative Example C1 C.I. I. Direct Green 1 3% Diethylene glycol mono-n-butyl ether 5% Ethylene glycol 15% Potassium hydroxide 0.1% Water Remainder Comparative Example C2 C.I. I. Direct Red 227 2.5% Diethylene glycol mono-n-butyl ether 15% Diethylene glycol 5% Glycerin 10% Water Remaining amount comparative example C3 C.I. I. Assidred 254 2.5% Diethylene glycol mono-n-butyl ether 7% Diethylene glycol 15% Water Remaining amount

Evaluation Test C The above ink compositions were printed on various recording papers shown in Table 3. The printing was evaluated in the same manner as the evaluation test A. The results are shown in Table 3 below.

[0054]

[Table 3]

Example D The ink compositions of Examples D1-8 and Comparative Examples D1-3 below were prepared according to a conventional method. Example D1 C.I. I. Direct Black 19 2% propylene glycol mono -n- butyl ether 10% Triethylene glycol monobutyl ether 10% 1,4-butanediol 2.5% 1,6-hexanediol 2.5% thiodiglycol 5% water balance carried Example D2 C.I. I. Food Black 2 2.5% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-n-butyl ether 10% Dipropylene glycol 3% Thiodiglycol 3% Urea 5% Water Remainder Example D3 C.I. I. Acid Green 9 2.5% Propylene Glycol Mono-n-butyl Ether 10% 1-Methyl-1-methoxybutanol 15% Propylene Glycol 5% Thiodiglycol 5% 1,5-Pentanediol 5% Water Remainder Example D4 Bi script black SP Liquid 20% dipropylene glycol mono -n- butyl ether 10% propylene glycol monoethyl ether 10% thiodiglycol 12% tripropylene glycol 3% 1,3-dimethyl-2-imidazolidinone 5% water balance carried example D5 direct Special black AXN 4% propylene glycol mono -n- butyl ether 9% dipropylene glycol monomethyl ether 12% thiodiglycol 15% 1,2-propanediol 4% N-methylpiperidin Pyrrolidone 5% water balance

Example D6 C.I. I. Reactive Red 6 4% Propylene glycol mono-n-butyl ether 9% Dipropylene glycol mono-n-butyl ether 5% Diethylene glycol mono-n-butyl ether 15% Thiodiglycol 20% 1,3-Butanediol 2% N-acylmethyl Sodium taurine 1.5% water Remainder Example D7 C.I. I. Basic Yellow 11 5% Propylene glycol mono-n-butyl ether 10% Triethylene glycol monobutyl ether 2% Glycerin 10% Trimethylolpropane 3% Trimethylolethane 1% Polyethylene glycol with a number average molecular weight of 400 1% Thiodiglycol 30% Surfynol 465 0.5% Water Remainder Example D8 C.I. I. Direct Green 1 3% C.I. I. Direct Green 28 1% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-t-butyl ether 5% Diethylene glycol mono-n-butyl ether 5% Diethylene glycol 10% Thiodiglycol 0.5% 1,3-Propanediol 5% Water residue amount

Comparative Example D1 C.I. I. Direct Green 1 3% Diethylene glycol mono-n-butyl ether 5% Ethylene glycol 15% Potassium hydroxide 0.1% Water Remaining amount comparative example D2 C.I. I. Direct Black 154 2.5% Diethylene glycol mono-n-butyl ether 15% Diethylene glycol 5% Glycerin 10% Water Remaining amount comparative example D3 C.I. I. Assidred 254 2.5% Diethylene glycol mono-n-butyl ether 7% Diethylene glycol 15% Water Remaining amount

Evaluation Test D1 The ink compositions above were printed on various recording papers shown in Table 4. The printing was evaluated in the same manner as the evaluation test A. The results were as shown in Table 4 below.

[0059]

[Table 4]

Evaluation Experiment D2 In the ink composition of Example D1, the concentration of thiodiglycol was changed (the amount of change was adjusted with water). The intermittent printing time of the ink was measured. The result is shown in Figure 4.
It was as shown in.

Example E The ink compositions of Examples E1-8 and Comparative Examples E1-3 below were prepared according to a conventional method. In the following Examples and Comparative Examples, Futagent 251 (manufactured by Neos Co., Ltd.) was used as the fluorine-based surfactant. Example E1 C.I. I. Direct Black 19 2% Propylene glycol mono-n-butyl ether 10% Triethylene glycol monobutyl ether 10% 1,4-Butanediol 2.5% 1,6-Hexanediol 2.5% Fluorosurfactant 0.02% Water Remaining Example E2 C.I. I. Food Black 2 2.5% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-n-butyl ether 10% Dipropylene glycol 3% Fluorosurfactant 0.03% Urea 5% Water Remaining Example E3 C.I. I. Acid Green 9 2.5% propylene glycol mono -n- butyl ether 10% 1-methyl-1-methoxybutanol 15% propylene glycol 5% fluorine surfactant 0.1% 1,5-pentanediol 5% water balance carried Example E4 Biscript Black SP Liquid 20% Dipropylene glycol mono-n-butyl ether 10% Propylene glycol monoethyl ether 10% Fluorosurfactant 0.2% Tripropylene glycol 3% 1,3-Dimethyl-2-imidazolidi Non-5% water Remainder Example E5 Direct Special Black AXN 4% Propylene glycol mono-n-butyl ether 9% Dipropylene glycol monomethyl ether 12% Fluorosurfactant 1 PPM 1,2-Propanediol 4% N- Methylpyrrolidone 5% Water remaining

Example E6 C.I. I. Reactive Red 6 4% Propylene glycol mono-n-butyl ether 9% Dipropylene glycol mono-n-butyl ether 5% Diethylene glycol mono-n-butyl ether 15% Fluorosurfactant 1.0% 1,3-Butanediol 2% N-acylmethyl taurine sodium 1.5% water balance Example E7 C.I. I. Basic Yellow 1 1 5% Propylene glycol mono-n-butyl ether 10% Triethylene glycol monobutyl ether 2% Glycerin 10% Trimeterol propane 3% Trimeterol ethane 1% Polyethylene glycol with a number average molecular weight of 400 1% Fluorosurfactant 0. 3% Surfynol 465 0.5% water Remainder Example E8 C.I. I. Direct Green 1 3% C.I. I. Direct Green 28 1% Propylene glycol mono-n-butyl ether 10% Diethylene glycol mono-t-butyl ether 5% Diethylene glycol mono-n-butyl ether 5% Diethylene glycol 10% Fluorosurfactant 0.5% 1,3-Propanediol 5% Water level

Comparative Example E1 C.I. I. Direct Green 13% Diethylene glycol mono-n-butyl ether 5% Ethylene glycol 15% Potassium hydroxide 0.1% Water Remaining amount comparative example E2 C.I. I. Direct Red 154 2.5% Diethylene glycol mono-n-butyl ether 15% Diethylene glycol 5% Glycerin 10% Water Remaining amount comparative example E3 C.I. I. Assidred 254 2.5% Diethylene glycol mono-n-butyl ether 7% Diethylene glycol 15% Water Remaining amount

Evaluation Test E The above ink compositions were printed on various recording papers shown in Table 5. The printing was evaluated in the same manner as the evaluation test A. The results are shown in Table 5 below.

[0065]

[Table 5]

[Brief description of drawings]

FIG. 1 is an ink composition of Example A1, in which an organic solvent of diethylene glycol monoethyl ether and 1,4-butanediol is added in an amount of 2 to 35% while the addition ratio is 2: 1. The penetrating time (●) of the ink composition changed by PGmBE, 10% of PGmBE was changed to 10% of Surfynol 465, and diethylene glycol monoethyl ether and 1,4-butanediol were changed.
Permeation time (◯) of the ink composition in which the addition amount was changed while maintaining the addition ratio of 2: 1 and PGmBE of 10%
In place of 10% of diethylene glycol mono-n-butyl ether and 1% of Surfynol 465 respectively, diethylene glycol monoethyl ether and 1,4-butanediol were added at a ratio of 2: 1. The graph which shows the penetration time (□ and Δ) of the ink composition in which the addition amount is changed.

FIG. 2 shows PGmB in the ink composition of Example A1.
E and diethylene glycol monoethyl ether 1:
The graph which shows the penetration time (O) of the ink composition which changed the addition amount with the addition ratio of 1 as it is, and the penetration time (O) of the same ink composition as Example A1 which replaced PGmBE with DPGmBE.

FIG. 3 is a graph showing the OD value of a printed matter obtained by changing the amount of urea added in the ink composition of Example B1.

FIG. 4 is a graph showing the intermittent printing time of the ink composition of Example D1 in which the concentration of thiodiglycol was changed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 6-97678 (32) Priority date Hei 6 (1994) May 11 (33) Country claiming priority Japan (JP) (31) Priority Claim number Japanese Patent Application No. Hei 6-199749 (32) Priority Date Hei 6 (1994) August 24 (33) Country of priority claim Japan (JP)

Claims (18)

[Claims] 1. A dye and propylene glycol mono-n-
Butyl ether (PGmBE) and / or dipropylene glycol mono-n-butyl ether (DPGmB)
An ink composition for ink jet recording comprising E) and a water-soluble glycol ether other than PGmBE and DPGmBE, which comprises PGmBE and DPGmB
The ink composition, wherein the total amount of E is 3 to 30% by weight based on the ink composition. 2. The ink composition according to claim 1, wherein the total amount of PGmBE and DPGmBE is 3 to 10% by weight based on the ink composition. 3. A water-soluble glycol ether is ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, triethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, and alkoxy substitution. The ink composition according to claim 1, which is selected from the group consisting of aliphatic alcohols. 4. The water-soluble glycol ether is ethylene glycol mono C _1-6 alkyl ether, diethylene glycol mono C _1-6 alkyl ether, triethylene glycol mono C _1-6 alkyl ether, propylene glycol mono C _{1-. 6. An} alkyl ether selected from the group consisting of ₆ alkyl ethers, dipropylene glycol mono C _1-6 alkyl ethers, and C _1-6 alkoxy-substituted C _1-6 aliphatic alcohols.
The ink composition described. 5. The ink composition according to claim 1, wherein the ratio of the amount of the water-soluble glycol ether added to PGmBE and DPGmBE is 0.5 or more. 6. The ink composition according to claim 1, wherein the amount of the water-soluble glycol ether is 5 to 60% by weight based on the ink composition. 7. The ink composition according to claim 1, further comprising urea and / or a urea modified product. 8. The urea modified product is ethylene urea, thiourea,
The ink composition according to claim 7, which is biurea, biuret, or tetramethylurea. 9. The ink composition according to claim 7, wherein the amount of urea and / or urea modified product is 2 to 20% by weight based on the ink composition. 10. Further comprising thiodiglycol,
The ink composition according to claim 1. 11. The ink composition according to claim 10, wherein the amount of thiodiglycol is 0.5 to 30% by weight based on the ink composition. 12. The ink composition according to claim 1, further comprising a surfactant. 13. The ink composition according to claim 12, wherein the surfactant is a fluorinated surfactant. 14. The concentration of the fluorinated surfactant is 1 to 10,
The ink composition according to claim 13, which has an amount of 000 ppm. 15. The ink composition according to claim 13, wherein the fluorochemical surfactant is an amphoteric surfactant or a nonionic surfactant. 16. The foamability at 15 ° C. according to the Rossmile method is 200 mm or less as an initial value and 100 mm after 5 minutes.
The ink composition according to claim 1, wherein: 17. The surface tension is 15 to 40 mN / m,
The ink composition according to claim 1. 18. The ink composition according to claim 1, wherein the advancing contact angle with respect to the nozzle surface of the inkjet recording head is 10 to 50 degrees.