JPH1025440A - Ink jet full-color recorded image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a full-color recorded image excellent, for example, in color rendering properties and light resistance by using, in a jet printer, a cyan ink, a magenta color ink and a yellow ink each containing a specified coloring agent. SOLUTION: (A) a cyan ink containing C.I. Pigment Blue 15:3 as a coloring agent, (B) a magenta ink containing C.1. Pigment Red 122 as a coloring agent, and (C) a yellow ink containing C.I. Pigment Yellow 154 are prepared. Using an on-demand-type ink jet printer, these inks are printed on various types of papers, sheets, films, etc., to obtain full-color recorded images. Preferably, in each coloring agent, the maximum particle diameter of the primary particles is 200nm and the average particle diameter of the primary particles is limited in the range of 10 to 100nm. Further, a black color ink containing, as a coloring agent, carbon black can be additionally used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a full-color recorded image comprising ink for a jet printer, and more particularly to a cyan, magenta and yellow jet which forms a full-color recorded image having excellent color rendering properties and light fastness. The present invention relates to a combination of pigments used for a printer ink.

[0002]

2. Description of the Related Art In a full-color image recorded by a jet printer, a beautiful image such as an electrophotograph or an offset print is provided. At present, dyes are used in these full-color recorded images.

On the other hand, inks for ink jet printers are shifting from dyes to pigments in terms of light resistance and water resistance. When transferring from dyes to pigments, high transparency, high definition, and excellent color rendering properties are required. For example, JP-A-3-76767 discloses diazobutylene maleic acid and a monoazo pigment having a specific chemical structure of yellow (CI pigment yellow 1, 3, 74, etc.).
Ink-jet recording liquid containing
No. 8 discloses an inkjet recording liquid containing a styrene-maleic acid copolymer and a quinacridone pigment, and JP-A-3-79680 discloses an inkjet recording liquid containing a styrene-maleic acid copolymer and a copper phthalocyanine pigment. Liquids and the like are disclosed, respectively, and indicate that a pigment is used as a colorant.

On the other hand, with the advent of the multimedia era, the use of inkjet printers has expanded from the office field to the personal field, and has been used for printing in small quantities.
Further, it is spreading to industrial uses such as printing. In these applications, by using the conventional pigment, a beautiful color image can be produced, but the light fastness is not always satisfactory. In addition, a combination of pigments that satisfies the light resistance of a color image has a problem in that the color rendering property for providing a beautiful color image is poor.

[0005]

The problem to be solved by the present invention is to provide a full-color recording image of a jet printer ink which has high color rendering properties and excellent light resistance that can withstand outdoor use. To provide images.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, C.I.
I. Pigment Blue 15: 3, and C.I. I. Pigment Red 122, and C.I. I. Pigment Yellow 154
It has been found that the use of is able to provide a full-color recorded image having high color rendering properties and light resistance higher than that of the conventional art, and completed the present invention.

That is, according to the present invention, in order to solve the above-mentioned problems, (1) in a full-color recording image composed of cyan, magenta and yellow jet printer inks, cyan is used as a colorant; I. Pigment
Blue: 15: 3, magenta color as a colorant. I. Pigment Red 122, and C.I. I. Pigment Yellow 1
In a full-color recorded image containing C.54 and (2) a full-color recorded image composed of cyan, magenta, yellow, and black, cyan is used as a colorant in C.I. I. Pigment Blue 15: 3, and the color of magenta is C.I. I. Pigment Red 1
22 and a yellow color is C.I. I. Pigment Yellow 154, wherein the black color provides a full-color recorded image containing carbon black as a colorant.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a cyan colorant, C.I.
I. Pigment Blue 15, 15: 1, 15: 2,
Phthalocyanine pigments such as 15: 3, 15: 4, and 15: 6 are exemplified. From the viewpoint of enhancing the color rendering properties, as a cyan colorant that forms a full-color image of the present invention,
C. I. Pigment Blue 15: 3. C.I. I. Pigment Blue 15: 3,
From the viewpoint of transparency, color density, and dispersibility of the pigment, the maximum particle diameter of the primary particles of the colorant is preferably 200 nm or less, and the average particle diameter of the primary particles is preferably in the range of 10 to 100 nm, preferably 20 to 70 nm. Are more preferably in the range of 20 to 60 nm.

The average particle size of the primary particles of the colorant is 10 nm.
If it is smaller, the dispersibility in the ink tends to deteriorate, and the average particle size of the primary particles of the colorant is 100 n.
If it is larger than m, the transparency is inferior and the color rendering properties in the superimposed color portion (intermediate colors such as green and violet) tend to deteriorate, which is not preferable.

The C.I. I. Pigment Blue
In addition to 15: 3, a pigment derivative, a pigment dispersant, a surfactant and the like can be used in combination.

C. I. Pigment Blue 15: 3 which can be used in combination with, for example, a halogen group,
Examples include phthalocyanine derivatives having a phthalimide group, a dialkylaminomethyl group, a sulfonamide group, a sulfonate amine base, or a sulfonate metal base.

Further, C.I. I. Pigment Blue 1
The polymer dispersant that can be used in combination with 5: 3 may be, for example, a polymer dispersant having a molecular weight of 1000 or more, such as “BYK-160” or “BYK” manufactured by BYK-Chemie.
-162 "," BYK-164 "," BYK-18 "
2 "," EFKA-401 "and" EFK "manufactured by EFKA
A-402 ", Zeneca" Sol Spurs 2400 "
0 "and the like, but are not limited thereto.

When a pigment derivative or a pigment dispersant is used in combination, the proportion of the pigment used is preferably 20 parts by weight or less, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the pigment.

C. used in the present invention. I. Pigment Blue 15: 3 obtained by a conventionally known production method is sufficient. Particularly preferred production methods include, for example, phthalic anhydride, urea, anhydrous cuprous chloride, ammonium molybdate and a solvent. A mixture of alkylbenzene having an alkyl group having 5 to 8 carbon atoms is reacted at a high temperature, washed and dried to produce a crude copper phthalocyanine pigment, which is formed into a pigment by a known method (of primary particle diameter (crystal)). A method of controlling the shape, size, and crystal form). Among the pigmentation methods, preferred methods include:
Using a dry mill such as an attritor, 5 to 5
After mixing balls and lots with a size of 50 mm and dry milling, heat treatment is performed in water, an organic solvent, or a mixed solution thereof, and a method of crystal growth, together with a grinding aid and a solvent. A wet grinding method using a machine such as a kneader or a Simpson mix muller may be used.

Among the above methods, especially in the case of dry grinding in terms of controlling the particle size, 100 parts of the crude pigment is used in 100 to 10,000 parts of a ball or lot, and the number of rotations is 5 parts.
It is preferable to carry out in the range of 0 to 1000 rpm and the grinding temperature in the range of room temperature to 100 ° C.

The type of the organic solvent to be subjected to the heat treatment after the dry grinding is, for example, an aliphatic hydrocarbon solvent such as hexane or mineral spirit; benzene, toluene, or the like.
Aromatic hydrocarbon solvents such as xylene; ester solvents such as butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol and isobutanol; dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine and the like And aprotic polar solvents. These solvents can be used alone or in combination of two or more. Of these, aromatic hydrocarbon solvents such as toluene and xylene, and alcohol solvents such as isopropyl alcohol and isobutanol are preferable from the viewpoint of controlling the particle diameter and the recovery of the solvent.

After dry milling, the proportion of the crude pigment and water or organic solvent used in the heat treatment in water, an organic solvent or a mixture thereof is based on 100 parts by weight of the crude pigment and water or organic solvent. The ratio of the solvent and the mixture thereof is preferably 500 parts by weight or more, and particularly preferably in the range of 600 to 3000 parts by weight. When the proportion of water or an organic solvent or a mixture thereof is less than 500 parts by weight, the crude pigment tends to be difficult to uniformly disperse in the solution, which is not preferable.
If the amount is more than 0 parts by weight, the economy and productivity tend to deteriorate, which is not preferable. Particularly preferred conditions are a mixture of water and an organic solvent, and the proportion of the organic solvent in the mixture is in the range of 5 to 50% by weight, more preferably 5 to 40% by weight.

After the dry grinding, the temperature of the heat treatment in water, an organic solvent, or a mixture thereof is 50 to 18
The temperature is preferably in the range of 0 ° C., particularly preferably in the range of 70 to 150 ° C., and the pressure is preferably in the range of normal pressure to 10 kg / m ² . When the treatment temperature is lower than 50 ° C., the crystal of the pigment does not grow, or even if it grows, it takes too much time and the productivity tends to deteriorate. This is not preferable because the particles tend to grow too much and the particle diameter tends to be large, and the color rendering properties of a full-color recorded image tend to be poor.

In the wet grinding, salt and sodium sulfate are used as grinding aids. The ratio of the grinding aid used is 100 pigments.
The range is preferably from 100 to 1000 parts by weight, more preferably from 300 to 800 parts by weight, based on parts by weight.

Examples of the solvent used in the wet grinding include, for example, aliphatic hydrocarbon solvents such as hexane and mineral spirit; aromatic hydrocarbon solvents such as benzene, toluene and xylene; and butyl acetate and the like. Ester solvents; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and isobutanol; glycol solvents such as ethylene glycol, diethylene glycol, and polyethylene glycol; aprotic solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and pyridine Polar solvents and the like. These solvents can be used alone or in combination of two or more. Among these solvents,
From the viewpoint of controlling the particle diameter and the recovery of the solvent, a glycol-based solvent is preferred.

The proportion of the solvent used in the wet grinding is preferably in the range of 50 to 1,000 parts by weight, particularly preferably 100 to 800 parts by weight, per 100 parts by weight of the pigment. When the use ratio of the solvent exceeds 1000 parts by weight, the liquid viscosity becomes low, and the grinding tends not to progress. Therefore, when the amount is less than 50 parts by weight, the liquid viscosity tends to be high and the grinding cannot be performed. This is not preferred.

The temperature at the time of wet milling is preferably in the range of from room temperature to the boiling point of the solvent used for wet milling, and is preferably 60 to 1
The range of 50 ° C. is most preferable both economically and productively.

The wet grinding time is preferably as short as possible, but is preferably in the range of 2 to 10 hours for controlling the particle size. If the time is shorter than 2 hours, coarse particles tend to remain, which is not preferable. Further, even if the wet grinding is performed for more than 10 hours, the grinding does not proceed and the particle size tends to be reduced. Performing for more than 10 hours is not efficient, as it is.

The ground material obtained by wet grinding is washed with water to remove the grinding solvent and grinding aid, dried, and ground to obtain a pigment. If necessary, there is no problem even in the form of a wet cake after washing.

The magenta colorant for forming a full-color image of the present invention includes C.I. I. Pigment Red
122, but the conventional C.I. I. Azo pigments such as CI Pigment Red 48: 3, 57: 1, 53: 1,
Due to insufficient light resistance, it cannot be used as a main component of the magenta colorant for forming a full-color image of the present invention under conditions used outdoors or the like. C.I. I. Pigment Red 122, in consideration of transparency, color density, and pigment dispersibility, the maximum primary particle diameter of the colorant is 200 nm or less, and the average primary particle diameter is 1
Those having a range of 0 to 100 nm are preferable, and 20 to 7 nm are preferable.
More preferably, the thickness is in the range of 0 nm to 20 to 60 n.
Those in the range of m are particularly preferred.

The primary particles of the colorant have an average particle diameter of 10 nm.
If it is smaller, the dispersibility of the pigment tends to be remarkably poor, and the average particle size of the primary particles of the colorant is 100 n.
If it is larger than m, the transparency is inferior, and the color rendering properties in the superimposed color portion (intermediate colors such as orange and violet) tend to deteriorate, which is not preferable.

Further, C.I. I. Pigment Red 12
2, other quinacridone pigments and pigment derivatives, pigment dispersants, nonionic, anionic and cationic surfactants and the like can also be used in combination.

C. I. Other quinacridone pigments that can be used in combination with CI Pigment Red 122 include, for example, unsubstituted quinacridone, 2,9-dicrolquinacridone,
3,10-dichloroquinacridone, 4,11-dichloroquinacridone, 2,9-dimethoxyquinacridone,
Quinacridone quinone and the like.

C. I. Examples of the pigment derivative that can be used in combination with Pigment Red 122 include a quinacridone derivative having a halogen group, a phthalimide group, a dialkylaminomethyl group, a sulfonamide group, a sulfonate amine group, or a sulfonate metal base. .

Further, C.I. I. Pigment Red 12
As a polymer dispersant that can be used in combination with 2, for example, a polymer dispersant having a molecular weight of 1000 or more may be used, and for example, “BYK-160” and “BYK-16” manufactured by BYK-Chemie.
2 "," BYK-164 "," BYK-182 ", EF
"EFKA-401" and "EFKA-40" manufactured by KA
2 "and" SOLSPERS 24000 "manufactured by Zeneca Corporation, but are not limited thereto.

When a pigment derivative or a pigment dispersant is used in combination, the proportion used is preferably 20 parts by weight or less, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the pigment.

C. used in the present invention. I. Pigment Red 122 can be obtained by a conventionally known production method, but a particularly preferable production method is, for example, a method in which 2,5-ditoluidinoterephthalic acid is dissolved in a polyphosphoric acid or a polyphosphate alkylester solution. The cyclization reaction solution obtained by performing the cyclization reaction was taken out into water and washed to produce a crude 2.9-dimethylquinacridone pigment, which was then pigmented by a known method (the shape and size of the primary particle diameter (crystal), the crystal size). Control method).

The method for producing 2.9-dimethylquinacridone crude pigment will be described more specifically. One part of 2,5-ditoluidinoterephthalic acid (part by weight, hereinafter the same) is used.
Using 2 to 10 parts of a condensing agent such as polyphosphoric acid or an alkyl acid polyphosphate having a phosphoric acid concentration of 110 to 125% by weight, at a temperature of 100 to 180 ° C, preferably 110 to 150 ° C, for 2 to 12 hours, preferably The mixture is condensed and cyclized with stirring for 2.5-7 hours. Next, this cyclization reaction solution is taken out into water at least 3 times the weight of the cyclization reaction solution. After taking it out into water, it is filtered and washed thoroughly with water.

A preferred method for pigmentation is:
After washing the wet cake-like crude pigment in water or organic solvent,
In these mixed solutions, a heat treatment is performed to grow crystals, or a dried crude pigment is treated with a sulfuric acid concentration of 90% by weight.
After dissolving in the above-mentioned sulfuric acid solution, a method of taking out into water at a temperature of 0 to 50 ° C. may be mentioned.

The wet pigment in the form of a wet cake is treated with water or an organic solvent or a mixture thereof in an organic solvent. Examples of the organic solvent include aliphatic hydrocarbon solvents such as hexane and mineral spirits; benzene and toluene. Hydrocarbon solvents such as benzene, xylene, etc .; ester solvents such as butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol, isobutanol, etc .; dimethylformamide, dimethyl sulfoxide, N
Aprotic polar solvents such as -methylpyrrolidone, pyridine and the like. These solvents can be used alone or in combination of two or more. Among these organic solvents, from the viewpoint of controlling the particle diameter and the recovery of the solvent, toluene, an aromatic hydrocarbon solvent such as xylene, or isopropyl alcohol, a mixture of an alcohol solvent of isobutanol and water are preferable. .

When the wet pigment is heated in a mixed solution of water or an organic solvent and water or an organic solvent, the ratio of the used amount of the crude pigment to water or the organic solvent is 100 parts of the crude pigment with respect to 100 parts of the crude pigment. The proportion of the solvent or their mixture is 500
Parts or more is preferable, and the range of 600 to 3000 parts is particularly preferable. The ratio of water, organic solvent, or a mixture thereof is 5
When the amount is less than 00 parts, the crude pigment tends not to be dispersed.
It is not preferable because economy and productivity tend to deteriorate. Particularly preferable conditions are a mixture of water and an organic solvent, and the proportion of the organic solvent in the mixture is 5 to 50% by weight.
Is preferable, and the range of 10 to 40% by weight is particularly preferable.

The temperature at which the wet pigment is subjected to heat treatment in water or an organic solvent or a mixture thereof is preferably in the range of 50 to 180 ° C., more preferably 70 to 150 ° C.
Is particularly preferable, and the pressure is from normal pressure to 10 kg / m ^2.
Is preferable. When the temperature is lower than 50 ° C., the crystal of the pigment does not grow, or even if it grows, it takes too much time and the productivity tends to deteriorate, which is not preferable. When the temperature exceeds 180 ° C., the crystal grows. This is not preferred because the particle size tends to be too large and the color rendering of a full-color recorded image tends to be poor.

In a method in which the dried crude pigment is dissolved in sulfuric acid and then taken out in water, the amount of the sulfuric acid solution may be 100
500 parts by weight of a sulfuric acid solution having a sulfuric acid concentration of 90% by weight or more
Parts or more is preferable, and the range of 600 to 2000 parts is more preferable.

The temperature at which the dried crude pigment is dissolved in sulfuric acid is preferably in the range of 0 to 80 ° C, particularly preferably in the range of 0 to 50 ° C. If the temperature at which the dried crude pigment is dissolved in sulfuric acid is higher than 80 ° C., quinacridone may be sulfonated, which results in dissolution in water, which is not preferable.

The amount of water when the sulfuric acid solution of the dried crude pigment is taken out into water is not limited as long as the amount of the precipitated pigment is obtained.

The temperature at which the dried sulfuric acid solution of the crude pigment is taken out into water is preferably as low as possible, and particularly preferably in the range of 0 to 50 ° C.

As a method of taking out a sulfuric acid solution of a dried crude pigment into water, for example, a method of slowly adding a sulfuric acid solution to stirred water and taking out the solution, mixing water and a sulfuric acid solution on a line mixer, At a glance.

The yellow colorant for forming a full-color image of the present invention includes C.I. I. Pigment Yellow 154 is used. C. I. Pigment Yellow 8
3, 17, 12, 13, 14 and the like are excellent in transparency and clarity, but are inferior in light resistance in applications where they are used outdoors. Therefore, yellow colorants for forming a full-color recorded image of the present invention are used. Cannot be used as the main component of Further, C.I. I. Pigment Yellow 154
There is no particular limitation as long as the light fastness is particularly good, but in consideration of transparency, color density, and dispersibility of the pigment, the maximum particle size of the primary particles of the colorant is 200 nm or less, and the average particle size of the primary particles. The diameter is preferably in the range of 10 to 100 nm, more preferably in the range of 20 to 80 nm, and particularly preferably in the range of 20 to 60 nm. If the average particle diameter of the primary particles is within this range, the particles may be treated with a pigment derivative, a pigment dispersant, a surfactant, rosin, or the like.

The average particle size of the primary particles of the colorant is 10 nm.
If it is smaller, the dispersibility of the pigment tends to be remarkably poor, and the average particle size of the primary particles of the colorant is 100 n.
If it is larger than m, the transparency is inferior and the color rendering properties in the superimposed color portion (intermediate colors such as orange and green) tend to deteriorate, which is not preferable.

C. used in the present invention. I. Pigment Yellow 154 can be obtained by a conventionally known production method, but a particularly preferable production method is, for example, a diazotization reaction in which an amine component is reacted with sodium nitrite under hydrochloric acid at a low temperature. A method of producing a azo-based crude pigment by performing a diazo coupling reaction with a coupling component and subjecting the azo-based pigment to a surface treatment with a resin such as rosin or a synthetic resin, or wet-grinding the crude pigment with an aqueous-based grinding medium Method and the like.

In the diazotization method, 1 to 15 parts of O-aminobenzotrifluoride is added to 100 parts of a 1 to 15% by weight aqueous hydrochloric acid solution with stirring, and the mixture is added at a low temperature (5 ° C.).
Under the following), a method of adding 0.5 to 10 parts of sodium nitrite and diazotizing the same is mentioned. Since impurities are contained in the reaction solution after the diazotization, it is desirable to purify the reaction solution by adding activated carbon and filtering. Furthermore, it is desirable to decompose excess nitrous acid using sulfamic acid.

Next, 5 to 25 parts of 5-acetoacetylaminobenzimidazolone is added to 100 parts of water,
Under stirring, add 1 to 15 parts of sodium hydroxide, keep the dissolved solution at 10 ° C. or lower, add 1 to 15 parts of acetic acid, precipitate acetoacetylaminobenzimidazolone, and after the precipitation is completed. , 0.3 to 5 parts by weight of sodium hydroxide to prepare the coupling component.

The diazo solution prepared above is slowly fed into the coupling component prepared above for 1 to 5 hours to cause a coupling reaction. When the reaction temperature is lower than room temperature, a cooling device is required, and when the reaction temperature is higher than 50 ° C., crystals grow, so the range of room temperature to 50 ° C. is preferable.

The slurry after the coupling reaction is converted into a natural resin such as alkali-soluble rosin, styrene-maleic acid,
By treating with a synthetic resin such as styrene acrylic acid or acrylic acid, the filterability is improved and the washing becomes easier. As a treatment method, a natural resin or a synthetic resin is added to the slurry after the coupling reaction, and the pH is adjusted to 8 by adding an alkali.
As described above, the mixture is stirred for 30 minutes or more, and heat treatment is performed as necessary. The conditions of the heat treatment are in the range of 50 to 95 ° C.
Processing times range from 1 to 5 hours. Next, to this slurry, an inorganic acid such as sulfuric acid and hydrochloric acid, or an organic acid such as formic acid and acetic acid is added for acid precipitation, or calcium chloride, salted out using an inorganic salt such as barium sulfate or aluminum sulfate, After the resin is precipitated on the surface of the pigment, the resin is filtered, washed with water, and, if necessary, dried to obtain a wet cake-like or powder-like azo pigment.

Examples of the alkali used in the above treatment method include inorganic salts such as sodium hydroxide and potassium hydroxide; and organic amines such as ammonia, triethylamine and dimethylaminoethanol.

The amount of the resin used in the above treatment method is preferably in the range of 2 to 50 parts, more preferably in the range of 5 to 20 parts, based on 100 parts of the pigment.

On the other hand, C.I. I. Pigment Yellow 1
Examples of a method of wet grinding the 54 crude pigments in the presence of a grinding medium in an aqueous system include wet grinding using a bead mill, a ball mill, a kneader or the like. In particular, wet grinding using a bead mill is preferable because a non-agglomerated pigment is obtained and productivity is excellent.

In the wet grinding using a bead mill, C.I.
I. Pigment Yellow 154 crude pigment in a ball,
It is wet-milled using a disperser together with beads and lots.

At the time of wet grinding, various dispersants, additives, resins, solvents and the like can be added. Among these,
The combined use of an alkali-soluble resin is particularly preferred from the viewpoint of preventing re-aggregation of the pigment during wet grinding. When an alkali-soluble resin is used, after wet milling, an acid is added to change the alkaline atmosphere to an acidic atmosphere to precipitate the resin, or a metal salt is added by adding an organic amine such as barium chloride, calcium chloride, or alkylamine. The surface treatment of the pigment can be performed by insolubilizing the resin by converting the resin into an amine salt.

The solvent used in the wet grinding is water,
Alternatively, any substance may be used as long as it is a substance in which a water-soluble organic solvent and various alkalis are dissolved in water, and there is no problem even if other additives are contained.

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

The amount of the water-soluble organic solvent added is water 10
The range of 0 to 100 parts by weight relative to 0 parts by weight is preferable.

Examples of the alkali include ethanolamine, diethanolamine, triethanolamine, N
-Methylethanolamine, N-dimethylethanolamine, N-ethyldiethanolamine, N-diethylethanolamine, diisopropanolamine, 2-amino-2-methylpropanol, 2-ethyl-2-amino-1,3-propanediol, Examples thereof include organic amines such as 2- (aminoethyl) ethanolamine, tris (hydroxymethyl) aminomethane, ammonia, triethylamine, piperidine, and morpholine, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

When these organic amines are used, the pH of the alkaline atmosphere is preferably 7 or more, more preferably 8 or more. If the pH is lower than 7, the resin may be precipitated, and the viscosity of the solution may increase, so that grinding may not be possible.

Examples of the alkali-soluble resin include natural resins such as rosin, styrene-maleic acid copolymers having acidic groups such as carboxyl groups and sulfonic acid groups, styrene-acrylic acid copolymers and acrylic acid resins. Known general resins such as a polyvinyl resin, a polyester resin, a urethane resin, and a synthetic resin of an amide resin are exemplified, but not particularly limited thereto.

The concentration of the crude pigment in the solution is preferably as high as possible as long as it can be dissolved.
The range is preferably from 40 to 40% by weight, more preferably from 10 to 30% by weight.

The concentration of the alkali-soluble resin in the solution is 40
% By weight or less, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight.

Examples of the acid used to change the alkaline atmosphere to an acidic atmosphere after the wet milling include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as acetic acid and formic acid. Preferably, it is used. The addition amount of these acids is sufficient as long as the resin can be precipitated on the pigment surface.

Examples of the dispersing machine used for wet grinding include a bead mill such as a DCP mill, a sand mill and a Dyno mill, an attritor, a ball mill and the like. In particular, among these, it is preferable to use a bead mill such as a DCP mill or a Dyno mill that can be manufactured continuously.

Examples of grinding media used for wet-grinding the crude pigment include steel beads, glass beads, ceramic beads and the like. The size of the grinding medium is preferably in the range of 0.1 to 30 mm, and 0.2 to 3 m
The range of m is particularly preferred.

The temperature at which the crude pigment is wet-milled is not particularly limited, but is preferably in the range from room temperature to the boiling point of the solvent to be used, since no equipment such as a pressure-resistant container or a cooling device is required, which is preferable.

The grinding time is not particularly limited, but a shorter time is preferable because no energy is required.

The peripheral speed of stirring of the dispersing machine depends on the type of the dispersing machine, the type of beads and the composition of the dispersing medium, and is not particularly limited as long as the particle size of the crude pigment can be adjusted to 10 to 100 nm.

The thus obtained C.I. I. Pigment Yellow 154 can be used as a wet cake, or as a dry pigment after dry pulverization, as a colorant for various articles such as printing inks, paints, plastics, printing agents, toners, and jet inks. Utilizing clarity, transparency and light resistance, it can be particularly suitably used for ink-jet inks.

The carbon black used as the black colorant is processed into various structures during the production process. Particularly preferred structures are those having a maximum primary particle diameter of 20%.
0 nm or less, and the average particle size of the primary particles is 10 to 10
Those having a range of 0 nm are preferable, and those having a range of 10 to 50 nm are particularly preferable. Further, as the type of carbon black, neutral or alkaline carbon black is preferable.

Each colorant is dispersed in an ink medium by using various dispersers such as a bead mill, a roll mill, a sand mill, a kneader and the like in order to prepare an ink for a jet printer.

The dispersion conditions are not limited because they vary depending on the type of disperser and the ink composition. However, in terms of the production cost of the ink, preferable conditions are that the pressure is in the range of normal pressure to 5 kg / m ² and the temperature is in the range of normal temperature to 100 ° C.

The content of the colorant in the ink medium is preferably in the range of 1 to 20% by weight based on 100% by weight of the ink.
A range of 1.5 to 10% by weight is particularly preferred.

The ink medium is composed of a solvent, a resin, a surfactant, a base, various additives and the like added as required.

The solvent constituting the ink medium generally comprises water, a water-soluble organic solvent or a mixture thereof.
In the case of a non-aqueous system, it comprises an organic solvent.

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

The content of the water-soluble organic solvent in the ink is as follows:
It is preferably at most 50% by weight, particularly preferably in the range of 0 to 30% by weight.

Examples of the resin optionally used in the ink medium include natural proteins such as glue, gelatin, casein, albumin, gum arabic, and fish grew, alginic acid, methylcellulose, carboxymethylcellulose, polyethylene oxide, hydroxyethylcellulose, and the like. Examples thereof include synthetic polymers such as polyvinyl alcohol, polyacrylamide, aromatic amide, polyacrylic acid, polyvinyl ether, polyvinylpyrrolidone, acryl, polyester, styrenemaleic acid, and styreneacrylic acid resin.

These resins are used as needed for the purpose of stabilizing the dispersion of the colorant, adjusting the fixability and viscosity, and improving the drying property. The water-soluble resin in the ink when used in the ink is used. The content of the resin is preferably 30% by weight or less, particularly preferably 20% by weight or less.

Examples of the surfactant used in the ink medium as required include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, and alkyl diphenyl ether disulfonates. Anionic surfactants such as salts, alkyl phosphates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl allyl sulfates, and cationics such as alkylamine salts, quaternary ammonium salts, alkyl betaines, and amine oxides And amphoteric surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, nonionic surfactants such as polyoxyethylene sorbitol fatty acid esters and glycerol fatty acid esters. These surfactants are used to adjust the interfacial tension of the ink or to improve the dispersibility of the colorant. When used in an ink, the content of the surfactant in the ink is as follows. , Preferably at most 10% by weight, particularly preferably at most 5% by weight.

The base used as needed in the ink medium includes an inorganic base and an organic amine. Examples of the inorganic base include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Examples of the organic amine include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethyldiethanolamine, and 2-amino-2-amine.
Methylpropanol, 2-ethyl-2-amino-1,3
-Propanediol, 2- (aminoethyl) ethanolamine, tris (hydroxymethyl) aminomethane, ammonia, piperidine, morpholine and the like.
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 an ink, the content of the base in the ink is preferably 10% by weight or less, and more preferably 5% by weight. The following are particularly preferred.

Further, additives such as a preservative, a viscosity adjuster, a pH adjuster and a chelating agent can be used in the ink medium.

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

Examples of the ink jet printer include, but are not particularly limited to, a piezo type using a piezoelectric element in a printer head; and a heat type that applies heat energy to a recording liquid to eject ink as droplets from micropores for recording. can give.

Further, the image can be fixed 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 ink.

The average particle size of the primary particles in the present invention is the average of the values obtained by sampling several tens of colorants from an electron micrograph of the colorant and dividing the value obtained by adding the major and minor diameters by two. is there.

[0088]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following, "part" and "%"
Represents "parts by weight" and "% by weight" unless otherwise specified.

<< Production of Colorant >><Production Example 1> (CI Pigment Blue 15: 3)
Production Example of Pigment) 1218 parts of phthalic anhydride, 1540 parts of urea, 200 parts of cuprous chloride, 5 parts of ammonium molybdate and 4000 parts of a mixture of alkylbenzene having an alkyl group having 5 to 8 carbon atoms as a solvent are reacted. The mixture was charged into a vessel, heated with stirring and heated to 200 ° C., and reacted at the same temperature for 2.5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, the remaining reaction product was added to 8000 parts of 2% hydrochloric acid, and the mixture was stirred at 70 ° C. for 1 hour, followed by suction filtration. After sufficiently washing the cake thus obtained with warm water of 80 ° C.,
Drying gave crude copper phthalocyanine.

Next, the crude copper phthalocyanine 350
Parts, 2450 parts of salt, and 450 parts of diethylene glycol were charged into a kneader, the temperature was 120 ° C., the number of revolutions was 40 rpm,
The wet grinding was performed for 8 hours. During grinding, 25 parts of diethylene glycol were added every hour. After the wet milling, the wet milling mixture was dispersed in 35,000 parts of a 1% aqueous hydrochloric acid solution and stirred for 2 hours to wash impurities. After washing, filtration, the residue collected by filtration was washed with water, and dried in a dryer at 96 ° C. for 12 hours.
By pulverizing, a copper phthalocyanine pigment (CI pigment blue 15: 3 pigment) was obtained.

The maximum primary particle diameter of particles obtained by photographing this pigment with an electron microscope was 95 nm, and the average primary particle diameter was 45 nm.

<Production Example 2> (Production of CI Pigment Blue 15: 3 Pigment) 100 parts of the copper phthalocyanine crude pigment obtained in Production Example 1
In the presence of 2700 parts of 0 mmφ steel balls, a cylindrical grinding container having a longitudinal axis, a rotating shaft arranged along this axis, and fixed to the rotating shaft, each of which is fixed to a side wall of the grinding container. A stirrer having two or more pairs of arms extending symmetrically outwardly, and using an attritor mill described in JP-A-58-29861, which is filled with steel balls as a grinding medium. The dry pulverization was performed under the conditions of a pulverization time of 5 hours, a rotation speed of 300 rpm, and a pulverized material temperature of 90 ° C.

After the dry pulverization, 100 parts of the pulverized crude pigment from which the balls were removed, 400 parts of isobutyl alcohol and 80 parts of water
0 parts were weighed and placed in a three-necked flask and subjected to a heat treatment at 90 ° C. for 5 hours. Thereafter, the solvent was distilled off, and suction filtration was performed. The cake thus obtained was sufficiently washed with warm water of 60 ° C.
After drying in a drier at C.C. I. Pigment Blue 15: 3 pigment was obtained.

The maximum primary particle diameter of particles obtained by photographing the pigment with an electron microscope was 110 nm, and the average primary particle diameter was 52 nm.

<Production Example 3> (Production of CI Pigment Red 122 pigment) 100 parts of 2,5-di (p-toluidino) terephthalic acid and 300 parts of polyphosphoric acid having a phosphoric acid concentration of 119.5% Is stirred at a temperature of 125 ° C. for 3 hours to give 2,
5-Di (p-toluidino) terephthalic acid was condensed and cyclized. The condensed liquid was added to 3000 parts of water to crystallize dimethylquinacridone. After crystallization, the residue was filtered and washed with water until the washing liquid of the filtered residue became neutral.
A wet cake of 2.0% crude pigment of dimethylquinacridone (CI Pigment Red 122) was obtained.

141 parts of this wet cake, 270 parts of isopropyl alcohol, and 174 parts of water were charged into an autoclave container and heated at 91 ° C. for 5 hours. After the heat treatment, the solvent was distilled off, and the residue collected by filtration was 40 to 60 ° C.
After washing with hot water and drying with a drier at 96 ° C., pulverization was performed to produce dimethylquinacridone (CI Pigment Red 122) pigment.

The maximum primary particle diameter of particles obtained by photographing this pigment with an electron microscope was 85 nm, and the average primary particle diameter was 48 nm.

<Production Example 4> (Production of CI Pigment Red 122 Pigment) The wet cake of the crude dimethylquinacridone pigment produced in Production Example 3 was dried overnight at 96 ° C. and then ground. Thus, a powdery crude pigment was obtained.

10 parts of this powdery crude pigment was slowly added to 100 parts of 98% sulfuric acid under stirring, and dissolved at a temperature of 20 ° C. or less. This solution was slowly added to 4000 parts of stirring ice water at 0 ° C. After the addition, stirring was continued for 2 hours in that state, followed by filtration. The residue obtained by filtration was washed with water, dried in a drier at 96 ° C, and then pulverized to obtain a dimethylquinacridone pigment (CI Pigment Red).・ 12
2) was manufactured.

The maximum primary particle diameter of particles obtained by photographing this pigment with an electron microscope was 55 nm, and the average primary particle diameter was 25 nm.

<Production Example 5> (Production of CI Pigment Yellow 154 pigment) 9 parts of 2-aminobenzotrifluoride, 100 parts of water and 23.1 parts of 35% hydrochloric acid were added to a reaction vessel, and cooled. Then 0
While maintaining the temperature at 5 ° C. and stirring, 4.2 parts of sodium nitrite was added to carry out a diazotization reaction. After continuing stirring for 2 hours as it was, 4 parts of activated carbon was added, and 6 parts of 10% sulfamic acid was added to the filtered filtrate to decompose excess sodium nitrite to prepare a diazo liquid.

Next, 120 parts of water and 5-
13.4 parts of acetoacetylaminobenzimidazolone and 25 parts of 20% sodium hydroxide were added to the reaction vessel, melted at room temperature, and 140 parts of ice was added to this solution to adjust the temperature of the solution to 5 ° C. 37.8 parts of 20% acetic acid was added to precipitate acetoacetylaminobenzimidazolone as a reaction product. After precipitation, 20% sodium hydroxide was added to the reaction mixture to adjust the pH of the reaction mixture to 4.5 to 6 to prepare a coupler component.

The diazo solution was added dropwise to the coupler component over about 2 hours, and while maintaining the pH in the range of 4 to 6.5,
The coupling reaction was performed at 30 ° C. After the completion of the coupling reaction, the temperature was raised to 85 ° C. and heat treatment was performed for 2 hours. Then, the reaction product was collected by filtration, the residue was washed with water, dried, and pulverized to obtain C.I. I. Pigment Yellow 154 was obtained.

100 parts of the above crude pigment, John Krill J61
J (manufactured by Johnson Polymer) 67 parts, isopropyl alcohol 50 parts and water 283 parts were mixed.

Using a stirrer type bead mill (“DCP Mill SF-12” manufactured by Dry Swerke), this mixture was stirred at an outer peripheral speed of 11 m / sec and a diameter of 0.20 mm.
Of zirconia beads (“Micro Haica Z200” manufactured by Showa Shell Sekiyu KK) with a filling amount of 83% and a suspension dispersion temperature of 28 ° C.
Was dispersed for 2 hours to obtain a pigment dispersion having a pH of 8.5.

To this pigment dispersion, 3800 parts of water was added and stirred, and 1N hydrochloric acid was added until the pH of the content became 4.9, whereby a resin was deposited on the pigment surface to obtain a suspension. This suspension was filtered to separate a wet cake-like suspension, and the wet cake-like suspension was washed with water until the pH of the washing solution became nearly neutral. Thereafter, the wet cake washed with water was dried and pulverized, and C.I. I. Pigment Yellow 154 pigment was obtained.

The maximum primary particle diameter of the particles obtained by photographing this pigment with an electron microscope was 140 nm, and the average primary particle diameter was 52 nm.

<Production Example 6> (Production of CI Pigment Yellow 154 pigment) 9 parts of 2-aminobenzotrifluoride, 100 parts of water and 23.1 parts of 35% hydrochloric acid were added to a reaction vessel, and cooled. Then 0
While maintaining the temperature at 5 ° C. and stirring, 4.2 parts of sodium nitrite was added to carry out a diazotization reaction. After continuing stirring for 2 hours as it was, 4 parts of activated carbon was added, and 6 parts of 10% sulfamic acid was added to the filtered filtrate to decompose excess sodium nitrite to prepare a diazo liquid.

Next, 120 parts of water and the coupler 5-
13.4 parts of acetoacetylaminobenzimidazolone and 25 parts of 20% sodium hydroxide were added to the reaction vessel, melted at room temperature, and 140 parts of ice was added to this solution to adjust the temperature of the solution to 5 ° C. 37.8 parts of 20% acetic acid was added to precipitate acetoacetylaminobenzimidazolone as a reaction product. After precipitation, 20% sodium hydroxide was added to the reaction mixture to adjust the pH of the reaction mixture to 4.5 to 6 to prepare a coupler component.

The diazo solution was added dropwise to this coupler component over about 2 hours, and while maintaining the pH in the range of 4 to 6.5,
The coupling reaction was performed at 30 ° C. After the completion of the coupling reaction, 22 parts of a 10% aqueous solution of rosin FF (manufactured by Hercules) was added, and the mixture was stirred for 1 hour. 1N hydrochloric acid was added until the pH of the content reached 5.0, thereby causing the resin to deposit on the pigment surface. To obtain a suspension. This suspension was filtered to separate a wet cake-like suspension, and the wet cake-like suspension was collected by filtration until the pH of the washing solution became about neutral, and washed with water. After that, the wet cake is dried and crushed,
C. I. Pigment Yellow 154 pigment was obtained.

The maximum primary particle diameter of particles obtained by photographing this pigment with an electron microscope was 180 nm, and the average primary particle diameter was 78 nm. << Preparation of ink for jet printer >>

<Preparation Example 1> Cyan ink The C.I. I. Pigment Blue 15: 3
4.0 parts, 6.7 parts of "Johncryl J-61J" (styrene-acrylic resin manufactured by Johnson Polymer Co., Ltd.), 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water, and 0.5 mmφ zirconia beads 150. Part of capacity 10
The solution was weighed into 0 ml polyvin and dispersed for 1 hour using a paint conditioner. To the obtained 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 "Emulgen 147" (a nonionic activator manufactured by Kao Corporation) 1.2
After mixing, the coarse particles were separated by filtration using a 1 μ filter to prepare a cyan ink having a volume average particle diameter of 134 nm.

<Preparation Example 2> Cyan ink In Preparation Example 1, C.I. I. Pigment Blue 15: 3 and the C.I. I.
A cyan ink having a volume average particle diameter of 157 nm was prepared in the same manner as in Preparation Example 1 except that Pigment Blue 15: 3 was used.

<Preparation Example 3> Cyan ink In Preparation Example 1, C.I. I. Pigment Blue 15: 3 instead of Fastogen Bl
ue FGF (C.I.
Pigment Blue 15: 3, volume average diameter 110n
A cyan ink having a volume average particle size of 185 nm was prepared in the same manner as in Preparation Example 1 except that m) was used.

<Preparation Example 4> Magenta Ink In Preparation Example 1, the C.I. I. Pigment Blue 15: 3 and the C.I. I.
Preparation Example 1 except that Pigment Red 122 was used.
In the same manner as in the above, a magenta ink having a volume average particle size of 188 nm was prepared.

<Preparation Example 5> In magenta ink Preparation Example 1, C.I. I. Pigment Blue 15: 3 and the C.I. I.
Preparation Example 1 except that Pigment Red 122 was used.
A magenta ink having a volume average particle diameter of 142 nm was prepared in the same manner as in the above.

<Preparation Example 6> Magenta ink In Preparation Example 1, C.I. I. Pigment Blue 15: 3 instead of Fastogen Su
per Magenta RE-03 (C.I. Pigment Red 122 manufactured by Dainippon Ink and Chemicals, Inc.)
A magenta ink having a volume average particle diameter of 197 nm was prepared in the same manner as in Preparation Example 1 except that the volume average particle diameter was 115 nm.

<Preparation Example 7> Yellow ink The C.I. I. Pigment Yellow 154
4.0 parts, 6.7 parts of “Joncryl J-61J”, 2.0 parts of isopropyl alcohol, 7.3 parts of ion-exchanged water and 150 parts of 0.5 mmφ zirconia beads in a capacity of 10
The mixture was weighed into 0 ml of polyvin and dispersed for 1 hour with a paint conditioner. After mixing 19.8 parts of ion-exchanged water, 2.5 parts of ethylene glycol, 5.0 parts of glycerin, 1.5 parts of diethanolamine and 1.2 parts of “Emulgen 147” with the obtained dispersion, a 1 μ filter was used. The coarse particles were separated by filtration to prepare a yellow ink having a volume average particle diameter of 145 nm.

<Preparation Example 8> Yellow ink In Preparation Example 7, C.I. I. Pigment Yellow 154, and the C.I. I.
A yellow ink having a volume average particle diameter of 193 nm was prepared in the same manner as in Preparation Example 7, except that Pigment Yellow 154 was used.

<Preparation Example 9> Yellow ink In Preparation Example 7, C.I. I. Pigment Yellow 154 instead of Symuler Fas
t Yellow 4192 (Dainippon Ink and Chemicals, Inc.)
C.I. I. Pigment Yellow 154, volume average diameter 220 nm), and a yellow ink having a volume average particle diameter of 394 nm was prepared in the same manner as in Preparation Example 7.

<Preparation Example 10> Yellow ink Symler Fast Yellow 10GH
(C.I. pigment manufactured by Dainippon Ink and Chemicals, Inc.)
Yellow, 3, volume average diameter 140 nm) 4.0 parts, "John Krill J-61J" 6.7 parts, isopropyl alcohol 2.0 parts, ion-exchanged water 7.3 parts and 0.5 mmφ
150 parts of zirconia beads were weighed into a 100 ml poly bottle and dispersed for 1 hour using a paint conditioner. To the obtained 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 "Emulgen 147" were added.
After mixing 2 parts, coarse particles were filtered off using a 1 μ filter to prepare a yellow ink having a volume average particle diameter of 260 nm.

<Preparation Example 11> Yellow ink In Preparation Example 10, the procedure of Symler Fast Ye was repeated.
Instead of llow 10GH, Symler Fas
t Yellow 8GTF (Dainippon Ink and Chemicals
C.I. I. Pigment Yellow 17, volume average diameter 40 nm), and a yellow ink having a volume average particle diameter of 210 nm was prepared in the same manner as in Preparation Example 10.

<Preparation Example 12> Black ink In Preparation Example 1, C.I. I. Pigment Blue 15: 3 instead of “Mitsubishi Carbon # 96
0 ”(Mitsubishi Chemical's carbon black, volume average diameter 1
8 nm), except that a black ink having a volume average particle diameter of 105 nm was prepared in the same manner as in Preparation Example 1.

<< Full Color Recorded Image >><Example1> The cyan ink obtained in Preparation Example 1, the magenta ink obtained in Preparation Example 4, and the yellow ink obtained in Preparation Example 6 were manufactured by Canon Inc. Into a cartridge of the ink jet printer "BJC-400J", and put on a "color BJ paper" (manufactured by Canon Inc.)
Magenta, cyan, blue, green and red color printing was performed to obtain a full-color image.

A full-color image was measured with a D65 light source and a 10-degree visual field using "SF500" manufactured by Datacolor Corporation. The results are shown in Table 1. The full-color image obtained in Example 1 had high color rendering properties and exhibited a beautiful image.

Further, among the color images obtained in Example 1, a light fastness test was performed on the three primary colors of yellow, magenta and cyan using a fade meter for 500 hours, and the results were compared before and after the light fastness test. The color difference ΔE is shown in Table 2. Regarding the light fastness of these images, the color difference was small, and very excellent results were obtained.

<Example 2> The cyan ink obtained in Preparation Example 2, the magenta ink obtained in Preparation Example 5, and Preparation Example 7
Is packed in a cartridge of an ink jet printer “BJC-400J” manufactured by Canon Inc., and placed on a “color BJ paper” (manufactured by Canon Inc.). yellow,
Magenta, cyan, blue, green, red and black color printing was performed to obtain a full-color image.

The color of the full-color image was measured with a D65 light source and a 10-degree visual field using "SF500" manufactured by Datacolor Inc. The results are shown in Table 1. The full-color image obtained in Example 2 had high color rendering properties and exhibited a beautiful image.

Further, among the color images obtained in Example 2, the images of the three primary colors of yellow, magenta and cyan and black were measured using a fade meter.
The light fastness test was performed for a time, and the results are shown in Table 2 in terms of the color difference ΔE before and after the light fastness test. Regarding the light fastness of these images, the color difference was small, and very excellent results were obtained.

<Comparative Example 1> (Example in which a colorant having a particle size exceeding 100 nm was used) The cyan ink obtained in Preparation Example 3, the magenta ink obtained in Preparation Example 6, and the ink obtained in Preparation Example 9 The yellow ink is transferred to the Canon inkjet printer "BJC"
−400 J ”, and color printing of yellow, magenta, cyan, violet, green and red was performed on“ color BJ paper ”(manufactured by Canon Inc.) to obtain a full-color image.

A full-color image was measured with a D65 light source and a 10-degree visual field using “SF500” manufactured by Data Color Corporation, and the results are shown in Table 1. The full-color image obtained in Comparative Example 1 had poor color rendering properties, and a beautiful image was not obtained.

Further, among the color images obtained in Comparative Example 1, the yellow, magenta and cyan images
The light fastness test was performed for 500 hours using a fade meter, and the results are shown in Table 2 with the color difference ΔE before and after the light fastness test. Regarding the light fastness of these images, the color difference was small, and very excellent results were obtained.

<Comparative Example 2> (Example using yellow CI Pigment Yellow 3) Cyan ink obtained in Preparation Example 1, magenta ink obtained in Preparation Example 4, and Preparation Example The yellow ink obtained in Step 10 was used as an ink jet printer "BJ" manufactured by Canon Inc.
C-400J "cartridge, and on a" Color BJ paper "(manufactured by Canon Inc.), yellow, magenta,
Cyan, violet, green and red color printing was performed to obtain a full color image.

The color of the full-color image was measured with a D65 light source and a 10-degree visual field using “SF500” manufactured by Datacolor Corporation. The results are shown in Table 1. The full-color image obtained in Comparative Example 2 had poor red and green color rendering properties, and a beautiful image could not be obtained.

Further, of the color images obtained in Comparative Example 2, a light fastness test was performed on the yellow image for 500 hours using a fade meter, and the result was evaluated by the color difference ΔE before and after the light fastness test. , <Table-2>. In these images, the yellow color disappeared and was not very lightfast enough to withstand outdoor use.

Comparative Example 3 (Example using CI Pigment Yellow 17 of yellow color) Cyan ink obtained in Preparation Example 1, magenta ink obtained in Preparation Example 4, and Preparation Example The yellow ink obtained in Step 11 can be used with an ink jet printer "BJ" manufactured by Canon Inc.
C-400J "cartridge, and on a" Color BJ paper "(manufactured by Canon Inc.), yellow, magenta,
Cyan, violet, green and red color printing was performed to obtain a full color image.

A full-color image was measured with a D65 light source and a 10-degree visual field using “SF500” manufactured by Data Color Corporation. The results are shown in Table 1. The full-color image obtained in Comparative Example 3 had a high color rendering property, and a very beautiful image was obtained.

Further, among the color images obtained in Comparative Example 3, the yellow, magenta and cyan images
The light fastness test was performed for 500 hours using a fade meter, and the results are shown in Table 2 with the color difference ΔE before and after the light fastness test. In these images, the yellow color disappeared and did not have light resistance that could withstand outdoor use.

[0139]

[Table 1]

[0140]

[Table 2]

[0141]

[Table 3]

[0142]

The ink-jet full-color recorded image of the present invention has high color rendering properties and excellent light resistance that can withstand outdoor use.

Claims (3)

[Claims] 1. In a full-color recorded image composed of a cyan ink, a magenta ink and a yellow ink for a jet printer, cyan ink is used as a colorant in C.I. I. Pigment Blue 15: 3,
Magenta ink is C.I. I. Pigment
Red. 122, and the yellow ink is C.I. I. Pigment Yellow 154, which is a full-color recorded image. 2. In a full-color recording image composed of a cyan ink, a magenta ink, a yellow ink and a black ink for a jet printer, the cyan ink is used as a colorant in a full color image. I. Pigment Blue
15: 3, and the magenta ink is C.I. I. Pigment Red 122, and yellow ink is C.I. I. Pigment Yellow 154, wherein the black ink contains carbon black as a colorant. 3. The maximum particle size of the primary particles of the colorant is 200.
nm or less, and the average particle diameter of the primary particles is 10 to 10
3. The full-color recorded image according to claim 1, wherein the image is in a range of 0 nm.