JPH10219166A - Ink for jet printer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink having improved dispersedness of pigment and giving a beautiful recorded image having high rendering properties for blue and red by using a solid solution pigment comprising at least two quinacridone compounds as the magenta pigment. SOLUTION: The quinacridone solid solution pigment used comprises at least two quinacridone compounds selected among unsubstituted quinacridone, 2,9-dimethylquinacridone, 2,9-dichloroquinacridone and 3,10-dichloroquinacridone and has a primary particle diameter in the range of 10-100nm. This pigment may contain a pigment derivative, a polymeric pigment dispersant and a surfactant. An ink having a hue angle of 354-356 deg. is desirable. Although not particularly limited, a desirable example of the process for producing the solid solution consists of condensing and cyclizing at least two 2,5-diarylaminoterephthalic acid derivatives. It is desirable that this pigment is used in an amount of 1.5-10wt.%, based on the ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink for a magenta jet printer useful for a jet printer, and is particularly useful as an ink for an on-demand type jet printer such as a thermal system or a piezo system.

[0002]

2. Description of the Related Art Quinacridone solid solution pigments have been studied for a long time and are known to exhibit different hue, physical properties such as weather resistance and heat resistance from those obtained by mixing two or more quinacridone pigments. For example, JP-A-60-35055 and JP-A-2-38463 describe methods for producing quinacridone solid solution pigments.
Vol. 603-613 (1968) and Vol. 42,
On pages 3 to 14 (1969), changes in hue and weather resistance in lacquer coatings of solid solution pigments of unsubstituted quinacridone and disubstituted quinacridone and two kinds of solid solution pigments of disubstituted quinacridone are examined.

On the other hand, with the advent of the multimedia era, ink jet printers and color copiers have expanded from the office field to the personal field, and have been expanding to small-volume printing applications.

[0004] Under these circumstances, inks for jet printers are shifting from dyes to pigments in view of weather resistance and water resistance. In the case of transition from dye to pigment, pigment dispersibility is required in terms of physical properties, and high transparency, high definition, and excellent color rendering properties are required in terms of the hue of the recorded image. For example, known jet printer inks having particularly improved pigment dispersibility include unsubstituted quinacridone, 2,9-
A jet printer ink (JP-A-3-76768) using a styrene-maleic acid resin as a polymer pigment dispersant together with quinacridone pigments such as dimethylquinacridone and 2,9-dichloroquinacridone is known. The styrene-maleic acid resin used in (1) shows excellent pigment dispersibility as compared with other polymer pigment dispersants.

[0005] However, although the ink for a jet printer has improved dispersibility, which is a physical property of a pigment, the hue is shifted as compared with a magenta dye ink. And the color gamut is reduced.

[0006]

The problem to be solved by the present invention is to provide a magenta pigment ink used for a jet printer, in which the dispersibility, which is the physical property of the pigment, is controlled by a polymer such as styrene-maleic acid resin. Improved without using a pigment dispersant, while maintaining the color rendering properties of the blue color area, increasing the color rendering properties of the red color area, used in magenta color used in offset printing, or used in jet printers An object of the present invention is to provide a hue close to the magenta color of a dye ink to make a recorded image beautiful.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that two or more quinacridone compounds such as unsubstituted quinacridone, 2,9
A quinacridone solid solution pigment composed of two or more quinacridone compounds selected from the group consisting of -dimethylquinacridone, 2,9-dichloroquinacridone and 3,10-dichloroquinacridone, preferably having an average primary particle diameter of 1
A jet printer ink containing a quinacridone solid solution pigment in the range of 0 to 100 nm, preferably a jet printer ink in which the hue angle H * is in the range of 354 to 6 degrees, is obtained by dispersing a polymer pigment such as a styrene-maleic acid resin. Even without the use of an agent, the pigment dispersibility is good, and the color rendering properties (saturation and color gamut) of the blue color area, which is a superimposed color, are maintained, and the color rendering properties of the red color area are high. Since the hue range between them is widened, the inventors have found that it is possible to provide a hue close to the magenta color used for offset printing or the magenta color of a dye ink used for an ink jet printer, and have completed the present invention. .

That is, the present invention provides (1) an ink for a jet printer, which comprises a quinacridone solid solution pigment comprising two or more quinacridone compounds.
(2) The quinacridone solid solution pigment is a solid solution comprising two or more quinacridone compounds selected from the group consisting of unsubstituted quinacridone, 2,9-dimethylquinacridone, 2,9-dichloroquinacridone, and 3,10-dichloroquinacridone. The ink for a jet printer according to the above (1), wherein the quinacridone solid solution pigment is an unsubstituted quinacridone and / or 3,10-dichloroquinacridone, and a 2,9-dimethylquinacridone and / or
Or the ink for a jet printer according to the above (1), which is a quinacridone pigment solid solution comprising 2,9-dichloroquinacridone; and (4) the quinacridone solid solution pigment having an average primary particle diameter of 10 to 100 nm. ), The ink for a jet printer according to (2) or (3), and (5) the ink according to any one of (1) to (4), wherein the hue angle H * is in a range of 354 to 6 degrees. Ink for a jet printer.

The quinacridone solid solution pigment used in the present invention is not particularly limited as long as it is a quinacridone solid solution pigment composed of two or more quinacridone compounds, and the type, amount, production method and the like of the two or more quinacridone compounds are not limited.

The quinacridone compounds include, for example, the following general formula (I): X _n -QY _m (I) wherein Q represents a quinacridone residue or a quinacridone quinone residue; Represents a hydrogen atom, a methyl group, a chloro group or a methoxy group, and n and m each represent an integer of 1 to 4.), specifically, unsubstituted quinacridone, 2,9-dimethylquinacridone, 2,9-dichloroquinacridone, 2,9-dimethoxyquinacridone, 3,
10-dimethylquinacridone, 3,10-dichloroquinacridone, 3,10-dimethoxyquinacridone, 4,1
Examples include, but are not limited to, 1-dimethylquinacridone, 4,11-dichloroquinacridone, 4,11-dimethoxyquinacridone, quinacridonequinone, and the like.

The combination of two or more quinacridone compounds is not particularly limited, but is preferably a group consisting of unsubstituted quinacridone, 2,9-dimethylquinacridone, 2,9-dichloroquinacridone and 3,10-dichloroquinacridone. And a combination of two or more quinacridone compounds selected from the group consisting of unsubstituted quinacridone and / or 3,10-dichloroquinacridone and 2,9-dimethylquinacridone and / or 2,9-dichloroquinacridone. Combinations are preferred.

Specific examples of the quinacridone solid solution pigment containing the quinacridone-based compound in a desired combination and in a desired amount are shown below, but the quinacridone solid solution pigment used in the present invention is not limited to these.

20 to 90 parts by weight of unsubstituted quinacridone and 80 to 10 parts by weight of 2,9-dimethylquinacridone, particularly preferably 35 to 80 parts by weight of unsubstituted quinacridone,
A quinacridone solid solution pigment containing 65 to 20 parts by weight of 9-dimethylquinacridone.

Unsubstituted quinacridone is 40 to 90 parts by weight and 2,9-dichloroquinacridone is 60 to 10 parts by weight, particularly preferably 50 to 85 parts by weight of unsubstituted quinacridone and 50 to 15 parts by weight of 2,9-dichloroquinacridone. And a quinacridone solid solution pigment.

3,10-dichloroquinacridone 30 to
90 parts by weight and 2,9-dichloroquinacridone 70 to 10
Parts by weight, particularly preferably 45 to 85 parts by weight of 3,10-dichloroquinacridone and 5,9-dichloroquinacridone 5
A quinacridone solid solution pigment containing 5 to 15 parts by weight.

3,10-dichloroquinacridone 30 to
60 parts by weight and 2,9-dimethylquinacridone 40 to 70
Parts by weight, particularly preferably 35 to 50 parts by weight of 3,10-dichloroquinacridone and 5,9-dimethylquinacridone 5
A quinacridone solid solution pigment containing 0 to 65 parts by weight.

The quinacridone solid solution pigment used in the present invention preferably has an average primary particle diameter in the range of 10 to 100 nm, particularly 10 to 60 nm in consideration of transparency, color density and dispersibility of the pigment. Are preferred.

If the average primary particle size of the quinacridone solid solution pigment is less than 10 nm, the dispersibility and weather resistance of the pigment tend to decrease, and if it exceeds 100 nm, the transparency decreases, and the overlapping color portion (red area or blue area) (Intermediate color of the color region) tends to be poor.

The average primary particle diameter is an average of values obtained by sampling several tens of colorants from an electron micrograph of the colorant, adding the major axis and the minor axis, and dividing by two.

The quinacridone solid solution pigment used in the present invention has no problem even if a pigment derivative, a high molecular pigment dispersant, a nonionic, anionic or cationic surfactant or the like is added.

Examples of the above-mentioned pigment derivatives include quinacridone derivatives having a halogen atom, a phthalimide group, a dialkylaminomethyl group, a sulfamoyl group, a sulfonic acid group and a salt thereof.

As the high molecular weight pigment dispersant, a high molecular weight compound having a molecular weight of 1,000 or more is preferable. For example, styrene-maleic acid resin, styrene-acrylic resin, rosin, BYK-160, 162, 164, 182 (Big Chemie) Urethane polymer compound), EFKA-4
01, 402 (acrylic dispersant manufactured by EFKA), Solsperse 24000 (polyester polymer compound manufactured by Zeneca), and the like, but are not limited thereto.

The amount of the pigment derivative and / or the high molecular pigment dispersant is usually 20 parts by weight or less, preferably 2 to 10 parts by weight, based on 100 parts by weight of the pigment.

The method for producing the quinacridone solid solution pigment used in the present invention is not particularly limited, and a generally known production method is usually employed. Particularly preferred production methods are two or more 2,5- It is more preferable that the diarylaminoterephthalic acid derivative is condensed and cyclized, and then subjected to a pigmentation treatment (a method for controlling the shape, size, and crystal form of the primary particle diameter (crystal)).

As a method for condensing and cyclizing two or more 2,5-diarylaminoterephthalic acid derivatives, two or more 2,5-diarylaminoterephthalic acid derivatives are cyclized with a polyphosphoric acid or a polyphosphate alkylester solution. And then taking out the cyclization reaction solution into water. More specifically, with respect to 1 part by weight of a mixture of two or more 2,5-diarylaminoterephthalic acid derivatives, a condensing agent 2 such as polyphosphoric acid or an acidic polyphosphate alkyl ester having a phosphoric acid concentration of 110 to 125% by weight is used. Using 10 parts by weight, the mixture is condensed and cyclized at a temperature of 100 to 180 ° C., preferably 110 to 150 ° C. with stirring for 2 to 12 hours, preferably 2.5 to 7 hours. A method of taking out into water, a water-soluble organic solvent or a mixture thereof two times or more the weight of the reaction solution is preferable.

Examples of the water-soluble organic solvent used for removing the cyclization reaction solution include alcohols such as methyl alcohol, ethyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-propyl alcohol and isopropyl alcohol. Amides such as dimethylformaldehyde and dimethylacetamide; and ketones such as acetone and methyl ethyl ketone.

The preferred method of performing the pigmentation treatment is as follows:
For example, after a cyclization reaction, the wet pigment in the form of a wet cake obtained by taking out and washing is subjected to a heat treatment in water, an organic solvent, or a mixture thereof to grow crystals, After dissolving the pigment in a sulfuric acid solution having a sulfuric acid concentration of 90% by weight or more, a method of extracting the pigment into water at a temperature of 0 to 50 ° C. may be used.

As the organic solvent used in the heat treatment,
For example, aliphatic hydrocarbon solvents such as hexane and mineral spirit; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as butyl acetate; methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol And aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine and the like. These solvents may be used in combination. Among them, an aromatic hydrocarbon solvent or a mixture of an alcohol solvent and water is preferred from the viewpoint of controlling the particle diameter and the recovery of the organic solvent.

The amount of water, organic solvent, or mixture thereof used in the heat treatment is usually 500 parts by weight or more, preferably 600 to 300 parts by weight, per 100 parts by weight of the crude pigment.
0 parts by weight. Water used here, an organic solvent, or a particularly preferable one among these mixtures is a mixture of water and an organic solvent, and the proportion of the organic solvent in the mixture is usually 5 to 5.
It is 50% by weight, preferably 10 to 40% by weight.

Regarding the temperature of the heat treatment, the degree of crystal growth is appropriate, the color rendering of recorded images is excellent, and the productivity is also good.
The temperature is preferably in the range of 0 to 180 ° C, especially 70 to 150 ° C, and the pressure is preferably in the range of normal pressure to 10 kg / cm ² .

In the method of dissolving in a sulfuric acid solution having a sulfuric acid concentration of 90% by weight or more and taking out the same with water, the amount of the sulfuric acid solution used is preferably 500 parts by weight or more based on 100 parts by weight of the crude pigment, and 600 to 2000 parts by weight. A range of parts by weight is more preferred.

The temperature for dissolving the crude pigment is as follows:
A range of 0 to 80 ° C is preferable, and a range of 0 to 50 ° C is more preferable. Above 80 ° C., quinacridone may be sulfonated.

After dissolving in a sulfuric acid solution, the pigment may be taken out into water, for example, by slowly adding a sulfuric acid solution in which the crude pigment is dissolved while stirring the water, and precipitating and taking out the water. A method in which a sulfuric acid solution in which a crude pigment is dissolved is mixed on a line mixer to precipitate the pigment at a stroke.

The amount of water for removing the pigment into water is as follows:
The amount of the pigment is not limited as long as the amount of the pigment precipitates.
5000 parts by weight or more of water is preferred based on parts by weight. As the temperature at the time of taking out, a lower temperature is more preferable, and 0 to 50 ° C.
Is particularly preferred.

The quinacridone solid solution pigment used in the present invention can be particularly suitably used as an ink for an ink jet printer as a wet cake or as a dry pigment after drying and pulverization.

The quinacridone solid solution pigment is dispersed in an ink medium for a jet printer using various dispersers such as a bead mill, a roll mill, a sand mill, and a kneader in an ink for a jet printer.

The conditions for dispersing the quinacridone solid solution pigment in the ink medium for a jet printer are not particularly limited because they vary depending on the type of disperser and the ink composition. However, in terms of the production cost of the ink for a jet printer, preferable conditions are that the pressure is in the range of normal pressure to 5 kg / cm ² and the temperature is in the range of normal temperature to 100 ° C.

The content of the quinacridone solid solution pigment in the ink medium for a jet printer is preferably in the range of 1 to 20% by weight, more preferably 1.5 to 10% by weight, based on 100% by weight of the ink for a jet printer.

Examples of the ink medium for a jet printer include, but are not particularly limited to, those comprising a solvent and, if necessary, a resin, a surfactant, a base, and various additives. In the case of an aqueous solvent, the solvent generally includes water, a water-soluble organic solvent, or a mixture thereof, and in the case of a non-aqueous solvent, an organic solvent.

Examples of the water-soluble organic solvent used in the above solvent include methyl alcohol, ethyl alcohol, n-
Butyl alcohol, isobutyl alcohol, tert-
Alcohols such as butyl alcohol, n-propyl alcohol and isopropyl alcohol; amides such as dimethylformaldehyde and dimethylacetamide; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, dioxane, ethylene glycol methyl ether, ethylene glycol ethyl ether and diethylene glycol methyl ether Ethers such as, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc .; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Polyhydric alcohols such as diethylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; N-methyl-pyrrolidone, 1,3-dimethyl-2-
And imidazolidinone. Among these water-soluble organic solvents, polyhydric alcohols and ethers are preferable.

The content of the water-soluble organic solvent in the ink for a jet printer is preferably 50% by weight or less.
A range of 30% by weight is particularly preferred.

Examples of the resin used as needed in the ink for a jet printer include, for example, natural proteins such as glue, gelatin, casein, albumin, gum arabic, fish grew, alginic acid, methylcellulose, carboxymethylcellulose, polyethylene oxide, hydroxyethylcellulose. Polyvinyl alcohol, polyacrylamide, aromatic amide, polyacrylic acid, polyvinyl ether, polyvinylpyrrolidone, polyester, copolymers of acrylic acid-acrylates, synthetic polymers such as styrene-maleic acid, styrene-acrylic acid resin, etc. Is mentioned.

These resins are used as necessary for the purpose of stabilizing the dispersion of the quinacridone solid solution pigment, adjusting the fixing property and viscosity, and improving the drying property. Is preferably 30% by weight or less, particularly preferably 20% by weight or less.

As the surfactant used as needed in the ink for a jet printer, for example, a fatty acid salt, an alkyl sulfate salt, an alkylbenzene sulfonate,
Anionic surfactants such as alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl sulfates, polyoxyethylene alkylphenyl sulfates, etc., coconut amine Alkylamine salts such as acetate and stearylamine acetate, quaternary ammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride, alkylbetaines such as laurylbentaine and stearylbentaine, and cationic and amphoteric interfaces such as lauryldimethylamine oxide Activator, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, emulgen A-5
Nonionic surfactants such as polyoxyethylene derivatives of 00 (manufactured by Kao Corporation), oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters and glycerin fatty acid esters, etc. Is mentioned. These surfactants
It is used to adjust the interfacial tension of the ink or to improve the dispersibility of the pigment. When used in an ink for a jet printer, the content of the surfactant in the ink is 10% by weight. Or less, particularly preferably 5% by weight or less.

The base used as needed in the ink for a jet printer includes an inorganic base and an organic amine. Examples of the inorganic base include sodium hydroxide, potassium hydroxide and lithium hydroxide. Examples of the organic amine include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethyldiethanolamine, 2-amino-
2-methylpropanol, 2-ethyl-2-amino-
Examples thereof include 1,3-propanediol, 2- (aminoethyl) ethanolamine, tris (hydroxymethyl) aminomethane, ammonia, piperidine, and morpholine. These bases are used as a neutralizing agent for a water-soluble resin, a wetting agent for an ink, and the like. When used in a jet printer ink, the content of the base in the ink is preferably 10% by weight or less, Particularly preferred is 5% by weight or less.

Further, the ink for a jet printer of the present invention has no problem even if additives such as a preservative, a viscosity adjuster, a pH adjuster and a chelating agent are contained.

As a method of forming a full-color recorded image using the ink for a jet printer prepared as described above, various types of paper, sheet, film, fiber,
There is a method of printing on metal or the like.

The ink jet printer is not particularly limited. For example, a piezo method using a piezoelectric element in a printer head or a thermal method in which thermal energy is applied to a recording liquid to discharge ink as droplets from micro holes to perform recording are used. No. Further, it is also possible to fix the image by applying energy such as heat or ultraviolet light after printing.

An electric signal of an image to be recorded is given to these ink jet printers, and a full-color recorded image is obtained using the above-mentioned ink.

The ink for a jet printer according to the present invention preferably has a hue angle H * in the range of 354 to 6 degrees, and the hue angle H * is, for example, as follows. The color image can be obtained by obtaining a color image by using the above method and measuring the color.

4.0 parts of quinacridone solid solution pigment, 6.7 parts of Joncryl J-61J (styrene-acrylic resin manufactured by Johnson Polymer Co.), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 3 mmφ glass beads 80 parts are weighed into a 100 ml polyvin, and dispersed by a paint conditioner until the volume average particle diameter of the quinacridone solid solution pigment is 200 nm or less (however, if the volume average particle diameter does not become 200 nm or less, the dispersion is continued for 4 hours). After the dispersion, 44.4 parts of ion-exchanged water, 4.0 parts of ethylene glycol, 8.0 parts of glycerin, 2.4 parts of diethanolamine, and 1.2 parts of Emulgen 147 (nonionic activator manufactured by Kao Corporation) are mixed, and the pore size is mixed. The coarse particles are filtered using a 1 μm filter to prepare a jet printer ink containing a quinacridone solid solution pigment.
The volume average particle diameter is, for example, “UPA-150”
(Laser Doppler type particle size distribution meter manufactured by JGC Corporation).

The ink for a jet printer thus prepared was applied to an ink jet printer BJC-400 manufactured by Canon Inc.
A color image is obtained by performing color printing of magenta on color BJ paper (manufactured by Canon Inc.) in the cartridge J. This color image was obtained by using a D65 light source and a 10-degree field of view on an SPE manufactured by datacolor (UK).
The color is measured by CTRAFIASH 500, and the hue angle H * is obtained.

The quinacridone solid solution pigment used in the present invention may be used in printing inks, paints, plastics, metal inks, as wet cakes, or as dry pigments after drying and pulverization, in addition to the inks for jet printers.
It can be used as a colorant for various articles such as printing agents, stationery, toners, jet inks, etc. Among them, it can be suitably used as a color toner by utilizing its hue and transparency.

[0054]

The present invention will be described in more detail with reference to the following reference examples, examples and comparative examples. In the following, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

Reference Example 1 (Production of quinacridone solid solution pigment) 80 parts of 2,5-di (p-toluidino) terephthalic acid
80 parts of 2,5-dianilinoterephthalic acid and 465 parts of polyphosphoric acid having a phosphoric acid concentration of 116.1% were condensed and cyclized by stirring at 125 ° C. for 3 hours. The condensed liquid was added to 3000 parts of water to crystallize a solid solution of dimethylquinacridone and unsubstituted quinacridone. After crystallization, the mixture was filtered and washed with water until the filtrate became neutral, to obtain a wet cake of a solid solution crude pigment comprising 50% of 2,9-dimethylquinacridone having a nonvolatile content of 25.3% and 50% of unsubstituted quinacridone. Was.

177.9 parts of this wet cake, 180 parts of isobutyl alcohol and 227.1 parts of water were charged into an autoclave vessel and heated at 123 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, filtered, washed with hot water at 40 to 60 ° C, dried with a dryer at 96 ° C, and pulverized.
A quinacridone solid solution pigment comprising 50% 2,9-dimethylquinacridone and 50% unsubstituted quinacridone (SP-
1) was manufactured. The average primary particle diameter of the quinacridone solid solution pigment (SP-1) obtained by photographing with an electron microscope is 38 n.
m.

Reference Example 2 (same as above) Instead of 80 parts of 2,5-di (p-toluidino) terephthalic acid and 80 parts of 2,5-dianilinoterephthalic acid,
In the same manner as in Reference Example 1 except that 96 parts of 2,5-di (p-toluidino) terephthalic acid and 64 parts of 2,5-dianilinoterephthalic acid were used, 2,9-component having a non-volatile content of 28.3% was used.
Dimethylquinacridone 60% and unsubstituted quinacridone 40
% Was obtained as a solid solution crude pigment.

159 parts of this wet cake, 180 parts of isobutyl alcohol and 246 parts of water were charged into an autoclave container and heated at 123 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, filtered, washed with hot water at 40 to 60 ° C., dried with a drier at 96 ° C., pulverized, and 60% 2,9-dimethylquinacridone and 40% unsubstituted quinacridone.
A quinacridone solid solution pigment (SP-2) consisting of The average primary particle diameter of the quinacridone solid solution pigment (SP-2) obtained by photographing with an electron microscope was 45 nm.

Reference Example 3 (same as above) Instead of 80 parts of 2,5-di (p-toluidino) terephthalic acid and 80 parts of 2,5-dianilinoterephthalic acid,
In the same manner as in Reference Example 1 except that 96 parts of 2,5-di (p-toluidino) terephthalic acid and 64 parts of 2,5-dianilinoterephthalic acid were used, 2,9-component having a non-volatile content of 28.3% was used.
Dimethylquinacridone 60% and unsubstituted quinacridone 40
% Was obtained as a solid solution crude pigment.

159 parts of this wet cake and 426 parts of isobutyl alcohol were charged into an autoclave container,
Heat treatment was performed at 150 ° C. for 5 hours. After the heat treatment, water was added to distill off the solvent, followed by filtration, washing with hot water at 40 to 60 ° C., drying with a drier at 96 ° C., pulverization, and no substitution with 60% 2,9-dimethylquinacridone. A quinacridone solid solution pigment (SP-3) consisting of 40% quinacridone was produced. The average primary particle diameter of the quinacridone solid solution pigment (SP-3) obtained by photographing with an electron microscope was 105 nm.

Reference Example 4 (same as above) 2,5-di (p-chloroanilino) terephthalic acid 64
96 parts of 2,5-dianilinoterephthalic acid and 697.5 parts of polyphosphoric acid having a phosphoric acid concentration of 116.1%
The mixture was stirred at a temperature of 3 ° C. for 3 hours to condense and cyclize. The condensed liquid was added to 4500 parts of water to crystallize a solid solution of dichloroquinacridone and unsubstituted quinacridone. After crystallization, the mixture was filtered, washed with water until the filtrate became neutral, and 2,9-dichloroquinacridone 4 having a nonvolatile content of 18%.
A wet cake of a solid solution crude pigment containing 0% and 60% of unsubstituted quinacridone was obtained.

The wet cake (250 parts), isobutyl alcohol (180 parts), and water (155 parts) were charged into an autoclave vessel and heated at 123 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, filtered, washed with hot water at 40 to 60 ° C., dried with a drier at 96 ° C., and pulverized to obtain 40% of 2,9-dichloroquinacridone and 60% of unsubstituted quinacridone 60. %
A quinacridone solid solution pigment (SP-4) consisting of The average primary particle diameter of the quinacridone solid solution pigment (SP-4) obtained by photographing with an electron microscope was 32 nm.

Reference Example 5 (same as above) Instead of 64 parts of 2,5-di (p-chloroanilino) terephthalic acid and 96 parts of 2,5-dianilinoleterephthalic acid,
The same procedure as in Reference Example 4 was carried out except that 32 parts of 2,5-di (p-chloroanilino) terephthalic acid and 128 parts of 2,5-diaanilinoterephthalic acid were used.
A wet cake of a solid solution crude pigment containing 20% of 9-dichloroquinacridone and 80% of unsubstituted quinacridone was obtained.

229.6 parts of this wet cake, 180 parts of isobutyl alcohol and 175.4 parts of water were charged into an autoclave vessel and heated at 123 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, filtered, washed with hot water at 40 to 60 ° C, dried with a dryer at 96 ° C, and pulverized.
A quinacridone solid solution pigment comprising 20% 2,9-dichloroquinacridone and 80% unsubstituted quinacridone (SP-
5) was produced. The average primary particle diameter of the quinacridone solid solution pigment (SP-5) obtained by photographing with an electron microscope is 35 n.
m.

Reference Example 6 (same as above) In place of 64 parts of 2,5-di (p-chloroanilino) terephthalic acid and 96 parts of 2,5-diaanilinoterephthalic acid,
80 parts of 2,5-di (p-chloroanilino) terephthalic acid and 80 parts of 2,5-di (m-chloroanilino) terephthalic acid
In the same manner as in Reference Example 4 except that
4.1% 2,9-dichloroquinacridone 50% and 3,3
A wet cake of a solid solution crude pigment containing 50% of 10-dichloroquinacridone was obtained.

186.7 parts of this wet cake, 180 parts of isobutyl alcohol and 218.3 parts of water were charged into an autoclave vessel and heated at 123 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, filtered, washed with hot water at 40 to 60 ° C, dried with a dryer at 96 ° C, and pulverized.
A quinacridone solid solution pigment (SP-6) comprising 50% 2,9-dichloroquinacridone and 50% 3,10-dichloroquinacridone was produced. The average primary particle diameter of the quinacridone solid solution pigment (SP-6) obtained by photographing with an electron microscope was 40 nm.

Reference Example 7 (same as above) Instead of 64 parts of 2,5-di (p-chloroanilino) terephthalic acid and 96 parts of 2,5-diaanilinoterephthalic acid,
48 parts of 2,5-di (p-chloroanilino) terephthalic acid and 11 of 2,5-di (m-chloroanilino) terephthalic acid 11
In the same manner as in Reference Example 4 except that 2 parts were used, the nonvolatile content 2
0.9% 2,9-dichloroquinacridone 30% and 3,3
A wet cake of a solid solution crude pigment containing 70% of 10-dichloroquinacridone was obtained.

215.3 parts of this wet cake, 180 parts of isobutyl alcohol and 189.7 parts of water were charged into an autoclave vessel and heated at 123 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, filtered, washed with hot water at 40 to 60 ° C, dried with a dryer at 96 ° C, and pulverized.
A quinacridone solid solution pigment (SP-7) comprising 30% 2,9-dichloroquinacridone and 70% 3,10-dichloroquinacridone was produced. The average particle size of the quinacridone solid solution pigment (SP-7) obtained by photographing with an electron microscope was 37 nm.

Reference Example 8 (same as above) Instead of 64 parts of 2,5-di (p-chloroanilino) terephthalic acid and 96 parts of 2,5-diaanilinoterephthalic acid,
96 parts of 2,5-di (p-chloroanilino) terephthalic acid and 64 parts of 2,5-di (m-chloroanilino) terephthalic acid
In the same manner as in Reference Example 4 except that
9.2% of 2,9-dichloroquinacridone 60% and 3,9%
A wet cake of a 40% solid solution crude pigment of 10-dichloroquinacridone was obtained.

154.1 parts of this wet cake, 180 parts of isobutyl alcohol and 250.9 parts of water were charged into an autoclave vessel and heated at 123 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, filtered, washed with hot water at 40 to 60 ° C, dried with a dryer at 96 ° C, and pulverized.
A quinacridone solid solution pigment (SP-8) comprising 60% 2,9-dichloroquinacridone and 40% 3,10-dichloroquinacridone was produced. The average primary particle diameter of the quinacridone solid solution pigment (SP-8) obtained by photographing with an electron microscope was 52 nm.

Reference Example 9 (Production of cyan ink for jet printer) Fastogen Blue TGR (CI Pigment Blue 15: 3 manufactured by Dainippon Ink and Chemicals, Inc.)
4.0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 3 parts
80 parts of mmφ glass beads were weighed into a 100 ml poly bottle and dispersed with a paint conditioner for 4 hours.
After the dispersion, 44.4 parts of ion-exchanged water, 4.0 parts of ethylene glycol, 8.0 parts of glycerin, 2.4 parts of diethanolamine, and 1.2 parts of Emulgen 147 (nonionic activator manufactured by Kao Corporation) are mixed, and the pore size is mixed. The coarse particles were filtered using a 1 μm filter to prepare a cyan ink for a jet printer having a pigment having a volume average particle diameter of 157 nm.

Reference Example 10 (Production of Yellow Ink for Jet Printer) Symuler Fast 8GF (CI Pigment Yellow 17 manufactured by Dainippon Ink and Chemicals, Inc.) 4.
0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 3 mm
80 parts of φ glass beads were weighed into a 100 ml poly bottle and dispersed with a paint conditioner for 4 hours. After the dispersion, 44.4 parts of ion-exchanged water, 4.0 parts of ethylene glycol, 8.0 parts of glycerin, 2.4 parts of diethanolamine, and 1.2 parts of Emulgen 147 (nonionic activator manufactured by Kao Corporation) are mixed, The coarse particles were filtered using a filter having a pore size of 1 μm to prepare a yellow ink for a jet printer having a pigment having a volume average particle size of 194 nm.

Example 1 The quinacridone solid solution pigment prepared in Reference Example 1 (SP-
1) 4.0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 80 parts of 3 mmφ glass beads in 100 ml. It was weighed into a polybin and dispersed with a paint conditioner for 2 hours. After the dispersion, 44.4 parts of ion-exchanged water, 4.0 parts of ethylene glycol, 8.0 parts of glycerin, 2.4 parts of diethanolamine, and 1.2 parts of Emulgen 147 (nonionic activator manufactured by Kao Corporation) are mixed, and the pore size is mixed. The coarse particles were filtered using a 1 μm filter, and the quinacridone solid solution pigment (SP-
A magenta ink for a jet printer having a volume average particle diameter of 155 nm in 1) was prepared. This quinacridone solid solution pigment (SP-1) had a volume average particle diameter of 200 nm or less in a dispersion time of 2 hours in a paint conditioner, and was described later without using a polymer pigment dispersant such as a styrene-maleic acid resin. C. of Comparative Example 1 I. Pigment Red 122 was superior in dispersibility.

Next, the cyan ink for a jet printer obtained in Reference Example 12, the yellow ink for a jet printer obtained in Reference Example 13, and the magenta ink for a jet printer prepared above were combined with an ink jet printer manufactured by Canon Inc. Red, magenta, and blue color printing was performed on color BJ paper (manufactured by Canon Inc.) in a BJC-400J cartridge to obtain three color images.

The obtained color image was converted to a D65 light source,
Degrees field of view, Datacolor, UK
Color measurement with SPECTRAFASH 500
The chroma C * and the hue angle H * were determined, and the color gamut ΔH * between the red and blue colors was calculated. The colorimetric results are shown in Table 1. These color images have higher chroma C * in each of the red, magenta and blue colors, as well as the red and blue colors, as compared with the color images of Comparative Examples 1 and 2 described later. Color gamut ΔH between colors
* Became large and the hue range was very wide, showing high color rendering properties.

Comparative Example 1 C.I. which is generally used as a magenta color for a jet printer I. Pigment Red 122 (Fasto)
gen Super Magenta RTS: dimethylquinacridone pigment manufactured by Dainippon Ink and Chemicals, Inc.) 4.0
Part, Hyros X-205L (Styrene manufactured by Seiko Chemical Co., Ltd.)
8.0 parts of maleic acid resin, 2.0 parts of isopropyl alcohol, 6.0 parts of ion-exchanged water and 80 parts of 3 mmφ glass beads are weighed into a 100 ml polybin and dispersed with a paint conditioner for 3 hours. A magenta ink for a jet printer was prepared in the same manner as in Example 1 except that the volume average particle diameter of the dimethylquinacridone pigment was 176 nm. This dimethylquinacridone pigment had a volume average particle diameter of 200 nm or less in a dispersion time of 3 hours, and was excellent in dispersibility.

Then, a three-color image was obtained in the same manner as in Example 1 except that the magenta ink for a jet printer obtained above was used as the magenta ink, and the obtained color image was obtained in the same manner. Was measured. The colorimetric results are shown in Table 1. These color images were obtained in Example 1.
Color gamut between red and blue compared to the color image of
H * is small and hue range is narrow, and red color saturation C
* Was low and the color rendering properties were poor.

Comparative Example 2 C.I. which is generally used as a magenta color for a jet printer I. Pigment Red 122 (Fasto)
gen Super Magenta RTS: dimethylquinacridone pigment manufactured by Dainippon Ink and Chemicals, Inc.) 4.0
Parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 3 mmφ
Measure 80 parts of glass beads into 100 ml poly bottle,
After dispersing with a paint conditioner for 4 hours, a magenta ink for a jet printer having a volume average particle diameter of 198 nm of a dimethylquinacridone pigment was prepared in the same manner as in Example 1 except that this dispersion was used. This dimethylquinacridone pigment took 4 hours to disperse and was inferior in dispersibility.

Next, a three-color image was obtained in the same manner as in Example 1 except that the above-obtained magenta ink for a jet printer was used as the magenta ink. Was measured. The colorimetric results are shown in Table 1. These color images were obtained in Example 1.
Color gamut between red and blue compared to the color image of
H * is small and hue range is narrow, and red color saturation C
* Was low and the color rendering properties were poor.

Example 2 The quinacridone solid solution pigment prepared in Reference Example 2 (SP-
2) 4.0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 80 parts of 3 mmφ glass beads in 100 ml. After weighing into a polybin and dispersing for 3 hours with a paint conditioner, the procedure of Example 1 was repeated, except that this dispersion was used.
A magenta ink for a jet printer having a volume average particle diameter of quinacridone solid solution pigment (SP-2) of 185 nm was prepared. This quinacridone solid solution pigment (SP-2)
Has a volume average particle diameter of 200 nm or less in 3 hours of dispersion time without using a polymer pigment dispersant such as styrene-maleic acid resin, and C.I. of Comparative Example 2 described later. I. Pigment Red 122 was superior in dispersibility.

Next, a three-color image was obtained in the same manner as in Example 1 except that the above-obtained magenta ink for a jet printer was used as the magenta ink. Was measured. The colorimetric results are shown in Table 1. These color images are shown in Comparative Example 1.
Compared to the color images 2 and 2, the saturation C * is higher in each of the red, magenta, and blue colors, and the color gamut ΔH * between the red and blue colors is larger, and the hue range is broader, showing high color rendering properties. I was

Example 3 The quinacridone solid solution pigment prepared in Reference Example 4 (SP-
4) 4.0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water, and 80 parts of 3 mmφ glass beads in 100 ml. After weighing into a polybin and dispersing for 3 hours with a paint conditioner, the procedure of Example 1 was repeated, except that this dispersion was used.
A magenta ink for a jet printer having a volume average particle diameter of a quinacridone solid solution pigment (SP-4) of 193 nm was prepared. This quinacridone solid solution pigment (SP-4)
Has a volume average particle diameter of 200 nm or less in 3 hours of dispersion time without using a polymer pigment dispersant such as styrene-maleic acid resin. I. Pigment Red 122 was superior in dispersibility.

Next, a three-color image was obtained in the same manner as in Example 1 except that the above-obtained magenta ink for a jet printer was used as the magenta ink. Was measured. The colorimetric results are shown in Table 1. These color images are shown in Comparative Example 1.
Compared to the color images of and 2, the saturation C * in the blue color is maintained, the saturation C * in the red and magenta colors is high, and the color gamut ΔH * between the red and blue colors is increased to increase the hue. The range was wide, and high color rendering properties were exhibited.

Example 4 The quinacridone solid solution pigment prepared in Reference Example 5 (SP-
5) 4.0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 80 parts of 3 mmφ glass beads are 100 ml. After weighing into a polybin and dispersing for 3 hours with a paint conditioner, the procedure of Example 1 was repeated, except that this dispersion was used.
A magenta ink for a jet printer having a volume average particle diameter of 191 nm of a quinacridone solid solution pigment (SP-5) was prepared. This quinacridone solid solution pigment (SP-5)
Has a volume average particle diameter of 200 nm or less in 3 hours of dispersion time without using a polymer pigment dispersant such as styrene-maleic acid resin. I. Pigment Red 122 was superior in dispersibility.

Next, a three-color image was obtained in the same manner as in Example 1 except that the above-obtained magenta ink for a jet printer was used as a magenta ink. Was measured. The colorimetric results are shown in Table 1. These color images are shown in Comparative Example 1.
Compared to the color images of and 2, the saturation C * in the blue color is maintained, the saturation C * in the red and magenta colors is high, and the color gamut ΔH * between the red and blue colors is increased to increase the hue. The range was wide, and high color rendering properties were exhibited.

Example 5 The quinacridone solid solution pigment (SP-
6) 4.0 ml, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 80 parts of 3 mmφ glass beads in 100 ml. After weighing into a polybin and dispersing for 3 hours with a paint conditioner, the procedure of Example 1 was repeated, except that this dispersion was used.
A magenta ink for a jet printer having a volume average particle diameter of 186 nm of a quinacridone solid solution pigment (SP-6) was prepared. This quinacridone solid solution pigment (SP-6)
Has a volume average particle diameter of 200 nm or less in 3 hours of dispersion time without using a polymer pigment dispersant such as styrene-maleic acid resin. I. Pigment Red 122 was superior in dispersibility.

Next, a three-color image was obtained in the same manner as in Example 1, except that the magenta ink for a jet printer obtained above was used as the magenta ink. Was measured. The colorimetric results are shown in Table 1. These color images are shown in Comparative Example 1.
Compared to the color images 2 and 2, the red, magenta, and blue colors each have a higher saturation C *, and the color gamut ΔH * between the red and blue colors is larger, resulting in a wider hue range and higher color rendering properties. I was

Example 6 The quinacridone solid solution pigment (SP-
7) 4.0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 80 parts of 3 mmφ glass beads are 100 ml. After weighing into a polybin and dispersing for 3 hours with a paint conditioner, the procedure of Example 1 was repeated, except that this dispersion was used.
A magenta ink for a jet printer having a volume average particle diameter of 196 nm of a quinacridone solid solution pigment (SP-7) was prepared. This quinacridone solid solution pigment (SP-7)
Has a volume average particle diameter of 200 nm or less in 3 hours of dispersion time without using a polymer pigment dispersant such as styrene-maleic acid resin. I. Pigment Red 122 was superior in dispersibility.

Next, a three-color image was obtained in the same manner as in Example 1 except that the above-obtained magenta ink for a jet printer was used as the magenta ink, and the obtained color image was obtained in the same manner. Was measured. The colorimetric results are shown in Table 1. These color images are shown in Comparative Example 1.
Compared to the color images 2 and 2, while maintaining the saturation C * in the blue color, the saturation C * in the red and magenta colors is high, and the color gamut ΔH * between the red and blue colors is increased, resulting in a hue. The range was wide, and high color rendering properties were exhibited.

Example 7 The quinacridone solid solution pigment (SP-
8) 4.0 parts, 6.7 parts of John Krill J-61J (styrene-acrylic resin manufactured by Johnson Polymer), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 80 parts of 3 mmφ glass beads are 100 ml. After weighing into a polybin and dispersing for 3 hours with a paint conditioner, the procedure of Example 1 was repeated, except that this dispersion was used.
A magenta ink for a jet printer having a volume average particle diameter of 167 nm of a quinacridone solid solution pigment (SP-7) was prepared. This quinacridone solid solution pigment (SP-7)
Has a volume average particle diameter of 200 nm or less in 3 hours of dispersion time without using a polymer pigment dispersant such as styrene-maleic acid resin. I. Pigment Red 122 was superior in dispersibility.

Next, a three-color image was obtained in the same manner as in Example 1 except that the magenta ink for a jet printer obtained above was used as the magenta ink, and the obtained color image was obtained in the same manner. Was measured. The colorimetric results are shown in Table 1. These color images are shown in Comparative Example 1.
Compared to the color images 2 and 2, while maintaining the saturation C * in the blue color, the saturation C * in the red and magenta colors is high, and the color gamut ΔH * between the red and blue colors is increased, resulting in a hue. The range was wide, and high color rendering properties were exhibited.

[0092]

[Table 1]

[0093]

The ink for a jet printer according to the present invention has good pigment dispersibility and color rendering properties in a blue color region, which is a superimposed color, without using a high-molecular pigment dispersant such as styrene-maleic acid resin. (Saturation and color gamut) while maintaining high color rendering in the red color area and widening the hue range between the red and blue colors. Used for magenta or ink jet printers used in offset printing, etc. Hue close to the magenta color of the dye ink used.

Claims (5)

[Claims] 1. An ink for a jet printer, comprising a quinacridone solid solution pigment comprising two or more quinacridone compounds. 2. The quinacridone solid solution pigment is selected from two or more quinacridone compounds selected from the group consisting of unsubstituted quinacridone, 2,9-dimethylquinacridone, 2,9-dichloroquinacridone and 3,10-dichloroquinacridone. The ink for a jet printer according to claim 1, which is a pigment solid solution. 3. A quinacridone solid solution pigment comprising an unsubstituted quinacridone and / or 3,10-dichloroquinacridone, and 2,9-dimethylquinacridone and / or 2,9-quinacridone.
The ink for a jet printer according to claim 1, which is a quinacridone solid solution pigment comprising dichloroquinacridone. 4. The ink for a jet printer according to claim 1, wherein the quinacridone solid solution pigment has an average primary particle diameter in a range of 10 to 100 nm. 5. The ink for a jet printer according to claim 1, wherein the hue angle H * is in a range of 354 to 6 degrees.