JPH093379A - Ink composition and ink jet recording method using the same - Google Patents

Abstract

(57) Abstract: To provide an ink composition capable of high-quality recording on plain paper and excellent in water resistance of a recorded image. An ink composition comprising a dye represented by the following general formula (I). Embedded image [In the above formula, M represents an optionally substituted ammonium, R ¹ represents COOM, and R ² represents -P (= O) n-.
(OM) ₂ (n represents 0 or 1) and R ³ is C
Represents OOM or SO ₃ M, R ⁴ and R ⁵ each independently represent H, an alkyl group, or an alkoxyl group, and R ⁶ represents H, an optionally substituted phenyl group,
An alkylcarbonyl group, or an alkyl group which may be substituted with a hydroxyl group or an alkoxyl group,
m represents 0 or 1. ]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition and an inkjet recording method using the same.

[0002] As the ink used in the background art ink jet recording method,
Generally, various dyes are dissolved in water, an organic solvent, or a mixed solution thereof. However, in various characteristics, the ink used for ink jet recording is required to have more strict performance, as compared with the ink for writing instruments such as a fountain pen and a ballpoint pen.

The properties required of such ink jet recording inks are, for example, appropriate physical properties such as viscosity and surface tension, high optical density, giving clear color tone and image, water resistance, Examples include giving an image having excellent fastness such as light resistance, excellent storage stability, less likely to cause nozzle clogging, and excellent odor and safety.

Many of these properties are satisfied by using an aqueous ink prepared by dissolving a water-soluble dye in water or a mixed liquid of water and a water-soluble organic solvent. Therefore, the ink used in the inkjet recording method has been continuously improved on the basis of a water-based ink.

For example, in order to quickly fix the ink on the paper, attempts have been made to improve the permeability of the ink. In this regard, JP-A-4-183761, US Pat. No. 5,183,502, US Pat. No. 5,156.
No. 67 discloses the addition of diethylene glycol monobutyl ether as an ink component, the addition of both glycol ethers and nonionic acetylene glycol-based surfactants, and the like. But,
Since these penetrating inks penetrate into the paper, in some cases, sufficient color developability and image density cannot be obtained, and a clear image may not be obtained. On the other hand, if the dye concentration is increased to solve this problem, the solid content increases, so that precipitation easily occurs near the nozzle, which may cause clogging. Furthermore, if you increase the amount of wetting agent to prevent clogging, the viscosity of the ink will increase,
In particular, the ink jet method may be disadvantageous.

Further, since performances such as color tone, water resistance, and light resistance are largely influenced by the characteristics of the dye, various dyes have been studied so far. Furthermore, recently, among various ink characteristics, there has been an increasing demand for water resistance of printed matter. For example, JP-A-3-79681
JP-A-3-91577 and JP-A-6-73.
No. 320 and JP-A-6-172668 disclose that an ink composition having good water resistance can be obtained by using a specific dye.

However, it can be said that even these ink compositions have room for improvement in their various properties.

[0008]

SUMMARY OF THE INVENTION The present invention is an ink composition satisfying various properties required for an ink jet ink, particularly an ink composition capable of recording with high image quality on plain paper and having excellent water resistance of a recorded image. Its purpose is to provide.

The present inventors have now found that the above object can be achieved by using a specific dye.

That is, the present invention is an ink composition containing a dye represented by the following general formula (I).

[0011]

Embedded image [In the above formula, M represents H, alkali metal, optionally substituted ammonium, morpholinium, or piperidinium, and R ¹ is H, NH ₂ , or COOM (wherein
M is as defined above, R ² is COOM, or -P (= O) n- (OM) ₂ (where M is as defined above and n is 0 or 1). R ³ represents H, COOM, or SO ₃ M (where M has the same meaning as described above), R ⁴ and R ⁵ are each independently H, alkyl having 1 to 6 carbon atoms. A group, or 1 to 1 carbon atoms
6 represents an alkoxyl group, R ⁶ represents H, an optionally substituted phenyl group, an alkylcarbonyl group, or a hydroxyl group or an alkyl group optionally substituted by an alkoxyl group, and m represents 0 or 1. ]

[0012]

DETAILED DESCRIPTION OF THE INVENTION In the present specification, an alkyl group as a group or a part of a group may be linear or branched.

In the general formula (I), M is
Represents H, alkali metal, optionally substituted ammonium, morpholinium, or piperidinium. The alkali metal represented by M is preferably lithium, potassium or sodium. Further, the optionally substituted ammonium substituent represented by M is preferably an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), which may be optionally substituted with a hydroxyl group.

Examples of ammonium-forming amines in which M may be substituted include, for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, Examples thereof include isobutylamine, sec-butylamine, tert-butylamine and dibutylamine. The dye used in the present invention is an ammonium salt,
The substituted ammonium salt, morpholinium salt, or piperidinium salt need not be a single salt, and may be a mixture with an alkali metal salt or the like. In that case,
It is preferable that the ratio of M which is an alkali metal salt to the number of M of the dye represented by the general formula (I) is 50% or less.

The dye represented by the general formula (I) can itself form a recording having excellent water resistance. Furthermore, the salt with the amines can further improve the water resistance. The reason is presumed as follows. That is, the amines are generally volatile, and the amines volatilize from the paper after recording. As a result, M in the general formula (I) becomes H, forming a carboxyl group or a phosphate group. Since the dissociation constants of the carboxyl group and the phosphoric acid group are generally small, even if water adheres to the recorded paper, the dye represented by the general formula (I) does not reappear on the adhered water. It becomes difficult to dissolve. This seems to further improve the water resistance of recording.

Further, in the general formula (I), one or more hydrogen atoms of the phenyl group represented by R ⁶ may be substituted, and a preferable example of the substituent is a carboxyl group, and this carboxyl group is In some cases, it may be an ammonium salt. The alkyl group portion of the alkylcarbonyl group represented by R ⁶ preferably has 1 to 1 carbon atoms.
It is a C6 alkyl group, More preferably, it is a C1-C4 alkyl group. One or more hydrogen atoms of this alkyl group may be substituted, and examples of the substituent include a hydroxyl group or an alkoxyl group (preferably an alkoxyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms). And an alkoxyl group).

Preferred specific examples of the compound represented by the above general formula (I) used in the present invention include those listed in the following table.

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

Embedded image

[0024]

Embedded image The compound represented by the general formula (I) can be prepared by a known method (for example,
It can be produced through the diazotization and coupling steps described in "New Dye Chemistry" (Gihodo) by Yutaka Hosoda.

A specific manufacturing method is as shown in the following scheme.

[0026]

Embedded image The diazo compound represented by the formula (II) and the compound represented by the formula (III) are reacted in water at a temperature of about 0 to 5 ° C. for 40 minutes to 2.5 hours to give a compound represented by the formula ( I
The monoazo compound of V) can be obtained.

Further, the compound of the formula (IV) is diazotized according to a conventional method to obtain a compound of the formula (V), and this compound and the compound of the formula (VI) are almost the same as the conditions for obtaining the monoazo compound. By reacting under the condition of
The disazo compound of II) can be obtained.

Further, the compound of formula (VII) is further diazotized according to a conventional method to obtain a compound of formula (VIII). The compound and the compound of formula (IX) are heated in water at about 5 to 10 ° C. By reacting at the temperature of 1 to 2 hours, the trisazo compound of the formula (I) can be obtained.

The content of the dye represented by the general formula (I) in the whole ink is determined depending on the kind of the solvent component, the characteristics required for the ink, etc. Its content is preferably 1 to 1
The range is 0% by weight, more preferably 2 to 8% by weight.
When the added amount of the dye of the general formula (I) is within the above range,
Good image density and image quality, and good printing characteristics without clogging can be obtained.

According to a preferred embodiment of the present invention, the ink composition preferably further comprises a nonionic acetylene glycol surfactant and glycol ethers. By adding these, a dot having a high roundness can be obtained without lowering the color developability. Further, sufficient drying property is satisfied and high quality printing can be obtained.

The nonionic acetylene glycol-based surfactant preferably used in the present invention is, for example, Surfynol 465, Surfynol TG, Surfynol 104 (above Air Products and Ch).
manufactured by E.Malicals Co., Ltd., and Surfynol TG is particularly preferable. The amount added is preferably 0.05 to 3% by weight, more preferably 0.8 to 2% by weight. Further, it is also preferable to add nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene fatty acid esters as the surfactant.

The glycol ethers preferably used in the present invention include, for example, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and diethylene glycol monobutyl ether. Propylene glycol monobutyl ether may be mentioned. The addition amount is preferably 3 to 30% by weight, more preferably 5 to 15% by weight.

Furthermore, according to a preferred embodiment of the present invention,
The ink composition preferably comprises a polyhydric alcohol. By adding the polyhydric alcohol, preferably, the moisturizing effect and the effect of preventing clogging can be further improved.

Examples of the polyhydric alcohols preferably used in the present invention include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol and propylene glycol,
Examples thereof include 1,3-propanediol, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerin, which may be used alone or in combination of two or more. The amount added is 1 to 30% by weight, preferably 3 to 20
% By weight.

Furthermore, according to a preferred embodiment of the present invention,
The ink composition preferably contains a nitrogen-containing cyclic compound. By adding the nitrogen-containing cyclic compound, the water resistance of printing, the image quality, and the stability of the ink composition can be improved. In particular, these nitrogen-containing cyclic compounds improve the dye dissolution stability and printing stability,
It also functions as a color forming auxiliary agent and a water resistance auxiliary agent, and is useful for the ink composition of the present invention.

Examples of the nitrogen-containing cyclic compound preferably used in the present invention include imidazolidinones (for example, 1,
3-dimethyl-2-imidazolidinone), pyrrolidones (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone), and caprolactams (eg, ε-caprolactam) are listed, and they may be used alone or in combination of two or more. Can be used. The amount added is 1 to 30% by weight, preferably 3 to 20% by weight.

According to a preferred embodiment of the present invention, the ink composition has a monovalent lower alcohol such as ethanol, 1-propanol or 2-propanol for promoting the drying property of the ink after image formation. It is preferable to include anionic surfactants such as salts and fatty acid salts and alkyl sulfate salts. The content of lower alcohols is 2 to 10% by weight, preferably 2 to 6% with respect to the total amount of the ink.
The content of the surfactant is preferably in the range of 0.01 to 2% by weight based on the total amount of the ink.

Further, in the ink composition of the present invention, amines such as thiodiglycol, triethanolamine and diethanolamine, fluorine-based or silicon-based surfactants, water-soluble polymers, water-soluble resins, and Antifoam,
A pH adjuster, an antifungal agent and the like may be added.

The ink composition of the present invention can be manufactured by a conventional method. For example, the ink can be prepared by a method in which the respective components are sufficiently mixed and dissolved, filtered under pressure with a membrane filter having a pore size of 0.8 μm, and then deaerated using a vacuum pump to prepare an ink.

The ink composition of the present invention can be used most effectively in a conventionally known ink jet recording apparatus, but is not limited to this, and can be used for general writing instruments,
It can be used even when used in a device such as a recorder or a pen plotter.

As the ink jet recording method, any conventionally known method can be used. Particularly, in the method of ejecting droplets by utilizing the vibration of the piezoelectric element or the method of utilizing thermal energy, excellent image recording is performed. It is possible.

[0042]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the examples do not limit the present invention. Dye synthesis example: Compound No. 9 m-aminobenzenephosphonic acid (87.0 g) was added to water (5
(00 ml) with stirring. To this, 35% hydrochloric acid (101.3 g) was added and cooled to 0 ° C. A 36% aqueous sodium nitrite solution (105.4 g) was gradually added dropwise to this solution so that the liquid mixture did not exceed 5 ° C., and the mixture was stirred for 50 minutes to diazotize m-aminobenzenephosphonic acid. Then, thiourea was added to the obtained aqueous solution to remove excess nitrous acid, to obtain a diazo component-containing liquid. On the other hand, 3
-Aminobenzoic acid (68.6 g) in methanol 800 m
1 and dispersed by heating at 55 ° C. to obtain a coupling component-containing solution. 0 solution containing coupling component
The solution was cooled to 0 ° C, and the above diazo component-containing solution was added dropwise thereto so that the liquid temperature did not exceed 5 ° C. After stirring at 3 to 5 ° C for 18 hours, the generated precipitate was collected by filtration and washed with water to obtain a monoazo compound; m- (2-carboxy-4-amino-phenylazo) benzenephosphonic acid (about 125.3 g).

The obtained monoazo compound (64.2 g) was dispersed in water (700 ml), and 45% aqueous sodium hydroxide solution (35.6 g) was added and dissolved. 36 in this liquid
% Sodium nitrite aqueous solution (42.2 g) was added, and the temperature was 5 ° C.
And cooled. Further, add 20% hydrochloric acid (127.6 g) at 10 ° C.
The monoazo compound was diazotized by gradually adding so as not to exceed 10 ° C. and then stirring at 10 ° C. or lower for 80 minutes. Then, sulfamic acid was added to the obtained aqueous solution to remove excess nitrous acid to obtain a diazo component-containing solution. On the other hand, 2.5-dimethoxyaniline (30.6 g)
Was dissolved in 600 ml of methanol to obtain a coupling component-containing solution. The coupling component-containing solution is cooled to 0 ° C. or lower, and the above diazo component-containing solution is gradually added dropwise thereto while paying attention so that the liquid temperature does not exceed 5 ° C.
The mixture was stirred at 8 ° C for 18 hours. The precipitate is collected by filtration, washed with water,
Disazo compound; m- (2-carboxy-4- (2.5
-Dimethoxy-4-aminophenylazo) phenylazo) benzenephosphonic acid (about 82.6 g) was obtained.

The obtained disazo compound (72.8 g) was dispersed in water (700 ml), and a 45% aqueous sodium hydroxide solution was added and dissolved. A 36% sodium nitrite aqueous solution (32.6 g) was added to this liquid, and the mixture was cooled to 5 ° C.
20% hydrochloric acid (82.0 g) was gradually added dropwise thereto so that the liquid temperature did not exceed 10 ° C., and the disazo intermediate was diazotized by stirring at 10 ° C. or lower for 90 minutes. afterwards,
Sulfamic acid was added to the obtained aqueous solution to remove excess nitrous acid to obtain a diazo component-containing solution. Meanwhile, gamma-acid (1-hydroxy-7-amino-3-naphthylsulfonic acid, (35.9 g) was added to water (600 ml), and
Dissolve with a 5% aqueous sodium hydroxide solution (30.0 g),
A coupler solution was prepared by cooling to 3 ° C. Then, the previously prepared diazo component-containing solution was added dropwise so that the reaction temperature did not exceed 8 ° C. and the reaction pH was kept at 8.5 or more by adding a 20% aqueous sodium hydroxide solution.
The mixture was stirred at 8 ° C for 4 hours. Crystals are precipitated by salting and acid precipitation, and the compound No. is obtained by filtration, washing with water and drying.
9 compound (67.0 g) was obtained. This compound was dispersed in ion-exchanged water, purified and concentrated using a reverse osmosis membrane, and further, using ammonia water, the compound No. The ammonium salt of 9 was obtained. Compound No. The compounds 1 to 8 and 10 to 23 were also synthesized in the same manner as above.

Experimental Examples Ink compositions of Examples and Comparative Examples were produced at the compounding ratios shown in Tables 1 and 2. The numerical values in Tables 1 and 2 represent weight% of each component with respect to the total amount of ink, and the balance is water.

[0046]

[Table 1]

[0047]

[Table 2] Of the ink compositions, No. 1 to 23 are the dyes according to the invention listed in the table above. On the other hand, No. 24 is a dye outside the scope of the present invention, which is a dye represented by the following formula.

[0048]

Embedded image As described above, the following evaluations were performed using the obtained ink composition. In the evaluation test, inkjet printer M
J-500 (manufactured by Seiko Epson Corporation) was used.

<Test 1: Water resistance> (1) EPP paper (Epson Sales Co., Ltd.) (acidic paper), (2) Xerox P (Fuji Xerox Co., Ltd.)
Alphabet was printed on (neutral paper). Water droplets were dropped on the printed sample, and the state of the sample after natural drying was visually observed and evaluated as follows. ⊚: No change from the initial state. ○: The dye is slightly dissolved, but the characters are clearly readable. Δ: Characters can be read although there is bleeding. ×: Characters are bleeding and unreadable.

<Test 2: Image quality> (1) EPP paper, (2) Xerox P, (3) Xe
rox 4024 (Xerox Co.), (4) Ri
Alphabet printing and / or graphic printing was performed on copy 6200 (Ricoh Co., Ltd.). The printed matter was visually evaluated as follows. ⊚: No bleeding and high density. ◯: Some bleeding is seen, but the image is not affected and the density is high. Or there is no bleeding, but the density is slightly low. B: Little bleeding, but low density. X: Conspicuous bleeding or low density.

<Test 3: Recovery from clogging> After the ink was filled in the recording head of the printer, the recording head was left at 40 ° C. for one month while being displaced from the cap position. After that, the number of cleanings until normal printing was possible was evaluated as follows. A: 0 to 2 times. ◯: 3 to 5 times. Δ: 5 to 10 times. X: It did not recover after going to 10 times.

<Test 4: Printing stability> Continuous printing was carried out using a self-check pattern mounted on the ink jet printer MJ-500, and the time for stable printing was evaluated as follows. A: 24 hours or more. ◯: 10 hours or more and less than 24 hours. X: less than 10 hours.

<Test 5: Storage stability> MJ of printer
-Fill the ink cartridge for 500 with ink, and-3
It was left at 0 ° C. and 70 ° C. for 2 weeks. The physical properties of the ink before and after the change, color tone change, and the presence or absence of foreign matter / precipitates were observed and evaluated as follows. ◯: No change in physical properties or color tone, no generation of foreign matter or precipitate. X: There was a change in physical properties / color tone, or foreign matter / precipitates were observed. The evaluation results are shown in Tables 3 to 5.

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location C09D 11/02 PTH B41J 3/04 101Y (72) Inventor Hiroko Hayashi Sanwa 3-chome, Suwa City, Nagano Prefecture 3-5 Seiko Epson Co., Ltd. (72) Inventor Junko Takatsuna 3-5 Yamato, Suwa City, Nagano Prefecture 3-5 Seiko Epson Co., Ltd. (72) Inventor Masahiro Ya Take 3-chome Yamato, Suwa City, Nagano Prefecture No. 3-5 Seiko Epson Co., Ltd. (72) Inventor, Takeshi Ono 4-51-17, Lawn-cho, Takatsuki-shi, Osaka (72) Inventor, Yoshihiro Saruwatari, B15-402, B15 Building, Otokoyama, Yawata, Kyoto (72) Inventor Tatsuya Yagyu 4-3 Ouricho, Neyagawa City, Osaka Prefecture

Claims (10)

[Claims] 1. An ink composition comprising a dye represented by the following general formula (I). Embedded image [Wherein, M represents H, an alkali metal, an optionally substituted ammonium, morpholinium, or piperidinium, and R ¹ represents H, NH ₂ , or COOM (where M has the same meaning as described above). , R ² is COOM, or -P (= O) n- (OM)
₂ (wherein M is as defined above and n is 0 or 1), R ³ is H, COOM or SO ₃ M (where M is as defined above) , R ⁴ and R ⁵ are each independently H and have 1 to 6 carbon atoms.
Represents an alkyl group or an alkoxyl group having 1 to 6 carbon atoms, R ⁶ represents H, an optionally substituted phenyl group, an alkylcarbonyl group, or an alkyl group optionally substituted by a hydroxyl group or an alkoxyl group, m represents 0 or 1. ] 2. A nonionic acetylene glycol-based surfactant, further comprising glycol ethers.
The ink composition according to claim 1. 3. The ink composition according to claim 1 or 2, further comprising a polyhydric alcohol. 4. The ink composition according to claim 1, further comprising a nitrogen-containing cyclic compound. 5. Dyes 1 to 10 represented by the general formula (I)
The ink composition according to claim 4, wherein the ink composition comprises 1 wt%, 1 to 30 wt% of a polyhydric alcohol, and 1 to 30 wt% of a nitrogen-containing cyclic compound. 6. A dye containing 2 to 8% by weight of the dye represented by the general formula (I), 3 to 20% by weight of a polyhydric alcohol, and 3 to 20% by weight of a nitrogen-containing cyclic compound. The ink composition according to item 5. 7. The dye according to any one of claims 1 to 6, which comprises a dye represented by the general formula (I), in which M represents at least one of optionally substituted ammonium, morpholinium, and piperidinium. The ink composition described. 8. The ratio of M as an alkali metal salt to the number of M in the entire dye represented by the general formula (I) is 50.
The ink composition according to claim 7, which is not more than%. 9. An ink jet recording method comprising a step of ejecting the ink composition according to any one of claims 1 to 8 as droplets from fine pores to perform recording on a recording medium. 10. A recorded matter recorded by the method according to claim 9.