JP3486966B2 - Recording liquid - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording liquid. Specifically, it relates to a recording liquid suitable for inkjet recording.

[0002]

2. Description of the Related Art A so-called ink jet recording method has been put into practical use in which droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acid dye are ejected from a minute ejection orifice to perform recording. Regarding this recording liquid, P of electrophotographic paper is used.
Fast fixing to general-purpose office paper such as PC (plain paper copier) paper and fan-hold paper (continuous paper for computers), and good print quality, that is, bleeding In addition to being required to have a clear outline and a good stability during storage as a recording liquid, the solvent that can be used is significantly limited.

On the other hand, dyes for recording liquids have sufficient solubility in the above-mentioned limited solvents and are stable even when stored as recording liquids for a long period of time.
Further, although it is required that the printed image has a high density and is excellent in water resistance and light resistance, it has been difficult to satisfy many of these requirements at the same time. Therefore, various methods (for example, JP-A-61-101574, JP-A-61-101576, JP-A-61-195176) are used.
No. 61-62562, JP-A 61-2477.
71, JP-A-62-156168, JP-A-63-6.
3765, JP-A-63-295685, JP-A-1-
123866, JP-A-2-16171, JP-A-3-
122171, JP-A-3-203970, JP-A-4
No. 15327, JP-A No. 4-279671, etc.) have been proposed, but they have not yet fully satisfied the market demands.

[0004]

DISCLOSURE OF THE INVENTION The present invention has good print quality even when recorded on plain paper for ink jet recording, writing instruments, etc., and has a high density of recorded images, light resistance and It is an object of the present invention to provide a magenta recording liquid which is excellent in water resistance and color tone of a recorded image and has good stability when stored for a long period of time.

[0005]

The present inventors have accomplished the present invention by confirming that the above objects can be achieved when a specific dye is used as a recording liquid component. That is, the gist of the present invention is to provide an aqueous medium and at least one of the dyes whose free acid form is represented by the general formula (1).
It exists in the recording liquid containing the seed.

The present invention will be described in detail below. The dye used in the present invention has a free acid form represented by the general formula (1) in claim 1. Specifically, in the general formula (1), R ₁ , R ₂ , R ₃ , R ₈ , R ₉ and R
Each of the substituents represented by ₁₀ independently has 1 carbon atom.
To 9 substituted or unsubstituted alkyl groups (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, trifluoromethyl group, dimethylaminomethyl group, etc.), alkoxy group having 1 to 9 carbon atoms (eg, methoxy group, isopropoxy group, n-butoxy group, etc.), halogen atom (eg, fluorine atom, chlorine atom) , Bromine atom, etc.), hydrogen atom, hydroxyl group, substituted or unsubstituted carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, phenylcarbamoyl group, etc.),
A substituted or unsubstituted sulfamoyl group (eg, sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group , P-carboxyphenylsulfamoyl group, etc.), a substituted or unsubstituted amino group (eg, N-methylamino group, carbamoylamino group, N, N-diethylamino group, acetylamino group, etc.), nitro group, sulfonic acid Examples thereof include ester groups (eg, phenoxysulfonyl group etc.), sulfonyl groups (eg, hydroxyethylsulfonyl group, benzylsulfonyl group, etc.) and carboxylic ester groups (eg, methoxycarbonyl group, etc.).

M represents 0, 1 or 2. R ₄ , R ₅ ,
The substituents represented by R ₆ and R ₇ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (eg, ethyl group, n-butyl group, n-octyl group, Ethylhexyl group, hydroxyethyl group, carboxypropyl group, carboxycyclohexylmethyl group, 1-carboxy-2-mercaptoethyl group, 1-carboxy-2-carbamoyl-ethyl group, 1-isopropyl-1-carboxymethyl group, 1,2 -An alkyl group having a carboxyl group such as a dicarboxypropyl group), a substituted or unsubstituted alkenyl group having 1 to 18 carbon atoms (e.g., 2-methyl-1-propenyl group, vinyl group, allyl group, etc.), substituted Or an unsubstituted aryl group (eg, 3,4-dicarboxyphenyl group, 4-butylphenyl group, 4-carboxyphenyl group) Phenyl group), a substituted or unsubstituted aralkyl group (eg, benzyl group, 1-carboxy-2-phenyl-ethyl group, 1-carboxy-2
-Hydroxyphenylethyl group, 4-carboxybenzyl group, etc.), substituted or unsubstituted alicyclic group (eg, cyclohexyl group, 4-carboxycyclohexyl group, etc.), substituted or unsubstituted heterocyclic group (eg, pyridyl) Group, thiadiazolyl group, benzothiazolyl group, etc.) and the like. And these R ₄ , R
_At least one of ₅ , R _{6 and} R ₇ is 1 to 4 COO
It must be an alkyl group, an alkenyl group, an aryl group, an alicyclic group, an aralkyl group or a heterocyclic group which is substituted with an H group. More preferably, at least one group represented by R ₄ , R ₅ , R ₆ or R ₇ is a group represented by a to e below.

[0008] a carbon number the alkyl carboxylic acid b aryl carboxylic acid c carbon atoms of 8-18 aralkyl carboxylic acid d alicyclic mosquito carboxylic acid e heterocyclic carboxylic acid group of 3 to 18, Y Represents a divalent linking group, and preferably has the following structure.

A substituted or unsubstituted aliphatic group having 2 to 18 carbon atoms, more preferably 8 to 18 carbon atoms (for example, alkylene group, cycloalkylene group,

[0010]

[Chemical 4]

(A is a number of 1 to 6) and the like). Substituted or unsubstituted phenylene group and naphthalene group Carbonyl group

[0012]

[Chemical 5]

[0013] having a structure substituted or unsubstituted diphenyl body (X is _{-O -, - CH 2 -,} - C 2 H 4 -, - S -, - S
_{O 2 -, - C 6 H} 12 -, - NHCONH -, - NH -, -
CH = CH-,-(single bond), -CONH-, -CO
-,

[0014]

[Chemical 6]

Is a bonding chain selected from S, S represents 0 to 4 optional substituents, and T represents 0 to 4 optional substituents. ) A substituted or unsubstituted phenylene group and naphthalene group through an aliphatic carbon atom (for example,

[0016]

[Chemical 7]

A group represented by (1 is an integer of 1 to 6,
Each may be the same or different, U represents 0 to 4 optional substituents, and V represents 0 to 4 optional substituents. ) The dye used in the present invention may be used as it is in the free acid form represented by the general formula (1), or may be used as it is when it is obtained in the salt form at the time of production, or may be in the desired salt form. May be converted to A part of the acid group may be a salt type, and a salt type dye and a free acid type dye may be mixed. Examples of such a salt type include salts of alkali metals such as Na, Li and K, salts of ammonium which may be substituted with an alkyl group or hydroxyalkyl group, and salts of organic amine. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

In the structure of the dye used in the present invention, when a plurality of acid groups are contained in one molecule, the plurality of acid groups may be salt type or acid type and different from each other. Good. Specific examples of these dyes include, for example, Nos. Examples thereof include dyes having the structures shown in 1 to 31.

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

[0027]

[Chemical 16]

[0028]

[Chemical 17]

[0029]

[Chemical 18]

[0030]

[Chemical 19]

[0031]

[Chemical 20]

In the present invention, a dye whose free acid form is represented by the following general formula (2) is particularly preferably used.
This dye is particularly preferable among the dyes used in the present application in terms of color tone, water resistance, and practicality.

[0033]

[Chemical 21]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , m, Y
Is the same definition as the above-mentioned general formula (I)) In the above general formula (2), it is particularly preferable that R ⁴ represents a COOH group of 1
An alkyl group, an alkenyl group, which is substituted with one to four,
Examples thereof include those which are aryl groups, aralkyl groups or cyclohexyl groups.

The dye represented by the general formula (1) can be produced according to a method known per se. For example, the dye represented by No. 1 can be produced by the steps (A) to (B). (A) A conventional method from 4-aminotoluene-3-sulfonic acid and 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid (H acid) [for example, "New dye chemistry" by Yutaka Hosoda (Showa 48). December 21, published by Gihodo) 396
~ Page 409], a monoazo compound is produced through a diazotization coupling step.

(B) The obtained monoazo compound is added to a cyanuric chloride suspension while maintaining pH 4-6 and a temperature of 0 to 5 ° C., and the reaction is carried out for several hours. Next, at room temperature, a weak alkaline solution of ethylenediamine is added to carry out a condensation reaction for several hours. Next, a β-alanine aqueous solution is added at 50 to 60 ° C., and a condensation reaction is performed for several hours to complete the reaction.

After cooling, salting out with 20% saline gives the desired dye. The content of the dye of the general formula (1) in the recording liquid is preferably 0.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total amount of the recording liquid.
As the solvent used in the present invention, water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol (#
200), polyethylene glycol (# 400), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethyl sulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether. It preferably contains ether, 2-pyrrolidone, sulfolane, ethyl alcohol, isopropanol and the like. These water-soluble organic solvents are usually used in an amount of 1 to 50% by weight based on the total amount of the recording liquid.
Used in the range of. On the other hand, water is used in the range of 45 to 95% by weight with respect to the total amount of the recording liquid.

The recording liquid of the present invention contained 0.
1-10 wt% urea, preferably 0.5-5 wt% urea,
By adding a compound selected from thiourea, biuret, and semicarbazide, or by adding 0.001 to 5.0% by weight of a surfactant, the quick-drying property after printing and the printing quality can be further improved. it can.

[0039]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Example 1 10 parts by weight of diethylene glycol, 3 parts by weight of isopropyl alcohol, No. Water was added to 3 parts by weight of dye 1 and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight. The composition was thoroughly mixed and dissolved, pressure-filtered with a Teflon filter having a pore size of 1 μm, and then deaerated with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid.

Using the obtained recording liquid, an ink jet printer (trade name: HG-3000, manufactured by Epson Corporation) was used to perform ink jet recording on electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) to obtain a high density magenta color printed matter. Got
The results of various evaluations by the methods (a), (b) and (c) are shown below. (A) Light resistance of recorded image: The recording paper was irradiated with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 100 hours, but the discoloration and fading after irradiation was small.

(B) Water resistance of recorded image: Water resistance test (c) Storage stability of recording liquid: The recording liquid was sealed in a Teflon container and examined for changes after storing at 5 ° C. and 60 ° C. for 1 month. As a result, no precipitation of insoluble matter was observed.

Water resistance test (1) Test method After the recorded image was immersed in tap water for 5 minutes, the bleeding of the image was visually examined. The OD value of the solid printed portion before and after the immersion was measured with a Macbeth densitometer (TR927).

(2) Test Results The above-mentioned results showed little bleeding in the image. Further, the change in the density of the solid printed portion before and after the immersion was shown by the OD residual rate by the following formula, and was 86.1%.

[0044]

[Equation 1] Example 2 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol, No. Water was added to 2.5 parts by weight of the dye of No. 2 and the pH was adjusted to 9 with ammonia water so that the total amount was 100 parts by weight. The composition was treated by the method described in Example 1 to prepare a recording liquid. . Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a high density magenta color recorded product was obtained. Further, for this recorded matter, (a) to
Various evaluations according to (c) were performed. As a result, good results were obtained as in the case of Example 1.

The OD residual rate was 91.3%. [Example 3] 10 parts by weight of diethylene glycol, 5 parts by weight of N-methylpyrrolidone, 3 parts by weight of isopropyl alcohol, Water was added to 3 parts by weight of the dye of 3, and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight,
This composition was treated by the method described in Example 1 to prepare a recording liquid. Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a high density magenta color recorded product was obtained.
Further, various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. As a result, good results were obtained as in the case of Example 1.

The OD residual rate was 90.6%. [Examples 4 to 39] The No. 1 used in Example 1 was used.
Instead of the dye of No. 1, 4 to No. A recording liquid was prepared and printing was carried out by the method of Example 1 except that the 31 dyes were used, and Example 1 was applied to the recorded matter.
Various evaluations according to (a) to (c) were performed. As a result, as in Example 1, good results were obtained.

No. When the dye of No. 4 was used, the OD residual rate was 89.7%, and No. 4 was used. When the dye of 5 was used, it was 93.3%.

[0048]

INDUSTRIAL APPLICABILITY The recording liquid of the present invention is used for ink jet recording and writing instruments, and when recorded on plain paper, a magenta color recorded matter can be obtained, and its printing density, light resistance and water resistance are excellent. In addition to excellent properties, it also has good storage stability as a recording liquid.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-226575 (JP, A) JP-A-4-279671 (JP, A) Special Tables 8-8505889 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C09D 11/00-11/20 B41J 2/01-2/01 B41M 5/00 C09B 35/06 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A recording liquid containing an aqueous medium and at least one dye selected from the dyes represented by the following general formula (1) in the form of a free acid. [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , R ₈ , R ₉ and R ₁₀ each independently have 1 to 9 carbon atoms which may have a substituent selected from a fluorine atom and a dimethylamino group. An alkyl group having 1 to 9 carbon atoms; a halogen atom; a hydrogen atom; a hydroxyl group; and a substituent selected from a phenyl group and a methyl group which may be substituted with a hydroxyethylsulfonyl group. Carbamoyl group which may be substituted; phenyl group which may be substituted by carboxyl group , methyl
Sulfamoyl group optionally having substituent (s) selected from group and ethyl group ; amino group optionally having substituent (s) selected from methyl group, ethyl group , carbamoyl group and acetyl group; nitro group; sulfonic acid Ester group; hydr
It has a substituent selected from a roxyethyl group and a benzyl group.
Optionally a sulfonyl group ; or a carboxylic acid ester group, m and n each represent a number of 0, 1 or 2, and R ₄ , R ₅ , R ₆ and R ₇ each independently represent hydrogen. atom,
A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted ari Represents a cyclic group or a substituted or unsubstituted heterocyclic group, and represents a group in which at least one of R ₄ , R ₅ , R ₆ and R ₇ is substituted with 1 to 4 carboxyl groups; Represents a divalent linking group. ) 2. The recording liquid according to claim 1, wherein the divalent bonding group represented by Y in the general formula (1) has a structure of any one of the following. A substituted or unsubstituted aliphatic group having 2 to 18 carbon atoms, a substituted or unsubstituted phenylene group and a naphthalene group carbonyl group A substituted or unsubstituted diphenyl compound having a structure (X is —O—, —CH ₂ —, —C ₂ H ₄ —, —S—, —S
_{O 2 -, - C 6 H} 12 -, - NHCONH -, - NH -, -
CH = CH-,-(single bond), -CONH-, -CO
-, S represents a 0 to 4 arbitrary substituent group, and T represents a 0 to 4 arbitrary substituent group. )
Substituted or unsubstituted phenylene group and naphthalene group through an aliphatic carbon atom 3. R ₄ , R ₅ , R ₆ and R _{7 in the} general formula (1).
3. The recording liquid according to claim 1, wherein at least one of the following is any of a to e below. a alkyl carboxylic acid group having 3 to 18 carbon atoms b aryl carboxylic acid group c aralkyl carboxylic acid group having 8 to 18 carbon atoms d alicyclic carboxylic acid group e heterocyclic carboxylic acid group 4. A dye for recording liquid, wherein the free acid form is represented by the following general formula (1). [Chemical 4] (In the formula, R ₁ , R ₂ , R ₃ , R ₈ , R ₉ and R ₁₀ each independently have 1 to 9 carbon atoms which may have a substituent selected from a fluorine atom and a dimethylamino group. An alkyl group having 1 to 9 carbon atoms; a halogen atom; a hydrogen atom; a hydroxyl group, a phenyl group which may be substituted with a hydroxyethylsulfonyl group, and a substituent selected from a methyl group. Carbamoyl group which may be substituted; phenyl group which may be substituted by carboxyl group , methyl
Sulfamoyl group optionally having substituent (s) selected from group and ethyl group ; amino group optionally having substituent (s) selected from methyl group, ethyl group , carbamoyl group and acetyl group; nitro group; sulfonic acid Ester group; hydr
It has a substituent selected from a roxyethyl group and a benzyl group.
Optionally a sulfonyl group ; or a carboxylic acid ester group, m and n each represent a number of 0, 1 or 2, and R ₄ , R ₅ , R ₆ and R ₇ each independently represent hydrogen. atom,
A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted ari Represents a cyclic group or a substituted or unsubstituted heterocyclic group, and represents a group in which at least one of R ₄ , R ₅ , R ₆ and R ₇ is substituted with 1 to 4 carboxyl groups; Represents a divalent linking group. ) 5. The recording liquid according to claim 4, wherein the divalent linking group represented by Y in the general formula (1) has a structure of any of the following. A substituted or unsubstituted aliphatic group having 2 to 18 carbon atoms, a substituted or unsubstituted phenylene group and a naphthalene group carbonyl group A substituted or unsubstituted diphenyl compound having a structure (X is -O
_{-, - CH 2 -, -} C 2 H 4 -, - S -, - SO 2 -, - C
_{6 H 12 -, - NHCONH -} , - NH -, - CH = CH
-,-(Single bond), -CONH-, -CO-, and S represents a 0 to 4 arbitrary substituent group, and T represents a 0 to 4 arbitrary substituent group. )
Substituted or unsubstituted phenylene group and naphthalene group through an aliphatic carbon atom 6. R ₄ , R ₅ , R ₆ and R _{7 in the} general formula (1).
6. The recording liquid according to claim 4, wherein at least one of the following is any of the following a to e. a alkyl carboxylic acid group having 3 to 18 carbon atoms b aryl carboxylic acid group c aralkyl carboxylic acid group having 8 to 18 carbon atoms d alicyclic carboxylic acid group e heterocyclic carboxylic acid group