JPS62190275A - Recording liquid - Google Patents

Abstract

PURPOSE:To provide a recording liquid containing specific two kinds of dyes, having excellent recording characteristics, storage stability and fixability to recording material, giving recorded image having excellent color clarity, light- resistance, weather-resistance, water-resistance, alcohol-resistance, etc., and suitable for ink jet recording. CONSTITUTION:The objective recording liquid contains (A) a dye of formula I [R1 and R2 are substituent group; R3 is COCH3, group of formula II or formula III (R4 is H or Cl); M is alkali metal, NH4 or organic amine] and (B) a dye of formula IV (Ar is substituted phenyl or substituted naphthyl; R2 is H or sulfonic acid residue; M is Cr, Co, Ni or Cu; the sulfonic acid is present as a salt with a base such as alkali metal, etc.) or formula V (R1 and R2 are H, halogen, alkyl, nitro, COOH or sulfonic acid residue; R3 is H or sulfonic acid residue; R4 and R5 are H, sulfonic acid residue, -NHCOCH3 etc.; the sulfonic acid is present as a salt with a base such as alkali metal).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a new recording liquid (hereinafter referred to as ink), and in particular, ink is ejected from fine ejection ports (ejection orifices) provided in a recording head, and the ink is The present invention relates to an ink suitable for a method of recording by flying droplets.

(Prior art) Writing instruments (fountain pens,
(Felt-tip pens, etc.) use inks prepared by dissolving various dyes in water or other organic solvents.

Furthermore, in the so-called inkjet method, in which recording is performed by ejecting ink in the recording head from an ejection orifice using vibrations caused by a piezo vibrator or electrostatic attraction caused by the application of high voltage, various dyes are dissolved in water or organic solvents. ink is used. However, compared to ink for pomegranates such as general fountain pens and felt pens, inkjet ink has many characteristics that require stricter conditions.

The inkjet system generates little noise and can perform high-speed recording or color recording without special fixing processing during sheet feeding, and various types of inkjet systems are being actively researched.

There are various methods for this type of method, but in all of them, the ink used must have physical properties such as viscosity and surface tension within appropriate ranges, have high dissolution stability of the recording agent, and have a fine ejection orifice. It is required to have various properties such as not clogging, recording images of sufficiently high density, and not causing changes in physical properties or precipitation of solids during storage.

In addition to the above characteristics, recording can be performed without limiting the type of recording material, fast fixing speed, water resistance, solvent resistance (alcohol resistance at 4 yen), light resistance, abrasion resistance, and Properties such as providing recorded images with excellent resolution are also required.

However, images recorded using conventional inks, particularly water-based inks, tend to bleed, fade, or fade due to the aging of the wood or exposure to light. This tendency is particularly noticeable in magenta recording, and there is a strong desire for an ink that has improved these drawbacks.

From this point of view, many proposals regarding inks have been made, but almost no practical ink that satisfies all of the above conditions has been obtained.

Regarding magenta, there are almost no known dyes that have both color clarity and high light resistance.

That is, dyes with bright color tone such as xanthine dyes have extremely low light fastness, and dyes with good light fastness such as alloy metal azo dyes have the disadvantage of lacking color brightness.

An object of the present invention is to provide a magenta ink that satisfies all of the conditions described in 1-1. That is, the objective is to provide an ink that does not cause clogging of ejection orifices, deterioration during storage, or generation of precipitates, and has excellent recording performance, ejection stability, and ejection response. Another objective is to provide an ink with excellent color tone and contrast of recorded images. Another object of the present invention is to provide an ink with excellent fixing properties in which recorded images have water resistance, alcohol resistance, light resistance, and resolution.

Thus, the present invention was completed by finding a dye suitable for the ink used for this purpose as a result of intensive studies.

(Disclosure of the Invention) That is, the present invention provides a recording liquid containing a recording agent which is a component for forming the Q image and a liquid medium for dissolving or dispersing this recording agent. ) and a dye represented by general formula (B) or (C).

(However, R1 and R2 in the above formula are optional substitutions) 1 (
and R3 is cocH3, -5o20cu3 or -
co f) 4) 2 R4 represents a hydrogen atom or a chlorine atom, M represents one type of salt selected from alkali metals, ammonium, and organic amines. (However, Ar in the above formula is alkylno, (, nitro group,
phenylno, (or naphthylno, () substituted with a halogen atom or sulfonic acid group, R1 represents an alkylno, q, phenyl group or carbamoyl group,
R2 represents a hydrogen atom or sulfone resistance, M is Cr
, Co, Ni, or Cu, and the sulfonic acid group is salt-formed with one type of base selected from alkali metals, ammonium, and organic amines. ) (However, R1 and R2 in the two notations represent a hydrogen atom, a halogen atom, an alkyl group, a nitro group, a carboxyl group, or a sulfonic acid group), (R3 represents a hydrogen atom or a sulfonic acid group, and R4 and R5 is a hydrogen atom, 7.)y
*N-resistant group, -NHCOCH3, -5Ho, -NHco
() or -NHCO-4S (S = sulfone,
0, and the sulfonic acid group forms a salt with one type of base selected from alkali metals, ammonium, and organic amines. ) Next, to explain the present invention in more detail, in order to achieve the purpose of the above-mentioned unreleased rJ+, Unreleased Town Name conducted detailed research on dyes, which are recording agent components of ink, and discovered that a specific combination of dyes Dyes are suitable as ink recording agents, especially ink recording agents used in inkjet systems, and by employing such a specific combination of dyes as ink recording agents, color tones can be improved when used in inkjet systems. It has been discovered that an ink that provides recorded images that are extremely clear and satisfies required performances such as water resistance, light resistance, resolution, alcohol resistance, etc. can be used.

The dyes represented by the above general formulas (A), CB) and (C) used in the present invention and which characterize the present invention as ↑ are included in the above general formulas (A), (B) and (C). Any dye may be used as long as it is used, but particularly preferred examples include the following. Sho 1
Although sodium salts are given as examples, the salts are not limited to sodium salts, and may be formed with any base such as lithium salts, potassium salts, ammonium salts, organic amine salts, and the like.

Sul, 7h, + 5Iuvr+a
,) u, ota doctor'' Jυ9muniA 桝j''Jυ虻Munij 杝llΔl虻N二j桝''Jυ虻N21 +5U3Na 5L13Na Kaijitobori Hiri 2V Ikitei''J日E Shadow 2U Kaiji' KoroLL2η 5LI3Na SO3Na However, the dyes (A), (B) and (C) are
A) is an essential component, and dye (B) is added to this dye (A).
) and/or dye (C) is the main feature of the present invention, and the ink obtained by such a specific combination has significantly superior color tone clarity, This provides a recorded image that has both light resistance and water resistance.

The total content of the above dyes depends on the type of liquid medium components,
It is determined depending on the characteristics required for the ink, but generally the main star percentage is 0.1% based on the total weight of the ink.
~20%, preferably 0.5~15%, more preferably 1~10%. Regarding the amount of these dyes used, the effect of the present invention is most noticeable when the dye (A) is used in a ratio of 10 to 90% by weight, preferably 20 to 80% by weight of the total dye. achieved. Of course, in addition to these specific dyes, various dyes such as other direct dyes and durable dyes can be used in combination.

A suitable solvent for use in the uninvented ink is a mixed solvent of water or wood and a water-soluble organic solvent, and particularly suitable is a mixed solvent of water and a water-soluble organic solvent. , contains polyhydric alcohol, which is effective in preventing ink from drying out, as a water-soluble organic solvent. In addition, for wood, it is preferable to use deionized water rather than ordinary water containing various ions.Water-soluble organic solvents used in combination with water include, for example, methyl alcohol, ethyl alcohol, etc. , C1-4 alkyl alcohols such as n-propyl alcohol, isopropyl alcohol, D-butyl alcohol, 5ee-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol Amides such as dimethylformamide and dimethylacetamide; a, setone Ketones or keto alcohols such as , diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Polyargylene glycols such as polyethylene glycol and polypropylene glycol: ethylene glycol, propylene glycol, butylene gelicol, triethylene glycol, l.

2. Alkylene glycols in which the fullylene group contains 2 to 6 carbon atoms, such as 6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol; glycerin; ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ) Lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monomethyl (or ethyl) ether; N-methyl-2-pyrrolidone, 1.
Examples include 3-dimethyl-2-imidazolidinone.

Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferred.

The content of the water-soluble organic solvent in the ink is generally in the range of 5 to 95% by weight, preferably 10 to 80% by weight, more preferably 20 to 50% by weight based on the total weight of the ink. be.

The water content at this time is determined within a wide range depending on the type of the solvent component, its composition, and the desired characteristics of the ink, but it is generally 10 to 90% of the total weight of the ink.
Preferably 10-7%, more preferably 20-70%
is considered to be within the range that occupies

The ink of the present invention, which is formulated from such components, has excellent recording properties (signal response, stability of droplet formation, ejection stability, long-term continuous recording, ejection after a long recording pause). Stability) Storage stability, fixability to recording materials, color sharpness of recorded images, light resistance, weather resistance, water resistance, alcohol resistance, etc. are all well-balanced and excellent. In order to further improve such characteristics, various conventionally known sardine additives may be further added and contained.

For example, viscosity modifiers such as polyvinyl alcohol, celluloses, and water-soluble resins; various cationic, anionic, or nonionic surfactants; surface tension modifiers such as jetanolamine, triethanolamine, etc.;
Conditioners, fungicides, etc. can be mentioned.

Furthermore, in order to prepare ink used in an inkjet system that charges the ink, resistivity adjusters such as inorganic salts such as lithium chloride, ammonium chloride, and sodium 111ide are added.

Note that when applied to an inkjet system in which ink 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.

The ink of the present invention as described above is useful as a recording ink for various writing instruments, recording instruments, etc., and is particularly useful as an ink for inkjet use.

As a preferable example, the inkjet method may be any method as long as it can effectively separate the ink from the nozzle and apply the ink to the recording material that is the projectile. , Representative methods of these methods include, for example, IEEE Trans Actions on Industry Applications (IEEE Trans Actions on Industry Applications).
ons onIndustry A'pplicat
ions) Volj^-13, No. 1 (1977
(February/March issue), Nikkei Electronics, 4/1978
Jj 19th issue, January 29th 1973 issue and 1974
It is listed in the May 6th issue. The methods described above are suitable for the use of the ink of the present invention. To explain some of them, there is an electrostatic suction method. A method in which a strong electric field is applied between the accelerating electrode and the ink particles is drawn out from the nozzle one after another, and an information signal is given to the deflection electrodes while the drawn ink flies between the deflection electrodes to record the ink particles. There is a method of ejecting ink particles in response to an information signal without deflecting the information signal, and both methods are effective for the ink of the present invention.

The second method is to forcibly eject minute ink particles by applying high pressure to the ink with a small pump and mechanically vibrating the nozzle with a crystal oscillator. At the same time as the injection, it is charged according to the information signal. When the charged ink particles pass between the deflection electrode plates, they are deflected according to the charge: 11. Another method using this method is called the microdot inkjet method, and in this method, the ink pressure,
The excitation conditions are kept within a certain range of appropriate values, and two types of ink droplets, large and small, are generated from the nozzle tip, and only these small and medium-sized droplets are used for recording. The feature of this method is that even a nozzle diameter as large as that of a conventional method can produce a group of minute droplets.

A third method is a piezo element method, in which a piezo element is used as a pressure means for applying pressure to the ink, rather than a mechanical means such as a pump as in other methods. This method applies an electric signal to a piezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from a nozzle.

In addition, there is an inkjet method in which the ink subjected to the action of thermal energy undergoes a rapid volume change, and the acting force due to this state change is used to eject the ink from a nozzle. can also be used effectively.

The ink of the present invention as described above employs a specific combination of blended dyes as its recording agent, and thus has excellent long-term storage stability and is suitable not only as an ink for general recording, but also as an ink for use in inkjet systems in particular. Discharge stability,
It has recording properties such as ejection response, and when applied to the recording material, it exhibits excellent ink fixing properties, and has particularly excellent color clarity, light resistance, water resistance, alcohol resistance, resolution, etc. It provides a recorded image.

Next, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Usage Examples. In the first sentence, parts or percentages are based on small amounts unless otherwise specified.

Example 1 Exemplified compound (1) (sodium 1) 2 parts Exemplified compound (
+3) (Sodium salt) 3 parts diethylene glycol 30 parts ion exchange water
65 parts The above components were thoroughly mixed and dissolved in a container, filtered under pressure through a Teflon filter with a pore diameter of liLm, and then degassed using a vacuum pump to obtain the ink (1) of the present invention.

Comparative Example 1 Exemplified Compound (1) (sodium salt) 5 parts diethylene glycol 30 parts ion exchange water
Ink (II) of Comparative Example was obtained in the same manner as in Example 1 except that 65 parts of the above components were used.

Comparative Example 2 Exemplified Compound (13) (sodium salt) 5 parts Diethylene glycol 30 parts Ion-exchanged water 65 parts Using the above components,
Ink (m) of a comparative example was obtained in the same manner as in Example 1.

Usage Example 1 Using the inks (I) to (m) obtained above, an on-demand recording head (discharge orifice diameter 50 μLm, piezo vibrator drive voltage 80 V, frequency 3 KHz) that discharges ink using a piezo vibrator was created. Recording was performed using a recording device, and the results shown in Table 1 below were obtained.

1≦PiL-in! -・(I)
No change No change Luminous (II) Quite fading Quite fading Clear (m) No change
Almost no change. (Turn to the right corner.) Light resistance was determined visually after 100 hours of irradiation with a xenon fade meter.

Water resistance was determined visually after being immersed in water for 24 hours.

The color tone was determined visually.

Examples 2 to 6 Inks having the compositions shown in Table 2 below were prepared in the same manner as in Example 1 and examined in the same manner as in Example 1, and similarly excellent images were obtained.

In addition, regarding these inks, on-demand type multi-heads (with an ejection orifice diameter of 35
The same study as in Example 1 was conducted using a recording device with a heating resistor resistance of 150 Ω, a driving voltage of 30 V, and a frequency of 2 KHz, and excellent results were obtained in all the study experiments.

Q-2 == Example 2 Exemplified compound (3) (lithium salt) 5 parts Exemplified compound (22) (for lithium) 3 parts ethylene glycol 2 parts water
72 parts Example 3 Exemplified compound (9) (triethanolamine 11) 3 parts Exemplified compound (18) (triethanolamine I! 3)
Part diethylene glycol 30 parts Water
64 parts Example 4 Exemplified compound (7) (lithium fl) 2 parts Exemplified compound (26) (lithium ji!)
3 parts N-methyl-2-pyrrolidone 25 parts water
7
Part Example 5 Exemplified Compound (12) (Ammonium Salt) 4 Parts Exemplified Compound (15) (Ammonium Salt) 3 Parts Ethylene Glycol Monomethyl Ether 30 Parts Water
63 parts Example 6 Exemplified compound (4) (sodium salt) 4 parts Exemplified compound (33) (sodium salt) 5 parts 1.
3-dimethyl-2-imidazolidinone 20 parts water
Part 71 Patent Applicant Canon Co., Ltd. Agent Patent Attorney Ao ``■ Katsuhiro r, ゛; ,',
:'+'-1・, 1L Mi.

Claims (1)

[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, a dye represented by the following general formula (A) as a recording agent and a general A recording liquid characterized by containing a dye represented by formula (B) or (C). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (However, R1 and R2 in the above formula represent arbitrary substituents, R3 is COCH3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas, chemical formulas , there are tables, etc. Show ▼ (
R4 represents a hydrogen atom or a chlorine atom, and M represents one type of base selected from alkali metals, ammonium, and organic amines. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(B) (However, Ar in the above formula represents a phenyl group or naphthyl group substituted with an alkyl group, nitro group, halogen atom or sulfonic acid group, and R1 is an alkyl group. R2 represents a hydrogen atom or a sulfonic acid group, M represents Cr, Co, Ni or Cu, and the sulfonic acid group is 1 selected from alkali metals, ammonium and organic amines. ▲Mathematical formulas, chemical formulas, tables, etc.▼(C) (However, R1 and R2 in the above formula are hydrogen atoms, halogen atoms, alkyl groups, nitro groups, carboxyl groups, etc.) Represents a sulfonic acid group, R3 represents a hydrogen atom or a sulfonic acid group, R4 and R5 represent a hydrogen atom, a sulfonic acid group, -NHC
OCH3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (S = sulfonic acid group), and the sulfonic acid group is an alkali metal , ammonium and organic amines. )