Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B69/00—Dyes not provided for by a single group of this subclass
  • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
  • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0041—Blends of pigments; Mixtured crystals; Solid solutions mixtures containing one azo dye
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0046—Mixtures of two or more azo dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/09—Colouring agents for toner particles
  • G03G9/0906—Organic dyes
  • G03G9/091—Azo dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/09—Colouring agents for toner particles
  • G03G9/0906—Organic dyes
  • G03G9/0914—Acridine; Azine; Oxazine; Thiazine-;(Xanthene-) dyes

Definitions

• the present invention relates to a novel compound, a pigment dispersing agent, a pigment composition and a pigment dispersion that contain the compound, and a full-color toner that uses the pigment composition as a colorant .
• Fine pigment tends to demonstrate strong cohesive force between pigment particles in a medium such as an organic solvent or molten resin, and aggregated pigment ends up causing a decrease in tinting strength.
• Various pigment dispersing agents and pigment compositions containing such pigment dispersing agents have been proposed for improving pigment dispersibility.
• an example has been disclosed that combines the use of a pigment having an azo skeleton and a binder resin having an acidic group (Patent Document 1) .
• a toner has been disclosed that contains a block copolymer or graft copolymer, obtained by polymerizing a styrene-based monomer and acrylate-based monomer (or methacrylate-based monomer) , carbon black and a binder resin in order to improve the dispersibility of carbon black in the toner (Patent Document 2) .
• an azo compound has been disclosed that has a styrene/acrylic-based polymer segment in order to improve the dispersibility of an azo pigment (Patent Document 3) .
• An object of the present invention is to solve the above-mentioned problems. Namely, the present invention provides a compound having both high affinity for various types of pigments as well as high affinity for polymerizable monomers, binder resins and
• the present invention provides a pigment composition having favorable
• the present invention provides a pigment dispersion that demonstrates a favorable dispersed state in a non-water-soluble solvent.
• the present invention provides a full-color toner having high tinting strength by applying a pigment composition using the pigment dispersing agent as a toner colorant.
• the present invention provides a compound in which a partial structure represented by the following formula (1) is bound to a polymer having a monomer unit represented by the following formula ( 2 ) :
• Ar represents an aryl group
• Ar, Ri and ⁇ 3 ⁇ 4 satisfy at least one of the following conditions (i) and (ii) :
• Ar has a linking group that composes a bonding moiety with the polymer obtained by bonding to a carbon atom in the aryl group;
• Ri or R 2 is a linking group that composes a bonding moiety with the polymer
• Ri and R 2 each independently represent hydrogen atoms, alkyl groups, phenyl groups or aralkyl groups, and
• X represents 0, NH or S
• R 3 represents a hydrogen atom or alkyl group
• R 4 represents a phenyl group, carboxyl group, carboxylic acid ester group or carboxylic acid amide group
• the present invention provides a pigment dispersing agent, a pigment composition, a pigment dispersion and a full-color toner that contain the above-mentioned novel compound.
• a novel compound is provided by the present invention.
• a compound in which a partial structure represented by the above-mentioned formula (1) is bound to a polymer having a monomer unit represented by the aforementioned formula (2) demonstrates high affinity for a non-water-soluble solvent, and particularly affinity for a nonpolar solvent and affinity for various types of pigments. Consequently, a pigment composition having improved pigment dispersibility is provided by using the compound according to the present invention as a dispersing agent.
• a pigment dispersion, and preferably a styrene pigment dispersion which has superior
• the pigment composition dispersibility in a non-water-soluble solvent
• a full-color toner having high tinting strength is provided by using the pigment composition as a colorant.
• the partial structure represented by formula (1) is also referred to as an "azo skeleton structure".
• a compound in which an azo skeleton structure is bound to a polymer having a monomer unit represented by formula (2) is also referred to as a "compound having an azo skeleton structure”.
• a compound indicating only a polymer having a monomer unit represented by formula (2) to which an azo skeleton structure is not bound is referred to as a "polymer segment”.
• FIG. 1 is a drawing representing the 13 C-NMR spectrum of a compound (C-l) relating to the present invention as determined in CDC1 3 , at room temperature and at 150 MHz.
• FIG. 2 is a drawing representing the 13 C-NMR spectrum of a compound (C-15) relating to the present invention as determined in CDC1 3 , at room temperature and at 150 MHz.
• FIG. 3 is a drawing representing the 13 C-NMR spectrum of a compound (C-16) relating to the present invention as determined in CDC1 3 , at room temperature and at 150 MHz.
• FIG. 4 is a drawing representing the 13 C-NMR spectrum of a compound (C-44) relating to the present invention as determined in CDC1 3 , at room temperature and at 150 MHz.
• the compound of the present invention is composed of an azo skeleton structure that has high affinity for pigment and is represented by formula (1) and a polymer segment that has high affinity for a non-water-soluble solvent and has a monomer unit represented by formula (2) :
• Ar represents an aryl group
• Ar, Ri and R 2 satisfy at least one of the following conditions (i) and (ii):
• Ar has a linking group that composes a bonding moiety with the polymer obtained by bonding to a carbon atom in the aryl group;
• Ri or R 2 is a linking group that composes a bonding moiety with the polymer
• Ri and R 2 are not linking groups
• Ri and R 2 each independently represent hydrogen atoms, alkyl groups, phenyl groups or aralkyl groups, and
• X represents 0, NH or S
• R 3 represents a hydrogen atom or alkyl group
• R 4 represents a phenyl group, carboxyl group, carboxylic acid ester group or carboxylic acid amide group
• Ar represents an aryl group.
• Ar, R x and R 2 satisfy at least one of the following conditions (i) and
• Ar has a linking group that composes a bonding moiety with the polymer obtained by bonding to a carbon atom in the aryl group;
• Ri or R 2 is a linking group that composes a bonding moiety with the polymer.
• Ri and R 2 are not linking groups
• Ri and R 2 each independently represent hydrogen atoms, alkyl groups, phenyl groups or aralkyl groups.
• alkyl groups represented by Ri and R 2 in the above-mentioned formula (1) include linear, branched or cyclic alkyl groups such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group or cyclohexyl group.
• Examples of aralkyl groups represented by Ri and R 2 in the above-mentioned formula (1) include a benzyl group and phenethyl group.
• Substituents of R x and R 2 in the above-mentioned formula (1) may be further substituted with substituents provided they do not significantly inhibit affinity for pigment.
• substituents that may be substituted include a halogen atom, nitro group, amino group, hydroxyl group, cyano group and trifluoromethyl group .
• R x and R 2 in the aforementioned formula (1) can be arbitrarily selected from the previously listed substituents, phenyl group, hydrogen atom and substituents for bonding with a polymer as a linking group thereof, the case in which they are hydrogen atoms is preferable from the viewpoint of affinity for pigment.
• X in the above-mentioned formula (1) can be arbitrarily selected from an oxygen atom (0) , NH and sulfur atom (S) , the case in which it is O is preferable from the viewpoint of raw material availability.
• Ar in the above-mentioned formula (1) represents an aryl group as previously described.
• aryl groups include a phenyl group and naphthyl group.
• Ar in the above-mentioned formula (1) may be further substituted with a substituent provided it does not significantly inhibit affinity for pigment.
• substituents that may be substituted include an alkyl group, alkoxy group, halogen atom, hydroxyl group, cyano group, trifluoromethyl group, carboxyl group, carboxylic acid ester group and carboxylic acid amide group.
• Ar preferably has a linking group composed of a bonding moiety with the polymer that is obtained by bonding to a carbon atom in the aryl group, and preferably does not have a group other than the linking group as a substituent from the viewpoint of affinity for pigment.
• the partial structure represented by the above-mentioned formula (1) is preferably a partial structure represented by the following formula (3) from the viewpoint of production ease. Namely, the case in which Ar in formula (1) is a phenyl group that may or may not have a substituent is preferable:
• Ri, R 2 and R5 to R 9 is a substituent for bonding with the polymer as a linking group, and in the case Ri, R2 and R 5 to Rg are not linking groups, Ri, R 2 and R 5 to Rg each independently represent a hydrogen atom, COOR10 group or CONR R 12 group, and Ri 0 to R i2 each independently represent a hydrogen atom or alkyl group) .
• R12 in the above-mentioned formula (3) include linear, branched or cyclic alkyl groups such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group or cyclohexyl group.
• Rio to R 12 in the above-mentioned formula (3) can be arbitrarily selected from the previously listed substituents or a hydrogen atom, the case in which R 10 is a methyl group, R is a hydrogen atom and Ri 2 is a methyl group or hydrogen atom is preferable from the viewpoint of affinity for pigment.
• R 5 to R 9 in the above-mentioned formula (3) can be arbitrarily selected from a hydrogen atom, COOR10 group, CONR11R12 group and substituent for bonding with polymer as the linking group, the case in which at least one of R5 to R 9 is a linking group while all other R 5 to R 9 that are not linking groups are hydrogen atoms is preferable from the viewpoints of production ease and affinity for pigment .
• linking group with the polymer is a divalent linking group
• examples thereof include a linking group having a carboxylic acid ester bond, a linking group having a sulfonic acid ester bond and a linking group having a carboxylic acid amide bond.
• a linking group having a carboxylic acid ester bond or carboxylic acid amide bond is preferable from the viewpoint of production ease.
• the linking group is formed by a reaction between a functional group possessed by the polymer before linking and a functional group possessed by the azo compound before linking.
• the functional groups for forming the linking group include a functional group having a hydroxyl group, a functional group having -a sulfonate group, a functional group having an amino group and a functional group having a carboxyl group.
• Examples of functional groups having a hydroxyl group include hydroxyl group, hydroxyalkyl groups such as a hydroxymethyl group, hydroxyethyl group or hydroxypropyl group, and groups represented by -R51-O-R52-OH (wherein, R 51 and R52 each independently represent an alkylene group having 1 to 4 carbon atoms) .
• Examples of functional groups having a sulfonate group include sulfonate groups and sulfoalkyl groups such as a sulfomethyl group, sulfoethyl group or sulfopropyl group .
• Examples of functional groups having an amino group include amino groups and aminoalkyl groups such as an aminomethyl group, aminoethyl group or aminopropyl group.
• Examples of functional groups having a carboxyl group include carboxyl groups and carboxyalkyl groups such as a carboxymethyl group, carboxyethyl group or carboxypropyl group .
• linking group include those represented by the following formulas:
• alkyl group represented by R 3 in the above-mentioned formula (2) examples thereof include linear, branched and cyclic alkyl groups such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group or cyclohexyl group.
• carboxylic acid ester group represented by R 4 in the above-mentioned formula (2) examples thereof include linear and branched ester groups such as a methyl ester group, ethyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, sec-butyl ester group, tert-butyl ester group, octyl ester group, nonyl ester group, decyl ester group, undecyl ester group, dodecyl ester group, hexadecyl ester group, octadecyl ester group, eicosyl ester group, docosyl ester group,
• Examples of carboxylic acid amide groups represented by R 4 in the above-mentioned formula (2) include linear and branched amides such as a N-methylamide group, N, N-dimethylamide group, N-ethylamide group,
• N-octylamide group N, N-dioctylamide group, N-nonylamide group, N, -dinonylamide group, N-decylamide group,
• N-octadecylamide group N-phenylamide group
• a substituent of R 4 in the above-mentioned formula (2) may be further substituted, and there are no particular limitations thereon provided it does not inhibit polymerizability of the polymerizable monomer that forms a monomer unit or cause a significant decrease in solubility of the above-mentioned compound having an azo skeleton structure.
• substituents that may be substituted include alkoxy groups such as a methoxy group or ethoxy group, amino groups such as an N-methylamino group or N, N-dimethylamino group, acyl groups such as an acetyl group, and halogen atoms such as a fluorine atom or chlorine atom.
• R 4 in the above-mentioned formula (2) can be suitably selected from the previously listed substituents , phenyl group or carboxyl group.
• the case in which it is a phenyl group or carboxylic acid ester group is preferable from the viewpoints of dispersibility and compatibility in a medium of the above-mentioned compound having an azo skeleton structure .
• Affinity with the above-mentioned polymer segment and dispersion medium can be controlled by changing the proportion of the monomer unit represented by the above-mentioned formula (2).
• the dispersion medium is a nonpolar solvent in the manner of styrene
• increasing the proportion of a monomer unit in which R 4 in the above-mentioned formula (2) is represented with a phenyl group is preferable from the viewpoint affinity with the dispersion medium.
• the dispersion medium is a solvent having a certain degree of polarity in the manner of acrylic acid ester, increasing the proportion of a monomer unit in which R 4 in the above-mentioned formula (2) is represented with a carboxyl group, carboxylic acid ester group or carboxylic acid.amide group is preferable from the viewpoint of affinity with the dispersion medium.
• a polymer containing a monomer unit in which R 4 is a carboxyl group can be used for the polymer before being linked to the partial structure represented by formula (1) .
• a linking group can be formed by using this carboxyl group.
• the linking group is preferably that which contains a carboxylic acid ester bond or carboxylic acid amide bond from the viewpoint of production ease.
• formula (1) may be that which has a carboxyl group on the end of the molecular chain.
• a linking group can be formed by using this carboxyl group.
• examples of the linking group include a group that contains an ester bond or carboxylic acid amide bond.
• Examples of methods that can be applied for the method used to introduce the above-mentioned carboxyl group onto the end of a molecular chain include an atom transfer radial polymerization (ATRP) method to be subsequently described, a method that uses a polymerization initiator having a carboxyl group, and a method that uses a mercaptan-based chain transfer agent having a carboxyl group.
• ATRP atom transfer radial polymerization
• the number average molecular weight thereof is preferably 500 or more from the viewpoint of improving pigment dispersibility .
• a larger molecular weight is more effective for improving pigment dispersibility.
• the number average molecular weight of the polymer segment is preferably 200,000 or less.
• the number average molecular weight of the polymer segment is more preferably within the range of 2,000 to 50,000 in consideration of production ease.
• the location of the azo skeleton structure in the above-mentioned compound having an azo skeleton structure may be a random location or may be unevenly distributed by forming one or a plurality of blocks on one end.
• the number of substitutions of the azo skeleton structure in the above-mentioned compound having an azo skeleton structure is such that dispersibility in pigment increases if the number of substitutions is high to a certain degree.
• the number of substitutions of the above-mentioned azo skeleton structure is preferably 0.5 to 10 and more preferably 0.5 to 5 based on 100 monomers that form the polymer segment.
• the azo skeleton structure represented by the above-mentioned formula (1) has tautomers represented by the following formulas (4) and (5) . These tautomer are also included within the scope of the present invention.
• Ri, R 2 , Ar and X respectively represent the same meanings as Ri, R2, Ar and X in formula
• the azo skeleton structure represented by the above-mentioned formula (1) can be synthesized in accordance with a known method.
• Examples of methods used to synthesize the compound having an azo skeleton structure include the methods indicated by the following (i) to (iv) .
• method (i) a compound having an azo skeleton structure is synthesized by respectively synthesizing an azo skeleton structure and polymer segment in advance and bonding the two materials by a condensation reaction and the like.
• n represents an integer of 1 to 5
• Ari represents an arylene group
• h represents a substituent that forms a linking group by reacting with Pi (substituent for bonding with the polymer as a linking group)
• R x , R 2 and X respectively represent the same meanings as Ri, R 2 and X in the above-mentioned formula (1)
• R lr R 2 , X, Ari, n and Q x respectively represent the same meanings as Ri, R 2 , X, Ari, n and Qi in formulas (6) and (7)
• P- ⁇ represents a polymer segment obtained by polymerizing a polymerizable monomer that forms a monomer unit represented by the above-mentioned formula (2) .
• a compound having an azo skeleton structure represented by the above-mentioned formula (1) can be synthesized by a step 1, in which an azo compound (8) is synthesized by subjecting an aniline derivative represented by formula (6) and a barbituric acid analogue represented by formula (7) to diazo coupling, and a step 2, in which the azo compound (8) and a polymer segment Pi are bonded by a condensation reaction.
• step 1 An explanation is first provided of step 1.
• a known method can be used in step 1.
• An example thereof is the method indicated below.
• a diazotizing agent such as sodium nitrite or nitrosylsulfuric acid in a methanol solvent and in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid to synthesize the corresponding diazonium salt.
• this diazonium salt is coupled with the barbituric acid analogue (7) to synthesize the azo compound (8) .
• the present step can be carried out in the absence of solvent, it is preferably carried out in the presence of a solvent to prevent excessively rapid progression of the reaction.
• a solvent there are no particular limitations on the solvent provided it does not inhibit the reaction.
• solvents include alcohols such as methanol, ethanol or propanol, esters such as methyl acetate, ethyl acetate or propyl acetate, ethers such as diethyl ether, tetrahydrofuran or dioxane, hydrocarbons such as benzene, toluene, xylene, hexane or heptane, halocarbons such as dichloromethane, dichloroethane or chloroform, amides such as N, -dimethylformamide , N-methylpyrrolidone or N, N-dimethylimidazolidinone, nitriles such as acetonitrile or propionitrile , acids such as formic acid,
• two or more types of the above-mentioned solvents may be used as a mixture, and the mixing ratio when using a mixture can be arbitrarily determined corresponding to the solubility of the substrate.
• the amount of the above-mentioned solvent used can be determined arbitrarily, it is preferably within the range of 1.0 times by mass to 20 times by mass of the compound represented by the above-mentioned formula (6) from the viewpoint of the reaction rate.
• Step 1 is normally carried out within a temperature range- of -50°C to 100°C and is normally completed within 24 hours .
• radical polymerization is used preferably from the viewpoint of production ease.
• Radical polymerization can be carried out by using a radical polymerization initiator, irradiating with radiation or laser light and the like, combining the use of a photopolymerization initiator and irradiation with light or by heating.
• the radical polymerization initiator is only required to be that which generates radicals and is able to initiate a polymerization reaction, and is selected from compounds that generate radicals by the action of heat, light, radiation or an oxidation-reduction reaction and the like.
• radical polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, organometallic compounds and
• azo-based polymerization initiators such as 2, 2 1 -azobis (isobutyronitrile) ,
• organic peroxide-based polymerization initiators such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl
• peroxyisopropylcarbonate tert-hexyl peroxybenzoate or tert-butyl peroxybenzoate
• inorganic peroxide-based polymerization initiators such as potassium persulfate or ammonium persulfate
• redox-based polymerization initiators such as ferrous hydrogen peroxide-based, benzoyl peroxide-dimethylaniline-based or cerium (IV) salt-alcohol-based initiators.
• photopolymerization initiators include benzophenones , benzoin ethers, acetophenones and thioxanthones . Two or more types of these radical polymerization initiators may be used in combination.
• the amount o'f polymerization initiator used at this time is preferably adjusted to within a range of 0.1 parts by mass to 20 parts by mass based on 100 parts by mass of monomer so as allow the obtaining of a copolymer having a target molecular weight distribution.
• the polymer segment represented by the above-mentioned i can be produced using any of solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization or block polymerization, and there are no particular limitations thereon.
• Solution polymerization in a solvent capable of dissolving each component used during production is preferable..
• Examples thereof include polar organic solvents in the manner of alcohols such as methanol, ethanol or 2-propanol, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or diethyl ether, ethylene glycol monoalkyl ethers or acetates thereof, propylene glycol monoalkyl ethers or acetates thereof and diethylene glycol monoalkyl ethers.
• a nonpolar solvent such as toluene or xylene can also be used alone or as a mixture.
• solvents having a boiling point within a temperature range of 100°C to 180°C are more preferable either alone or as a mixture.
• the preferable temperature range of the present invention is the preferable temperature range of the present invention.
• polymerization temperature varies according to the type of initiator used, and there are no particular limitations thereon. For example, a temperature range of -30°C to 200°C is typical and a more preferable temperature range is 40°C to 180°C.
• the molecular weight distribution and molecular structure of the above-mentioned polymer segment represented by Pi can be controlled using a known method.
• a polymer segment can be produced for which molecular weight distribution and molecular structure have been controlled by using a method that uses an
• addition-fragmentation chain transfer agent see Japanese Patent No. 4254292 and Japanese Patent No. 3721617
• NMP method that uses dissociation and binding of amine oxide radicals
• an ATRP method in which polymerization is carried out using a heavy metal and ligand and using a halide as polymerization initiator
• Masami Kamigaito, et al., "Chemical Reviews” (USA) American Chemical Society, 2001, Vol. 101, pp.
• step 2 A known method can be used in step 2.
• a compound having the above-mentioned azo skeleton structure in which the linking group has a carboxylic acid ester bond can be synthesized by using the polymer segment Pi having a carboxyl group and the azo compound (8) in which Qi is a substituent having a hydroxyl group.
• a compound having the above-mentioned azo skeleton structure in which the linking group has a sulfonic acid ester bond can be synthesized by using the polymer segment Pi having a hydroxyl group and the azo compound (8) in which Qi is a substituent having a sulfonic acid group.
• a compound having the above-mentioned azo skeleton structure in which the linking group has a carboxylic acid amide bond can be synthesized by using the polymer segment Pi having a carboxyl group and the azo compound (8) in which Qi is a substituent having an amino group. More specifically, examples thereof include a method that uses
• hydrochloride and the like as a dehydration condensation agent (see, for example, Melvin S. Newman, et al., "The Journal of Organic Chemistry” (USA) , American Chemical Society, 1961, Vol. 26, No. 7, pp. 2525-2528), and the Schotten-Baumann method (see, for example, Norman 0. V. Stanford, “Chemical Reviews” (USA) , American Chemical Society, 1953, Vol. 52, No. 2, pp. 237-416) .
• the present step can be carried out in the absence of solvent, it is preferably carried out in the presence of a solvent to prevent excessively rapid progression of the reaction.
• a solvent there are no particular limitations on the solvent provided it does not inhibit the reaction, and examples of solvents include ethers such as diethyl ether, tetrahydrofuran or dioxane, hydrocarbons such as benzene, toluene, xylene, hexane or heptane, halocarbons such as dichloromethane, dichloroethane or chloroform, amides such as N, N-dimethyl ormamide,
• N-methylpyrrolidone or N, -dimethylimidazolidinone and nitriles such as acetonitrile or propionitrile .
• two or more types of the above-mentioned solvents may be used as a mixture and the mixing ratio when using a mixture can be arbitrarily determined corresponding to the solubility of the substrate.
• the amount of the above-mentioned solvent used can be determined arbitrarily, it is preferably within the range of 1.0 times by mass to 20 times by mass of the above-mentioned polymer segment represented by Pi from the viewpoint of the reaction rate .
• the present step is normally carried out within a temperature, range of 0°C to 250°C and is normally completed within 24 hours.
• the following provides a detailed explanation of method (ii) by indicating an example of the scheme thereof.
• a compound having the above-mentioned azo skeleton structure is synthesized by preliminarily ' synthesizing an azo compound having a polymerizable functional group, and copolymerizing with a polymerizable monomer that forms a monomer unit represented by the above-mentioned formula (2).
• Ri, R 2 , Ari, X, Qi and n respectively represent the same meanings as R x , R 2 , Ar x , X, Qi and n in formula (8) in the scheme of the above-mentioned method (i) .
• Q 2 in formula (9) represents a substituent that forms Q 3 in formula (10) by reacting with G in formula (8)
• R13 represents a hydrogen atom or alkyl group.
• R lf R 2 , Ari, X, n and R13 in formula (10) respectively represent the same meanings as R lf R 2 , Ari, ⁇ ⁇ ⁇ n and R13 in formulas (8) and (9), and Q 3 represents a linking group formed by a reaction between Qi in formula (8) and Q 2 in formula (9) .
• a compound having the above-mentioned azo skeleton structure can be synthesized by a step 3, in which a vinyl group-containing compound represented by formula (9) is introduced into an azo compound represented by formula (8) to synthesize an azo compound (10) having a polymerizable functional group, and a step 4, in which the azo compound
• step 3 the azo compound (10) having a polymerizable functional group can be synthesized using the same method as step 2 of the above-mentioned method (i).
• the above-mentioned azo compound in which the linking group has a carboxylxc acid ester bond can be synthesized by using the vinyl group-containing compound (9) having a carboxyl group and the azo compound (8) in which Q 1 is a substituent having a hydroxyl group.
• the above-mentioned azo compound in which the linking group has a sulfonic acid ester bond can be synthesized by using the vinyl
• the above-mentioned azo compound in which the linking group has a carboxylxc acid amide bond can be synthesized by using the vinyl group-containing compound (9) having a carboxyl group and the azo compound (8) in which C is a substituent having an amino group.
• group-containing compound (9) are sold commercially and are readily available. In addition, they can be easily
• step 4 a compound having the above-mentioned azo skeleton, structure can be synthesized by using the same method as that used to synthesize the polymer segment Pi of the above-mentioned method (i) .
• azo skeleton structure is synthesized by using a preliminarily synthesized azo compound having a halogen atom as a polymerization initiator and
• Formula (8) Step 5 Formula (12) Step 6 [0045]
• R lr R 2 , Ar X/ X, Qi and n respectively represent the same meanings as Ri, R2, Ari, X, Qi and n in formula (8) in the scheme of the above-mentioned method (i) .
• Q 4 in formula (11) represents a substituent that forms Q5 in formula (12) by reacting with Qi in formula (8)
• J represents a chlorine atom, bromine atom or iodine atom.
• Ri, R 2 , Ari, X, n and J in formula (12) respectively represent the same meanings as Ri, R 2 , Ari, X, n and J in formulas (8) and (11), and Q5 represents a linking group formed by a reaction between Qi in formula (8) and Q 4 in formula ( 11 ) .
• a compound having an azo skeleton structure can be synthesized by a step 5, in which a halogen atom-containing compound represented by formula (11) is introduced into an azo compound represented by formula (8) to synthesize an azo compound (12) having a halogen atom, and a step 6, in which the azo compound (12) having a halogen atom is used as a polymerization initiator to polymerize a polymerizable monomer that forms a monomer unit represented by the above-mentioned formula (2).
• step 5 the azo compound (12) ' having a halogen atom can be synthesized using the same method as step 2 of the above-mentioned method (i) .
• the above-mentioned azo compound in which the linking group has a carboxylic acid ester bond can ultimately be synthesized by using the halogen atom-containing compound (11) having a carboxyl group and the azo compound (8) in which Q 1 is a substituent having a hydroxyl group.
• the above-mentioned azo compound in which the linking group has a sulfonic acid ester bond can ultimately be synthesized by using the halogen atom-containing compound (11) having a hydroxyl group and the azo compound (8) in which Q 1 is a substituent having a sulfonic acid group.
• the above-mentioned azo compound in which the linking group has a carboxylic acid amide bond can ultimately be synthesized by using the halogen atom-containing compound (11) having a carboxyl group and the azo compound (8) in which Q 1 is a substituent having an amino group.
• Examples of the above-mentioned halogen atom-containing compound (11) having a carboxyl group include chloroacetic acid, a-chloropropionic acid, a-chlorobutyric acid, a-chloroisobutyric acid,
• a-chlorocaproic acid a-chlorophenylacetic acid, oc-chlorodiphenylacetic acid, a-chloro-a-phenylpropionic acid, a-chloro- -phenylpropionic acid, bromoacetic acid, a-bromopropionic acid, a-bromobutyric acid,
• atom-containing compound (11) having a hydroxyl group include 1-chloroethanol , 1-bromoethanol , 1-iodoethanol ,
• a compound having an azo skeleton structure can be synthesized by using the azo compound (11) having a halogen atom as a polymerization initiator, and polymerizing a polymerizable monomer that forms the above-mentioned monomer unit (2) in the presence of a metal catalyst and ligand using the ATRP method in the above-mentioned method (i) .
• low valence metals used include metals selected from the group consisting of Cu + , Ni°, Ni + , Ni 2+ , Pd°, Pd + , Pt°, Pt 2+ , Rh + , Rh 2+ , Rh 3+ , Co + , Co 2+ , Ir°, Ir + , Ir 2+ , Ir 3+ , Fe 2+ , Ru 2+ , Ru 3+ , Ru 4+ , Ru 5+ , Os 2+ , Os 3+ , Re 2+ , Re 3+ , Re 4+ , Re 6+ , Mn + and Mn 3+ .
• Cu + , Ru 2+ , Fe 2+ or Ni 2+ is preferable and Cu + is particularly preferable.
• monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide and cuprous cyanide, and the above-mentioned copper compounds can be used preferably from the viewpoint of raw material availability.
• An ordinary organic ligand is used for the ligand used in the ATRP . method. Although examples thereof include 2 , 2 1 -bipyridyl and derivatives thereof,
• tris [2- (dimethylamino) ethyl] amine, triphenylphosphine and tributylphosphine, aliphatic polyamines in the manner of N, , N 1 , '', ' 1 -pentamethyldiethylenetriamine are preferable from the viewpoint of raw material availability.
• a compound having an azo skeleton structure can be synthesized by a step 7, in which a nitro group-containing arylene group (13) is introduced into the polymer segment P x to synthesize a polymer segment (14) having a nitro group-containing arylene group, a step 8, in which the polymer segment (14) having a nitro group-containing arylene group is reduced to synthesize a polymer segment (15) having an amino group-containing arylene group, and a step 9, in which the polymer segment (15) having an amino group-containing arylene group and a barbituric acid analogue (7) are subjected to diazo coupling.
• step 7 the polymer segment (14) having a nitro group-containing arylene group can be synthesized using the same method as step 2 of the above-mentioned method (i) .
• the polymer segment (14), in which the linking group has a carboxylic acid ester bond in the form of a nitro group-containing arylene group can be synthesized by reacting the polymer segment ⁇ having a carboxyl group with the nitro-group containing arylene group (14) in which Q 6 is a substituent having a hydroxyl group.
• the polymer segment (14), in which the linking group has a carboxylic acid amide bond in the form of a nitro group-containing arylene group can be synthesized by using the polymer segment Pi having a carboxyl group and the nitro group-containing arylene group (14) in which Q 6 is a substituent having an amino group.
• step 8 A known method can be used in step 8.
• An example of a method that uses a metal compound and the like is described in "Experimental Chemistry”, Maruzen Co., Ltd., 2nd edition, Vol. 17-2, pp. 162-179, and an example of a catalytic hydrogenation method is described in "New Experimental Chemistry”, Maruzen Co., Ltd., 1st edition, Vol. 15, pp. 390 to 448 or in WO 2009/060886.
• the present step can be carried out in the absence of solvent, it is preferably carried out in the presence of a solvent to prevent excessively rapid progression of the reaction.
• a solvent there are no particular limitations on the solvent provided it does not inhibit the reaction, and examples of solvents include alcohols such as methanol, ethanol or propanol, esters such as methyl acetate, ethyl acetate or propyl acetate, ethers such as diethyl ether, tetrahydrofuran or dioxane, hydrocarbons such as benzene, toluene, xylene, hexane or heptane, and amides such as N, -dimethylformamide, N-methylpyrrolidone or N, -dimethylimidazolidinone .
• two or more types of the above-mentioned solvents may be used as a mixture and the mixing ratio when using a mixture can be arbitrarily determined.
• the amount of the above-mentioned solvent used can also be determined arbitrarily corresponding to the solubility of the substrate. It is preferably within the range of 1.0 times by mass to 20 times by mass of the compound represented by the above-mentioned nitro group-containing arylene group (14) from the viewpoint of the reaction rate.
• the present step is normally carried out within a temperature range of 0°C to 250°C and is normally completed within 24 hours.
• step 9 a compound having an azo skeleton structure can be synthesized by applying the same method as step 1 of the above-mentioned method (i) .
• the compounds can be obtained at high purity by carrying out purification using these methods alone or by combining two or more thereof.
• the compounds represented by the above-mentioned formulas (8), (10) and (12) obtained in the above-mentioned steps can be identified and quantified by nuclear magneticresonance spectroscopic analysis (ECA-400, JEOL Ltd.), ESI-TOFMS (LC/MSD TOF, Agilent Technologies Inc . ) and HPLC analysis (LC-20A, Shimadzu Corp.).
• the pigment dispersing agent and pigment composition of the present invention Since the compound having an azo skeleton structure of the present invention demonstrates high affinity with various types of pigments and high affinity for non-water-soluble solvents, one type alone or two or more types can be combined for use as a pigment dispersing agent .
• the pigment dispersing agent of the present invention is only required to contain the compound having an azo skeleton structure of the present invention.
• the pigment composition of the present invention is used in paint, ink, toner and resin moldings and the like, and is characterized by containing pigment and at least one type of the compound having an azo skeleton structure of the present invention as a pigment dispersing agent.
• a yellow pigment can be used for the yellow pigment contained in the pigment composition of the present invention by suitably selecting from among, for example, yellow pigments described in the "Organic Pigments Handbook", 2006 edition (editor/publisher: Isao Hashimoto) (such as monoazo-based pigments, bisazo-based pigments, polyazo-based pigments, isoindoline-based pigments, condensed azo-based pigments, azomethine-based pigments, anthraquinone-based pigments or quinoxaline-based pigments) .
• monoazo-based pigments such as monoazo-based pigments, bisazo-based pigments, polyazo-based pigments, isoindoline-based pigments, condensed azo-based pigments, azomethine-based pigments, anthraquinone-based pigments or quinoxaline-based pigments.
• monoazo-based pigments such as monoazo-based pigments, bisazo-based pigments, polyazo-based pigments, iso
• bisazo-based pigments polyazo-based pigments and isoindoline-based pigments can be used preferably.
• acetoacetanilide-based pigments represented by C. I . Pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 128, C.I. Pigment Yellow 155, C.I. Pigment Yellow 175 and C.I. and Pigment Yellow 180 and the like, and isoindoline-based pigments represented by C.I. Pigment Yellow 139 and C.I. Pigment Yellow 185 are preferable due to their high affinity with the compound having an azo skeleton structure of the present invention.
• C.I. Pigment Yellow 155, C.I. Pigment Yellow 180 or C.I. Pigment Yellow 185 is more preferable due to the high dispersion effect attributable to the compound having an azo skeleton structure of the present invention.
• the above-mentioned yellow pigments may be used alone or two or more types may be used as a mixture.
• colorants that can be used in combination include compounds typically represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, quinophthalone compounds and allylamide compounds .
• one or more types can be selected from C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 94, 95, 97, 109, 110, 111, 120, 127, 129, 139, 147, 151, 154, 168, 174, 176, 181, 191, 194, 213 and 214, C.I. Vat Yellow 1, 3 and 20, mineral fast yellow, navel yellow, naphthol yellow S, hansa yellow G, permanent yellow NCG, and C.I. Solvent Yellow 9, 17, 24, 31, 35, 58, 93, 100, 102, 103, 105, 112, 162, 163 and the like.
• a magenta pigment can be used for the magenta pigment contained in the pigment composition of the present invention by suitably selecting from among, for example, magenta pigments described in the "Organic Pigments Handbook", 2006 edition (editor/publisher: Isao Hashimoto) (such as quinacridone-based pigments,
• monoazonaphthol-based pigments monoazonaphthol-based pigments, disazonaphthol-based pigments, perylene-based pigments, thioindigo-based pigments, diketopyrrolopyrrole-based pigments, naphthol AS-based pigments or BONA lake-based pigments
• quinacridone-based pigments diketopyrrolopyrrole-based pigments
• naphthol AS-based pigments and BONA lake-based pigments can be used preferably .
• naphthol AS-based and BONA lake-based pigments represented by the following formula (18) used in the pigment composition of the present invention are preferable due to their high affinity with the compound having an azo skeleton structure of the present invention.
• Ri 4 to R 2 i each independently represent a hydrogen atom, chlorine atom or methyl group.
• R 22 to R 31 each independently represent a hydrogen atom, chlorine atom, t-butyl group, cyano group or phenyl group.
• R 32 to R 34 each independently represent a hydrogen atom, methoxy group, methyl group, nitro group, chlorine atom, N, N-diethylaminosulfonyl group, sulfonic acid group or salt thereof or CONHR 36 group
• R 35 represents an amino group, carboxylic acid group or salt thereof or CONHR 37 group
• R 3S and R 37 each independently represent a hydrogen atom or phenyl group.
• Examples of quinacridone-based pigments represented by the above-mentioned formula (16) include C.I. Pigment Red 202, 122, 192 and 209.
• R 14 to R 2 i in the above-mentioned formula (16) can be arbitrarily selected from the previously listed substituents, the case in which R 14 , Ri 5 , Ri 7 to R 19 and R 2i are hydrogen atoms and R i6 and R 2 o are hydrogen atoms, chlorine atoms or methyl groups is preferable from the viewpoint of affinity with the compound having an azo skeleton structure of the present invention.
• Examples of diketopyrrolopyrrole-based pigments represented by the above-mentioned formula (17) include C.I. Pigment Red 255, 254 and 264.
• R 22 to R31 in the above-mentioned formula (17) can be arbitrarily selected from the previously listed substituents, the case in which R 22 , R 2 3, R 2 5 to R 28 , R 30 and R31 are hydrogen atoms and R 24 and R 29 are hydrogen atoms or phenyl groups is preferable from the viewpoint of affinity with the compound having an azo skeleton structure of the present invention.
• naphthol AS-based pigments represented by the above-mentioned formula (18) include C.I. Pigment Red 2, 3, 5, 6, 7, 23, 150, 146, 184 and 269.
• BONA lake-based pigments represented by the above-mentioned formula (18) include C.I. Pigment Red 48:2, 48:3, 48:4 and 57: 1.
• R 32 to R 37 in the above-mentioned formula (18) can be arbitrarily selected from the previously listed substituents, the case in which at least one of R 32 to R 34 is a CONHR 3 6 group and R 35 is a CONHR 37 group is preferable. Moreover, the case in which R 37 is a hydrogen atom is preferable from the viewpoint of affinity with the compound having an azo skeleton structure of the present invention.
• quinacridone-based pigments such as C.I. Pigment Red 122 or 202,
• diketopyrrolopyrrole-based pigments such as C.I. Pigment Red 255 or 264, and naphthol AS-based pigments such as C.I. Pigment Red 150 in particular are more preferable from the viewpoint of affinity with the compound having an azo skeleton structure of the present invention.
• magenta pigments may be used alone or two more types may be used as a mixture.
• magenta pigments can be used in combination with the magenta colorant contained in the pigment composition of the present invention provided they do not inhibit pigment dispersibility .
• magenta colorants examples include condensed azo compounds,
• anthraquinone compounds basic dye lake compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds.
• Examples thereof include one or more types selected from C.I. Pigment Red 81:1, 144, 16.6, 169, 177, 185, 220, 221 and 238.
• Phthalocyanine pigments represented by the following formula (19) can be preferably used for the cyan colorant contained in the pigment composition of the present invention .
• R 38 to R 41 each independently represent a hydrogen atom, alkyl group, sulfonic acid group or salt thereof and M represents a metal or hydrogen atom.
• M represents a metal or hydrogen atom.
• C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5 and 15:6 in particular are more preferable due to the high dispersion effect attributable to the compound having an azo skeleton structure of the present invention.
• One type of the above-mentioned phthalocyanine pigments may be used alone or two or more types may be used as a mixture.
• phthalocyanine pigments can be used in combination for the cyan colorant contained in the pigment composition of the present invention provided they do not inhibit pigment dispersibility .
• cyan colorants able to be used in combination include one or more types selected from C.I.
• Pigment Blue 1 1:2, 1:3, 2, 2:1, 2:2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 10:1, 11, 12, 13, 14, 18, 19, 20, 21, 22, 23, 24, 24:1, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 36:1, 52, 53, 56, 56:1, 57, 58, 59, 60, 61, 61:1, 62, 63, 64, 65, 66, 67, 69, 71, 72, 73, 74, 77, 78, 80, 81, 82, 83 and 84.
• a colorant other than a cyan colorant can be used to create the proper color tone.
• a colorant other than a cyan colorant can be used to create the proper color tone.
• C.I. Pigment Green 7 mixed into C.I. Pigment Blue 15:3 makes it possible to improve the color purity of cyan.
• Carbon black can be preferably used for the black colorant of the present invention.
• carbon black obtained according to a production method such as a thermal method, acetylene method, channel method, furnace method or lamp black method can be used.
• the average primary particle diameter of the carbon black used in the present invention is preferably 14 nm to 80 nm and more preferably 25 nm to 50 nm. By making the average primary particle diameter to be larger than 14 mm, color tone is less likely to demonstrate a reddish tint making it suitable for use as black pigment . On the other hand, in the case the average primary particle diameter of the carbon black is smaller than 80 nm, tinting strength of printed images becomes favorable in the case of using the pigment composition as a colorant.
• average primary particle diameter of the carbon black can be measured by capturing an enlarged photograph thereof with a scanning electron microscope.
• DBP absorption of the carbon black used in the present invention is preferably 30 mL/100 g to 200 mL/100 g and more preferably 40 mL/100 g to 150 mL/100 g.
• the carbon black disperses favorably and tinting strength of printed images is favorable.
• a carbon black dispersion can be produced with a suitable amount of dispersion medium when producing a carbon black dispersion, thereby making this preferable.
• DBP absorption of carbon black is the amount of dibutyl phthalate (DBP) absorbed by 100 g of carbon black, and can be measured in compliance with JIS K6217.
• the pH of carbon black can be determined by measuring a mixed liquid of carbon black and distilled water with a pH electrode.
• the specific surface area of the carbon black used in the present invention is preferably 300 m 2 /g or less and more preferably 100 m 2 /g or less. On the other hand, although there are no particular limitations on the lower limit thereof, it is normally 30 m 2 /g or more. By making the specific surface area of the carbon black to be 300 m 2 /g or less, dispersibility of the carbon black by the above-mentioned compound having an azo skeleton structure is favorable.
• specific surface area of carbon black refers to the BET specific surface area, and can be measured in compliance with JIS K4652.
• One type of the above-mentioned carbon black may be used alone or two or more types may be used as a mixture.
• carbon black can be used in combination with the black colorant used in the present invention provided they do not inhibit pigment dispersibility of the carbon black.
• black colorants examples include one or more types selected from C.I. Pigment Black 1, 10 and 31, C.I. Natural Black 1, 2, 3, 4, 5 and 6, and activated carbon.
• magenta colorant cyan colorant or yellow colorant
• cyan colorant cyan colorant or yellow colorant
• a pigment other than yellow pigment, magenta pigment, cyan pigment or carbon black as described above can also be preferably used as pigment able to be used in the present invention provided it has affinity with the pigment dispersing agent of the present invention, and there are no limitations thereon.
• These may be crude pigments or prepared pigment compositions provided they do not significantly inhibit the effects of the above-mentioned compound having an azo skeleton structure.
• the composite mass ratio of the pigment and compound having an azo skeleton structure in the pigment composition of the present invention is within the range of 100:0.1 to 100:100 is preferable.
• the case in which the composite mass ratio is within the range of 100:0.5 to 100:20 is more preferable.
• the pigment composition can be produced by a wet method or dry method. Since the azo compound of the present invention has high affinity with non-water-soluble solvents, it is preferably produced by a wet method that allows a homogeneous pigment composition to be easily produced . For example, the pigment composition is obtained in the manner described below.
• a pigment dispersing agent and a resin as necessary are dissolved in a dispersion medium followed by gradually adding a pigment powder while stirring and adequately mixing into the dispersion medium.
• the pigment dispersing agent is adsorbed onto the pigment particle surfaces by applying mechanical shear force with a disperser such as a kneader, roll mill, ball mill, paint shaker, dissolver, attritor, sand mill or high-speed mill, and the pigment is stably and finely dispersed in the form of uniform fine particles.
• An assistant may be further added to the pigment composition of the present invention at the time of production.
• examples thereof include a surfactant, dispersing agent, filler, standardizer, resin, wax, antifoaming agent, antistatic agent, dust reducing agent, thickener, shading colorant, preservative, drying inhibitor, rheological control additive, wetting agent, antioxidant, UV absorber, photostabilizer and combinations thereof.
• the pigment dispersing agent of the present invention may also be added in advance during production of crude pigment.
• the pigment dispersion of the present invention is composed of the above-mentioned pigment composition and a non-water-soluble solvent.
• the above-mentioned pigment composition may be dispersed in the non-water-soluble solvent or each constituent of the above-mentioned pigment composition may be dispersed in the non-water-soluble solvent.
• the pigment dispersion is obtained in the following manner. A pigment dispersing agent and a resin are dissolved as necessary in a dispersion medium followed by gradually adding a pigment or pigment composition powder while stirring and adequately mixing into the dispersion medium.
• the pigment can be stably dispersed in the form of uniform fine particles byapplying mechanical shear force with a disperser such as a ball mill, paint shaker, dissolver, attritor, sand mill or high-speed mill.
• non-water-soluble solvent able to be used in the pigment dispersion of the present invention is determined corresponding to the target application of the dispersion, and there are no particular limitations thereon.
• non-water-soluble solvents include esters such as methyl acetate, ethyl acetate or propyl acetate, hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene or xylene, and halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene or
• the non-water-soluble solvent able to be used in the pigment dispersion of the present invention may also be a polymerizable monomer.
• examples thereof include styrene, oc-methylstyrene , oc-ethylstyrene , o-methylstyrene, m-methylstyrene , p-methylstyrene, p-methoxysytrene, p-phenylstyrene, p-chlorostyrene , 3, 4-dichlorostyrene, p-ethylstyrene, 2, 4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene , p-n-hexylstyrene , p-n-octylstyrene, p-n-nonylstyrene , p
• methacrylate behenyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, behenyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone-, vinyl naphthalene,
• pigment composition examples thereof include polystyrene resin, styrene copolymer, polyacrylic acid resin, polymethacrylic acid resin, polyacrylic acid ester resin, polymethacrylic acid ester resin, acrylic acid ester copolymer, methacrylic acid ester copolymer, polyester resin, polyvinyl ether resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyurethane resin and polypeptide resin. In addition, two or more of these resins can be used as a mixture.
• the pigment composition of the present invention is preferable as colorant of a toner containing toner particles including a binder resin and colorant. Since the use of the pigment composition of the present invention makes it possible to favorably maintain the dispersibility of pigment in the toner particles, a toner having high tinting strength is provided.
• binder resin of the toner of the present invention examples include commonly used
• styrene-methacrylic acid copolymer styrene-methacrylic acid copolymer
• styrene-acrylic acid copolymer polyester resin
• epoxy resin epoxy resin
• styrene-butadiene copolymer Monomers for forming these binder resins are used in methods in which toner particles are obtained directly by a polymerization method.
• monomers examples include styrene-based monomers such as styrene, a-methylstyrene, a-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene or p-ethylstyrene, methacrylate-based monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl
• methacrylate octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate,
• diethylaminoethyl methacrylate, methacrylonitrile or methacrylic acid amide acrylate-based monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylonitrile or acrylic acid amide, and olefin-based monomers such as butadiene, isoprene or cyclohexene.
• acrylate-based monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, beheny
• a polar resin such as a polyester resin or polycarbonate resin
• a nonpolar resin such as polystyrene
• the polar resin is added during the polymerization reaction from the dispersion step to the polymerization step.
• the polar resin is added
• a crosslinking agent can be used when synthesizing the binder resin in order to enhance the mechanical strength of the toner particles as well as control the molecular weight of the above-mentioned particle constituent molecules.
• bifunctional crosslinking agents used in the toner particles of the present invention include divinyl benzene, bis ( 4-acryloxypolyethoxyphenyl ) propane, ethylene glycol diacrylate, 1, 3-butylene glycol diacrylate, 1, 4-butanediol diacrylate, 1 , 5-pentanediol diacrylate, 1 , 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol
• diacrylate tetraethylene glycol diacrylate, respective diacrylates of polyethylene glycol #200, #400 and #600, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type diacrylates, and those in which the diacrylate has been substituted with dimethacrylate.
• polyfunctional crosslinking agents examples include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate,
• crosslinking agents are used within a range of preferably 0.05 parts by mass to 10 parts by mass and more preferably 0.1 parts by mass to 5 parts by mass based on 100 parts by mass of the above-mentioned monomer from the viewpoint of toner fixing performance and offset
• a wax component can also be used when synthesizing the binder resin to prevent adhesion to a fixing member.
• wax components able to be used in the present invention include petroleum-based waxes such as paraffin wax, microcrystalline wax or petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax obtained according to the Fischer-Tropsch method and derivatives thereof, polyolefin wax as exemplified by polyethylene and derivatives thereof, and natural waxes such as carnauba wax or candelilla wax and derivatives thereof.
• the derivatives thereof include oxides, block copolymers with vinyl monomers and graft modification products.
• waxes include alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid or palmitic acid, fatty acid amides, fatty acid esters, hydrogenated castor oil and derivatives thereof, plant waxes and animal waxes. These can be used alone or in combination.
• the amount of the above-mentioned wax component added is such that the content thereof is preferably within the range of 2.5 parts by mass to 15.0 parts by mass and more preferably within the range of 3.0 parts by mass to 10.0 parts by mass based on 100 parts by mass of the binder resin.
• An added amount of 2.5 parts by mass or more facilitates oilless fixing.
• the added amount is 15.0 parts by mass or less, the amount of wax component in the toner particles is suitable and desired charging characteristics are easily obtained.
• the toner of the present invention can also be used after mixing in a charge control agent as necessary.
• the addition thereof makes it possible to control the toner to the optimum triboelectric charge quantity corresponding to the developing system.
• a known agent can be used for the charge control agent, and a charge control agent having a rapid charging speed that is able to stably maintain a constant charge quantity is particularly preferable. Moreover, in the case of producing toner particles directly by polymerization, a charge control agent that exhibits little inhibition of polymerization and is substantially free of substances that are soluble in an aqueous dispersion medium is particularly preferable .
• examples of charge control agents that control the toner to a positive charge include nigrosine-modified products obtained from nigrosine and a fatty acid metal salt and the like, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate or tetrabutylammonium tetrafluoroborate, analogues thereof in the form of onium salts such as phosphonium salts and lake pigments thereof, triphenylmethane dyes and lake pigments thereof (wherein examples of lake pigments include phosphotungstic acid, phosphomolybdic acid,
• phosphotungstomolybdic acid tannic acid, lauric acid, gallic acid, ferricyanide and ferrocyanide
• metal salts of higher fatty acids diorganotin oxides such as dibutyltin oxide, dioctyltin oxide or dicyclohexyltin oxide, diorganotin borates such as dibutyltin borate, dioctyltin borate or dicyclohexyltin borate, and resin-based charge control agents.
• diorganotin oxides such as dibutyltin oxide, dioctyltin oxide or dicyclohexyltin oxide
• diorganotin borates such as dibutyltin borate, dioctyltin borate or dicyclohexyltin borate
• resin-based charge control agents One type of these can be used alone or two or more types can be used in combination.
• An inorganic fine powder may also be added to the toner particles of the toner of the present invention as a fluidizing agent.
• inorganic fine powders that can be used include fine powders of silica, titanium oxide, alumina or complex oxides thereof and
• Examples of methods used to produce the toner particles that compose the toner of the present include conventionally used methods such as a pulverization method, suspension polymerization method, suspension granulation method or emulsion polymerization method.
• the toner particles are particularly preferably obtained by a production method such as suspension polymerization or suspension granulation, in which the toner particles are granulated in an aqueous medium, from the viewpoints of environmental burden during production and particle diameter controllability.
• Toner particles of the present invention produced by suspension polymerization are produced, for example, in the manner described below.
• a colorant containing the pigment composition of the present invention a colorant containing the pigment composition of the present invention, a pigment having a color difference between the pigment composition of the present invention and a pigment having a color difference between the pigment composition of the present invention and a pigment having a color difference between the pigment composition of the present invention.
• polymerizable monomer a wax component and a polymerization initiator and the like are mixed to prepare a polymerizable monomer composition.
• the polymerizable monomer composition is dispersed in an aqueous medium followed by granulation of particles of the polymerizable monomer composition.
• the polymerizable monomer present in the particles of the polymerizable monomer composition is then polymerized in an aqueous medium to obtain toner particles.
• the polymerizable monomer composition in the above-mentioned step is preferably prepared by mixing a liquid dispersion, obtained by dispersing the
• a known polymerization initiator can be used for the polymerization initiator used in the
• suspension polymerization method examples thereof include azo compounds, organic peroxides, inorganic peroxides, organometallic compounds and photopolymerization initiators.
• azo-based polymerization initiators such as 2,2'-azobis ( isobutyronitrile ) ,
• peroxide-based polymerization initiators such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl
• peroxyisopropylmonocarbonate tert-hexyl peroxybenzoate or tert-butyl peroxybenzoate
• inorganic peroxide-based polymerization initiators such as potassium persulfate or ammonium persulfate
• ferrous hydrogen peroxide-based BPO-dimethylaniline-based and cerium (IV)
• photopolymerization initiators include acetophenones , benzoin ethers and ketals. One type of these can be used alone or two or more types can be used in combination.
• polymerization initiator is preferably 0.1 parts by mass to 20 parts by mass and more preferably 0.1 parts by mass to 10 parts by mass based on 100 parts by mass of polymerizable monomer. Although varying slightly according to the polymerization method, one type of the above-mentioned polymerization initiator is used alone or two or more types are used as a mixture with reference to the 10-hour half-life temperature.
• the aqueous medium used in the above-mentioned suspension polymerization method preferably contains a dispersion stabilizer.
• a known inorganic or organic dispersion stabilizer can be used for the dispersion stabilizer .
• inorganic dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica and alumina.
• organic dispersion stabilizers examples include polyvinyl alcohol, -gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt and starch.
• nonionic, anionic and cationic surfactants can also be used.
• Examples thereof include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate and potassium oleate.
• a water-insoluble inorganic dispersion stabilizer that is soluble in acid is preferably used in the present invention.
• a water-insoluble inorganic dispersion stabilizer that is soluble in acid is preferably used in the present invention.
• a water-insoluble inorganic dispersion stabilizer that is soluble in acid is preferably used in the present invention.
• the use of these dispersion stabilizers at a ratio within the range of 0.2 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of polymerizable monomer is preferable from the viewpoint of drop stability in the aqueous medium of the polymerizable monomer composition.
• the aqueous medium is preferably prepared using water within a range of 300 parts by mass to 3,000 parts by mass based on 100 parts by mass of the polymerizable monomer composition.
• the aqueous medium in the case of preparing an aqueous medium with the above-mentioned water-insoluble inorganic dispersion stabilizer dispersed therein, although a commercially available dispersion stabilizer can be used by directly dispersing therein, in order to obtain a dispersion stabilizer particles having a fine, uniform particle diameter, the aqueous medium is preferably prepared by forming the above-mentioned water-insoluble inorganic dispersion stabilizer while stirring at high speed in water.
• an aqueous sodium phosphate solution and an aqueous calcium chloride solution are mixed while stirring at high speed to form fine particles of calcium phosphate, thereby allowing the obtaining of a preferable dispersion stabilizer.
• Preferable toner particles can also be obtained for the toner particles of the present invention in the case of producing according to the suspension granulation method since the production process of the suspension granulation method does not reguire a heating step, compatibilization between resin and wax that occurs in the case of using a low melting point wax can be suppressed and a decrease in the glass transition temperature of the toner caused by compatibilization can be prevented.
• the suspension granulation method allows a wide selection range of toner materials capable of serving as the binder resin, it is easier to use a binder resin composed mainly of polyester resin, which is typically considered to be advantageous for fixing performance. Consequently, this production method is advantageous in the case of producing toner having a resin composition to which the suspension polymerization method cannot be applied.
• suspension granulation method are produced, for example, in the manner described below.
• a colorant containing the pigment composition of the present invention, a binder resin and a wax component and the like are mixed in a solvent to prepare a solvent composition.
• the solvent composition is dispersed in an aqueous medium followed by granulating the particles of the resin composition to obtain a toner particle suspension.
• Toner particles can then be obtained by removing the solvent by heating or reducing the pressure of the resulting suspension .
• the solvent composition in the above-mentioned step is preferably prepared by mixing a liquid dispersion, obtained by dispersing the above-mentioned colorant in a first solvent, with a second solvent. Namely, after having more adequately dispersed the above-mentioned colorant in the first solvent, mixing with the second solvent together with other toner materials makes it possible for the pigment to be present in the toner particles in a favorably dispersed state .
• One type of these can be used alone or two or more types can be used as a mixture.
• a solvent that has a low boiling point and is able to adequately dissolve the above-mentioned binder resin is used preferably to facilitate removal of solvent in the above-mentioned toner particle suspension.
• the amount of the above-mentioned solvent used is preferably 50 parts by mass to 5, 000 parts by mass and more preferably 120 parts by mass to 1,000 parts by mass based on 100 parts by mass of the binder resin.
• the aqueous medium used in the above-mentioned suspension granulation method preferably contains a dispersion stabilizer.
• a known inorganic or organic dispersion stabilizer can be used for the dispersion stabilizer .
• inorganic dispersion stabilizers include calcium phosphate, calcium carbonate, aluminum hydroxide, calcium sulfate and barium carbonate.
• organic dispersion stabilizers include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, hydroxyl ethyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, sodium polyacrylate or sodium polymethacrylate, anionic surfactants such as sodium dodecyl benzene sulfonate, sodium octadecyl sulfonate, sodium oleate, sodium laurate or potassium stearate, cationic surfactants such as lauryl amine acetate, stearyl amine acetate or lauryl trimethyl ammonium chloride, amphoteric surfactants such as lauryl dimethyl amine oxide, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers or polyoxyethylene
• the amount of the above-mentioned dispersing agent used is preferably 0.01 parts by weight to 20 parts by weight based on 100 parts by weight of the binder resin from the viewpoint of drop stability of the solvent composition in the aqueous medium.
• the weight-average particle diameter (to be described as D4 ) of the toner particles in the present invention is preferably 3.00 ⁇ to 15.0 ⁇ and more preferably 4.00 ⁇ to 12.0 ⁇ .
• the ratio of D4 to the number-average particle diameter (to be described as Dl) of the toner particles is preferably 1.35 or less and more preferably 1.30 or less.
• D4/D1 the ratio of D4 to the number-average particle diameter (to be described as Dl) of the toner particles
• D4/D1 the ratio of D4 to the number-average particle diameter (to be described as Dl) of the toner particles
• D4/D1 is preferably 1.35 or less and more preferably 1.30 or less.
• the method used to adjust D4 and Dl of the toner of the present invention differs depending on the method used to produce the toner particles. For example, in the case of the suspension polymerization method, D4 and Dl are adjusted by controlling the concentration of dispersing agent used when preparing the aqueous dispersion medium, the stirring speed during the reaction or the stirring time during the reaction.
• the toner of the present invention may be a magnetic toner or a non-magnetic toner.
• the toner particles that compose the toner of the present invention may be used as a mixture of magnetic materials.
• magnetic materials include irons oxides such as magnetite, maghemite or ferrite, iron oxides containing other metal oxides, metals such as Fe, Co or Ni, and alloys of these metals and metals such as Al, Co, Cu, Pb, g, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W or V, and mixtures thereof.
• a magnetic material that is particularly preferable for the object of the present invention is fine powder of triiron tetraoxide or ⁇ -diiron trioxide.
• the average particle diameter of these magnetic bodies is 0.1 ⁇ to 2 (and preferably 0.1 ⁇ to 0.3 ⁇ ) , and preferable magnetic properties during application of 795.8 kA/m from the viewpoint of toner developability consist of coercive force of 1.6 kA/m to 12 kA/m, saturation magnetization of 5 Am 2 /kg to 200 Am 2 /kg (and preferably 50 Am 2 /kg to 100 Am 2 /kg) and residual magnetization of 2 Am 2 /kg to 20 Am 2 / kg.
• the amount of these magnetic materials added is preferably 10 parts by mass to 200 parts by mass and more preferably 20 parts by mass to 150 parts by mass based on 100 parts by mass of the binder resin.
• the molecular weights of the above-mentioned polymer segment and compound having an azo skeleton structure are calculated based on polystyrene by size exclusion chromatography (SEC) . Measurement of molecular weight by SEC was carried out in the manner indicated below.
• a sample was added to the following eluent to a sample concentration of 1.0%, and the solution obtained by allowing to stand undisturbed for 24 hours at room temperature was filtered with a solvent-resistant membrane filter having a pore size of 0.2 ⁇ to obtain a sample solution that was measured under the conditions indicated below.
• a molecular weight calibration curve was used that was prepared from standard polystyrene resins (Tosoh Corp., TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-l, A-5000, A-2500, A-1000 and A-500) .
• the acid values of the above-mentioned polymer segment and compound having an azo skeleton structure were determined according to the method indicated below.
• the basic procedure is based on JIS K-0070.
• Titration is carried out with a potentiometric titration measuring apparatus using an ethanol solution having a KOH concentration of 0.1 mol/L (the Model COM-2500 automated titration measuring apparatus manufactured by Hiranuma Sangyo Corp., for example, can be used) .
• Acid value is then calculated according to the following equation.
• f represents the factor of the KOH solution .
• composition analysis by 13 C-NMR was carried out by reverse gate decoupling using chromium (III) acetyl acetonate for the relaxation reagent.
• a solution obtained by dissolving 8.97 parts of sodium carbonate in.35.9 parts of water and 2.33 parts of barbituric acid (C-48) were added to 30.0 parts of methanol followed by cooling with ice to 10°C or lower, adding the above-mentioned diazonium salt solution and reacting for 3 hours at 10°C or lower.
• the ratios of the number of carbon atoms that compose the copolymer assigned to each peak were quantified according to the results of analyzing the above-mentioned 13 C-NMR data. Calculation of the number of monomer units that compose compound (C-1) having an azo skeleton structure from these measurement results and the above-mentioned number average molecular weight determined by GPC analysis yielded 101 styrene units, 3 azo skeleton structures, 3 methyl acrylate units and 2 acrylic acid units.
• N, N, N ' , ' 1 , ' ' -pentamethyldiethylenetriamine were added to 5.0 parts of anisole followed by freezing and degassing three times and adding 0.69 parts of copper bromide in the presence of a nitrogen atmosphere. After allowing the solution to react for 8 hours at 100°C in the presence of a nitrogen atmosphere, the reaction solution was exposed to air to terminate the reaction. Following completion of the reaction, the reaction solution was concentrated and re-precipitated with methanol and the resulting precipitate was dissolved in tetrahydrofuran . This solution was passed through activated alumina to remove the copper bromide. After distilling off the solvent under reduced pressure, the precipitate was exsiccated under reduced pressure to obtain 40 parts of polymer compound (C-55) (yield: 80%) .
• a compound (C-16) having an azo skeleton structure represented by the following formula was produced in accordance with the scheme indicated below.
• the ratios of the number of carbon atoms that compose the copolymer assigned to each peak were quantified according to the results of analyzing the above-mentioned 13 C-NMR data. Calculation of the number of monomer units that compose compound (C-16) having an azo skeleton structure from these measurement results and the
• the ratios of the number of carbon atoms that compose the copolymer assigned to each peak were quantified according to the results of analyzing the above-mentioned 13 C-NMR data. Calculation of the number of monomer units that compose compound (C-44) having an azo skeleton structure from these measurement results and the above-mentioned number average molecular weight determined by GPC analysis yielded 102 styrene units and 4 azo skeleton structures .
• R-2 poly(X-co-Y,-co -2) 52 2 0 2 H H COOCH3 - - H
• R-3 poly(X-co -Y,-co -Z) 240 14 0 5 H H COOCH3 - - H
• R-4 poly (X-co -Y, -co -Z) 101 4 0 4 CH 3 CH 3 COOCH3 - - H
• R42 represents a hydrogen atom or alkyl group .
• R 43 represents a hydrogen atom or alkyl group and R 44 represents a carboxylic acid ester group or carboxylic acid amide group.
• R5 represents a hydrogen atom or alkyl group and R 46 represents a carboxylic acid ester group or carboxylic acid amide group.
• R 47 represents a hydrogen atom or alkyl group .
• Ri and R 2 each independently represent a hydrogen atom, alkyl group, phenyl group or aralkyl group, and X represents 0, NH or S.
• R 5 to R 9 each independently represent a hydrogen atom, COORio group or CON R11 R12 group.
• Rio to R12 each independently represent a hydrogen atom or alkyl group.
• at least one of Ri, R 2 and R 5 to R 9 has a substituent for bonding with the polymer as a linking group .
• the following comparative azo compound (C-46) was synthesized in compliance with Example 2 (Coloring Compound Synthesis Example 3) in the description of Japanese Patent Application Laid-open No. 2012-067285 as a comparative example of the compound having an azo skeleton structure of the present invention.
• Yellow pigment dispersions of the present invention were prepared according to the methods indicated below.
• an attritor Nippon Coke & Engineering Co., Ltd.
• Yellow pigment dispersions (Dis-Y2) to (Dis-Y44) were respectively obtained by. respectively carrying out the same procedure as the above-mentioned Yellow Pigment Dispersion Preparation Example 1 with the exception of changing the compound (C-l) having an azo skeleton structure to compounds (C-2) to (C-44) having an azo skeleton structure.
• Yellow pigment dispersions (Dis-Y45) and (Dis-Y46) were obtained by respectively carrying out the same procedure as the above-mentioned Yellow Pigment Dispersion Preparation Example 1 with the exception of changing- C.I. Pigment Yellow 155 (yellow pigment a) represented by formula (Pig-A) to C.I. Pigment Yellow 180 (yellow pigment b) represented by formula (Pig-B) or C.I. Pigment Yellow 185 (yellow pigment c) represented by formula (Pig-C) .
• Yellow pigment dispersions to serve as reference values for evaluation and yellow pigment dispersions for comparison were prepared according to the methods indicated below.
• a reference yellow pigment dispersion (Dis-Y48) was obtained by carrying out the same procedure as the above-mentioned Yellow Pigment Dispersion Preparation Example 1 with the exception of not adding compound (C-l) having an azo skeleton structure.
• Reference yellow pigment dispersions (Dis-Y49) and (Dis-Y50) were respectively obtained by respectively carrying out the same procedure as the above-mentioned Yellow Pigment Dispersion Preparation Example 3 with the exception of not adding compound (C-l) having an azo skeleton structure.
• a reference yellow pigment dispersion (Dis-Y51) was obtained by carrying out the same procedure as the ⁇ above-mentioned Yellow Pigment Dispersion Preparation Example 4 with the exception of not adding compound (C-l) having an azo skeleton structure.
• Magenta pigment dispersions of the present invention were prepared according to the methods indicated below.
• Magneticenta Pigment Dispersion Preparation Example 1 18.0 parts of a magenta pigment in the form of C.I. Pigment Red 122 (magenta pigment a) represented by the formula (Pig-D) , 1.80 parts of the above-mentioned compound
• Magenta pigment dispersions (Dis-M2) to (Dis-M44) were respectively obtained by respectively carrying out the same procedure as the above-mentioned Magenta Pigment Dispersion Preparation Example 1 with the exception of changing the compound (C-l) having an azo skeleton.structure to compounds (C-2) to (C-44) having an azo skeleton structure .
• Magenta pigment dispersions (Dis-M45) and (Dis-M46) were obtained by respectively carrying out the same procedure as the above-mentioned Magenta Pigment Dispersion Preparation Example 1 with the exception of changing C.I. Pigment Red 122 (magenta pigment a) represented by formula (Pig-D) to C.I. Pigment Red 255 (magenta pigment b) represented by formula (Pig-E) or C.I. Pigment Red 150 (magenta pigment c) represented by formula (Pig-F).
• magenta pigment in the form of C.I. Pigment Red 122 (magenta pigment a) represented by formula (Pig-D) and 4.2 parts of a pigment dispersing agent in the form of compound (C-1) having an azo skeleton structure were dry-mixed with the NHS-0 Hybridization System (Nara Machinery Co., Ltd.) to prepare a pigment composition. 19.8 parts of the resulting pigment composition were mixed with 180 parts of styrene and 130 parts of glass beads (diameter: 1 mm) followed by dispersing for 1 hour with a paint shaker (Toyo Seiki Seisaku-sho, Ltd. ) and filtering with a mesh to obtain a magenta pigment dispersion (Dis-M47) .
• a paint shaker Toyo Seiki Seisaku-sho, Ltd.
• Magenta pigment dispersions to serve as reference values for evaluation and magenta pigment dispersions for comparison were prepared according to the methods indicated belo .
• a reference magenta pigment dispersion (Dis-M48) was obtained by carrying out the same procedure as the above-mentioned Magenta Pigment Dispersion Preparation Example 1 with the exception of not adding compound (C-l) having an azo skeleton structure.
• Reference magenta pigment dispersions (Dis-M49) and (Dis-M50) were respectively obtained by respectively carrying out the same procedure as the above-mentioned Magenta Pigment Dispersion Preparation Example 3 with the exception of not adding compound (C-l) having an azo skeleton structure.
• a reference magenta pigment dispersion (Dis-M51) was obtained by carrying out the same procedure as the above-mentioned Magenta Pigment Dispersion Preparation Example 4 with the exception of not adding compound (C-l) .having an azo skeleton structure.
• Cyan pigment dispersions of the present invention were prepared according to the methods indicated below.
• Cyan pigment dispersions (Dis-C2) to (Dis-C44) were respectively obtained by respectively carrying out the same procedure as the above-mentioned Cyan Pigment Dispersion Preparation Example 1 with the exception of changing the compound (C-l) having an azo skeleton structure to compounds (C-2) to (C-44) having an azo skeleton structure.
• Cyan pigment dispersions (Dis-C45) and (Dis-C46) were obtained by respectively carrying out the same procedure as the above-mentioned Cyan Pigment Dispersion Preparation Example 1 with the exception of changing C.I. Pigment Blue 15:3 (cyan pigment a) represented by formula (Pig-G) to C.I. Pigment Blue 16 (cyan pigment b) represented by formula (Pig-H) or C.I. Pigment Blue 17:1 (cyan pigment c) represented by formula (Pig-I) .
• Cyan pigment dispersions to serve as reference values for evaluation and cyan pigment dispersions for comparison were prepared according to the methods indicated below.
• a reference cyan pigment dispersion (Dis-C48) was obtained by carrying out the same procedure as the above-mentioned Cyan Pigment Dispersion Preparation Example 1 with the exception of not adding compound (C-l) having an azo skeleton structure.
• a reference cyan pigment dispersion (Dis-C51) was obtained by carrying out the same procedure as the above-mentioned Cyan Pigment Dispersion Preparation Example 4 with the exception of not adding compound (C-l) having an azo skeleton structure.
• Black pigment dispersions of the present invention were prepared according to the methods indicated below.
• Black pigment dispersions (Dis-Bk2) to (Dis-Bk44) were respectively obtained by respectively carrying out the same procedure as the above-mentioned Black Pigment Dispersion Preparation Example 1 with the exception of changing the compound (C-1) having an azo skeleton structure to compounds (C-2) to (C-44) having an azo skeleton structure.
• Black pigment dispersions to serve as reference values for evaluation and black pigment dispersions for comparison were prepared according to the methods indicated below.
• a reference black pigment dispersion (Dis-Bk48) was obtained by carrying out the same procedure as the above-mentioned Black Pigment Dispersion Preparation Example 1 with the exception of not adding compound (C-l) having an azo skeleton structure.
• Reference black pigment dispersions (Dis-Bk49) and (Dis-Bk50) were respectively obtained by respectively carrying out the same procedure as the above-mentioned Black Pigment Dispersion Preparation Example 3 with the exception of not adding compound (C-l) having an azo skeleton structure .
• a reference black pigment dispersion (Dis-Bk51) was obtained by carrying out the same procedure as the above-mentioned Black Pigment Dispersion Preparation Example 4 with the exception of not adding compound (C-l) having an azo skeleton structure.
• the pigment dispersibility of the compound having an azo skeleton structure of the present invention was evaluated by carrying out a coated film gloss test using the above-mentioned yellow pigment dispersions (Dis-Yl) to (Dis-Y47) , the above-mentioned magenta pigment dispersions (Dis-Ml) to (Dis-M47), the above-mentioned cyan pigment dispersions (Dis-Cl) to (Dis-C47) and the above-mentioned black pigment dispersions (Dis-Bkl) to (Dis-Bk47). Namely, each pigment dispersion was aspirated with a dropper, placed on a straight line on the upper portion of Super Art Paper
• smoothness of the coated film improves and gloss improves the more finely the pigment is dispersed.
• gloss value improvement rates of the above-mentioned magenta pigment dispersions (Dis-Ml) to (Dis-M44) were evaluated using the gloss value of the reference magenta pigment dispersion (Dis- 48) as a reference value.
• Gloss value improvement rate of the above-mentioned magenta pigment dispersion (Dis-M45) was evaluated using the gloss value of the reference magenta pigment dispersion (Dis-M49) as a reference value.
• Gloss value improvement rate of the above-mentioned magenta pigment dispersion (Dis-M46) was evaluated using the gloss value of the reference magenta pigment dispersion (Dis-M50) as a reference value.
• Gloss value improvement rate of the above-mentioned magenta pigment dispersion (Dis-M47) was evaluated using the gloss value of the reference magenta pigment dispersion (Dis-M51) as a reference value.
• a gloss value improvement rate of 10% or more was judged to constitute favorable pigment dispersibility and be at a preferable level in terms of practical use.
• a gloss value of 50 or more was judged to constitute favorable pigment dispersibility and be at a preferable level in terms of practical use.
• yellow toners were produced by the suspension polymerization method according to the methods indicated below .
• composition was warmed to 60°C and uniformly dissolved and dispersed at 5,000 rpm using the T. K. Homo Mixer high-speed stirring apparatus (Primix Corp . ) .
• Polar resin saturated polyester resin (terephthalic acid-propylene oxide-modified bisphenol A, acid value: 15 mg KOH/g, peak molecular weight: 6,000): 10 parts
• the resulting dispersion of polymer fine particles was transferred to a washing container followed by the addition of dilute hydrochloric acid while stirring, stirring for 2 hours at pH 1.5 and dissolving a phosphoric acid and calcium compound containing Ca 3 (P0 4 ) 2 followed by solid-liquid separation with a filter to obtain polymer fine particles.
• the polymer fine particles were placed in water and stirred to again form a dispersion followed by solid-liquid separation with a filter. Re-dispersion of the polymer fine particles in water and solid-liquid separation were repeatedly carried out until the phosphoric acid and calcium compound containing Ca 3 (P0 4 )2 was adequately removed. Subsequently, polymer fine particles obtained following the final solid-liquid separation were adequately dried with a dryer to obtain toner particles.
• Yellow toners (Tnr-Y2) to (Tnr-Y44) of the present invention were obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 1 with the exception of changing the yellow pigment dispersion (Dis-Yl) to the above-mentioned yellow pigment dispersions (Dis-Y2) to (Dis-Y44) respectively.
• Yellow toners (Tnr-Y45) and (Tnr-Y46) were obtained by respectively carrying out the same procedure as the above-mentioned Yellow Toner Production Example 1 with the exception of changing the yellow pigment dispersion (Dis-Yl) to the above-mentioned yellow pigment dispersion (Dis-Y45) or (Dis-Y46) .
• Yellow toners serving as reference values during evaluation and comparative yellow toners were produced according to the methods indicated below for the yellow toner of the present invention produced in the
• a reference yellow toner (Tnr-Y47) was obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 1 with the exception of changing the yellow pigment dispersion (Dis-Yl) to yellow pigment dispersion (Dis-Y48).
• Reference yellow toners (Tnr-Y48) and (Tnr-Y49) were obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 1 with the exception of changing the yellow pigment dispersion (Dis-Yl) to yellow pigment dispersion (Dis-Y49) or (Dis-Y50) .
• Comparative yellow toners (Tnr-Y50) to (Tnr-Y52) were obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 1 with the exception of changing the above-mentioned yellow pigment dispersion (Dis-Yl) to yellow pigment dispersions (Dis-Y52) to (Dis-Y54) respectively.
• magenta toners were produced by the suspension polymerization method according to the methods indicated below .
• Magenta toner (Tnr-Ml) was obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 1 with the exception of changing the yellow pigment dispersion (Dis-Yl) to the magenta pigment dispersion (Dis-Ml).
• Magenta toners (Tnr-M2) to (Tnr-M44) of the present invention were obtained by carrying out the same procedure as the above-mentioned Magenta Toner Production Example 1 with the exception of changing the magenta pigment dispersion (Dis-Ml) to the above-mentioned magenta pigment dispersions (Dis-M2) to (Dis-M44) respectively.
• Magenta toners (Tnr-M45) and (Tnr-M 6). were obtained by respectively carrying out the same procedure as the above-mentioned Magenta Toner Production Example 1 with the exception of changing the magenta pigment dispersion (Dis-Ml) to the magenta pigment dispersion (Dis-M45) or (Dis-M46) .
• Reference magenta toners (Tnr-M48) and (Tnr-M49) were obtained by carrying out the same procedure as the above-mentioned Magenta Toner Production Example 1 with the exception of changing the magenta pigment dispersion (Dis-Ml) to magenta pigment dispersion (Dis-M49) or (Dis-M50) .
• Comparative magenta toners (Tnr-M50) to (Tnr-M52) were obtained by carrying out the same procedure as the above-mentioned Magenta Toner Production Example 1 with the exception of changing the above-mentioned magenta pigment dispersion (Dis-Ml) to magenta pigment dispersions (Dis-M52) to (Dis-M54) respectively.
• cyan toners were produced by the suspension polymerization method according to the methods indicated below .
• Cyan toner (Tnr-Cl) was obtained by carrying out the same procedure as the " above-mentioned Yellow Toner Production Example 1 with the exception of changing the yellow pigment dispersion (Dis-Yl) to the cyan pigment dispersion (Dis-Cl).
• Cyan toners (Tnr-C2) to (Tnr-C44) of the present invention were obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 1 with the exception of changing the cyan pigment dispersion (Dis-Cl) to the above-mentioned cyan pigment dispersions (Dis-C2) to (Dis-C44) respectively.
• Cyan toners (Tnr-C45) and (Tnr-C46) were obtained by respectively carrying out the same procedure as the above-mentioned Cyan Toner Production Example 1 with the exception of changing the cyan pigment dispersion (Dis-Cl) to. the cyan pigment dispersion (Dis-C45) or (Dis-C46).
• a reference cyan toner (Tnr-C47) was obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 1 with the exception of changing the cyan pigment dispersion (Dis-Cl) to cyan pigment dispersion (Dis-C48).
• Reference cyan toners (Tnr-C48) and (Tnr-C49) were obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 1 with the exception of changing the cyan pigment dispersion (Dis-Cl) to cyan pigment dispersion (Dis-C49) or (Dis-C50).
• Comparative Cyan Toner Production Example 1 Comparative cyan toners (Tnr-C50) to (Tnr-C52) were obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 1 with the exception of changing the above-mentioned cyan pigment dispersion (Dis-Cl) to cyan pigment dispersions (Dis-C52) to (Dis-C54) respectively.
• black toners were produced by the suspension polymerization method according to the methods indicated below .
• Black toner (Tnr-Bkl) was obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 1 with the exception of changing the yellow pigment dispersion (Dis-Yl) to the black pigment dispersion (Dis-Bkl) .
• Black toners (Tnr-Bk2) to (Tnr-Bk44) of the present invention were obtained, by carrying out the same procedure as the above-mentioned Black Toner Production Example 1 with the exception of changing the black pigment dispersion (Dis-Bkl) to the above-mentioned black pigment dispersions (Dis-Bk2) to (Dis-Bk44) respectively.
• Black toners (Tnr-Bk45) and (Tnr-Bk46) were obtained by respectively carrying out the same procedure as the above-mentioned Black Toner Production Example 1 with the exception of changing the black pigment dispersion (Dis-Bkl) to the black pigment dispersion (Dis-Bk45) or (Dis-Bk46) .
• a reference black toner (Tnr-Bk47) was obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 1 with the exception of changing the cyan pigment dispersion (Dis-Cl) to black pigment dispersion (Dis-Bk48).
• Reference black toners (Tnr-Bk48) and (Tnr-Bk49) were obtained by carrying out the same procedure as the above-mentioned Black Toner Production Example 1 with the exception of changing the black pigment dispersion (Dis-Bkl) to black pigment dispersion (Dis-Bk49) or (Dis-Bk50.) .
• Comparative black toners (Tnr-Bk50) to (Tnr-Bk52) were obtained by carrying out the same procedure as the above-mentioned Black Toner Production Example 1 with the exception of changing the above-mentioned black pigment dispersion (Dis-Bkl) to black pigment dispersions
• yellow toners were produced by the suspension granulation method according to the methods indicated below.
• the following composition was dispersed for 24 hours with a ball mill to obtain 200 parts of a toner composition mixed liquid.
• composition was dispersed for 24 hours with a ball mill followed by carboxymethyl cellulose to obtain an aqueous medium.
• Yellow toners (Tnr-Y54) to (Tnr-Y96) of the present invention were obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 4 with the exception of changing the compound (C-l) having an azo skeleton structure to compounds (C-2) to (C-44) respectively.
• Yellow toners (Tnr-Y97) and (Tnr-Y98) of the present invention were obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 4 with the exception of changing C.I. Pigment Yellow 155 represented by formula (Pig-A) (yellow pigment a) to C.I. Pigment Yellow 180 represented by formula (Pig-B) (yellow pigment b) or C.I. Pigment Yellow 185 represented by formula (Pig-C) (yellow pigment c) .
• Yellow toners to serve as reference values for evaluation and yellow toners for comparison were prepared according to the methods indicated below.
• a reference yellow toner (Tnr-Y99) was obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 4 with the exception of not adding compound (C-l) having an azo skeleton structure.
• Reference yellow toners (Tnr-Y100) and (Tnr-YlOl) were obtained by respectively carrying out the same procedure as the above-mentioned Yellow Toner Production Example 6 with the exception of not adding compound (C-l) having an azo skeleton structure.
• magenta toners were produced by the suspension granulation method according to the methods indicated below .
• Magenta toner (Tnr-M53) of the present invention was obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 4 with the exception of changing C.I. Pigment Yellow 155 represented by formula (Pig-A) (yellow pigment a) to C.I. Pigment Red 122 represented by formula (Pig-D) (magenta pigment a) .
• Magenta toners (Tnr-M54) to (Tnr-M96) of the present invention were obtained by carrying out the same procedure as the above-mentioned Magenta Toner Production Example 4 with the exception of changing the compound (C-l) having an azo skeleton structure to compounds (C-2) to (C-44) respectively.
• Magenta toners (Tnr-M97) and (Tnr-M98) of the present invention were obtained by carrying out the same procedure as the above-mentioned Magenta Toner Production Example 4 with the exception of changing C.I. Pigment Red 122 represented by formula (Pig-D) (magenta pigment a) to C.I. Pigment Red 255 represented by formula (Pig-E) (magenta pigment b) or C.I. Pigment Red 150 represented by formula (Pig-F) (magenta pigment c) .
• C.I. Pigment Red 122 represented by formula (Pig-D) (magenta pigment a)
• C.I. Pigment Red 255 represented by formula (Pig-E) (magenta pigment b)
• C.I. Pigment Red 150 represented by formula (Pig-F) (magenta pigment c) .
• Magenta toners to serve as reference values for evaluation and magenta toners for comparison were prepared according to the methods indicated below.
• cyan toners were produced by the suspension granulation method according to the methods indicated below .
• Cyan toner (Tnr-C53) of the present invention was obtained by carrying out the same procedure as the above-mentioned Yellow Toner Production Example 4 with the exception of changing C.I. Pigment Yellow 155 represented by formula (Pig-A) (yellow pigment a) to C.I. Pigment Blue 15:3 represented by formula (Pig-G) (cyan pigment a).
• C.I. Pigment Yellow 155 represented by formula (Pig-A) (yellow pigment a)
• C.I. Pigment Blue 15:3 represented by formula (Pig-G) (cyan pigment a).
• Cyan toners (Tnr-C54) to (Tnr-C96) of the present invention were obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 4 with the exception of changing the compound (C-l) having an azo skeleton structure to compounds (C-2) to (C-44)
• Cyan toners (Tnr-C97) and (Tnr-C98) of the present invention were obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 4 with the exception of changing C.I. Pigment Blue 15 : 3 represented by formula (Pig-G) (cyan pigment a) to C.I. Pigment Blue 16 represented by formula (Pig-H) (cyan pigment b) or C.I. Pigment Blue 17:1 represented by formula (Pig-I) (cyan pigment c) .
• Cyan toners to serve as reference values for evaluation and cyan toners for comparison were prepared according to the methods indicated below.
• a reference cyan toner (Tnr-C99) was obtained by carrying out the same procedure as the above-mentioned Cyan Toner Production Example 4 with the exception of not adding compound (C-l) having an azo skeleton structure.
• black toners were produced by the suspension granulation method according to the methods indicated below.
• Black toners (Tnr-Bk54) to (Tnr-Bk96) of the present invention were obtained by carrying out the same procedure as the above-mentioned Black Toner Production Example 4 with the exception of changing the compound (C-1) having an azo skeleton structure to compounds (C-2) to (C-44)
• a reference black toner (Tnr-Bk99) was obtained by carrying out the same procedure as the above-mentioned Black Toner Production Example 4 with the exception of not adding compound (C-l) having an azo skeleton structure.
• Reference black toners (Tnr-BklOO) and (Tnr-BklOl) were obtained by respectively carrying out the same procedure as the above-mentioned Black Toner Production Example 6 with the exception of not adding compound (C-l) having an azo skeleton structure.
• the yellow toner, magenta toner, cyan toner and black toner obtained in the present invention were evaluated according to the method indicated below.
• Image samples were output and compared and evaluated for image characteristics to be subsequently described using yellow toners (Tnr-Yl) to (Tnr-Y49) and (Tnr-Y53) to
• Tnr-M53 to (Tnr-MlOl)
• cyan toners to (Tnr-C49) and (Tnr-C53) to (Tnr-ClOl)
• black toners Tnr-Bkl
• LBP developing blade in the process cartridge
• SUS blade having a thickness of 8 ⁇
• V blade bias of -200 (V) was made to be able to be applied for the developing bias applied to the toner carrier in the form of a developing roll.
• Solid images having a toner mounting amount of 0.5 mg/cm 2 were produced on transfer paper (75 g/m 2 paper) in an environment at normal temperature and normal humidity
• the solid image density improvement rates of the above-mentioned yellow toners (Tnr-Yl) to (Tnr-Y44) were evaluated using the solid image density of the above-mentioned reference yellow toner (Tnr-Y47) as a reference value.
• the solid image density improvement rate of the above-mentioned yellow toner (Tnr-Y45) was evaluated using the solid image density of the above-mentioned reference yellow toner (Tnr-Y48) as a reference value.
• the solid image density improvement rate of the above-mentioned yellow toner (Tnr-Y46) was evaluated using the solid image density of the above-mentioned reference yellow toner
• the solid image density improvement rate of the above-mentioned cyan toner (Tnr-C45) was evaluated using the solid image density of the above-mentioned reference cyan toner (Tnr-C48) as a reference value.
• the solid image density improvement rate of the above-mentioned cyan toner (Tnr-C46) was evaluated using the solid image density of the above-mentioned reference cyan toner (Tnr-C49) as a reference value.
• Tnr-C99 above-mentioned reference cyan toner
• Tnr-C99 above-mentioned reference cyan toner
• the solid image density improvement rate of the above-mentioned cyan toner (Tnr-C97) was evaluated using the solid image density of the above-mentioned reference cyan toner (Tnr-ClOO) as a reference value.
• the solid image density improvement rate of the above-mentioned cyan toner (Tnr-C98) was evaluated using the solid image density of the above-mentioned reference cyan toner (Tnr-ClOl) as a reference value.
• the solid image density improvement ' rates of the above-mentioned black toners (Tnr-Bkl) to (Tnr-Bk44) were evaluated using the solid image density of the above-mentioned reference black toner (Tnr-Bk47) as a reference value.
• the solid image density improvement rate of the above-mentioned black toner (Tnr-Bk45) was evaluated using the solid image density of the above-mentioned reference black toner (Tnr-Bk48) as a reference value.
• the solid image density improvement rate of the above-mentioned black toner (Tnr-Bk46) was evaluated using the solid image density of the above-mentioned reference black toner (Tnr-Bk49) as a reference value.
• a solid image density improvement rate of 1% or more was judged to constitute favorable color tone.
• a solid image density improvement rate of 10% or more was judged to constitute favorable tinting strength.
• a solid image density improvement rate of 20% or more was judged to constitute favorable tinting strength.
• a solid image density improvement rate of 40% or more was judged to constitute favorable tinting strength.
• Tinting strength was evaluated using the same method as Example 15 for comparative yellow toners (Tnr-Y50) to (Tnr-Y52) and (Tnr-Y102) to (Tnr-Y104), comparative magenta toners (Tnr- 50) to (Tnr-M52) and (Tnr-M102) to (Tnr-M104), comparative cyan toners (Tnr-C50) to (Tnr-C52) and
• Tnr-C102 to (Tnr-C104) and comparative black toners (Tnr-Bk50) to (Tnr-Bk52) and (Tnr-Bkl02) to (Tnr-Bkl04) .
• the solid image density improvement rates of the above-mentioned comparative yellow toners (Tnr-Y102) to (Tnr-Y104) were evaluated using the solid image density of reference yellow toner (Tnr-Y99) as a reference value.
• the solid image density improvement rates of the above-mentioned comparative magenta toners (Tnr-M50) to (Tnr-M52) were evaluated usirig the solid image density of reference magenta toner (Tnr-M47) as a reference value.
• the solid image density improvement rates of the above-mentioned comparative magenta toners (Tnr- 102) to (Tnr-M104) were evaluated using the solid image density of reference magenta toner (Tnr-M99) as a reference value.
• the solid image density improvement rates of the above-mentioned comparative cyan toners (Tnr-C50) to (Tnr-C52) were evaluated using the solid image density of reference cyan toner (Tnr-C47) as a reference value.
• the solid image density improvement rates of the above-mentioned comparative cyan toners (Tnr-C102) to (Tnr-C104) were evaluated using the solid image density of reference cyan toner (Tnr-C99) as a reference value.
• the solid image density improvement rates of the above-mentioned comparative black toners (Tnr-Bk50) to (Tnr-Bk52) were evaluated using the solid image density of reference black toner (Tnr-Bk47) as a reference value.
• the solid image density improvement rates of the above-mentioned comparative black toners (Tnr-Bkl02) to (Tnr-Bkl04) were evaluated using the solid image density of reference black toner (Tnr-Bk99) as a reference value.

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