JPS6086181A - recording liquid - Google Patents

Abstract

PURPOSE:A recording liquid, containing C.I. Food Black 2, a yellow dye and a red dye, assuming black elementary color, having high solubility and solution stability for a long term without clogging extrusion orifices, and useful for ink jet recording and writing utensils. CONSTITUTION:A recording liquid consisting of a liquid composition containing (A) C.I. Food Black 2 and (B) one or more of yellow dyes, preferably C.I. Acid Yellow 17:1, 23, 49, 65, 104, 183, 155 or 194 or C.I. Direct Yellow 86, 104, 142, 194, etc. and (C) one or more red dyes, preferably C.I. Acid Red 8, 37, 50, 51, 52, 87, 92, 93, 95, 98, 287, 35, 1, etc. together as a water-soluble dye as a recording agent. Preferably, the mixing weight ratio of the dyes A:(B, C) is 100:(1-30), and that of the dyes B:C is (1:10)-(10:1). The total content of the dyes (A), (B) and (C) is preferably 1-10wt%. EFFECT:Improved water resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a recording liquid suitable for use in an ink-send recording method in which droplets are ejected from an orifice of a recording head or for use in a writing instrument, particularly an ideal black color. The present invention relates to a recording liquid.

Various types of ink-end recording methods are being actively researched because they generate less noise and can perform high-speed recording on plain paper without requiring any special fixing process. The recording liquid used in this type of ink side recording method must have physical properties such as viscosity and surface tension within appropriate ranges, must not clog the fine ejection openings (orifices), and must be clear and clear. It is required to have certain characteristics such as providing a recorded image with good color tone and sufficiently high density, and not causing changes in physical properties or precipitation of solid content during storage.

Furthermore, in addition to these characteristics, recording can be performed without limiting the type of recording material such as paper, fast fixing speed to the recording material, water resistance, solvent resistance (especially alcohol resistance) It is also required to have properties such as excellent light resistance, abrasion resistance, and the ability to provide images with excellent resolution.

The recording liquid used in the inkjet recording method is basically composed of a dye as a recording agent and its solvent, so the 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-mentioned properties is an extremely important technique in this technical field.

In particular, the solubility of the recording liquid in the liquid medium is important, and it is important to have sufficient solubility in water and in wetting agents, which are generally organic solvents, for good anti-clogging properties and This is the basis for maintaining the dissolution stability of the recording agent.

On the other hand, when printing black using the inkjet recording method, it is necessary to use a recording liquid of the black primary color.
Furthermore, when reproducing a full-color recorded image, a recording liquid of four primary colors is used, which is a recording liquid of the three primary colors of magenta, yellow, and cyan plus a recording liquid of the black primary color, and the color tone of the recorded image is changed by subtractive mixing of these colors. It is determined. In this case, in order to obtain a recorded image of the desired hue, it is necessary that the hue of each of these recording liquids exhibits the ideal primary colors of magenta, yellow, or cyan, which are not tinged with other colors. The liquid is also required to be ideal and not tinged with other colors. Therefore, it is an extremely important technique to select a dye as a recording material with due consideration to the color tone exhibited by the black recording liquid.

However, as for the conventionally known black recording liquids, there are almost none that fully satisfy the above-mentioned properties, especially solubility, color tone, and light resistance, and it is difficult to develop a black recording liquid that satisfies these characteristics. It was strongly desired.

The object of the present invention is to improve solubility in liquid medium components.

Another object of the present invention is to provide a recording liquid that has high long-term dissolution stability and is unlikely to cause clogging of the ejection orifice.Another object of the present invention is to provide a recording liquid that exhibits an ideal black primary color and has excellent light resistance. The goal is to provide liquid.

The above objects and more are achieved by the present invention as follows.

That is, the recording liquid of the present invention is composed of a liquid composition containing a water-soluble dye as a recording agent, and the dyes include C,1, Food Black 2 and (a) C,1, Acid Yellow 1.
7:1. C,1, Acid Yellow 23, C,1, Acid Yellow 49. C, 1,7 Shitsuto Yellow 65
°C11, acid yellow 104, C,1, acid yellow 183, 0.1. acid yellow 15
5, C,1, Acid Yellow 194, C,1,
Direct Yellow 86, C,1, Direct Yellow 108, C,1, Direct Yellow 142,
one or more selected from the group consisting of C, 1, Direct Yellow 194, and (b) (:, 1. Acid Red
8, C, 1, Acid Red 37. C, 1, Acid Red 50. C,1, Acid Red 51, C,1, Acid Red 52, C,1, Acid Left 87, C,
1, Acid Red 92, C, 1, Acid Red 93
, C,1, Acid Red 95, c, r, Acid Red 98, C, L, Acid Red 287, C,1, Acid Red 35, G, I.

Acid Red 1 is characterized by the combination of one or more selected from the group consisting of 1.

According to the present invention, the viscosity, surface tension, etc. are within appropriate ranges, the fine orifice is not clogged, a recorded image of sufficiently high density is provided, and physical property values change or solid content precipitation etc. are prevented during storage. It is possible to obtain a recording liquid that can perform recording on various members without limiting the type of recording material, has a high fixing speed, and provides images with excellent water resistance, light resistance, abrasion resistance, and resolution.

In the present invention, the dye used as the main component of the recording agent, C,
1. Food Black 2 is extremely excellent in terms of important properties as a recording agent of a recording liquid applied to the above-mentioned inkjet recording method, such as solubility and light resistance. However, in terms of color tone, it exhibits a slightly bluish black color, so this dye alone is not sufficient as a recording material for the black primary color.

On the other hand, the dyes in group (a) are all yellow dyes, and the dyes in group (b) are all red dyes. The recording liquid is extremely excellent in terms of important properties as a recording agent.

Therefore, in the present invention, C-1, Food Black 2, one or more dyes selected from group (a), and (b)
) By using one or more of the dyes selected from the groups (a) and (b), the dyes of the groups (a) and (b) can harmonize well with each other to achieve the slightly H-ish color tone exhibited by C, 1 and Food Black 2. By matching and canceling each other out, a recording liquid containing a recording agent exhibiting an ideal black primary color and excellent in important properties such as solubility, dissolution stability, and light resistance was obtained.

These recording agents in the recording liquid, namely C,1, Food Black 2, one or more dyes selected from group (a), and (
The total amount of dye selected from group b) is determined depending on the type of liquid medium, the characteristics required of the recording liquid, etc., but in general, it is determined based on the total amount of recording liquid. Against 0.
The content is in the range of 5 to 20% by weight, preferably 0.5 to 15%, more preferably 1 to 10%.

Also, at this time, C, 1, food black 2 and (a)
Mixing ratio with one or more dyes sent from the group, or C
, 1. The mixing ratio of food black 2 and one or more dyes selected from group (b) is such that the color tone or strength of the dye of group (a) or group (b) differs depending on the individual dye. Therefore, the optimum value is determined for each combination of these selections, but the weight mixing ratio of C,1, food black 2 and the dye selected from group (a) is 100:l~100
: Selected from within the range of 30, C,! , Rough-Black 2 and the dye selected from group (b) is selected from a range of 100:1 to 100:30. If the mixing ratio of these is less than 100:1, C,
1. Food black If the slightly bluish color tone exhibited by 2 is not sufficiently improved and the mixing ratio exceeds 100:30, the resulting recording liquid will have a reddish or yellowish black color. Furthermore, in order to more effectively exhibit a well-balanced and ideal black primary color, the weight mixing ratio of the dye selected from group (a) and the dye selected from group (b) should be adjusted. is selected from within the range of 10:1 to 1:1O. If the mixing weight ratio of these dyes is outside the range defined by this mixing ratio, that is, the weight mixing ratio of the dyes selected from group (a) is (
If the weight mixing ratio of the dyes selected from group b) is too high, the effect of the red dye will not be observed, and if it is too low, the effect of the yellow dye will not be observed, which is not preferred.

The recording liquid of the present invention has water as a main liquid medium component, but not only a water wheel but also a mixture of water and various water-soluble organic solvents are preferably used. Examples of water-soluble organic solvents include carbon atoms 1 to 4 such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol.
Amides such as dimethylformamide and dimethylacetamide; Ketones or ketone alcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; N-methyl-2-pyrrolidone and 1,3-dimethyl- Nitrogen-containing heterocyclic ketones such as 2-imidazolidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol: ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2.8-hexanetriol, thio Alkylene glycols in which the alkylene group has 2 to 6 carbon atoms, such as diglycol, hexylene glycol, diethylene glycol: glycerin; ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether and lower alkyl ethers of polyhydric alcohols.

Among these many water-soluble solvents, diethylene glycol, which is a polyhydric alcohol, and triethylene glycol monomethyl (or ethyl) ether, which is a lower alkyl ether of a polyhydric alcohol, are particularly preferred from the viewpoint of preventing clogging.

The content of the water-soluble organic solvent in the recording liquid is generally 5 to 95% by weight, preferably 1% by weight based on the total weight of the recording liquid.
The range is 0 to 80%, more preferably 20 to 50%.

The water content at this time is determined within a wide range depending on the type of solvent component, its composition, and the desired characteristics of the recording liquid, but it is determined based on the total weight of the recording liquid -c -14'k
The range is 10 to 90%, preferably 10 to 70%, more preferably 20 to 70%.

A recording liquid prepared from such components has its own recording properties (signal response, droplet formation stability, ejection stability,
(long-term continuous recording performance, ejection stability after long-term recording cessation), storage stability, fixation to the recording material, or the light resistance, weather resistance, water resistance, etc. of the recorded image. This is an excellent product with a good balance. In order to further improve such properties, various conventionally known additives may be further included. For example, viscosity regulators such as polyvinyl alcohol, celluloses, and water-soluble resins; cationic, anionic, or nonionic surfactants; surface tension regulators such as diethanolamine and triethanolamine; PH regulators using buffers; antifungal agents etc. can be mentioned.

In addition, in order to prepare the recording liquid used in the evening and f-print ink side recording methods that charge the recording liquid, resistivity adjusters such as inorganic salts such as lithium chloride, ammonium chloride, and sodium chloride are added. be done.

Note that when applied to an ink-end method in which recording liquid is ejected by the action of thermal energy, the thermal properties (e.g., specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted. be.

The present invention will be explained in more detail by the following examples.

Example 1 A black primary color recording liquid for inkjet recording was prepared according to the following formulation.

C,1, Food Black 2 3.0 Part by Weight C1, Acid Yellow 17:1 0.2 ttC,1, Acid Red 8 0.2 //Diethylene Gelcol 30.
Ott N-methyl-2-pyrrolidone 15 Ott ion-exchanged water (hereinafter abbreviated as water) Total remaining amount 100 tt The ingredients were thoroughly mixed and dissolved in a container, and filtered through a Teflon filter with a pore size of 0.45μ. After pressure filtration with
A recording liquid was prepared by degassing using a vacuum pump.

Using this recording liquid, an on-demand recording head (discharge orifice diameter 50 μ, piezo vibrator drive voltage 60 μ, frequency 4 KHz) ejects the recording liquid using a piezo vibrator.
), the ejection stability was investigated. As a result, room temperature (21'C), 5℃, 40℃,
Good ejection stability was maintained in both continuous ejection and intermittent ejection for 48 hours in each atmosphere at 60° C. (humidity 30%).

On the other hand, the long-term storage stability of the recording liquid was investigated at 0°C and 30-°C.
, and 60° C. for two years each, but no problems such as precipitation of the recording agent or discoloration occurred.

In addition, the color tone of the printed matter is clear and exhibits an ideal black color with no other color tinges, and the printed matter is fully legible even after a 50-hour irradiation test in a xenon fate meter, and has excellent light resistance. was also good.

Example 2 A black primary color recording liquid based on the following formulation was prepared in the same manner as in Example 1.

C, 1, Hood Black 2 3.0 parts by weight C, 1,7 cydoie 0-65 0.1 //C-1,7 JID L/
37 0,2 tt diethylene glycol 15.
Q'tt1.3-dimethyl-2-imidazolysi/7
15. Q tt polyethylene glycol (300) 1
5. Ott Water Total Remaining Amount I Q Q tt On the other hand, a yellow primary color recording liquid, a cyan primary color recording source, and a magenta primary color recording liquid were prepared in the same manner as above. However, in the black primary color recording liquid composition, instead of C,1, food black 2, C,1, acid yellow 65 and C,1, acid red 37, in the yellow primary color recording liquid, C.
, 1, Acid Yellow 23, C, 1, Direct Blue 86 for the cyan primary color recording liquid, and C, 1, Acid Red 35 for the magenta primary color recording liquid at 2% by weight each.

An on-demand type multi-head (discharge orifice diameter 35-1, heating resistor resistance 150Ω, drive voltage 30V, frequency 2KHz)
Supplied to a recording device with

A color printing test was conducted. Regarding the discharge stability, stable discharge was maintained in all cases under the same conditions as in Example 1. The images obtained were also full-color images with ideal color tones, and each recording liquid was evaluated to be excellent as a recording liquid for subtractive color mixing. Furthermore, Example 1
Even after the same lightfastness test as above, the prints were still legible.

Examples 3-14 C,1, Food Black 2, C,1, Acid Yellow 17:1 and G,1. A black primary color recording liquid was prepared in the same manner as in Example 1 except that the dyes shown in Tables 1 and 2 and their blending amounts were used instead of Asindred 8. These recording liquids were evaluated for ejection stability, long-term storage stability, color tone of printed matter, and light resistance in the same manner as in Example 1, and all were good, indicating that they are excellent as recording liquids for the black primary color. There was found.

Table 1 Table 2 Procedural amendment (voluntary) 1317, 1982 Commissioner of the Patent Office 1.Display of the incident 1981 Patent Application No. IE140?8 No. 2, Title of Invention recording liquid 3. Person who makes corrections Relationship to the case: Patent applicant Canon Co., Ltd. 4. Deputy manager Address: Akasaka 1-9-20-5, Minato-ku, Tokyo, subject to amendment Full statement 8. Contents of amendment The entire specification is amended as shown in the attached sheet.

Description 1, Title of the Invention Recording Liquid 2, Claims Comprising a liquid composition containing a water-soluble dye as a recording agent, where the dye is C,! , Suffu-Black 2, and one or more of Ll of 1'' and 1.1'' are used in combination.

3. Detailed Description of the Invention The present invention provides a recording liquid suitable for use in an ink-end recording method in which droplets are ejected from an orifice of a recording head or for use in a writing instrument, particularly an ideal black color. The present invention relates to a recording liquid.

Various types of inkjet recording methods are being actively researched because they generate less noise and can perform high-speed recording on plain paper without requiring special fixing treatment. The recording liquid used in such inkjet recording methods must have physical properties such as viscosity and surface tension within appropriate ranges, must not clog the fine ejection ports (orifices), and must have a clear color tone. Moreover, it is required to have various properties such as providing a recorded image with a sufficiently high density and not causing changes in physical properties or precipitation of solid content during storage. In addition to these characteristics, recording can be performed without limiting the type of recording material such as paper, fast fixing speed to recording materials, water resistance, solvent resistance (especially alcohol resistance). ), light fastness, abrasion resistance, and the ability to provide images with excellent resolution.

The recording liquid used in the inkjet recording method is basically composed of a dye as a recording agent and its solvent, so the characteristics of the recording liquid are influenced by the fixation properties of the dye. However, it is large. Therefore, selecting a dye so that the recording liquid has the above-mentioned properties is an extremely important technique in this technical field.

In particular, the solubility of the recording liquid in the liquid medium is important, and it is important to have sufficient solubility in water and in wetting agents, which are generally organic solvents, for good anti-clogging properties and This is the basis for maintaining the dissolution stability of the recording agent.

On the other hand, when printing black using the inkjet recording method, it is necessary to use a recording liquid with the primary colors of blank and black, and when reproducing a full-color recorded image, recording liquids with the three primary colors of magenta, yellow, and cyan are required. Four primary color recording liquids are used, and the color tone of the recorded image is determined by subtractive mixing of these colors. In this case, in order to obtain a recorded image with the desired hue, it is necessary that the hues of these recording liquids exhibit the ideal primary colors of macenta, yellow, or cyan, which are not tinged with other colors. The liquid is also required to be ideal and not tinged with other colors. Therefore, it is an extremely important technique to select a dye as a recording material with due consideration to the color tone exhibited by the black recording liquid.

However, as for the conventionally known black recording liquids, there are almost none that fully satisfy the above-mentioned properties, especially solubility, color tone, and light resistance, and it is difficult to develop a black recording liquid that satisfies these characteristics. It was strongly desired.

An object of the present invention is to provide a recording liquid that has high solubility in liquid medium components or long-term dissolution stability and is less likely to clog an ejection orifice.

Another object of the present invention is to provide a recording liquid that exhibits an ideal black primary color and has excellent light resistance.

The above objects and other objects are achieved by the present invention as follows.

That is, the recording liquid of the present invention is composed of a liquid composition containing a water-soluble dye as a recording agent, and the dyes include C,1, Food Black 2, one or more yellow dyes, and one red dye.
It is characterized by being used in combination with more than one species.

According to the present invention, the viscosity, surface tension, etc. are within appropriate ranges, and the viscosity and surface tension are sufficiently high.
It provides a high-quality recorded image, does not cause changes in physical properties or precipitation of solids during storage, can be recorded on various materials without limiting the type of recording material, has a high fixing speed, - water-based, A recording liquid that provides images with excellent light fastness, abrasion resistance, and resolution can be obtained.

In the present invention, the dye used as the main component of the recording agent, C,
L Foot Black 2 is extremely excellent in terms of important properties as a recording agent for a recording liquid used in the above-mentioned inkjet recording method, such as solubility and light resistance. However, in terms of color tone, it exhibits a slightly bluish black color, so this dye alone is not sufficient as a recording material for the black primary color.

On the other hand, in the present invention, other recording material components include C, 1,
The yellow dye and red dye used in combination with Food Black 2 are as follows: The yellow dye has a maximum absorption in its absorption spectrum in the range of 350 nm to 4 Hmn, and the red dye has a maximum absorption in its absorption spectrum in the range of 600 nm.
Chest within the range of m-700an.

A dye that is excellent in terms of important properties as a recording agent for a recording liquid used in the inkjet recording method, such as solubility, dissolution stability, and light resistance, and includes one or more of these yellow dyes and a red dye. One or more of the following are used in combination.

Among such yellow dyes and red dyes, preferred yellow dyes include, for example, C,1, Acid Yellow 1.
7=1, C, 1, acid yellow 23°C,! , Acid Yellow 48, C,1, Acid Yellow 65,
C, 1, acid yellow 104, 0.1. Acid Yellow 183, C,1, Acid Yellow 155
, 0.1. Acid Yellow 194, (,14'
Direct Yellow 86, C01, Direct Yellow 1
0B, C, 1, Direct Yellow 142, G
, 1. Examples of preferable red dyes include (:, 1. Acid Red 8, C, 1, Acid Red 37, C, 1).
, acid red 50, c, r, acid red 51,
C,1, Acid 7 Tread 52, C,1, Acid Red 87, C,1, Acid Red 92, C,1, Acid Red 93, C,1, Acid Red 85, C,1, Acid 7 Tread 88, C, 1, acid red 287,
C, 1, Ash, ・, Do []-, Do 35. C, I-Ashi1. I can name Dread 1st place.

The total amount of dye in the recording liquid, including C, 1, food blank 2, one or more yellow dyes, and one or more red dyes, depends on the type of liquid medium and the characteristics required of the recording liquid. Generally, it is 0.5-20% by weight, preferably 0.5% by weight based on the total amount of recording liquid.
~! 5%, more preferably in the range of 1 to 10%.

In addition, the mixing ratio of one or more yellow dyes or one or more red dyes to C, 1, foot black 2 at this time is such that the color tone or intensity of the yellow dye or red dye differs depending on the individual dye. The optimal value is determined for each combination of these selections, but the weight mixing ratio of C,1, Food Black 2 and one or more yellow dyes or one or more red dyes is 100: l to 100: Selected from within the range of 30.

If the mixing ratio of these is less than 100:1, the slightly bluish tone exhibited by C01 and Food Black 2 will not be sufficiently improved, and if the mixing ratio exceeds 100:30, the resulting recording liquid will have the opposite effect. It is not suitable because it exhibits a reddish or yellowish black color. Furthermore, in order to more effectively exhibit a well-balanced and ideal black primary color, the weight mixing ratio of one or more yellow dyes and one or more red dyes should be within the range of 10:1 to 1:1O. selected from. If there is a mixing weight ratio of these dyes outside the range defined by this mixing ratio, i.e. the weight mixing ratio of one or more yellow dyes is too higher than the weight mixing ratio of one or more red dyes. If it is too low, the effect of the red dye will not be observed, and if it is too low, the effect of the yellow dye will not be observed, which is not preferable.

The recording liquid of the present invention contains water as a main liquid medium component, and not only water alone but also preferably a mixture of water and various water-soluble organic solvents is used. Examples of water-soluble organic solvents include carbon atoms of 1 to 4, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ee-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol.
Amides such as dimethylformamide and dimethylacetamide; Ketones or ketone alcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; N-methyl-2-pyrrolidone and 1,3-dimethyl- Nitrogen-containing heterocyclic ketones such as 2-imidanlidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1.2.6-hexandriol, thiosif Alkylene glycols in which the alkylene group has 2 to 6 carbon atoms, such as licor, hexylene glycol, and diethylene glycol; glycerin; ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, etc. Examples include lower alkyl ethers of polyhydric alcohols.

Among these many water-soluble solvents, diethylene glycol, which is a polyhydric alcohol, and triethylene glycol monomethyl (or ethyl) ether, which is a lower alkyl ether of a polyhydric alcohol, are particularly preferred from the viewpoint of preventing clogging.

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

The water content at this time is determined within a wide range depending on the type of solvent component, its composition, or the desired characteristics of the recording liquid, but is generally 10 to 80% of the total weight of the recording liquid.
%, preferably 10-70%, more preferably 20-7
The range is 0%.

A recording liquid prepared from such components has its own recording properties (signal response, droplet formation stability, ejection stability,
The balance between long-term continuous recording performance, ejection stability after long-term recording interruptions), storage stability, fixation to the recording material, and the light resistance, weather resistance, and water resistance of the recorded image is important. It is an excellent product. In order to further improve such properties, various conventionally known additives may be further included. For example, viscosity modifiers such as polyvinyl alcohol, celluloses, water-soluble resins; cations, anions, etc. Other examples include various nonionic surfactants, surface tension adjusters such as diethanolamine and triethanolamine; pH adjusters using buffer solutions; antifungal agents, and the like.

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

Note that when applied to an inksheet 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.

The recording liquid of the present invention prepared in this way is obtained by using C,1, foot blank 2 as recording agent components together with one or more yellow dyes and one or more red dyes as defined above. , C, L, and Food Plaque 2. One or more types of yellow dyes and one or more types of red dyes harmonize with each other and cancel out the slightly bluish tone exhibited by Food Plaque 2, thereby creating the ideal black primary color. exhibiting and soluble,
This is a recording liquid containing a recording agent that is excellent in important properties such as dissolution stability and light resistance.

The present invention will be explained in more detail by the following examples.

Example 1 A black primary color recording liquid for inkjet recording was prepared according to the following formulation.

C, 1, Foot Black 2 3.0 Weight Parts C, 1, Acid Yellow 172 1 0.2 //C, 1, Acid Red 8 0.2 //Diethylene Gelcol
30, OttN-methyl-2-pyrrolidone 15
, Ott Ion-exchanged water (hereinafter abbreviated as water) Total remaining amount 100 tt The above ingredients are thoroughly mixed and dissolved in a container, and the pore size is 0.
．． After pressure filtration with a 45-mm Teflon filter, the solution was degassed using a vacuum pump to obtain a recording liquid.

Using this recording liquid, an on-demand recording head (discharge orifice diameter 50u+, piezo retractor drive voltage 60V, frequency 4KH) that discharges the recording liquid with a piezo vibrator
The ejection stability was investigated using a recording device having the following. As a result, room temperature (2 pC), 5°C14
48 in each atmosphere at 0°C and 160°C (humidity 30%)
Good ejection stability was maintained in both continuous ejection and intermittent ejection.

On the other hand, we investigated the long-term storage stability of the recording liquid at 0°C130
The test was carried out at 160°C for two years each, but no problems such as precipitation of the recording agent or discoloration occurred.

In addition, the color tone of the printed matter is clear and exhibits an ideal black color without any other color tones, and the printed matter is fully legible even after a 50-hour irradiation test in a xenon fate meter, and has good light resistance. It was good.

Example 2 A black primary color recording liquid based on the following formulation was prepared in the same manner as in Example 1.

c, r, foot black 2 3.0 parts by weight C, 1, acid yellow 85 0,1 ttG, 1. Acid Red 37 0.2 //Diethylene glycol 15
．． 0 //1.3-dimethyl-2-imidazolidinone 1
．． 5. Ott polyethylene glycol (300) +5
．． Ott water Total remaining amount: 100 tt On the other hand, a yellow primary color recording liquid, a cyan primary color recording liquid, and a magenta primary color recording liquid were prepared in the same manner as above. However, in the black primary color recording liquid composition, instead of C,1, foot black 2, C,1, acid yellow 65 and C,1, acid red 37, in the yellow primary color recording liquid, C.
, 1, Acid Yellow 23, C, 1, Direct Blue 86 for the cyan primary color recording liquid, and C, R, Acid Yellow 35 for the magenta primary color recording liquid at 2% by weight each.

An on-demand type multi-head (discharge orifice diameter of 35 μs, heating resistor resistance value of 150 Ω, drive voltage of 30 V, frequency of 2 KHz) performs recording by applying thermal energy to the recording liquid in the recording head to generate droplets.
), and a color printing test was conducted. Regarding the discharge stability, under the same conditions as in Example 1,
Stable discharge was maintained in all cases. In addition, the obtained image is also a full-color image with ideal color tone,
It was evaluated that each recording liquid was excellent as a recording liquid for subtractive color mixing. Furthermore, even after the same light fastness test as in Example 1, the printed matter was still legible.

Examples 3 to 14 In place of C,1, foot black 2, C,1, acinto yellow 17:1 and C,1, acin) red 8, the dyes shown in Tables 1 and 2 and their A blank primary color recording liquid was prepared in the same manner as in Example 1 except that the amounts used were different. These recording liquids were evaluated for ejection stability, long-term storage stability, color tone of printed matter, and light resistance in the same manner as in Example 1, and all were good, indicating that they are excellent as recording liquids for the black primary color. There was found.

Table 1 Table 2

Claims (1)

[Claims] (1) It consists of a liquid composition containing a water-soluble dye as a recording agent, and the dyes include C,1, Footblack 2, and (
a) C,1, Acid Yellow 17:1, C,1, Acid Yellow 23, C,1, Acid Yellow 49
, C,1, Acid Yellow 65, C,1, Acid Yellow 104, C,I. Acid Yellow 183, C,1, Acid Yellow 155, C,1, Acid Yellow 194,
C,1, Direct Yellow 86, C,1, Direct Yellow 106, C,1, Direct Yellow 142
, 0.1. one or more selected from the group consisting of Direct Yellow 194, and (b) C, 1, acin.
8, C, 1, Asynth
Do 37, C,1, Asin Trend 50, C,1, Asin Trend 51, C,1, Asin Trend 52, C,1,
Asin Trend 87, C, 1, Asin Dread 92, C
, 1, Ashinto Red 93, C, 1, Ashindo Red 95, C, 1, Ashinto Red 98, C, 1, Ashinto Red 287, C, 1, Ashinto Red 35, C,
1. Asindred A recording liquid characterized in that it is used in combination with one or more selected from the group consisting of 1.