JPS58213069A - Ink for ink jet recording - Google Patents

Abstract

PURPOSE:To prevent deposition of solid matter, clogging, etc. over a long term, and obtain glossy-black recorded images, by combining a particular black dye with an orange direct dye as a black dye in an ink for ink jet recording. CONSTITUTION:One or more of black dyes of formula I , II or III (wherein M is an alkali metal, formula IV, a nitrogen-contg. heterocyclic group; R1, R2, R3, R4 are each hydrogen or hydrocarbons) (A) and an orange direct dye (B) (e.g., C.I. Direct Orange 6, 8, 26) are mixed to attain a wt. ratio of component A to component B of about 1:0.02-1:1. A wetting agent, pH adjuster, antiseptic agent, etc. are added to the resulting mixed black dye, and the mixture is dissolved in water to yield the intended ink for jet recording. Incorporation of component B with component A enables the solubility of component A to be increased and the color tone of component A to approach black.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an inkjet recording ink, and particularly to an aqueous black ink that provides a pure black recorded image in the Infusiera 1 recording method.

One of the characteristics required of ink for inkjet recording is to provide images with high density, but for this purpose, the concentration of the dye used in the ink must be high, the absorption coefficient of the dye used must be high, etc. can be mentioned. However, because conventional dyes have low solubility, increasing the dye concentration may cause solid content to precipitate during storage or long-term use, or cause clogging of the discharge port (orifice), resulting in unstable jetting. The disadvantage is that it cannot be done.

In order to solve this problem, for example,
884 bow, Tokukai Sho 4! ] -07G 20th, OJ:
Japanese Patent Publication No. 51-137! i (N+ No. I C is interposed. J, sea urchin, dissolving the dye (/I, bird'!y) i-
N) (11 × 1', compound added to the ink)
method, IA di1f1/glycol derivative, polyA1-
I-'7-1 Non-1-thyls, alkylsulfur A^
tJ, 1 The method of adding interfacial 1rll'l agent such as 1 rll'l is 1r room. Moreover, the added compound has an odor\1) and has an i+1 effect on the human body.
There is Hl 1'l. Also, add more Rirudocho 1
0, surface tension, etc.) and odor (the ink that dominates the outgoing stable bamboo t'l ll+, oil droplets 11Z formation (J). 1. In addition, the latter method may cause unstable ejection due to ink bubbles, a decrease in inlet force, and turbulence. C1, which is widely used in Mizu M Kuroin/7, Dairef 1 to Bushiku 19 have excellent water resistance, a relatively large extinction coefficient, direct dyeing to cellulose, and low toxicity to the human body. On the other hand, as mentioned above, it has a sufficiently high solubility in water used in ink and polyhydric alcohols such as glycerol, diethylene glycol, and triethylene glycol, which are commonly used as wetting agents. However, there is a drawback that the outlet of the inkjet 1 to 1 may be clogged or the ejection may be unstable. This is because the solubility in the dye ↑11 is poor.Furthermore, the ink using the black dye 1 was not pure black, but could only give a bluish image.

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned conventional drawbacks, and more particularly, by using a soluble dye, precipitation of solids and clogging can be avoided over a long period of time. What happens <Z <, reliability H that provides stable jetting performance
The purpose of the present invention is to provide an inkjet recording ink with high -R inkjet recording ink, and furthermore, to provide a pure black (visible) 1' with excellent water resistance, light resistance, and abrasion resistance in the wavelength range of 1'. +1) Uchizono's goal is to provide an ink that exhibits almost uniform 4R absorption.

In view of the above purpose, as a result of 812 m till research 4/1a, the coloring agent (, I-, general +':, (T), (
J, using one kind of black dye II expressed in 1) and (I[) and orange direct dye O'11, etc.
Therefore, it is clear that the above-mentioned conventional drawbacks are solved at once and the present invention is achieved.

-5)- [In each of the ten general formulas, M may be the same or different (, respectively (or alkali metal, NRI R2R
3R4 (R1, R/, R3 and R4 may be the same or different and each represents hydrogen or an aliphatic or aromatic hydrocarbon group) or a nitrogen-containing heterocyclic group. ] In the present invention, the black dyes represented by the general formulas (I) and (I) are the main component and subcomponent of C21 and Direct Black 19, respectively, and as described above, have excellent water resistance and dyeability. Although it has a relatively high extinction coefficient and low toxicity, it is bluish-black in color and has poor solubility. Further, although the compound represented by the general formula (I) is a compound newly synthesized by the present inventors, it also has the same characteristics as the previous two compounds. The figure shows the spectral transmission curves of aqueous solutions of black dyes represented by general formulas (I), (IF), and (I) synthesized in the examples of the present invention. It is understood that the color is black with a bluish tint. However, as in the present invention, these black 6
- If the dye Fl is directly dyed 1:1 with no JL in the dye, the advantages of black dyes of general formulas (T), (II), and (Ilr) can be combined without any I:j. If it becomes blacker, the same +1. Its solution 1'l is 11'l+, 1; Adding an orange dye makes the ink black because the absorption wavelength range of the orange dye is 400 to 55.
It is clear from the fact that it is at 0 nm, and by adding an orange dye, the solubility of a certain black dye is 1.11 pil'. I"l
/ l]Although it is not clear, orange dye *+1 is combined in the black dye solution I] and is thought to be the main component (?2 dye tl)
11. In order to disrupt the meeting on 11, Sol VN published high;
Iru I) Throat can be considered.

In the above general formulas (T), (It), and (]U), examples of the alkali metal of M include lithium, sodium, potassium, rhizium, rasium, and francium.NR+R2R:l Examples of the fourth nonon t, -ram of R4 include NH4, alkyl, J
, Bizo derivatives, J3 and aryl groups, J, and its derivatives. Mention may be made of quaternary ammonium (
Monomethylamine, dimethylamine, trimethylamine, ethylamine, methylethylamine, diethylamine, triethylamine, Schiff [1hexylamine, cecylamine, stearylamine, 1helipropylamine, ethanolamine, jetanolamine, triethanolamine, Aniline, N-methylaniline, N
Salts such as N-dimethylamine and toluidine can be mentioned. Examples of the nitrogen-containing heterocyclic group of M include pyridine, pyrimidine, morpholine, pyrrolidone, allantoin, ε-caprolactam, pyrazine, indole, pyridazine, imidazole, virol, thij7zole, AkiI
Examples include t-zol, furazan, -1:norin, purine, and 11-razol.

Examples of orange direct dyes are C,1, Direct Orange 1,2,4,5,6,7
, 8゜9, 10.11.13.14.15.17.18
, 20, 23.2G.

27.28,29,31,33,34,36,37,3
8, 39, 40.

42.43,44,45,46,49,50,51,5
3,56,59° [io, 0+, 62. [i7. [i!
1,70,71,72,73,74,75°82.86
, 87, 118. O! l, Q(1,!11.Q2,93
,95,98°99,100.101,H)2.1
+13.014.10! i, 106.107.108
, 110, 111, etc. Among them, particularly preferred ones from b-melting (II) are C, I, die 1 nocto A range 6.8, 26.
39.49.107.2! l, [i2. I! The blending ratio of the 11 dyes (,1, general formula (1),
The weight pressure of (σ color direct dyeing) for the black dyes (I) and (■) is 1,00: (1,02-1,110:
A range of 1.00 is preferred, particularly preferred: l: L/<
l;11,00: 0.03-1.00: 0
．． By using 11 and J- in the range of 60, the above effect becomes 31, which is even more impressive! I will be beaten.

The constituent components of the ink are as follows: glycerin, 1
〜S``chi1.・ngri1-ru,-``dilene glycol,
Polyhydric alcohols such as non-glycyl, polypropylene, non-glycyl, polypropylene, etc.
-Als A) Ethers of polyhydric al-1-ols such as January nonguri, T1-rumonoedyl T-ful, and di-I'f lengelicol monomethyl T-thyl can be used as the 9-wetting agent.

Also, as an Il +-1 regulator, jetanolamine,
1-lini [amines such as tanolamine, hydroxylated]
- Lithium, lithium hydroxide, potassium hydroxide, carbonate 1
- Inorganic salts such as lithium can be used.

Further, as water-soluble preservatives and antifungal agents, sodium dehydroacetate, potassium sorbate, butyl 1-hydroxybenzoate, sodium 2-pyridine thiA-1-AV lead, etc. can be used frequently.

In addition, as a rust preventive agent, for example, acidic sulfite,
11111]~lium, thioglycol 1jlf 7
7 tons, diisopropylammonium di-1-lyi-1-
Pentaeryth 1-1 tetranitrate, dicyclohexyl ammonium nitrite, etc. can be used.

To Example 1・5 1-Amino-8-naphthol-3,6-disulfonic acid (
8-Amino-2.1 by reacting the sodium salt of 1-acid (hereinafter abbreviated as 1-acid) with p-nitrobenzenediazonium salt.
-bis(4-nitrophenylazo)-1-butto-3,6-disulfonic acid was obtained. This G 1 〇- Suazo body 4! Nif 2 S'C3%l, change the two 21·II lit bonded to the ring to I minor, and further react with NaNO7 to 1IC dil! It was made into a zonium salt.

The resulting dianozonium 10 was reacted with 111-phthalene diamine to obtain a black dye of the general formula (I) in which M is Na. The spectral transmission curve of the aqueous solution is indicated by <I> in the attached figure, and the transmittance of blue, green, and blue light is relatively high at 1.

Also, M/+~! 11? Is the compound of general formula (I) of /-j ion a water-soluble compound of the previous idi? 11 for 1k. Add acid to acidify the precipitate, wash the precipitate with water, and add alkali (K 011 'A-Ll, N
II 40 N) to dissolve the precipitate, and M in the formula
1, silver dyeing of the general formula (I) with N H < 1 (2).

Two small portions each of F and IN of the general rE (T))-1-rium salt, potassium salt, and anthinium salt were combined with ion-exchanged water and stirred at 70°C for about 4 hours. , - Left shallow, 47uφ, hole 1 ¥ 1 ttl Teflon filter (product name) I-11-1 bore, Sumitomo Electric! l
using a pressure of 1 kg/c! I tried filtration with J, but it was impossible to filtrate at all.

On the other hand, according to the present invention, 1 part by weight of the orange dye shown in the table below is added to 9 parts by weight of the black dye of the general formula (I), and the weight a of the black dye of the general formula (I) is 2 parts by weight. When the III excess (accumulated amount over 3 minutes) was measured in an aqueous solution expressed as %, it was found to be J in the Queen's table.

By adding an orange dye to the aqueous solution of the black dye of the general formula (I>), it is possible to approach black color [) and at the same time increase the solubility of the black dye H of the general formula (I). I was able to do that.

General formula (T) Addition #II
(manufactured by Nijibi Kaseijo) C, 1, Daire 12 N a Ri 41292978g
(Manufactured by Hoichigaya Chemical Co., Ltd.) C, 1, Daire Sen3 Na Ri I-A Range 26480
Made by Ryo Kasei Net 1) C, 1, Daire 4 l<” '/I, Ov, /962 42 (
1 Comparative Example INa IJ Og 1,21 (None og Dimension 3N+-14 None Og 13-Example 6 No-1-rium salt of 11 acid and p-2[-[]ben-diazonium salt were dissolved in an acidic aqueous solution of hydrochloric acid) 8-amino 7-(4-nitrophenylazo)-1-nono1
~--3,6=disulfonic acid was obtained. This monoazo compound was reduced with Na2S to change the nitro group bonded to the bempine ring to an amino group, and then diazotization was performed in an acidic solution of NaNO2 and other hydrochloric acid to obtain a diazonium salt. The produced diazonium salt was reacted with -phenylenediamine to obtain a disazo compound. After the generated disazo compound and p-ahytaminobenzenediazonium salt were reacted in an alkali, the reaction product was hydrolyzed by heating to obtain a black dye of general formula (I). The spectral transmission curve of the black dye is shown in the figure ([
)It was shown to.

<Test using mixed ink> Black dye of general formula (I) <Na salt) 2.2 parts by weight Black dye of general formula (I) (Na salt) 1.5II 14-C,1, Directiku i/It Nondi 15 (Outside the door 11) Sei? (manufactured by L) Q, 5 /+Gurishi・Rin 5.5+7di] Blengri-1-L iQJ II Dehi 1~11^1
Chuu J Triuno, 0,2Il trithorium thiosulfate
0. Ol #I∆n exchange water
73.5ri.

Heat the 111 compound consisting of J, to 70'', stir for 2 hours to dissolve, and after IJ, hole +Y (1,4,'+ /l
It was filtered through an Ill membrane filter.

This ink was subjected to -) (1·n).

(1) 1p within the color of the image: Using a nozzle of Hl 71 In, under the condition of atomization frequency 1001 < 112 - (...on a commercially available Ichika group - recorded by inkjet, and the image 1ψ of 1lia I
Q - I through each blue green and red filter 1
), the image density of blue (Y) was 1.19, green (M) Ill, illd (C) 1.15, and a black image was obtained.

(2) Jetting response After recording with an inkjet according to the method described in (1) above, the nozzle was left unwashed at room temperature and humidity for two months, and then the same procedure as in (1) (!I) was performed again. ] ~ I was able to make a stable record when I performed the funken.

Comparative Example 4 When an ink containing no orange dye was prepared according to the recipe of Example 6 and the same test 1- was carried out, the color of the recorded image was blue (Y), image density 1.19 green (M) n 1. o8 red (C)
1.16, and the image had a bluish tinge.

In addition, after leaving it for 2 months, the nozzle was clogged, so stable flowering properties were obtained.

Example 7 In the same manner as above, 8-amino-7-(4-nitrophenylazo)-1-naph]--3,6-disulfonic acid and 1
]-1 1~F Minoben 1! diazonium salt) in an alkaline aqueous solution to give 8-amino-7-(4-21-[1)1-lj'zo)-2-<4-aminophenylazo)-1 noft. -ru-3,6-disulfonic acid was obtained. After diazotizing one of this disj′zo with 4NaNOz,
Coupling reaction with m-no-1 nylenediamine U in 11
1 is reduced to give the black dye of general formula (I) as 11
11. Is this black dye pl-110, water J51J? The spectral transmission curve of the n solution is shown in (I) in the figure.

<For the blended ink, J, Ru-1-su 1-゛・Black of general formula (I) (Δ dye (Na 1 mouth) 2.2 parts by weight Black of general formula (l[) [L dye (10 Ru) 1.5〃C0], Direct A Range 15 (manufactured by Choryo Kasei T:) 0.5 nol Glychrin 5.5〃Diethylene Grinyl 1-16.5/.

Dehyde ``1~lium acetate 0.2〃17-diA 1~lium sulfate (1,01, deionized water 73.59Il) An ink with the above formulation was prepared in the same manner as in Example 6, and tested as follows. The results were obtained.

(1) Image color Blue (Y) Image density 1.20 Green (M) l! 1.23 Red (C) 1.19 (2) Injection response I was able to perform stable injection even after 5xit.

Comparative Example 5 When a similar ink was prepared by adding an orange dye to the recipe of Example 7 and the same test was conducted, the color of the recorded image was blue (Y), image density 1.04, green (M) 1 .13 Red (C) 1.18, giving an image with a bluish tinge.

Also, the recording after being left alone for 2 months resulted in an unstable jet direction of -18 = /j, and only 4t images could be obtained.

It is clear from the above results that the ink of the present invention is stable over a long period of time without causing solid matter precipitation, and that the ink of the present invention is stable over a long period of time without causing solid matter precipitation. There was a pure black i+!ii II r.Moreover, it was water resistant ↑l
l, light resistance ↑1, abrasion resistance i11 and 1) return 1'L/komono.

[Brief explanation of the drawing]

The figure shows examples of the present invention (・'Synthesized general ■((I), (I
It is a spectral transmission curve of an aqueous solution of Compound 111 of [> and (I). 1, 'I Tomari Tester Co., Ltd. 1st T1 - Agent Kataoshi; - Hidetake Komatsu 19 - Sister (yt→

Claims (1)

[Scope of Claims] An inkjet recording ink characterized by containing at least one black dye represented by the following general formulas (I), (I), and (I) and an orange direct dye. <I) [In each of the above general formulas, M may be the same or different, and each is an alkali metal, N] and 1R2R
3R4 (R1, R2, R3, R4 may be the same or different (each represents hydrogen or an aliphatic or aromatic hydrocarbon) or a nitrogen-containing heterocyclic group.]