JP2003105235A - Recording liquid and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording liquid and a recording method which are good in scratch resistance, water resistance, discharge stability and storage stability for an ink-jet recording. SOLUTION: The liquid for ink-jet recording is used, which contains water, a water-soluble organic solvent, a dye and/or pigment, a non-resinous compound having two or more carboxylic acid groups and sulfonic acid groups and a compound having two or more oxazoline groups, or a wax particulate having a melting point of 50 deg.C or more or colloidal silica or particulate derived from a natural product which may be colored, or salt-forming substance formed from a water-soluble resin having a basic group and a dye having an acid group or from a water-soluble resin having an acid group and a dye having a basic group, and if necessary, the heating after printing or forming an image produces a printing or image excellent in durability, especially in scratch resistance and water resistance, while maintaining the dispersion stability, storage stability and discharge stability of the liquid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a recording liquid. Specifically, it relates to an aqueous recording liquid suitable for ink jet.

[0002]

2. Description of the Related Art Inkjet recording methods have come into widespread use, and are often compared with photographs or printed matter by conventional methods, but this is a problem because the durability of images by the inkjet method is poor. Has become. Water-soluble dyes or pigments are used as colorants for recording liquids used in inkjet.
Water-soluble dyes have poor water resistance and insufficient light resistance and weather resistance. For this reason, water-soluble dyes having various structures have been proposed, but they have not yet fully satisfied the market demand. Further, many studies have been conducted on additives or image forming methods for improving durability. However, additives that satisfy other required performances such as stability of recording liquid, ejection stability, curl of recording material, or the like can be satisfied. The image forming method has not been found yet. On the other hand, it has been pointed out that the pigment is excellent in durability, but there is concern about dispersion stability or ejection stability, and the printed matter or the marker becomes dirty when the printed matter is rubbed with a marker or the like. In order to address such a problem (hereinafter referred to as abrasion resistance), JP-A-5-271,598 and JP-A-6-299,108
No. 7-118,548, 2000-30
No. 9,091, etc. have been proposed, but there are problems in dispersion stability and ejection stability of the pigment.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a recording liquid for ink jet recording, which is used for forming an image having excellent water resistance, weather resistance, light resistance of a recorded image, and particularly excellent abrasion resistance. It is what

[0004]

As a result of repeated studies to solve the above problems, the present inventor has found that water, water-soluble organic solvents, dyes and / or pigments, two or more carboxylic acid groups or sulfonic acid groups. Group-containing non-resinous compound and two or more oxazoline group-containing non-resinous compound or wax particles having a melting point of 50 ° C. or higher, optionally colored colloidal silica or even colored Fine salt derived from a good natural product or a salt-forming compound formed from a water-soluble resin having a basic group and a dye having an acidic group, or a salt-forming compound formed from a water-soluble resin having an acidic group and a dye having a basic group. A recording liquid containing a salt is excellent in durability, especially water resistance, light resistance, and abrasion resistance while maintaining dispersion stability and ejection stability, and clear and high density even on plain paper. It found that color. The reason why the recording liquid of the present invention is excellent in durability, especially water resistance, light resistance, and abrasion resistance while maintaining dispersion stability and ejection stability, and is clear on plain paper, and develops a high-concentration color is not clear. Since the additive to be used is a non-resinous compound or a dispersion, the viscosity increase of the ink is small even if water evaporates at the nozzle tip of the inkjet printer, and dispersion and ejection stability can be maintained. The non-resinous compound crosslinks to form a film on the surface of the dispersion or on the recording material, and colloidal silica or wax fine particles serve as a filler between the pigment fine particles, so that the abrasion resistance is excellent. It is considered to be a thing. When printing or image formation is carried out using these recording liquids, even if it is air-dried as it is for about one day, it is possible to obtain the robustness and abrasion resistance which are practically no problem.
Further, improved performance can be obtained by heating for 10 to 60 seconds.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. As the pigment used in the present invention, commercially available pigments as well as carbon black are used. As the structure, any structure such as azo type, anthraquinone type, quinophthalone type, phthalocyanine type, quinacridone type and dioxazine type can be used. Specifically, Colo
r Index (abbreviated as CI) Pigment Yell
ow-74, -128, -180CI Pigment
Red-122, -168, -179, -209 C
I Pigment Blue-15 and the like.
Further, a pigment whose surface is oxidized or sulfonated may be used, but a volatile amine derivative such as ammonium is preferable as the counter ion of the acidic group. The dye used in the present invention is Color In
What is described as an acid dye, a direct dye or an edible dye in dex can be used. Specifically, CI Acid Yellow-23, 142
CI Acid Red-35, 37, 52, 289
CI Acid Blue-9 CI Acid B
rack-24,94 CI Direct Yell
ow-86,142 CIDirect Red-8
0, 81, 89, 225 CI Direct Blu
e-86,199 CI Direct Black-
19.22.154,168 CI Food Bla
ck-2 and the like. These water-soluble dyes have a sulfonic acid group or a carboxylic acid group, and usually the counter ion is an alkali metal such as sodium, but for use in the present invention, the counter ion is ammonium such as ammonium. Exchange with a volatile amine derivative is preferred.

The amount of dye and / or pigment used is 0.2 to 8% by weight based on the total weight of the recording liquid.
If it is less than 0.2%, the coloring power is insufficient. If it is more than 8%, the ejection becomes unstable.

The non-resinous compound having two or more sulfonic acid groups or carboxylic acid groups used in the present invention reacts with the oxazoline group on the recording material to be solidified to be water resistant and scratch resistant. Functions to improve sex,
When the colorant is a pigment, it also functions as a dispersant. Of course, when the pigment has a self-dispersion function by particle surface treatment such as oxidation or sulfonation, the dispersion function is unnecessary. The compound may have a substituent such as a halogen atom, an optionally substituted amino group, a hydroxy group, an alkyl group or an alkoxy group in addition to the sulfonic acid group and the carboxylic acid group. Specifically, in the form of the free acid,
Saturated or unsaturated aliphatic polycarboxylic acids such as malonic acid, fumaric acid, maleic acid, malic acid, acetylenedicarboxylic acid, itaconic acid, butanetetracarboxylic acid, adipic acid, suberic acid, decanedicarboxylic acid, dodecanedicarboxylic acid Examples include isophthalic acid, terephthalic acid, sulfoisophthalic acid, trimellitic acid, pyromellitic acid, ethylene glycol bistrimellitate, diphenylsulfone tetracarboxylic acid, tetralin tetracarboxylic acid, 2,6-naphthalenedicarboxylic acid, pamoic acid, Benzene disulphonic acid, sulphobenzoic acid, diaminostilbene disulphonic acid, aminoisophthalic acid,
Aminoterephthalic acid, nonylaminoisophthalic acid, decanoylaminoisophthalic acid, nonyloxybenzenedisulphonic acid, decanoyloxynaphthalenedisulfonic acid, chloroisophthalic acid, nitroisophthalic acid, naphthalenedisulfonic acid, diaminoanthraquinonedisulphonic acid, diamino Examples thereof include aromatic polycarboxylic acids such as anthraquinone dicarboxylic acid and sulfonic acids, and a volatile amine derivative such as ammonium is preferable as a counter ion thereof.

The amount of the non-resinous compound having two or more sulfonic acid groups or carboxylic acid groups used is 0.3 to 3 weight ratio with respect to the dye and / or pigment. If it is 0.3 or less, water resistance and abrasion resistance are not sufficient, and if it is 3 or more, ejection becomes unstable.

The non-resinous compound having two or more oxazoline groups used in the present invention is specifically bisoxazoline, 1,3-benzobisoxazoline,
Examples include 1,4-benzobisoxazoline.

The amount of the non-resinous compound having two or more oxazoline groups used is 0.8 to 1.2 equivalents with respect to the compound having carboxylic acid or sulfonic acid. If it is less than 0.8, the water resistance and abrasion resistance are insufficient, and if it exceeds 1.2, it is meaningless.

As the colloidal silica used in the present invention, those commercially available from Nissan Chemical Co., Ltd. under the trade name of Snowtex can be used. Specific examples include Snowtex N, 20L, XL, YL, ZL and the like. The particle size is 4-150 nm, preferably 10-
100 nm can be mentioned. When it is less than 4, abrasion resistance is poor, and when it is more than 150, dispersion stability is poor.

The amount of colloidal silica used is 0.1 to 10% by weight in the recording liquid. If it is less than 0.1, the abrasion resistance is poor, and if it is more than 10, the dispersion stability is poor.

As a method of coloring colloidal silica, C
Mordant Dye at color Index
It is possible to color by using a dye belonging to the standard method according to a conventional method. Specifically, Mordat Yellow-10,
12 Modern Red-3, 11, 19 Mo
rdant Blue-10, 13, 14, 29, 79
Examples are Mortant Black-3, 11, 13, 17 and the like.

Examples of the wax fine particles used in the present invention include fatty acid amide, polyglycerin fatty acid ester, sucrose fatty acid ester or sorbitan fatty acid ester, and those having a melting point of 50 ° C. or more and an HLB of 5 to 15 are preferably used. it can. Specifically, fatty acid amides such as caproic acid amide, lauric acid amide, stearic acid amide or polyglycerin fatty acid ester such as diglycerin monooleic acid ester, tetraglycerin monostearic acid ester, hexaglycerin monolauric acid ester or sucrose. Examples thereof include sucrose fatty acid ester such as stearic acid ester and sucrose lauric acid ester, or sorbitan fatty acid ester such as sorbitan monostearate. As for its form, it can be used in a self-emulsified state, or can be used in a finely dispersed state with a nonionic or anionic dispersant. As a dispersing method, a wet mill such as a bead mill or a ball mill can be used.

The amount of the fine wax particles used is 0.1 to 10% by weight in the recording liquid. If it is less than 0.1, the water resistance and abrasion resistance are poor, and if it is more than 10, the dispersion stability is poor.

As a method for coloring the wax fine particles, Co
It is possible to use a dye belonging to Solvent Dye in the Color Index according to a conventional method. Specifically, Solvent Yellow-2,
3,7,14,33,94 Solvent Red-
19, 23, 24, 26, 27, 41, 43, 44, 4
5,49,72 Solvent Blue-35,3
7,39,59 Solvent Black-3,5
And so on.

The fine particles derived from natural products used in the present invention include fine particles of cellulose, silk and chitosan. As a form of use, fine particles having an average particle diameter of 1 micron or less are preferable, and it is preferable to use fine particles with a nonionic or anionic dispersant.
As a dispersing method, a wet mill such as a bead mill or a ball mill can be used. If the original particles before crushing are cellulose, for example, KC manufactured by Nippon Paper Industries Co., Ltd.
Examples include Flock W-400G and W-300G. For silk, for chitosan, Kimitsu chitosan from Kimitsu Chemical Co., Ltd. or chitosan from Yaizu Suisan Chemical Co., Ltd. can be mentioned.

The amount of the fine particles derived from natural products used is 0.1 to 10% by weight in the recording liquid. 0.1
If it is less, the water resistance and abrasion resistance are poor, and if it is more than 10, the dispersion stability is poor.

Regarding the coloring of the fine particles derived from natural products, the Color Index can be used in the same manner as the dyes used in the present invention.
Dyeing treatment can be carried out according to a conventional method using the acid dyes, direct dyes or dyes described as food dyes in the above.

Regarding the salt-forming body formed from the water-soluble resin having a basic group and the dye having an acidic group used in the present invention, the water-soluble resin having a basic group is 1 to
Any resin having a tertiary amino group or a quaternary ammonium group can be used. Specifically, polyallylamine, polyvinylamine, polyacrylic acid dimethylaminopropyl ester, polyacryltrimethylammoniumpropylamide, styrene-dimethylaminoethylmaleimide copolymer, poly (hydroxypropyltrimethylammonium), chitosan, carboxymethylchitosan, etc. can give. As the dye having an acidic group, the dyes described as an acidic dye, a direct dye or an edible dye in ColorIndex can be used as in the dye used in the present invention.

Regarding the salt-forming body formed from the water-soluble resin having an acidic group and the dye having a basic group used in the present invention, the water-soluble resin having an acidic group is a sulfonic acid group or a carboxylic acid. Any resin having a group can be used. Specific examples thereof include polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid, poly (styrene-maleic acid), naphthalene sulfonic acid formalin condensate, and melamine sulfonic acid formalin condensate. As the dye having a basic group, Col is
or Index dyes described as basic dyes, for example CI Basic Yellow-
1, 2 Basic Red-1, 2, 5, 9, 29
Basic Blue-6,7,11,12 Basi
In addition to c Black-8, CI Acid Red
-52,289 CI Acid Blue-9 and the like.

Regarding the method for preparing fine particles of the salt-forming body, the slurry obtained by stirring and mixing the above-mentioned ionic polymer and ionic dye is wet-milled using a medium such as a sand grinder or a ball mill, or the slurry is obtained. Known methods such as crushing by hitting the colliding plate with high pressure are mentioned. Further, in the present invention, when a pigment that requires separate fine particle treatment is used as a colorant in the present invention, a mixture of the pigment and the salt-forming slurry is prepared by the method as described above.
It may be dispersed by wet pulverization. Alternatively, in the presence of a pigment,
It is also possible to form a salt-forming slurry and wet-mill this mixture.

The amount of the salt-forming fine particles used is 0.1 to 10% by weight in the recording liquid. If it is less than 0.1, the water resistance and abrasion resistance are poor, and if it is more than 10, the dispersion stability is poor.

As the aqueous medium used in the recording liquid of the present invention, water and a water-soluble organic solvent are used. Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, N-methylpyrrolidone and diethylene glycol mono. Examples include butyl ether and isopropanol.

These water-soluble organic solvents are usually used in the recording liquid in an amount of 1 to 50% by weight. On the other hand, water is 4
Used from 5 to 95%.

The recording liquid of the present invention contains 0.5 to 5% by weight.
Urea and 0.001 to 0.5% by weight of a surfactant and the like can further improve the quick-drying property after printing and the printing quality.

After printing or forming an image using the recording liquid of the present invention, it is possible to heat from the front or back of the printing surface or the image forming surface using a heat roll or the like. The heat roll can also be used as a roll for feeding paper.

[0028]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The parts mean the meanings of parts by weight.

[Example 1] Diethylene glycol 10
Parts, 3 parts isopropanol, carbon black (MA1
00; manufactured by Mitsubishi Chemical Corporation) 5 parts, ammonium pamoate 5
And 2 parts of bisoxazoline were added, and the pH was adjusted to 10 with an aqueous solution of ammonium hydroxide to adjust the total weight to 100 parts. This composition was wet-ground for 48 hours with a sand grinder using glass beads having a diameter of 1 mm to obtain a dispersion liquid having an average particle diameter of 0.2 μm.

Using the obtained recording liquid, an inkjet printer (trade name: JetWind500C, product of Fuji Xerox Co., Ltd.) was used to perform inkjet recording on electrophotographic paper to obtain a black print. The results of evaluation by the methods (a), (b), (c) and (d) after the printed matter was left for one day are shown.

(A) Scratch resistance of recorded image: Rubbed with a commercially available stationery marker, but neither the paper nor the marker was stained.

(B) Water resistance of recorded image: The recorded image was immersed in tap water for 30 minutes, but the recorded image did not bleed.

(C) Discharge stability: printer for 30 minutes,
When the ink was ejected without any problem, it was operated continuously and after resting for 1 hour, it was operated again.

(D) Storage stability of recording liquid: The recording liquid was sealed in a glass bottle and stored at room temperature for 3 months. As a result of visual observation, no coarse aggregate was observed.

Example 2 5 parts of glycerin, 5 parts of ethylene glycol, 5 parts of N-methylpyrrolidone, CI Pi
gment Blue-15 3 parts, ammonium 1,4-diaminoanthraquinone-2,3-dicarboxylate 2
Water was added to 100 parts to bring the total weight to 100 parts, and wet grinding was carried out in the same manner as in Example 1, and then 2 parts of benzbisoxazoline was added. The average particle size of the pigment was 0.3 μm. As a result of printing using this recording liquid in the same manner as in Example 1, a cyan printed matter was obtained. After leaving this printed matter for 1 day,
The evaluation according to (a), (b), (c), and (d) of Example 1 was performed. As a result, good results were obtained in the same manner as in Example 1.

[Example 3] 5 parts of diethylene glycol,
5 parts of polyethylene glycol (# 400), 1 part of diethylene glycol monobutyl ether, 3 parts of carbon black (manufactured by Orient Chemical Co.) whose particle surface is oxidized with sodium hypochlorite, 3 parts of ammonium 2,6-naphthalenedicarboxylate, benzo Water was added to 2 parts of bisoxazoline and the pH was adjusted to 10 with aqueous ammonia to adjust the total amount to 100 parts to prepare a recording liquid. Using this recording liquid, printing was performed in the same manner as in Example 1 to obtain a black printed matter.
After leaving the printed matter for 1 day, the evaluation according to (a) to (d) of Example 1 was performed. As a result, good results were obtained in the same manner as in Example 1.

[Example 4] 4 parts of glycerin, 4 parts of triethylene glycol, 7 parts of N-methylpyrrolidone, 3 parts of the oxidized carbon black used in Example 3 (manufactured by Orient Chemical Co.), 2 parts of ammonium isophthalate ,
Bisoxazoline 1 part, AP1SA20 (wax emulsion, melting point 98-102 degrees C, Nippon Kasei Co., Ltd.)
Water was added to 3 parts (manufactured by K.K.) to make the total amount 100 parts to prepare a recording liquid. As a result of printing using this recording liquid in the same manner as in Example 1, a black printed material was obtained. Immediately print 70
After heating for 30 seconds, (a) and (b) of Example 1
The evaluation according to (c) and (d) was performed. As a result, Example 1
Similar results were obtained in the same manner as in.

[Example 5] A recording liquid was prepared by the method of Example 4 except that Snowtex XL (colloidal silica, manufactured by Nissan Kagaku Co., Ltd.) was used in place of the wax emulsion used in Example 4. Then, printing was performed and the printed matter was evaluated. As a result, similar results to those of Example 1 were obtained.

[Example 6] (Preparation of colored cellulose fine particles) KC Flock 40
0G (cellulose powder, manufactured by Nippon Paper Industries Co., Ltd.) 3 parts, CI
1 part of Direct Black-154, 1 part of triscarboxymethylamine ammonium and 30 parts of water were wet pulverized for 48 hours with a sand grinder using glass beads having a diameter of 1 mm to form fine particles and colored.
The average particle size was 1 micron. (Preparation, printing and evaluation of recording liquid) The recording liquid was prepared and printed by the method of Example 4 except that the colored cellulose fine particles were used in place of the wax emulsion used in Example 4, and the printed matter was printed. An evaluation was made. As a result, similar results to those of Example 1 were obtained.

Example 7 (Preparation of Fine Salt-Forming Particles) 1.5 parts of poly (hydroxypropyldimethylammonium chloride) was dissolved in 30 parts of water, and CI FoodBlac was added thereto while stirring.
1.5 parts of k-2 was added, and the resulting slurry was made into fine particles in the same manner as in Example 6. The average particle size was 0.7 micron. (Preparation, printing, and evaluation of recording liquid) The recording liquid was prepared and printed by the method of Example 4 except that the salt-forming fine particles were used in place of the wax fine particles used in Example 4, and printing was performed. An evaluation was made. As a result, similar results to those of Example 1 were obtained.

Example 8 (Preparation of colored wax fine particles) Laurylamide (melting point 8
0-89 degrees C) 1.5 parts, CI Solvent Bl
After dissolving 0.1 part of ack-5 in 20 parts of methanol, it was discharged into 20 parts of water containing 1 part of ammonium suberate to obtain a slurry. The slurry was wet pulverized for 24 hours using a sand grinder to obtain wax fine particles colored in black. (Adjustment of colored colloidal silica) Snowtex 20L
1.5 copies, CI Modern Black-3
0.03 part was added to 15 parts of water and treated at 60 ° C. for 3 hours to obtain black colloidal silica. (Preparation, printing and evaluation of recording liquid) Carbon black was dispersed in the same manner as in Example 1 except that suberic acid was used instead of the pamoic acid used in Example 1, and the colored wax fine particles and the colored colloidal silica were used. Was mixed to prepare a recording liquid. Printing is carried out in the same manner as in Example 1,
The printed matter was evaluated. As a result, similar results to those of Example 1 were obtained.

[Example 9] (Preparation of colored fine particles of chitosan) 3 parts of Kimitsu chitosan (chitosan powder, manufactured by Kimitsu Chemical Co., Ltd.), CI Acid
1 part of Black-24, 1 part of butanetetracarboxylic acid ammonium and 30 parts of water were wet pulverized for 48 hours with a sand grinder using glass beads having a diameter of 1 mm to form fine particles and colored. The average particle size was 0.9 micron. (Preparation, printing, evaluation of recording liquid) The recording liquid was prepared and printed in the same manner as in Example 8 except that the black colored chitosan fine particles were used instead of the colored colloidal silica in Example 8. An evaluation was made. Similar to Example 1, good results were obtained.

[Example 10] (Preparation of salt-forming fine particles) 1.5 parts of ammonium polystyrene sulfonate was dissolved in 30 parts of water, and 1.5 parts of CI Basic Black-8 was added thereto while stirring. Then, the produced slurry was made into fine particles in the same manner as in Example 6. The average particle size was 0.8 micron. (Preparation, printing, evaluation of recording liquid) A recording liquid was prepared and printed in the same manner as in Example 8 except that the black colored salt-forming fine particles were used in place of the colored colloidal silica in Example 8. Performed and evaluated. Similar to Example 1, good results were obtained.

[Example 11] (Preparation of fine colored silk particles) 1 part of silk powder (manufactured by Idemitsu Kabushiki Kaisha), CI Acid Black-24
0.02 part was added to 10 parts of water, and in the same manner as in Example 6, fine particles were formed while coloring. (Preparation, printing, and evaluation of recording liquid) The recording liquid was prepared, printed, and evaluated in the same manner as in Example 8 except that the silk particles were used in place of the wax particles in Example 8. Similar to Example 1, good results were obtained.

[Example 12] A recording liquid was prepared, printing was carried out and evaluated in the same manner as in Example 8 except that the salt-forming fine particles used in Example 7 were used in place of the wax fine particles in Example 8. I went. Similar to Example 1, good results were obtained.

[Example 13] A recording liquid was prepared, printed and evaluated in the same manner as in Example 12 except that the silk particles used in Example 11 were used in place of the colloidal silica in Example 12. It was Similar to Example 1, good results were obtained.

[Example 14] The recording liquid was prepared, printing was carried out and evaluated in the same manner as in Example 4 except that the colored wax fine particles used in Example 8 were used in place of the wax fine particles in Example 4. I went. Similar to Example 1, good results were obtained.

[Example 15] A recording liquid was prepared and printed in the same manner as in Example 5 except that the colored colloidal silica used in Example 8 was used instead of the colloidal silica in Example 5. I went. Similar to Example 1, good results were obtained.

[Example 16] Diethylene glycol 5
Parts, 5 parts of polyethylene glycol (# 400), 1 part of diethylene glycol monobutyl ether, 3 parts of carbon black whose surface has been oxidized with sodium hypochlorite (manufactured by Orient Chemical Co.), and 3 parts of 2,6-naphthalenedicarboxylate ammonium salt. , 2 parts of benzobisoxazoline, colored wax fine particles used in Example 8 and colored colloidal silica, and water were added, and the pH was adjusted to 10 with ammonia water to adjust the total amount to 100 parts to prepare a recording liquid. In the same manner, printing was performed and evaluation was performed. As a result, Example 1
Similar results were obtained in the same manner as in.

Example 17 Diethylene glycol 5
Parts, 5 parts of polyethylene glycol (# 400), 1 part of diethylene glycol monobutyl ether, CI Dir
Water was added to 3 parts of ectBlack-168, 3 parts of ammonium 2,6-naphthalenedicarboxylate and 2 parts of bisoxazoline, and the pH was adjusted to 10 with aqueous ammonia to adjust the total amount to 100 parts to prepare a recording liquid. Printing was performed in the same manner as in Example 1 using this recording liquid, and evaluation was performed in the same manner as in Example 1. As a result, good results were obtained in the same manner as in Example 1.

[Example 18] Glycerin 4 parts, triethylene glycol 4 parts, N-methylpyrrolidone 7 parts, CI
Direct Black-154 3 parts, ammonium isophthalate 2 parts, bisoxazoline 1 part, A
P1SA20 (wax emulsion, Nippon Kasei Co., Ltd.)
Water was added to 3 parts (manufactured by K.K.) to make the total amount 100 parts to prepare a recording liquid. Printing was performed using this recording liquid in the same manner as in Example 1, and the printed matter was immediately heated at 70 ° C. for 30 seconds,
Evaluation was carried out in the same manner as in Example 1. As a result, good results were obtained in the same manner as in Example 1.

Example 19 Instead of the wax emulsion used in Example 18, Snowtex XL was used.
(Colloidal silica, manufactured by Nissan Kagaku Co., Ltd.) was used, the recording liquid was prepared by the method of Example 18, printing was performed, and the printed matter was evaluated. As a result, similar results to those of Example 1 were obtained.

Example 20 Diethylene glycol 5
Parts, 5 parts of polyethylene glycol (# 400), 1 part of diethylene glycol monobutyl ether, CI Dir
Water was added to 3 parts of ectBlack-168, 3 parts of ammonium 2,6-naphthalenedicarboxylate, 2 parts of bisoxazoline and the colored wax fine particles prepared in Example 8, and the pH was adjusted to 10 with aqueous ammonia to adjust the total amount to 100.
The recording liquid was prepared as a part. Printing was performed in the same manner as in Example 1 using this recording liquid, and evaluation was performed in the same manner as in Example 1. As a result, good results were obtained in the same manner as in Example 1.

Example 21 A recording liquid was prepared in the same manner as in Example 20, except that the colored colloidal silica used in Example 8 was used in place of the colored wax fine particles in Example 20. Printing and evaluation were performed. Similar to Example 20, good results were obtained in all cases.

Example 22 A recording liquid was prepared in the same manner as in Example 20, except that the colored cellulose fine particles used in Example 6 were used in place of the colored wax fine particles in Example 20. Printing and evaluation were performed. Similar to Example 20, good results were obtained in all cases.

[Example 23] A recording liquid was prepared in the same manner as in Example 20 except that the salt-forming fine particles used in Example 7 were used in place of the colored wax fine particles in Example 20. Printing and evaluation were performed. Similar to Example 20, good results were obtained in all cases.

[0057]

INDUSTRIAL APPLICABILITY The recording liquid and recording method of the present invention are used for ink jet recording and are excellent in abrasion resistance, water resistance, ejection stability and storage stability as a recording liquid.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C056 EA13 FC02                 2H086 BA05 BA52 BA53 BA55 BA56                       BA59                 4J039 AB01 AB02 AB07 AB12 AD03                       AD09 AD10 AD13 AD22 AD23                       AE01 BA04 BA21 BB01 BC05                       BC07 BC09 BC12 BC19 BC20                       BC33 BC36 BC39 BC50 BC53                       BC54 BC60 BE01 BE03 BE04                       BE05 BE12 CA06 EA35 EA36                       EA38 EA44

Claims (26)

[Claims] 1. Containing water, a water-soluble organic solvent, a dye and / or a pigment, a non-resinous compound having two or more carboxylic acid groups or sulfonic acid groups, and a non-resinous compound having two or more oxazoline groups. A recording liquid characterized by: 2. The recording liquid according to claim 1, containing at least one substance selected from the following group. (Group 1) Fine wax particles having a melting point of 50 ° C. or higher (Group 2) Colloidal silica that may be colored (Group 3) Fine particle derived from a natural product (Group 4) base Salt-forming body formed from a water-soluble resin having a basic group and a dye having an acidic group, or a salt-forming body formed from a water-soluble resin having an acidic group and a dye having a basic group 3. The recording liquid according to claim 1, further comprising fine wax particles having a melting point of 50 ° C. or higher, which may be colored. 4. The recording liquid according to claim 1, containing colloidal silica which may be colored. 5. The recording liquid according to claim 1, which contains fine particles derived from a natural product which may be colored. 6. The recording liquid according to claim 1, which contains colored wax fine particles having a melting point of 50 ° C. or higher. 7. The recording liquid according to claim 1, which contains colored colloidal silica. 8. The recording liquid according to claim 1, which contains colored fine particles derived from a natural product. 9. A salt-forming body formed from a water-soluble resin having a basic group and a dye having an acidic group, or a salt-forming body formed from a water-soluble resin having an acidic group and a dye having a basic group. The recording liquid according to claim 1, further comprising: 10. The recording liquid according to claim 1, containing wax fine particles having a melting point of 50 ° C. or higher, which may be colored, and colloidal silica which may be colored. 11. The recording liquid according to claim 1, which contains fine wax particles having a melting point of 50 ° C. or higher, which may be colored, and fine particles derived from a natural product, which may be colored. 12. A salt-forming body formed from a wax fine particle having a melting point of 50 ° C. or higher, which may be colored, a water-soluble resin having a basic group and a dye having an acidic group, or a water-soluble resin having an acidic group. The recording liquid according to claim 1, which further comprises a salt-forming body formed from a dye having a basic group. 13. A salt-forming body formed from colloidal silica which may be colored and a water-soluble resin having a basic group and a dye having an acidic group, or a water-soluble resin having an acidic group and a basic group. The recording liquid according to claim 1, which contains a salt-forming body formed from a dye. 14. A recording liquid containing fine particles derived from a natural product which may be colored and colloidal silica which may be colored. 15. A salt-forming body formed from fine particles derived from an optionally colored natural product, a water-soluble resin having a basic group and a dye having an acidic group, or a water-soluble resin having an acidic group and basic The recording liquid according to claim 1, further comprising a salt-forming body formed from a dye having a group. 16. A colored wax fine particle having a melting point of 50 ° C. or higher and colored colloidal silica are contained.
Recording liquid described. 17. The recording liquid according to claim 1, which contains colored wax fine particles having a melting point of 50 ° C. or higher and colored fine particles derived from a natural product. 18. A salt-forming body formed from a colored wax fine particle having a melting point of 50 ° C. or higher, a water-soluble resin having a basic group and a dye having an acidic group, or a water-soluble resin having an acidic group and a basic group. The recording liquid according to claim 1, further comprising a salt-forming body formed from a dye having 19. A salt-forming body formed from colored colloidal silica and a water-soluble resin having a basic group and a dye having an acidic group, or a water-soluble resin having an acidic group and a dye having a basic group. The recording liquid according to claim 1, which contains a salt-forming compound. 20. A recording liquid containing colored fine particles derived from a natural product and colored colloidal silica. 21. A salt-forming product formed from colored natural product-derived fine particles and a water-soluble resin having a basic group and a dye having an acidic group, or a water-soluble resin having an acidic group and a dye having a basic group. The recording liquid according to claim 1, further comprising a salt-forming body formed from 22. The counter ion of the acidic group is ammonium, 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
Recording liquid described in 17, 18, 19, 20 and 21. 23. The pigment as described above, wherein the surface of the pigment is oxidized or sulfonated.
2,3,4,5,6,7,8,9,10,11,12,
13, 14, 15, 16, 17, 18, 19, 20, 2
The recording liquid according to 1 or 22. 24. An anionic dispersant is contained, 1, 2, 3, 4, 5, 6, 7, 8, 9, 1.
0,11,12,13,14,15,16,17,1
Recording liquid according to 8, 19, 20, 21 and 22. 25. Claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 20, 21, 22, 23 or 2
A recording method comprising heating a printed matter or an image after printing or forming an image using the recording liquid according to 4. 26. The recording method according to claim 25, wherein the heating temperature is 50 to 150 degrees and the heating time is 10 to 60 seconds.