JPS60108481A - Recording solution containing naphthalene disazo dye - Google Patents

Abstract

PURPOSE:A black recording solution suitable for ink jet recording, having improved recording characteristics, shelf stability, grab to materials to be recorded, light resistance and water resistance of recorded image, etc., containing a novel naphthalene disazo dye having a specific structural formula. CONSTITUTION:The desired recording solution containing preferably 0.1-20wt% black dye (e.g., compound shown by the formula II, etc.) shown by the formula I [X is 1-4C alkylcarbonylamino, arylcarbonylamino, 1-4C alkylsulfonylamino, arylsulfonylamino, (substituted) carbonamide, (substituted) sulfonamide, -SO3M (M is alkali metal, ammonium, etc.); R<1> is H, 1-8C alkyl, 2-8C alkylcarbonyl, 1-4C alkylsulfonyl, arylsulfonyl, etc.; R<2> is H, 1-8C alkyl; n is 0 or 1] as a recording agent. EFFECT:Affords no clogging of extruding orifice.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording liquid containing a black naphthalene disazo dye. For more information.

The present invention relates to a novel recording liquid, and particularly to a recording liquid suitable for a recording method in which recording is performed by ejecting the liquid from fine ejection orifices (ejection orifices) provided in a print head and flying the liquid as droplets.

BACKGROUND ART Writing instruments (fountain pens, felt pens, etc.) that record on recording materials such as paper have traditionally used inks prepared by dissolving various dyes in water or other organic solvents.

In addition, recording is performed by ejecting liquid (droplets called ink) in the recording head from the ejection orifice using vibrations caused by a piezo vibrator or electrostatic attraction caused by applying a high voltage. An intermittent inkjet recording method is known.

Also used for this purpose is a recording liquid in which various dyes are dissolved in water or an organic solvent. Compared to ink for stationery such as general fountain pens and felt-tip pens, inkjet recording liquids require more stringent conditions in terms of many characteristics.

Such a recording liquid is a recording agent (a dye or a pigment is used).
The basic components are a liquid medium for dissolving or dispersing it (water or various organic solvents or mixtures thereof are used), and various additives are added as necessary.

Favorable conditions for this glazed recording liquid include (1) liquid physical properties (viscosity) that match the ejection conditions (piezoelectric element drive voltage, dynamic frequency, orifice shape and material, orifice diameter, etc.);

surface tension, electrical conductivity, etc.).

(2) It should be stable for long-term storage and should not cause clogging.

(3) Fixation is fast and the periphery of the dot is smooth and there is little blurring against the recorded material (eg, film, etc.).

(4) The color tone of the printed image is clear and the density is high.

(5) The printed image has excellent water resistance and light resistance.

(6) The recording liquid is attached to surrounding materials (containers, connecting tubes).

Do not damage the seal material.

(7) It is said that the material has excellent safety characteristics such as odor, toxicity, and flammability, but it is extremely difficult to satisfy all of these characteristics at the same time.

Furthermore, since the recording liquid used for such recording purposes is basically composed of a dye and its solvent, the above-mentioned characteristics of the recording liquid are largely influenced by the inherent properties of the dye. Therefore, selecting a dye so that the recording liquid has the above characteristics is an extremely important technique in this technical field.

Conventionally, as a recording liquid of this extreme, for example, Tokkosho! O-♂3 and No. 7, Tokko Akij / -4t041 and Da, Tokko Aki! λ
-/3/2≦ issue, special public Akio λ-/31.27 issue, special public Akio! As shown in each publication of θ-9!007, various dyes,
Pigments dissolved or dispersed in aqueous or non-aqueous solvents are known, and black dyes include the following (a):
) dyes are used.

4- (A) [C0 work, direct black-y (0, ■, 27
72θ)] (6 mouths [0, work, acid black-, 2 (0, work, !04t
2θ]] (c) [0, Tech, Acid Black-3/ (0, ■, 77!
Chromium complex salt 02N [0, ■, acid black-9B (0, engineering, /37
//)] In addition, as a black naphthalenedis azo yarn dye, the following structural formula [0,1, food black-, 2 (a, engineering, :vyt
t)] is known.

An object of the present invention is to provide a recording liquid that simultaneously satisfies the above characteristics (1) to (5).

That is, 1 the present invention provides a recording liquid containing a recording agent as a component for forming a recorded image and a liquid medium for dissolving or dispersing this recording agent. M (wherein, (b) represents a carbonamide group, a sulfonamido group optionally substituted with an alkyl group with carbon number/~g, or -[+, M group) jl represents a hydrogen atom, and jl represents a hydrogen atom, carbon number/~? an alkyl group having 2 to r carbon atoms, an alkylsulfonyl group having 2 to 3 carbon atoms, an allylsulfonyl group, or 10H
280, represents a group of M, Ht is a hydrogen atom or carbon V
/ represents an alkyl group of 7-. However, when X is a group of 18o, M, R1 and R
2 does not take hydrogen atoms at the same time. M represents alkali metal, ammonium or amines [2゜n〜cross θ/
The gist of the invention is a recording liquid containing a naphthalene di-azo dye, which is characterized by containing a dye represented by the following formula.

The present invention will be explained in detail below.

In the above formula [I], examples of the allyl group in X and R' include phenyl group, paratolyl group, etc.; examples of the alkali gold ingot in M include lithium, sodium, potassium, etc.; For example, 1.

Examples include triethanolamine.

In addition, in formula 5 [IE, X is preferably an acetylamino group, a propionyl group, an allylcarbonylamino group, particularly a benzoylamino group among alkylcarbonylamino groups having 7 to 2 carbon atoms, and -8o, M Groups are preferred. Let's call it R1.

is a hydrogen atom, an alkyl group with carbon number/~t, carbon number co~
Preferably, r is an alkylcarbonyl group or an 8-metal. Specific examples of the dye according to the present invention include those shown in Table 1 below.

The dye of the present invention can be used, for example, in a thin 1) Nagaku "Shin Dye Kagaku" (published on December 27, 1987), Gihodo.

Page 397, lines 27-39? It can be manufactured by the following method according to the description on page 1, etc.

The amines represented by the following general formula [11] (wherein X represents the above content) are diazoxed using sodium nitrite etc. in a mineral acid such as hydrochloric acid or sulfuric acid, and then converted to the following general formula [■] So , H to obtain a monoazo compound represented by the following general formula [■] 19- (wherein X represents the above content).

This monoazo compound is similarly diazotized using sodium nitrite or the like in a mineral acid such as hydrochloric acid or sulfuric acid, and then is expressed by the following general formula [■] (wherein R1, R2 and n represent the above contents). It can be easily obtained by coupling with 7 tolls.

The content of dye in the recording liquid of the present invention is determined depending on the type of liquid medium components, the characteristics required of the recording liquid, etc.
Generally, the percentage of single buds is 0.7 to -0%, preferably 0% based on the total weight of the recording liquid.
．． j~/! %, preferably in the range of / to /θ. The dye can of course be used alone.

< can be used in combination of two or more glazes, or in combination with the dye as an essential component and various dyes such as other direct dyes and acid dyes.

Liquid medium components for composing the recording liquid of the present invention include:
Water or a mixture of water and various water-soluble organic solvents is used. Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, n-7' lobil alcohol, isopropyl alcohol, n-methyl alcohol,
Alkyl alcohols with a carbon number of 1 to 5, such as 5ec-phtyl alcohol, tθrt-7′ tyl alcohol, and isobutyl alcohol; Amides, such as dimethylformamide and dimethylacetamide; acetone.

Ketones or ketone alcohols such as diacetone alcohol; ethers such as tetrahydrofuran and dioxane
N-methyl--virolidone.

/, nitrogen-containing heterocyclic ketones such as 3-dimethyl-imidazolidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, / , 2. Alkylene glycols in which the alkylene group contains - ~ carbon atoms such as t-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol; glycerin; ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol Examples include lower alkyl ethers of polyhydric alcohols such as monomethyl (or ethyl) ether.

What is the content of the water-soluble organic solvent in the recording liquid?

In general, it is expressed as a weight percent of the total weight of the recording liquid.
〕, preferably /θ~♂0%, 〕preferably 10~!
The range is θ-.

The water content at this time depends on the type of solvent component mentioned above.

Although it is determined over a wide range depending on the composition and desired characteristics of the recording liquid, generally /θ is determined based on the total weight of the recording liquid.
~? θ%, preferably 70 to 70%, more preferably
It is within the range of 2.0 to 7θ.

The method for producing the recording liquid of the present invention does not require particularly difficult processing, and the necessary components may be mixed in a conventional manner.

The recording liquid of the present invention has recording properties (signal responsiveness,
Droplet formation stability, ejection stability, long-term continuous recording performance,
ejection stability after a long period of recording interruption), storage stability, and fixability to the recording material.

Alternatively, the recorded image has excellent light resistance, weather resistance, water resistance, etc., all of which are well-balanced.

In order to further improve such properties, various conventionally known additives may be further added and contained. Examples: Viscosity modifiers such as polyvinyl alcohol, cellulose, water-soluble resins; cationic type .

Various anionic or nonionic surfactants.

23- Surface tension adjusters such as jetanolamine and triethanolamine: pH adjusters using buffer solutions.

Antifungal agents and the like can be mentioned.

Further, in order to prepare a recording liquid used in an inkjet recording method in which the recording liquid is charged, a resistivity adjuster such as inorganic salts such as lithium chloride, ammonium chloride, and sodium chloride is added.

Similarly, when applied to an inkjet system in which recording liquid is ejected by the action of thermal energy, thermal physical property values (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

According to the present invention, the physical property values such as viscosity and surface tension are within appropriate ranges, the minute discharge orifices are not obstructed, a recorded image of sufficiently high density is provided, and the physical property values do not change during storage. It can record on a variety of materials without causing solid content precipitation, without limiting the type of recording material, has a high fixing speed, and has excellent water resistance, light resistance, abrasion resistance, and resolution of -24~. A recording liquid that provides an image is obtained.

The inkjet recording method will be explained below.

There are two types of ink shed recording methods depending on the method of generating droplets and the method of controlling the flight direction of the droplets. That-
An example is shown in FIG.

That is, the apparatus shown in FIG. 7 applies a recording signal to a recording head section having a piezo vibrator, and performs recording by generating droplets of recording liquid in response to the signal. m/% included in the figure/
is a recording head, which includes a piezo vibrator 2a, a diaphragm 2b, a recording liquid inlet 3, a liquid chamber in the head, and an ejection port (ejection orifice)! I have it. A recording liquid 7 stored in a storage tank B is introduced into the liquid chamber Z through a supply pipe l. Similarly, depending on the case, there may be intermediate treatment means such as a pump or filter in the middle of the supply pipe ♂. may be provided. The piezo vibrator jaK is applied with a recording signal 87>1 converted into a pulse by the signal processing means (for example, a pulse converter) 10, and a pressure change is caused in the recording liquid in the liquid chamber in accordance with the signal. arise. As a result, the recording liquid 7 is ejected from the ejection orifice j in the form of droplets // and is recorded on the surface of the first class recording material /2.

Furthermore, various types of devices other than the above-mentioned devices are known, for example, as shown in FIG.

As a modification of FIG. 1, the liquid chamber 4t is shaped like a nozzle.

There is a device in which a cylindrical piezoelectric vibrator is installed on the outer periphery (the mechanism of generation of short strips in this device is essentially the same as the device shown in FIG. 1). Also, an apparatus that continuously generates charged droplets and uses a portion of the droplets for recording.

The recording liquid in the chamber of the recording head corresponds to the recording signal t.

There are also known devices that generate droplets by applying thermal energy.

Seven examples are shown in Fig. 3-a, Fig. 3-b, and Fig. 9.

The head /3 is made of glass, ceramics, or plastic plate, etc., having a groove /Z through which ink passes.

Heat generation used for thermal recording/! (Although a thin film head is shown in the figure, the KVM is not defined here). The heating head/j is a protection plate made of silicon oxide or the like/4. Aluminum electrode/
7-/, /7-2, heating resistor layer formed of nichrome etc./? , heat storage J@/9. It is made of alumina thick substrate λθ with good heat dissipation.

The ink 2 comes from the discharge orifice 22, and the pressure P
It forms a cymeniscus, 23.

Now, when an electric signal is applied to IM, pole /7-/, /7-, the heating head /! The area indicated by n in @ generates intense heat, bubbles are generated in the ink 2/ that is in contact with this area, the meniscus 23 protrudes due to the pressure, and the ink 2/ is ejected from the orifice 22 to form a small recording surface. The droplet becomes 241, and the recorded abduction,
2! fly towards. FIG. V shows an external view of a multi-head in which a large number of heads shown in FIG. 3-a are arranged. The multi-head is made by gluing a glass plate 27 having multi-grooves 2 and a heat generating plate 27 similar to that shown in FIG. 3-a.

Note that FIG. 3-a is a cross-sectional view of the head 3 along the ink flow path, and FIG.

Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples.

Fu example/ Diethylene glycol +2j [ Dye for the first surface / 2 Ion exchange water (hereinafter abbreviated as water) remaining amount Total /θ0v The above components are thoroughly mixed in a container mt-.

After pressurizing with a Teflon filter with pore size/μ,
It was degassed using a vacuum pump and used as a recording liquid. An on-demand recording head (discharge orifice diameter! θ
μ, piezo vibrator drive voltage 6θV1 frequency KHz)
When the following studies (T1) to (T,) were carried out using a recording apparatus having the following, good results were obtained in all cases.

(Long-term storage stability of TO recording liquid: Even after storing the recording liquid in a sealed glass container at 1-30°C and 30°C for 6 months, no precipitation of insoluble matter was observed, and there were no changes in the physical properties or color tone of the liquid. There was no.

(T2) Ejection stability: Continuous ejection was performed for one hour in an atmosphere of room temperature, 1° C., and 0° C. Under all conditions, stable high-quality recording was achieved from beginning to end.

(T,) Ejection response: Intermittent ejection every 2 seconds and ejection after one month of standing were investigated, and in both cases, clogging at the tip of the orifice was recorded stably and uniformly.

(T4) Quality of recorded image: The recorded image had high density and was clear. After three months of exposure to indoor light, the concentration reduction rate was less than 7%.

There was very little smearing per image when immersed in water for 1 minute.

(TII) Fixability for various recording systems: Printing with the recording materials listed in the table below/! After 9 seconds, the printed area was rubbed with a finger to determine the presence or absence of image shift and blurring, and both showed excellent fixing properties with no image shift or blurring.

Example a N-methyl-copyrrolidone /! 2 Diethylene glycol /9? Dye of Table 1 I6.2 Gu? Water remaining amount meter 7009 A recording liquid having the above composition was prepared in the same manner as in Example/, and an on-demand type multi-head (
Discharge orifice diameter 3! μ1 heating resistor resistance value/jθΩ,
(T1) to (T,) were investigated in the same manner as in Example 1 using a recording device having a driving voltage of 3θ, 1 frequency, and 2KH2, and excellent results were obtained in all of the study experiments. Ta.

Example 3 Ethylene glycol co θ2 /, 3-dimethyl-co imidazolidinone 30f! 1st
Dye T2 Water Remaining Amount A recording liquid with the above composition was prepared in the same manner as in Example 1, and an on-demand type multi-layer printer was prepared by applying thermal energy to the recording liquid in the recording head to generate droplets to perform recording. head(
Discharge orifice diameter 3-tμ1 heating resistor resistance value/! 0Ω
(T1) to (T,) were investigated in the same manner as in Example 31 using a recording device having a driving voltage of 30 V and a frequency of 2 KHz. Got the results.

Example: Diethylene glycol 3tf Dye from Table 7 I6/3 4tf Total: 1ooy A recording liquid having the above composition was prepared in the same manner as in Example, and thermal energy was applied to the recording liquid in the recording head to generate droplets. On-demand type multi-head for recording (
Discharge orifice diameter 3jμ1 heating resistor resistance value/! θΩ,
Using a recording device having a drive voltage jOV and a frequency of 2 KH2), tests (T1) to (T,) were conducted in the same manner as in Example 1, and excellent results were obtained in all the tests.

Example! Diethylene glycol monomethyl ether 302 No. 1
Dye in Table 4/7 V 32- Total /θθf Example A recording liquid with the above composition is prepared as in the example, and thermal energy is applied to the recording liquid in the recording head to generate droplets and perform recording. On-demand type multi-head (
Discharge orifice diameter 3, tμ1 heating resistor resistance value/jO
Ω, a driving voltage of 30 V, and a frequency of 2 KH2) were used to study (TI) to (T,) in the same manner as in Example/, but excellent results were obtained in all of the study experiments. Ta.

Examples 3 to 10 Recording liquids having the compositions shown in Examples 1 to 10 in Table 2 below were prepared in the same manner as in Example. These compositions were filled into 4-inch felt and written on medium-quality paper (Hakubotan Nihonshu Paper Co., Ltd.) to examine water resistance and writing properties after being left for 2 hours with the cap removed.

The recording liquid of this example had excellent water resistance and excellent writing properties after being left standing.

7. In Table 1, in Example A, 4t% of dye compound A/7 was used instead of dye compound A/7. /, 10. //, /ko, /da.

/j%#, /r11/? lIJ/, 23, λ! and 2
Good results were obtained in both cases.

Reference example/ [Synthesis of dye shown in Table 7 A3] (1) Production of first diazo liquid Sulfanilic acid/7. J f woj % increase M3g otsud
and stirred for 3 hours to make a uniform slurry. Add ice cubes θ01 to this and cool to 3℃. This slurry medium,
An aqueous solution of 2.32 parts of sodium nitrite dissolved in 73 parts of water was added. Next, the mixture was stirred at 3° C. for 7 hours to undergo diazotization, and then 3F sulfamic acid was added to eliminate the remaining sodium nitrite to obtain a first diazo solution.

(2) Manufacture of No. 1 cociazo liquid/7 crepe acid λ2,3 f is added to water! θ- and stirred for 2 hours to form a uniform slurry. Add to this 300F ice.

The first diazo liquid obtained in (1) above and Co! Add hot soda/θgo at temperature θ~3°C and pH 2~3/! After stirring for an hour to perform coupling, one common salt solution θor was added to perform salting out. After filtering the precipitated monoazo compound, it was washed with 10% saline water J-θθd and dried to obtain monoazo compounds 3g and 4f. The obtained monoazo compound, 2Q,
Da 1! In addition to thihydrochloric acid 10-! After stirring for an hour to make a uniform slurry, 30θ2 of ice was added and the mixture was cooled to 3°C. During this slurry.

3. Sodium nitrite in 31 water. ? An aqueous solution containing v was added. Next, the mixture was stirred at 3° C. for 7 hours, diazotized, and then sulfamine #/l was added to eliminate the remaining sodium nitrite to obtain a cocyazotide solution.

(3) Coupling/-hydroxy-2-butylamino-naphthalene-3,
After adding ≦-disulfonic acid/rJf to 4t of water and θ-,
To this, an ice cube Oθ2, the first cociazo liquid obtained in (2) above, and λ! Chika soda! ! - to pHf~10. Temperature 2~! Coupling was performed at °C.

After stirring at the same temperature and pH for 5 hours, add salt, 2! θ2 was added to precipitate the dye. After dispersing the precipitated dye over P/θ
Wash with 300 tnl of attack ground water and wet cake 2/θV
I got it. This wet cake was desalted and then dried to obtain 3 pieces of the desired dye H803'Na and 2 pieces. The yield is 7. ? , Tachi de Ryo, Tsuta.

The results of elemental analysis were as follows.

Reference example - [Table 1 A! Synthesis of dye] (1) Production of first diazo liquid A first diazo liquid was obtained according to the method of (1) of Reference Example, except that guamino-acetanilide/j,Of was used in place of sulfanilic acid.

(2) Production of the diazo liquid of the following monoazo compound So, Na (the diazo liquid of the following monoazo compound So, Na) except that the first diazo liquid obtained in the above (1) was used. ) was obtained.

(3) Coupling/-Hydroxy-7-asano-naphthalene-3, B-disulfonic acid/6. Except for using θf, the reference example/(3
) to dye the desired color 39-〇H +30. Na 3 J, JE f were obtained. The yield was rt, o%.

The result of elemental analysis was first order.

Reference Example 3 [Synthesis of the dye of Table 1 A-B] Using the No. Koshiazo liquid obtained by the methods (1) and (2) of Reference Example-, %! -Hydroxy-6-sulfonic acid-2 Naphthylamino-methanesulfonic acid M So, H r, t f were obtained. Yield 2! ,! It was Chi.

The results of elemental analysis were as follows.

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic diagrams of an inkjet recording apparatus, respectively. Figures J-A and J-B are a longitudinal cross-sectional view and a transverse cross-sectional view of a main part of another recording apparatus. FIG. 9 is an external perspective view of a multi-head head shown in FIGS. J-A and J-2). However, in Figure 1/...recording head 1.2a...piezo vibrator 1.2
b...Vibration plate, 3...Inlet, G...Liquid chamber, j...
...Discharge oriice, storage tank, Z...recording liquid, ? ...Supply pipe? ...intermediate processing means, 10.
...signal processing means, //...droplet, /2,23...
Recorded material, S...recording signal, /DA...liquid chamber, /!・
・・Heating head, /6・・Rubber layer % /7・・Electrode, /r・・Heating resistor layer, /de・・Heat storage layer, 20・
...Substrate, 26...groove. Patent Applicant: Canon Co., Ltd. and 7 others Attorney: Patent Attorney Hase Yo - and 7 others 43- Kou 1 Figure 2 Hisu＼ 01

Claims (2)

[Claims] (1) In a recording liquid containing a recording agent which is a component for forming a recorded image and a liquid medium for dissolving or dispersing this recording agent, the recording agent has the following general formula [ ] (where X is the carbon number /~Z alkylcarbonylamino group, allylcarbonylamino group. Carbon number/~Z alkylsulfonylamino group. Arylsulfonylamino group, carbon number/~Z optionally substituted alkyl group, carbon number/~
R1 represents a sulfonamide group or -So, M group which may be substituted with an alkyl group of Z; R1 is a hydrogen atom, an alkyl group having a carbon number of 1 to 1, an alkylcarbonyl group having a carbon number of - to ♂, a carbon number/ - represents an alkylsulfonyl group, allylsulfonyl, indahH-0H2So, M group, and R1 represents a hydrogen atom or an alkyl group having carbon number/-r. however,. When X is an 18o3M group, R1 and R2 do not have a hydrogen atom at the same time. M is an alkali metal. represents ammonium or amines, n is O or/
A recording liquid containing a naphthalene di-azo dye, characterized in that it contains a dye represented by: (2) The naphthalene disazo dye represented by the general formula [1] is contained in an amount of θ/~20 weight percent based on the total weight of the recording liquid. Recording liquid containing dyes.