JPS58183767A - Recording solution for ink jet - Google Patents

Abstract

PURPOSE:The titled black recording solution, containing a specific compound and a yellow direct dye, and capable of giving recorded images of high density having improved water, light and abrasion resistance without clogging nozzles. CONSTITUTION:A recording solution containing at least one of a compound of formula I , II or III [M is alkali metal, NR1R2R3R4 (R1-R4 are H, aliphatic or aromatic hydrocarbon) or a nitrogen-containing heterocyclic group] and a yellow direct dye, e.g. C.I. Direct Yellow 28, preferably at (1:0.03)-(1:0.6) weight ratio. EFFECT:The jetting is carried out stably without depositing solids even on storage for a long term.

Description

[Detailed description of the invention] The present invention relates to a black recording liquid for inkjet use.

One of the characteristics required for inkjet ink is fib! The purpose of this purpose is to provide a recorded image with high resolution, but for this purpose, it is essential that the number of dye strokes in the ink be low and that the extinction coefficient of the dye used be low. However, if the dye # in the ink is contaminated, there will be problems such as precipitation of solid content during storage and clogging of the ejection ports (orisuisu), resulting in unstable ejection.

In order to solve this problem, as disclosed in Japanese Patent Publication No. 52-14645, Japanese Patent Publication No. 56-6881, Japanese Patent Application Publication No. 49-97620, and Japanese Patent Publication No. 51-137505, dyes have been developed. Many proposals have been made for adding organic compounds to the ink to improve its solubility, and adding surfactants such as thiodiethylene glycol derivatives, polyoxyethylene ethers, and alkyl sulfonates.

However, the former method does not have sufficient effects, the compounds added have odor and are harmful to the human body, and increasing the dose causes the physical properties of the ink, such as viscosity and surface tension, to become unsuitable for inkjet printing. There are problems such as storage. Furthermore, the latter method has problems such as bubbling of the ink, unstable jetting due to a decrease in surface tension, and changes in ink properties at low temperatures.

Therefore, it has excellent water resistance, light resistance, and abrasion resistance.

It gives a recorded image of ＾m degree and the nozzle is visible! I
It has a long temperature, does not precipitate solids and does not change its properties even after long-term storage, and sprays stably. s [2 record i
Il! igj! It has been desired to develop an ink that satisfies all physical properties such as being black (showing almost uniform absorption over the entire wavelength range of visible light).

Conventionally, the general formula l [wherein M may be the same or different (each is an alkali gold ICNRIR2R5R4 (R1%R2, R
3 and R4 may be the same or different tf'
It is known as the main component of commercially available O, 1, Direct Bufusoku 19 and 2. The compound represented by the general formula U (wherein has the same meaning as above) is contained as a by-product in commercially available c, r, Direct Black 19 dyes. The above-mentioned dyes are widely used as dyes in printing inks because of their relatively high absorption coefficient, near-black color, direct dyeing of cellulose, and low toxicity to the human body. ing. However, when these dyes are used in inkjet inks, they are not soluble in water or in polyhydric alcohols such as glycerin, diethylene glycol, and triethylene glycol, which are commonly used as wetting agents. This tendency is noticeable because the compound of the general formula (1) has poor solubility in water, whereas the compound of formula (1) has the drawbacks of clogging of the discharge and unstable jetting.

Furthermore, the compounds of the general formula (wherein M has the same meaning as above) have the same percentage differences and disadvantages as the compounds of the general formulas I and I above.

So, to Himi! Persons A and others repeatedly considered the use of the compounds of the above three woodworkers as a dispensing liquid for ink jets containing mold as a dye. It has been realized that it is possible to overcome the drawbacks of the above compounds and provide an excellent black recording liquid.

The object of the present invention is to have excellent water resistance, light resistance, and peeling resistance. ^
Provides an image of the new factory layout. The nozzle does not become distorted, and even after long-term storage, there is no precipitation of solids and the characteristics do not change.
To provide an inkjet distribution liquid that satisfies physical properties such as stable jetting and jet black recording (uniform absorption across the entire wavelength range of visible light). It is.

That is, the liquid formulation for ink dinits of the present invention has the following general formula:
R4 (Rls R2s R5 and R4 may be the same or different and each represents water lA or an aliphatic or aromatic footed water group) or nitrogen-containing 111 bulk ring group t1] % mold contains 41 camphor and yellow 9 direct vibration dye.

In the above general formula, examples of the alkali metal M include lithium, sodium, potassium, rubidium, cesium, and francium.
Examples of IR4 include, in addition to NH4, R1-R4 are methyl, ethyl, propyl, cecyl, stearyl, cyclohexyl, hydroxyethyl, phenol, tolylnato (D amine can be substituted), and M is a nitrogen-containing heterocyclic group. Examples include pyridine, pyrimidi/, heptalforine, pyrrolido/, allantoin, ε-capro2cutam, pyrazine, indole, pyridazine, imidazole, virol, thiazole.

Oxanol, pyrazole, furazane, quinoline, purine, tetrazole, etc. can be used.

The figure shows spectral transmittance curves for aqueous solutions of the compounds of the above general formulas 1, I, and Rin (all of them are sodium salts), and the curves show that these compounds have a large absorption of red light components and a blue light component. You can tell that the taste is southern. When these compounds coexist with the yellow direct dye in the ink, the ink becomes blacker and at the same time its solubility increases. The reason why the ink becomes black by adding the yellow dye t-m is that the wavelength range of the yellow dye is 400 to 500 nmK.
It is clear from the fact that the solubility of the black dye, which is the main component, is further improved by adding yellow dye.
! The mechanism behind this is still not clear. In any case, it is thought that this is because the yellow dye associates with the above compound in the bath, and the association and crystallization of the black dye, which is the main component, is hindered.

In the present invention, any known yellow lk dye may be used, but representative examples thereof are as follows.

U, 1. Tie Left Yellow 1.6.4, 5.6, 7, 8, 9.10, 11.12.
13.17.20, 22.2.5.24.26, 27.
28.29.50, 32.53, 54.59.41.4
2.44.45.49.50, 51.54.57.51
:l, 59.61, 62.63.66% 67.69.
70.71.72.76.74.75.76.77.7
8, mu 1.8-2.86, 84.8ri, 86.87.8
8% 89.90.91.92. Solo, 94% 95°C1 work, Direct Yellow 96.9B, 99,100.101,102,106.
104.105.106.107.1-08.109.
110.111.113.114.116° Among the above direct dyes, C, L Direct Yellow 2 B, 86s 87s 10 Us142 and 144 are particularly preferred from the viewpoint of dye solubility.

In the present invention, the weight ratio of the yellow dye to the compound of the general formula 1% M and 厘 is too:α02~too:t
The range of oo is preferable, and the range of too:ct is particularly preferable.
The above effects can be obtained by using in the range of o6 to t00:α60.

In addition to the above-mentioned compounds and hostile dyes, the components constituting the inkjet recording liquid of the present invention include a wetting agent pHW4! Antioxidants, water-soluble preservatives, antifungal agents, antirust agents, etc. can be used. Examples of wetting agents include polyhydric alcohols such as glycerin, triethylene glycol, ethylene glycol, diethylene glycol, polypropylene glycol, and polyethylene glycol, and polyhydric fluorols such as ethylene glycol heptamethyl ether and diethylene glycol heptamethyl ether. There are ethers, etc.

Examples of quaternary pufA modifiers include amines such as diethanolamine and triethanolamine.

Sodium hydroxide, lithium hydroxide, aqueous potassium,
Chew inorganic salts such as charcoal-based sodium.

Examples of antiseptic and antifungal agents include /Hydroh
Examples include a-soda, sorbin-satsu potassium, and p-hydroxybenzoin dibutyl ester 2-birinonethiol-1-oxide sodium.

Furthermore, examples of rust preventives include acid sulfite, sodium thioglycolate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol nitrate, and synchrohexylammonium nitrite.

Next, the present invention will be further explained using examples together with comparative examples, but is not limited thereto.

5*Example 1 1-amino-8-naphthol-5,6-disulfone #J
8-amino-2,7-bis(
4-nitrophenylazo)-1-naphthol-6,6-
Obtain disulfonic acid.

This disazo compound is reduced with N112B to change the two nitro groups bonded to the benzene ring to amino groups, and further NaN
It was reacted with O2 to form a diazonium salt.

The obtained fL diasonium salt was reacted with m-phenylenediamine to obtain a compound of general formula I.

To replace the cations, add hydrochloric acid to the resulting aqueous solution of the dye to make it acidic and precipitate it. After washing the precipitated dye with water, add alkali (KOH%NH4OH). 1 in the figure shows the spectral characteristics of an aqueous solution of the sodium salt of this compound at pH 10, which has a bluish color. 112 parts of the sodium salt, potassium salt, and ammonium salt of this compound were mixed with 112 parts of ion-exchanged water and 98 parts by weight of ion-exchanged water, stirred at 70°C for about 4 hours, and then left for 1 day and night. I tried to filter it at a pressure of 1 #/012 using a 1 μm Teflon filter (trade name: Norolobos Sumitomo Electric Co., Ltd.), but it turned out that <P:iA was impossible. On the other hand, according to the present invention, 1 part by weight of a yellow dye is added to 9 parts by weight of the compound of general formula I, and an aqueous solution containing 2 parts of the weight of the dye is added (accumulated over 6 minutes). When the amount) was measured, the values were as shown in the table below.

Hereinafter, by adding yellow direct '4'+ to the water bath solution of the compound of general formula 1 as shown in E, it is possible to make it more similar to a bear, and at the same time, it is possible to increase the solubility of the compound of general formula I.

Example 2 The sodium salt of H acid and the p-nitrobenzenediazonium salt were prepared in aqueous solution in aqueous solution, 8-amino-7-(4-nitrophenylazo)-1-naphthol-5,6 - Disulfone mt Tokutomo. This monobuzo form is Na
The nitro group bonded to the benzene ring was changed to an amino group by reduction with 2B, and the diazonium salt was obtained by diazotization in an IR solution of NaNO2 and salt. The obtained diazonium salt and m-phenylenediamine were reacted to obtain a disazo compound. The obtained disazo compound and p-arydoaminobenzenediazonium salt were reacted in an alkali, and after death, the reaction product was hydrolyzed by heating to obtain a compound of general formula (1). The spectral characteristics of the sodium salt of this compound are shown in ■ in the figure.

Test using mixed ink> Compound of general formula I (Na salt) 2.2 parts by weight Compound of general formula (Na salt) 15 l Glycerin
5.51 diethylene glycol
16.51 Sodium dehydroacid
[L2 1-thiochloride sodium
101 'Ion Father Water Replacement 73.
A mixture consisting of #69 was heated to 70°C, stirred for 2 hours, and dissolved in a bath.The mixture was filtered through a mengla/filter with a hole diameter of 45 μm and used as an ink.

The physical properties of the ink were determined as follows.

Surface tension r = 62 dyne/as (25°C)
Viscosity η = t 9 c, p, (30°C) pH = 9.8 = 2.4 mU /cjR The following tests were performed on this ink.

(1) Image color: Jet recording of ink from a nozzle with an internal diameter of 50 μm onto commercially available high-quality paper at a particleization frequency of 100 μm - C1 Part 1
When the density of 111I scratches was measured through each of the blue, green, and red fiscita's, the following results were obtained:
I I t16 and a black image was obtained at 7''.

(2) Injection response After jet recording was performed according to the method described in AiJ (1), the nozzle was left unwashed at room temperature and humidity for two months, and jet recording was performed in (1). I was able to make stable recordings.

Comparative Example 2 When a yellow dye was not added to the formulation of Example 2 and an ink was prepared and the same test was conducted, 111 if
Personal record l1iIi My color blue (Y) image 11F1.0
1 Green (Ml # 1.08 red (CI 1 116 C), the image was bluish.

(2) Records after being left at room temperature and humidity for two months were unstable and poor due to the nozzle's self-recognition.

Example 3 811 ii Same as self 4>i V strain-C1:l-7mi/
-7-(4-nitrophenylazo)-1-naphthol-
A-ami/-7-(4-nitrophenylazo)-2-(4-
7<nophenylazo)-1-naphthol-3,6-,)
Sulfone got. This disazo compound was diazotized with NaNO2 and then subjected to a coupling reaction with m-phenylenediamine, and the resulting compound was reduced to obtain a compound of the general formula.

<Test using mixed ink> Compound of general formula 1 (Na salt) 2.2
] 1 m part Compound with general formula Oboro (Na salt)
t5 #C5■, Direct Yellow 142
04 # (manufactured by Sumitomo Chemical Co., Ltd.) Glycerin
5.51 diethylene glycol
16.51 dehydro&j&sodium
α2 f, JLffip thio i! Sodium removal 101 'Ion-exchanged water 73.69 #Make the ink of the above formulation like So8ki and II.]-C11 Go1-L0 I/
The physical properties of the material were determined by the next flight.

r = 61 dyne /3 (25°C) η = 1
．． 9 c, p, (30°C) pli = 1 [11 to = 2.4 muy/bikoCi/regarding the above and 10] Vkoboost Ii
Then the next result appeared.

(il = blue color blue tY+ th Ano [1,18 green (group l 117 leno white C)
#t17 (1) Injection response Stable injection after being left unused for one month 75: Samurai 7''.

Regarding other compounds and yellow direct dyes used in the present invention, see above! ir′, L as in the method described in the Examples
When an inkjet recording liquid was prepared and the performance of 7'Lc) was tested, similarly good results were obtained.

[Brief explanation of the drawing]

The drawings with mu are general formulas! Indicates the spectral transmission surface l1liI of an aqueous solution of the compound (sodium salt) of

Claims (1)

[Claims] The following general formulas 1, 2 and 2 may each represent an alkali metal, NRIR2
R3R4 (R1% Rt* Rs and R4 may be the same or different and n represents water ice or an aliphatic or aromatic hydrocarbon group) or a Miyamuro Takani group] characterized in that it contains at least one compound and a yellow direct dye. Inkjet diary
liquid.