WO2010067784A1 - アゾ顔料、アゾ顔料の製造方法、アゾ顔料を含む分散物、及び着色組成物 - Google Patents
アゾ顔料、アゾ顔料の製造方法、アゾ顔料を含む分散物、及び着色組成物 Download PDFInfo
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- WO2010067784A1 WO2010067784A1 PCT/JP2009/070510 JP2009070510W WO2010067784A1 WO 2010067784 A1 WO2010067784 A1 WO 2010067784A1 JP 2009070510 W JP2009070510 W JP 2009070510W WO 2010067784 A1 WO2010067784 A1 WO 2010067784A1
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- azo pigment
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- ink
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- 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
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
- C09B33/12—Disazo dyes in which the coupling component is a heterocyclic compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- 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
- C09B67/0001—Post-treatment of organic pigments or dyes
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- 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
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0002—Grinding; Milling with solid grinding or milling assistants
-
- 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
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0028—Crystal modifications; Special X-ray patterns of azo compounds
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- 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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/0086—Non common dispersing agents anionic dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Definitions
- the present invention relates to an azo pigment, a method for producing an azo pigment, a dispersion containing an azo pigment, and a coloring composition.
- a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. Further, a color filter is used for recording and reproducing a color image on an image pickup device such as a CCD in a photographing apparatus and on an LCD or PDP in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixing method and subtractive color mixing method are used to display or record full color images. The fact is that there are no fast-acting dyes that have absorption characteristics that can satisfy the above conditions and that can withstand various use conditions and environmental conditions, and improvements are strongly desired.
- the dyes and pigments used in each of the above applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under environmental conditions to be used, for example, light resistance, heat resistance, good resistance to oxidizing gases such as ozone, and the like.
- the pigment when the pigment is a pigment, it is further substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but they are in a trade-off relationship and are difficult to achieve both.
- the pigment in addition to having a particle size and a particle shape necessary for expressing the desired transparency, fastness under the environmental conditions used, such as light resistance, heat resistance, Good resistance to oxidative gases such as ozone, and other chemical fastness to organic solvents and sulfurous acid gas. Disperse even fine particles in the medium used, and stable dispersion. , Etc. are also required.
- the required performance for pigments is more diverse than dyes that require performance as pigment molecules, and not only the performance as pigment molecules, but also the above requirements as solids (fine particle dispersions) as aggregates of pigment molecules All performance needs to be satisfied.
- the group of compounds that can be used as pigments is extremely limited compared to dyes, and even if high-performance dyes are derived into pigments, there are only a few that can satisfy the required performance as fine particle dispersions. It cannot be developed. This is confirmed by the fact that the number of pigments registered in the color index is less than 1/10 of the number of dyes.
- azo pigments are widely used as printing inks, ink-jet inks, electrophotographic materials, and color filter pigments because of their high lightness and excellent light resistance and heat resistance.
- pigments are required to have stability over time in a use medium that is even better than the level normally used for printing inks, gravure inks, and colorants.
- organic pigments are polymorphic, and it is known that such pigments take two or more crystalline forms despite having the same chemical composition.
- Some organic pigments such as azo pigments, can obtain finely sized particles by selecting appropriate reaction conditions during synthesis, such as copper phthalocyanine green pigments during synthesis.
- the very fine and agglomerated particles that are produced are pigmented by particle growth and sizing in the subsequent process, such as copper phthalocyanine blue pigment, coarse and irregular particles that are produced during synthesis are refined in the subsequent process, Some pigments are made by sizing.
- a diketopyrrolopyrrole pigment is generally synthesized by reacting an oxalic acid diester and an aromatic nitrile in an organic solvent (see, for example, Patent Document 1).
- the crude diketopyrrolopyrrole pigment is made into a form suitable for use by heat treatment in water or an organic solvent and then powdering such as wet grinding (for example, see Patent Document 2).
- C. I. For pigment red 254, ⁇ -type and ⁇ -type crystal forms are known (see, for example, Patent Document 3).
- C.I. which is an azo pigment.
- I. Pigment Yellow 181 has several known crystal forms (see, for example, Patent Document 4).
- the present invention relates to an azo pigment which is a novel crystal form of an azo pigment in which a pyrazole ring having a specific substituent is connected via an azo group and a triazine ring, and its excellent performance and production method have not been known so far.
- an object of the present invention is to provide an azo pigment having very good color reproducibility, dispersibility, and pigment dispersion stability, and having excellent hue and coloring power.
- An object of the present invention is to provide an azo pigment having a length in the major axis direction of 0.01 ⁇ m to 10 ⁇ m when observed with a transmission microscope. Furthermore, this invention aims at providing the coloring composition containing this azo pigment.
- An object of the present invention is to provide a method for producing an azo pigment that can be produced with high reproducibility and high efficiency while controlling to a specific structural isomerism and crystal polymorphism. Furthermore, it aims at providing the coloring composition containing the dispersion of this azo pigment.
- an azo pigment having a characteristic X-ray diffraction peak at a specific position in the embodiment of the present invention has extremely high color reproducibility, dispersibility, and pigment dispersion stability. It was found to be good and have excellent hue and tinting strength.
- the coloring composition in which the pigment is dispersed has excellent color reproducibility, and can produce an ink for ink jet recording having excellent pigment dispersion stability and ink liquid stability with stable pigment particle diameter over time. I found.
- the inventors have found a method for producing an azo pigment capable of producing an azo pigment with high reproducibility and high efficiency while controlling to specific structural isomerism and crystal polymorphism, and have completed the present invention.
- the present invention is as follows. [1] The following formula (1) having characteristic X-ray diffraction peaks at Bragg angles (2 ⁇ ⁇ 0.2 °) of 7.2 °, 13.4 °, 15.0 °, and 25.9 ° in CuK ⁇ characteristic X-ray diffraction Or an tautomer thereof.
- the method includes the step of subjecting a diazonium salt derived from a heterocyclic amine represented by the following formula (2) and a compound represented by the following formula (3) to an azo coupling reaction, the following formula (1)
- a diazonium salt derived from a heterocyclic amine represented by the following formula (2) and a compound represented by the following formula (3) to an azo coupling reaction, the following formula (1)
- the manufacturing method of the azo pigment represented by these, or its tautomer is a diazonium salt derived from a heterocyclic amine represented by the following formula (2) and a compound represented by the following formula (3) to an azo coupling reaction, the following formula (1)
- the manufacturing method of the azo pigment represented by these, or its tautomer is derived from a heterocyclic amine represented by the following formula (2) and a compound represented by the following formula (3) to an azo coupling reaction, the following formula (1)
- an azo pigment that is excellent in color characteristics such as coloring power, is stable in pigment particle diameter over time, and is excellent in pigment dispersion stability and ink liquid stability.
- a pigment dispersion having excellent color characteristics, dispersion stability and ink liquid stability can be obtained.
- the pigment dispersion can be used, for example, in printing inks such as inkjet, color toners for electrophotography, displays such as LCDs and PDPs, color filters used in image sensors such as CCDs, paints, and colored plastics. it can.
- FIG. 4 is an X-ray diffraction pattern of a crude pigment (1-2) synthesized according to Synthesis Example 1-1.
- FIG. 3 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -1 synthesized according to Synthesis Example 1-1.
- FIG. 3 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -2 synthesized according to Synthesis Example 1-2.
- FIG. 3 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -3 synthesized according to Synthesis Example 1-3.
- FIG. 4 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -4 synthesized according to Synthesis Example 1-4.
- FIG. 3 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -1 synthesized according to Synthesis Example 1-1.
- FIG. 3 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1)
- FIG. 6 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -5 synthesized according to Synthesis Example 1-5.
- FIG. 6 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -6 synthesized according to Synthesis Example 1-6.
- FIG. 7 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -7 synthesized according to Synthesis Example 1-7.
- FIG. 7 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -8 synthesized according to Synthesis Example 1-8.
- FIG. 6 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -9 synthesized according to Synthesis Example 1-9.
- FIG. 3 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -10 synthesized according to Synthesis Example 1-10.
- FIG. 11 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -11 synthesized according to Synthesis Example 1-11.
- FIG. 11 is an X-ray diffraction pattern of an ⁇ -type crystal form pigment (1) -12 synthesized according to Comparative Synthesis Example 1-12.
- the azo pigment of the present invention or a tautomer thereof may be a hydrate, a solvate or a salt thereof.
- the azo pigment in the embodiment of the present invention has characteristic Bragg angles (2 ⁇ ⁇ 0.2 °) in CuK ⁇ characteristic X-ray diffraction of 7.2 °, 13.4 °, 15.0 ° and 25.9 °. It is an azo pigment represented by the following formula (1) having a peak, or a tautomer thereof.
- the X-ray diffraction peaks characteristic of Bragg angles (2 ⁇ ⁇ 0.2 °) of 7.2 °, 13.4 °, 15.0 °, and 25.9 ° in CuK ⁇ characteristic X-ray diffraction are as follows.
- the azo pigment represented by the formula (1) having the formula is referred to as ⁇ -type crystal form azo pigment.
- the X-ray diffraction measurement of the ⁇ -type crystal form azo pigment represented by the above formula (1) is performed in accordance with Japanese Industrial Standard JISK0131 (general rules for X-ray diffraction analysis). (Manufactured by Rigaku Corporation).
- the molecules become dense and the intermolecular interaction becomes strong.
- the solvent resistance, thermal stability, light resistance, gas resistance and printing density are increased, and the color reproduction range is further expanded. Therefore, the azo pigment represented by the formula (1) and its tautomer are characterized by Bragg angles (2 ⁇ ⁇ 0.2 °) of 7.2 ° and 25.9 ° in CuK ⁇ characteristic X-ray diffraction.
- a crystalline form having an X-ray diffraction peak is preferred.
- Crystal forms having characteristic X-ray diffraction peaks at 7.2 °, 13.4 °, 15.0 °, and 25.9 ° are 7.2 °, 13.4 °, 15.0 °
- Crystal forms exhibiting X-ray diffraction patterns with significant X-ray diffraction lines at 19.8 ° and 25.9 ° are more preferred.
- X-ray diffraction having remarkable X-ray diffraction lines at 7.2 °, 8.2 °, 10.0 °, 13.4 °, 15.0 °, 19.8 °, and 25.9 ° Most preferred is a crystalline form exhibiting a pattern.
- the primary particles When the primary particles are observed with a transmission microscope and the length in the major axis direction is 0.01 ⁇ m or less, the fastness to light and ozone is remarkably reduced or the particles are easily agglomerated so that they are difficult to disperse. It may become.
- the particle size is 10 ⁇ m or more, the dispersion may be overdispersed when the volume average particle diameter is set to a desired volume average particle size, and the storage stability of the pigment dispersion may be deteriorated because it tends to aggregate.
- the pigment dispersion exhibits high fastness to light and ozone, and the pigment dispersion is excellent in storage stability and is preferable.
- the length in the major axis direction when the primary particles of the ⁇ -type crystal form azo pigment represented by the above formula (1) are observed with a transmission microscope is preferably 0.01 ⁇ m or more and 10 ⁇ m or less.
- the thickness is more preferably 0.02 ⁇ m or more and 5 ⁇ m or less, and most preferably 0.03 ⁇ m or more and 3 ⁇ m or less.
- the ⁇ -type crystal form azo pigment represented by the formula (1) (hereinafter sometimes simply referred to as “azo pigment” or “pigment”) can be synthesized by the production method of the present invention.
- the production method of the present invention includes a step of subjecting a diazonium salt derived from a heterocyclic amine represented by the following formula (2) and a compound represented by the following formula (3) to an azo coupling reaction.
- Preparation of the diazonium salt and the coupling reaction between the diazonium salt and the compound represented by the formula (3) can be carried out by conventional methods.
- the diazonium salt preparation of the heterocyclic amine represented by the formula (2) is prepared in a reaction medium containing an acid (for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.)
- an acid for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.
- Conventional diazonium salt preparation methods using nitrosonium ion sources such as nitrous acid, nitrite or nitrosylsulfuric acid are applicable.
- Examples of more preferred acids include the case where acetic acid, propionic acid, methanesulfonic acid, phosphoric acid and sulfuric acid are used alone or in combination, among which phosphoric acid or a combined system of acetic acid and sulfuric acid, acetic acid and propion A combined system of acid, a combined system of acetic acid, propionic acid and sulfuric acid is more preferable, and a combined system of acetic acid and propionic acid and a combined system of acetic acid, propionic acid and sulfuric acid are particularly preferable.
- reaction medium organic acids and inorganic acids are preferably used, and phosphoric acid, sulfuric acid, acetic acid, propionic acid, and methanesulfonic acid are particularly preferable. Among these, acetic acid and propionic acid are preferable.
- nitrosonium ion sources examples include nitrites, nitrites, nitrosylsulfuric acid and the like. Among them, isopentyl nitrite, sodium nitrite, potassium nitrite, and nitrosylsulfuric acid are more preferable, and sodium nitrite and nitrosylsulfuric acid are particularly preferable. For example, nitrosylsulfuric acid is used in the preferable acid-containing reaction medium. However, a diazonium salt can be prepared stably and efficiently.
- the amount of the solvent used with respect to the diazo component of the formula (2) is preferably 0.5 to 50 times by mass, more preferably 1 to 20 times by mass, and particularly preferably 3 to 15 times by mass.
- the diazo component of the formula (2) may be dispersed in a solvent, or may be in a solution state depending on the type of the diazo component.
- the amount of the nitrosonium ion source used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.10 equivalents, relative to the diazo component. Is preferred.
- the reaction temperature is preferably ⁇ 15 ° C. to 40 ° C., more preferably ⁇ 5 ° C. to 35 ° C., and still more preferably 0 ° C. to 30 ° C. Below -15 ° C, the reaction rate is remarkably slow and the time required for the synthesis is remarkably long, which is not economical. When synthesis is performed at a high temperature exceeding 40 ° C, the amount of by-products increases, which is preferable. Absent.
- the reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.
- the compound represented by the formula (3) can be produced using, for example, a method described in JP-A-2006-265185.
- the step of coupling reaction can be carried out in an acidic reaction medium to a basic reaction medium, but the azo pigment of the present invention is preferably carried out in an acidic to neutral reaction medium, particularly in an acidic reaction medium. It is possible to efficiently induce the azo pigment by suppressing the decomposition of the diazonium salt.
- reaction medium water, organic acid, inorganic acid, and organic solvent can be used.
- organic solvent is particularly preferable, and does not cause a liquid separation phenomenon during the reaction and presents a uniform solution with the solvent.
- a solvent is preferred.
- alcoholic organic solvents such as water, methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol, amyl alcohol, ketone organic solvents such as acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol
- diol organic solvents such as dipropylene glycol and 1,3-propanediol
- ether organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether, tetrahydrofuran, dioxane, acetonitrile, and the like.
- the solvent may be a mixture of two or more.
- the organic solvent has a polarity parameter (ET) value of 40 or more.
- ET polarity parameter
- a glycol solvent having two or more hydroxyl groups in a solvent molecule an alcohol solvent having 3 or less carbon atoms, a ketone solvent having a total carbon number of 5 or less, preferably an alcohol having 2 or less carbon atoms.
- Solvents for example, methanol, ethylene glycol
- ketone solvents having a total carbon number of 4 or less for example, acetone, methyl ethyl ketone
- the amount of the solvent used is preferably 1 to 100 times by mass of the coupling component represented by the above formula (3), more preferably 1 to 50 times by mass, and even more preferably 2 to 30 times by mass.
- the coupling component of the formula (3) may be dispersed in a solvent, or may be in a solution state depending on the type of coupling component.
- the amount of the coupling component used is preferably from 0.95 to 5.0 equivalents, more preferably from 1.00 to 3.00 equivalents, particularly from 1.00 to 1.50, based on the azo coupling site. It is preferable that it is equivalent.
- the reaction temperature is preferably ⁇ 30 ° C. to 50 ° C., more preferably ⁇ 15 ° C. to 45 ° C., still more preferably ⁇ 10 ° C. to 40 ° C. Less than ⁇ 30 ° C. is not economical because the reaction rate is remarkably slow and the time required for the synthesis is remarkably increased, and it is preferable to synthesize at a high temperature exceeding 50 ° C. because the amount of by-products increases. Absent. Further, when the reaction temperature is low, the primary particle size becomes small, but problems such as filtration leakage may occur during filtration, making isolation difficult. On the other hand, when the reaction temperature is high, the primary particle size becomes large and isolation is easy without causing problems such as filtration leakage. However, since the pigment dispersion tends to aggregate, post-treatment such as salt milling A process may be required.
- the reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.
- the product (crude azo pigment) obtained by these reactions may be subjected to a normal organic synthesis reaction post-treatment method and then purified or used without purification. it can.
- the product liberated from the reaction system can be used without being purified, or can be purified by recrystallization, salt formation or the like alone or in combination.
- reaction solvent is distilled off, or it is poured into water or ice without being distilled off, and the liberated product is extracted with neutralization or without neutralization, or extracted with an organic solvent / aqueous solution. It can also be used after purification or refining by recrystallization, crystallization, salt formation or the like, either alone or in combination.
- reaction solvent was not distilled off and poured into water or ice, and the operation was performed by precipitating the precipitated solid and neutralizing or purifying by decantation. It can also be served later.
- the method for producing an azo pigment of the present invention comprises a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the above formula (2) and a compound represented by the above formula (3).
- the coupling reaction is carried out after dissolving or suspending the compound of 3) in an organic solvent.
- the diazoniumation reaction of the heterocyclic amine represented by the above formula (2) can be performed, for example, in an acidic solvent such as sulfuric acid, phosphoric acid, acetic acid and the like with a reagent such as sodium nitrite and nitrosylsulfuric acid at a temperature of 30 ° C. or less for 10 minutes to The reaction can be carried out for about 6 hours.
- the coupling reaction can be performed by reacting the diazonium salt obtained by the above-described method with the compound represented by the above formula (3) at 50 ° C. or less, preferably 40 ° C. or less for about 10 minutes to 12 hours. preferable.
- the above-described tautomerization and / or crystal polymorphism can be controlled by the production conditions during the coupling reaction.
- a method for producing the ⁇ -type crystal of the present invention which is a more preferred form, for example, the method of the present invention in which the compound represented by the above formula (3) is once dissolved in an organic solvent and then a coupling reaction is performed. It is preferable to use it.
- the organic solvent that can be used at this time include alcohol solvents and ketone solvents.
- the alcohol solvent methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol and the like are preferable, and methanol is particularly preferable among them.
- ketone solvent acetone, methyl ethyl ketone, cyclohexanone and the like are preferable, and acetone is particularly preferable among them.
- a mixed solvent with water may be used.
- Another method for producing an azo pigment according to the present invention is a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the formula (2) and a compound represented by the formula (3).
- the coupling reaction is performed in the presence of an aprotic solvent.
- ⁇ -type crystals can also be produced efficiently by a method in which a coupling reaction is carried out in the presence of a polar aprotic solvent.
- polar aprotic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, acetonitrile, and mixed solvents thereof Etc.
- acetone, methyl ethyl ketone, N, N-dimethylacetamide, and acetonitrile are particularly preferable.
- the compound of the above formula (3) may or may not be completely dissolved in the solvent.
- the compound obtained by the above production method may or may not be adjusted to pH by adding a base as a purification step.
- the pH is preferably 4 to 10.
- the pH is more preferably 4.5 to 8, and particularly preferably 5.5 to 7.
- the hue does not increase reddish, which is preferable from the viewpoint of hue.
- the pH is 4 or more, for example, when used as an ink for ink jet recording, problems such as corroding the nozzle hardly occur, which is preferable.
- the compound represented by the above formula (1) is obtained as a crude azo pigment (crude).
- the present invention also relates to an ⁇ -type crystal form azo pigment produced by the above production method.
- the post-treatment step refers to pigment particle control by solvent heating treatment.
- the crystal form, the size and shape of the particles can be adjusted.
- Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, methanol, isopropanol, and isobutanol.
- Examples thereof include alcohol solvents, N, N-dimethylformamide, N-methyl-2-pyrrolidone, polar aprotic organic solvents such as acetone, methyl ethyl ketone, acetonitrile, glacial acetic acid, pyridine, and mixtures thereof.
- An inorganic or organic acid or base may be further added to the solvents mentioned above.
- the temperature of the solvent heat treatment varies depending on the desired primary particle diameter of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C.
- the treatment time is preferably 30 minutes to 24 hours.
- the pigment dispersion of the present invention is characterized by containing at least one azo pigment of the present invention. Thereby, it can be set as the pigment dispersion excellent in chromatic characteristics, durability, and dispersion stability.
- the pigment dispersion of the present invention may be aqueous or non-aqueous, but is preferably an aqueous pigment dispersion.
- aqueous liquid in which the pigment is dispersed in the aqueous pigment dispersion of the present invention a mixture containing water as a main component and optionally adding a hydrophilic organic solvent can be used.
- hydrophilic organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol and other alcohols, ethylene glycol, diethylene glycol
- Polyhydric alcohols such as triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol butyl ether, diethylene glycol mono Chill ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diprop
- the aqueous pigment dispersion of the present invention may contain an aqueous resin.
- the aqueous resin include water-soluble resins that dissolve in water, water-dispersible resins that disperse in water, colloidal dispersion resins, and mixtures thereof.
- Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.
- surfactants and dispersants may be used to improve pigment dispersion and image quality.
- the surfactant include anionic, nonionic, cationic and amphoteric surfactants. Any surfactant may be used, but anionic or nonionic surfactants may be used. It is preferable to use it.
- anionic surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls.
- Examples thereof include ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester, and the like.
- Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin Examples include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based resins, and silicon-based materials.
- the non-aqueous pigment dispersion is obtained by dispersing the pigment represented by the formula (1) in a non-aqueous vehicle.
- Resins used in non-aqueous vehicles are, for example, petroleum resins, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber , Phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin , Drying oil, synthetic drying oil, styrene / maleic acid resin, styrene / acrylic resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin chlorinated polypropylene, buty
- Examples of the solvent used in the non-aqueous vehicle include aromatic solvents such as toluene, xylene, and methoxybenzene, and acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.
- aromatic solvents such as toluene, xylene, and methoxybenzene
- acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.
- Solvents propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
- Ketone solvents aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, ⁇ -butyrolactam, - methyl-2-pyrrolidone, aniline, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as ⁇ - butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid.
- the pigment dispersion of the present invention can be obtained by dispersing the above azo pigment and an aqueous or non-aqueous medium using a dispersing device.
- Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, bead mill, attritor, roll mill, jet mill, paint shaker, agitator mill, etc.), ultrasonic method
- a high-pressure emulsification dispersion system high-pressure homogenizer; specific commercially available devices such as gorin homogenizer, microfluidizer, DeBEE2000, etc.
- the volume average particle diameter of the pigment particles in the pigment dispersion is preferably 0.01 ⁇ m to 0.15 ⁇ m.
- the volume average particle diameter of the pigment particles in the pigment dispersion is 0.01 ⁇ m or more, it is preferable because the temporal stability of the dispersion is increased and aggregation is difficult.
- the volume average particle diameter of the particles is 0.15 ⁇ m or less, the optical density becomes high, the density of the printed matter becomes high, the color reproducibility of the mixed color portion such as red or green is improved, and the transparency is improved. This is preferable because it becomes high and nozzle clogging is less likely to occur when printing with an inkjet or the like.
- the volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself, or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the colorant.
- a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) can be used as a measuring device for the volume average particle diameter of pigment particles. The measurement can be performed according to a predetermined measurement method by placing 3 ml of the pigment dispersion in a measurement cell. As parameters input at the time of measurement, the ink viscosity is used as the viscosity, and the pigment density is used as the density of the dispersed particles.
- a more preferable volume average particle size is 20 nm or more and 150 nm or less, more preferably 30 nm or more and 130 nm or less, and most preferably 50 nm or more and 100 nm or less.
- the volume average particle diameter of the ⁇ -type crystal form azo pigment particles within the above range, for example, the following method can be used. 0.25 part of the azo pigment, 0.05 part of sodium oleate, 0.5 part of glycerin and 4.2 part of water are mixed, and 10 parts of zirconia beads having a diameter of 0.1 mm are mixed with a planetary ball mill every minute. By carrying out dispersion at 300 rpm for 1 hour and 30 minutes, the volume average particle diameter can be adjusted in the range of 0.06 to 0.10 ⁇ m (60 nm to 100 nm).
- the volume average particle diameter can be adjusted in the range of 0.04 to 0.07 ⁇ m (40 nm to 70 nm). Further, by carrying out dispersion for 4 hours, the volume average particle diameter can be adjusted in the range of 0.03 to 0.06 ⁇ m (30 nm to 60 nm).
- the concentration of the pigment contained in the pigment dispersion of the present invention is preferably in the range of 1 to 35% by mass, more preferably in the range of 2 to 25% by mass. If the density is less than 1% by mass, sufficient image density may not be obtained when the pigment dispersion is used alone as the ink. If the concentration exceeds 35% by mass, the dispersion stability may decrease.
- azo pigments of the present invention include image recording materials for forming images, particularly color images.
- image recording materials for forming images, particularly color images.
- thermal recording materials described in detail below, thermal recording materials, Pressure recording material, recording material using an electrophotographic method, transfer type silver halide photosensitive material, printing ink, recording pen, etc., preferably an ink jet recording material, a thermal recording material, a recording material using an electrophotographic method, More preferred are ink jet recording materials.
- a solid-state image pickup device such as a CCD
- a color filter for recording / reproducing a color image used in a display such as an LCD or a PDP
- a dyeing solution for dyeing various fibers.
- the azo pigment of the present invention can be used in an emulsified and dispersed state and further in a solid dispersed state depending on the system used.
- the colored composition of the present invention means a colored composition containing at least one azo pigment of the present invention.
- the coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording.
- the coloring composition of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium and dispersing the azo pigment of the present invention in the medium. Preferably, an aqueous medium is used.
- the coloring composition of the present invention includes an ink composition excluding a medium.
- the coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention.
- additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Known additives (described in JP-A No. 2003-306623) such as foaming agents, viscosity modifiers, dispersants, dispersion stabilizers, rust preventives, chelating agents and the like can be mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. In the case of oil-soluble ink, it is common to add to the dispersion after preparation of the azo pigment dispersion, but it may be added to the oil phase or water phase at the time of preparation.
- the pigment dispersion described above can be used as the ink.
- it is prepared by mixing a water-soluble solvent, water and the like.
- the pigment dispersion of the present invention may be used as it is.
- the ink for ink jet recording in the present invention contains the pigment dispersion of the present invention, and the ink in the present invention can also be used as the ink for ink jet recording. Further, the coloring composition containing the pigment of the present invention can be preferably used as an ink for inkjet recording.
- the ink dispersion for ink jet recording (hereinafter sometimes referred to as “ink”) uses the pigment dispersion described above. Preferably, it is prepared by mixing a water-soluble solvent, water and the like. However, if there is no particular problem, the pigment dispersion of the present invention may be used as it is.
- the content ratio of the pigment dispersion in the ink is preferably in the range of 1 to 100% by mass, considering the hue, color density, saturation, transparency, etc. of the image formed on the recording medium, and is preferably 3 to 20% by mass.
- the range is particularly preferable, and the range of 3 to 10% by mass is most preferable.
- the pigment of the present invention is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and more preferably 1 to 10 parts by mass in 100 parts by mass of the ink. It is more preferable to contain. Further, in the ink of the present invention, other pigments may be used in combination with the pigment of the present invention. When two or more kinds of pigments are used in combination, the total content of the pigments is preferably within the above range.
- the ink can be used not only for forming a single color image but also for forming a full color image.
- a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.
- pigments can be used simultaneously in addition to the azo pigment according to the present invention.
- yellow pigments that can be applied include C.I. I. P. Y. -74, C.I. I. P. Y. -128, C.I. I. P. Y. -155, C.I. I. P. Y. -213, and applicable magenta pigments include C.I. I. P. V. -19, C.I. I. P. R. -122, and examples of applicable cyan pigments include C.I. I. P. B. -15: 3, C.I. I. P. B. -15: 4, and any of these can be used separately.
- Applicable black materials include disazo, trisazo, and tetraazo pigments, as well as carbon black dispersions.
- water-soluble solvent used in the ink polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents and the like are used.
- polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerin.
- polyhydric alcohol derivative examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diglycerin. And ethylene oxide adducts.
- nitrogen-containing solvent examples include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine.
- alcohols include alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol.
- the solvent examples include thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like.
- propylene carbonate, ethylene carbonate, or the like can be used.
- the water-soluble solvent used in the present invention may be used alone or in combination of two or more.
- the content of the water-soluble solvent is 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 40% by mass or less of the entire ink.
- a sufficient optical density may not be obtained.
- the amount is more than 60% by mass, the viscosity of the liquid increases. In some cases, the ejection characteristics of the ink liquid become unstable.
- the preferred physical properties of the ink in the present invention are as follows.
- the surface tension of the ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 35 mN / m or less. If the surface tension is less than 20 mN / m, liquid may overflow on the nozzle surface of the recording head, and printing may not be performed normally. On the other hand, if it exceeds 60 mN / m, the permeability to the recording medium after printing may be slow, and the drying time may be slow.
- the surface tension was measured under the environment of 23 ° C. and 55% RH using a Wilhelmy surface tension meter as described above.
- the viscosity of the ink is preferably from 1.2 mPa ⁇ s to 8.0 mPa ⁇ s, more preferably from 1.5 mPa ⁇ s to less than 6.0 mPa ⁇ s, still more preferably from 1.8 mPa ⁇ s to 4. It is less than 5 mPa ⁇ s.
- the viscosity is greater than 8.0 mPa ⁇ s, the dischargeability may be reduced.
- it is smaller than 1.2 mPa ⁇ s the long-term jetting property may deteriorate.
- the viscosity (including those described later) was measured using a rotational viscometer Rheomat 115 (manufactured by Contraves) at 23 ° C. and a shear rate of 1400 s ⁇ 1 .
- water is added to the ink in a range that achieves the above-described preferable surface tension and viscosity.
- the amount of water added is not particularly limited, but is preferably 10% by mass to 99% by mass, and more preferably 30% by mass to 80% by mass with respect to the entire ink.
- cellulose derivatives such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, polysaccharides and derivatives thereof, other water-soluble polymers, acrylics Polymer emulsion, polyurethane emulsion, polymer emulsion such as hydrophilic latex, hydrophilic polymer gel, cyclodextrin, macrocyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamide, silicone surfactant, fluorine-based A surfactant or the like can be used.
- cellulose derivatives such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, polysaccharides and derivatives thereof, other water-soluble polymers, acrylics Polymer emulsion, polyurethane emulsion, polymer emulsion such as hydrophilic latex, hydrophilic poly
- alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, 2-amino-2-methyl
- Nitrogen-containing compounds such as 1-propanol, alkaline earth metal compounds such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid and nitric acid, strong acid and weak alkali salts such as ammonium sulfate, and the like can be used.
- pH buffering agents antioxidants, fungicides, viscosity modifiers, conductive agents, ultraviolet absorbers, etc. can be added as necessary.
- the ink jet recording method is a method of forming an image on the surface of a recording medium by using ink for ink jet recording and discharging the ink from the recording head to the surface of the recording medium in accordance with a recording signal.
- the ink jet recording apparatus includes a recording head that uses ink for ink jet recording and ejects ink (if necessary, treatment liquid) onto the surface of the recording medium. It is an apparatus to form.
- the ink jet recording apparatus supplies an ink tank for ink jet recording (hereinafter sometimes referred to as “ink tank”) that can supply ink to the recording head and is detachable from the main body of the ink jet recording apparatus. You may have. In this case, ink is stored in the ink tank for ink jet recording.
- a normal ink jet recording apparatus having a printing method capable of using ink for ink jet recording can be used.
- a heater for controlling the drying of the ink as necessary is provided. It may be mounted, or may be equipped with an intermediate transfer mechanism, and a mechanism for discharging (printing) ink and processing liquid onto the intermediate and then transferring it to a recording medium such as paper.
- an ink tank for ink jet recording is detachable from an ink jet recording apparatus equipped with a recording head, and can be used as long as it has a configuration capable of supplying ink to the recording head while attached to the ink jet recording apparatus.
- a known ink tank can be used.
- the ink jet recording method preferably employs a thermal ink jet recording method or a piezo ink jet recording method from the viewpoint of the effect of improving bleeding and intercolor bleeding.
- the thermal ink jet recording method the ink is heated at the time of ejection and has a low viscosity, but the viscosity rapidly increases because the temperature of the ink is lowered on the recording medium. For this reason, there is an effect of improving bleeding and intercolor bleeding.
- the piezo ink jet method it is possible to discharge a high-viscosity liquid, and the high-viscosity liquid can suppress spreading in the paper surface direction on the recording medium. There is an improvement effect on intercolor bleeding.
- replenishment (supply) of ink to the recording head is preferably performed from an ink tank filled with ink liquid (including a treatment liquid tank if necessary).
- the ink tank is preferably of a cartridge type that can be attached to and detached from the apparatus main body, and ink can be easily replenished by exchanging the cartridge type ink tank.
- the content of the azo pigment in 100 parts by weight of the color toner is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 to 20 parts by weight, and most preferably 2 to 10 parts by weight. preferable.
- a binder resin for a color toner into which an azo pigment is introduced all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
- Inorganic fine powders and organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging.
- Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These have a number average primary particle size of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.
- release agent all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazole wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.
- the charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.
- the carrier either an uncoated carrier composed only of magnetic material particles such as iron or ferrite, or a resin-coated carrier in which the magnetic material particle surface is coated with a resin or the like may be used.
- the average particle diameter of this carrier is preferably 30 to 150 ⁇ m in terms of volume average particle diameter.
- the image forming method to which the toner is applied is not particularly limited.
- a method of forming a color image by repeatedly forming a color image on a photoconductor to form an image, or an image formed on a photoconductor For example, a method of sequentially transferring to an intermediate transfer member or the like, forming a color image on the intermediate transfer member or the like, and then transferring the image to an image forming member such as paper to form a color image.
- the heat-sensitive recording material includes an ink sheet in which the azo pigment of the present invention is coated on a support together with a binder, and an image-receiving sheet that fixes a pigment that has migrated in response to thermal energy applied from a thermal head in accordance with an image recording signal. Composed.
- the ink sheet can be formed by preparing an ink liquid by dispersing the azo pigment of the present invention in the form of fine particles in a solvent together with a binder, applying the ink on a support, and drying it appropriately.
- the amount of ink applied on the support is not particularly limited, but is preferably 30 to 1000 mg / m 2 .
- As a preferable binder resin, ink solvent, support, and image receiving sheet those described in JP-A-7-137466 can be preferably used.
- a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of full-color image recording, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image, and heat diffusion capable of forming a magenta image. It is preferable to form a magenta ink sheet containing a reactive magenta dye and a yellow ink sheet containing a heat diffusible yellow dye capable of forming a yellow image by sequentially coating the support. In addition, an ink sheet containing a black image forming substance may be further formed as necessary.
- [Color filter] As a method for forming a color filter, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, and JP-A-4-175653. Thus, there is a method of forming a pattern with a photoresist to which a dye is added. Any of these methods may be used as a method for introducing the coloring matter of the present invention into a color filter. Preferred methods are described in JP-A-4-175753 and JP-A-6-35182.
- the positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating on a substrate, exposing through a mask and developing the exposed portion. Then, a positive resist pattern is formed, the positive resist pattern is exposed on the entire surface, and then the exposed positive resist pattern is cured, and a color filter forming method can be mentioned.
- a black matrix is formed according to a conventional method, and an RGB primary color system or Y, M, C complementary color system color filter can be obtained.
- the amount of the azo pigment of the present invention is not limited, but is preferably 0.1 to 50% by mass.
- thermosetting resin quinonediazide compound, cross-linking agent, and solvent used in this case and the amounts used thereof are preferably those described in the above-mentioned patent documents.
- the X-ray diffraction measurement of the ⁇ -type crystal form azo pigment uses CuK ⁇ rays in a powder X-ray diffraction measurement device RINT2500 (manufactured by Rigaku Corporation) in accordance with Japanese Industrial Standard JISK0131 (general rules for X-ray diffraction analysis) The test was conducted under the following conditions.
- Measuring instrument Automatic X-ray diffractometer RINT2500 manufactured by Rigaku X-ray tube: Cu Tube voltage: 55KV Tube current: 280 mA Scanning method: 2 ⁇ / ⁇ scan Scanning speed: 6 deg. / Min Sampling interval: 0.100 deg. Start angle (2 ⁇ ): 5 deg. Stop angle (2 ⁇ ): 55 deg. Divergence slit: 2 deg. Scattering slit: 2 deg. Receiving slit: 0.6mm Using vertical goniometer
- the obtained crystals were suspended in 750 mL of water without drying, and 8N aqueous potassium hydroxide solution was added to adjust the pH to 5.7. After stirring at room temperature for 20 minutes, the obtained crystals were separated by filtration, thoroughly washed with water, and then washed with 80 mL of methanol to obtain a crude pigment (1-1).
- the obtained crude pigment (1-1) was dried at room temperature for 12 hours to obtain a crude pigment (1-2).
- a transmission microscope manufactured by JEOL Ltd .: JEM-1010 electron microscope
- the length of the primary particles in the major axis direction was about 40. It was ⁇ 500 nm.
- the obtained ⁇ -type crystal form azo pigment (1) -2 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of the primary particles in the long axis direction was observed. Was about 40-160 nm.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 °.
- characteristic X-ray diffraction peaks at 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG.
- the obtained ⁇ -type crystal form azo pigment (1) -3 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed. Was about 30-140 nm.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 °.
- characteristic X-ray diffraction peaks at 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG.
- the obtained ⁇ -type crystal form azo pigment (1) -4 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed. Was about 40-120 nm.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 °.
- characteristic X-ray diffraction peaks at 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG.
- the obtained ⁇ -type crystal form azo pigment (1) -5 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed. Was about 30-110 nm.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 °.
- characteristic X-ray diffraction peaks at 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG.
- Synthesis of ⁇ -type crystal form azo pigment (1) -7 10 g of the crude pigment (1-2) obtained in Synthesis Example 1-1 was suspended in 200 mL of acetone, and then refluxed for 2 hours. Stir. Thereafter, the obtained crystals were filtered off with heating and dried at room temperature for 12 hours to obtain 8.5 g of ⁇ -type crystal form azo pigment (1) -7 represented by the formula (1) having the crystal form of the present invention. (Yield 85.0%). The obtained ⁇ -type crystal form azo pigment (1) -7 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed.
- a transmission microscope manufactured by JEOL Ltd .: JEM-1010 electron microscope
- Synthesis of ⁇ -type Crystal Form Azo Pigment (1) -8 10 g of the crude pigment (1-2) obtained in Synthesis Example 1-1 was suspended in a mixed solvent of 100 mL of acetone and 100 mL of water. Thereafter, the mixture was stirred at an internal temperature of 60 ° C. for 2 hours. Thereafter, the obtained crystals were filtered off with heating and dried at room temperature for 12 hours to obtain 9.0 g of an ⁇ -type crystal form azo pigment (1) -8 represented by the formula (1) having the crystal form of the present invention. (Yield 90.0%).
- the obtained ⁇ -type crystal form azo pigment (1) -8 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed. Was about 50-160 nm.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 °.
- characteristic X-ray diffraction peaks at 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG.
- Synthesis of ⁇ -type crystal form azo pigment (1) -10 10 g of the crude pigment (1-2) obtained in Synthesis Example 1-1 was suspended in a mixed solvent of 100 mL of methanol and 100 mL of water. Thereafter, the mixture was stirred at an internal temperature of 70 ° C. for 2 hours. Thereafter, the obtained crystals were filtered off with heating and dried at room temperature for 12 hours to obtain 9.4 g of an ⁇ -type crystal form azo pigment (1) -10 represented by the formula (1) having the crystal form of the present invention. (Yield 94.0%).
- the obtained ⁇ -type crystal form azo pigment (1) -10 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed. Was about 40-130 nm.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 °.
- characteristic X-ray diffraction peaks at 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG.
- urea was dividedly added at the same temperature and stirred for 15 minutes at the same temperature to obtain a diazonium salt solution.
- 30.3 g of intermediate (e) was suspended in 518 mL of methanol at room temperature, and the internal temperature was cooled to 15 ° C. At the same temperature, the above diazonium salt solution was added so that the internal temperature was 30 ° C. or lower. After completion of the addition, the mixture was stirred for 2 hours to obtain an azo compound reaction liquid. Separately, 810 mL of water was prepared, and an azo compound reaction solution was added. After stirring at room temperature for 30 minutes, 8N aqueous sodium hydroxide solution was added to adjust the pH to 6.0.
- the obtained ⁇ -type crystal form azo pigment (1) -11 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed. Was about 60-250 nm.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 Characteristic X-ray diffraction peaks were exhibited at ° and 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG.
- Synthesis of ⁇ -type Crystal Form Azo Pigment (1) -12 10 g of the crude pigment (1-2) obtained in Synthesis Example 1-1 was mixed with 100 mL of N, N-dimethylacetamide and 100 mL of water. Then, the mixture was stirred at an internal temperature of 80 ° C. for 2 hours. Thereafter, the obtained crystals were filtered off with heating and dried at room temperature for 12 hours to obtain 9.0 g of ⁇ -type crystal form azo pigment (1) -12 represented by the formula (1) having the crystal form of the present invention. (Yield 90.0%).
- the obtained ⁇ -type crystal form azo pigment (1) -12 was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), and the length of primary particles in the long axis direction was observed. was about 60 nm to 2 ⁇ m.
- the Bragg angle (2 ⁇ ⁇ 0.2 °) was 7.2 °, 13.4 °, 15.0 °.
- characteristic X-ray diffraction peaks at 25.9 °.
- a CuK ⁇ characteristic X-ray diffraction diagram is shown in FIG. 13.
- Example 1 Preparation of Pigment Dispersion 1 2.5 parts of ⁇ -type crystal form azo pigment (1) -1 synthesized in Synthesis Example 1-1, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After the completion of dispersion, zirconia beads were separated to obtain a yellow pigment dispersion 1 (volume average particle diameter; Mv ⁇ 90.3 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- a yellow pigment dispersion 1 volume average particle diameter; Mv ⁇ 90.3 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.
- Example 2 Preparation of Pigment Dispersion 2 2.5 parts of ⁇ -type crystal form azo pigment (1) -6 synthesized in Synthesis Example 1-6, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 2 (volume average particle diameter; Mv ⁇ 70.1 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 3 Preparation of pigment dispersion 3 2.5 parts of ⁇ -type crystal form azo pigment (1) -6 synthesized in Synthesis Example 1-6, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 300 parts per minute for 3 hours using a planetary ball mill together with 100 parts of zirconia beads having a diameter of 0.1 mm. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 3 (volume average particle diameter; Mv ⁇ 65.2 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 4 Preparation of pigment dispersion 4 2.5 parts of ⁇ -type crystal form azo pigment (1) -6 synthesized in Synthesis Example 1-6, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The components were mixed, and dispersed at 300 rpm for 4 hours using a planetary ball mill together with 100 parts of zirconia beads having a diameter of 0.1 mm. After completion of the dispersion, zirconia beads were separated to obtain a yellow pigment dispersion 4 (volume average particle diameter; Mv ⁇ 45.9 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 5 Preparation of pigment dispersion 5 2.5 parts of the ⁇ -type crystal form azo pigment (1) -2 synthesized in Synthesis Example 1-2, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 5 (volume average particle diameter; Mv ⁇ 71.3 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 6 Preparation of pigment dispersion 6 2.5 parts of ⁇ -type crystal form azo pigment (1) -3 synthesized in Synthesis Example 1-3, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 6 (volume average particle diameter; Mv ⁇ 75.2 m: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 7 Preparation of pigment dispersion 7 2.5 parts of ⁇ -type crystal form azo pigment (1) -4 synthesized in Synthesis Example 1-4, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 7 (volume average particle diameter; Mv ⁇ 69.2 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 8 Preparation of pigment dispersion 8 2.5 parts of ⁇ -type crystal form azo pigment (1) -5 synthesized in Synthesis Example 1-5, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After the completion of dispersion, zirconia beads were separated to obtain yellow pigment dispersion 8 (volume average particle diameter; Mv ⁇ 62.8 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 9 Preparation of pigment dispersion 9 2.5 parts of ⁇ -type crystal form azo pigment (1) -7 synthesized in Synthesis Example 1-7, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 9 (volume average particle diameter; Mv ⁇ 85.4 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 10 Preparation of Pigment Dispersion 10 2.5 parts of ⁇ -type crystal form azo pigment (1) -8 synthesized in Synthesis Example 1-8, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 10 (volume average particle size; Mv ⁇ 78.8 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- a yellow pigment dispersion 10 volume average particle size; Mv ⁇ 78.8 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.
- Example 11 Preparation of Pigment Dispersion 11 2.5 parts of ⁇ -type crystal form azo pigment (1) -9 synthesized in Synthesis Example 1-9, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 11 (volume average particle diameter; Mv ⁇ 70.9 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 12 Preparation of pigment dispersion 12 2.5 parts of ⁇ -type crystal form azo pigment (1) -10 synthesized in Synthesis Example 1-10, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 12 (volume average particle diameter; Mv ⁇ 64.7 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 13 Preparation of pigment dispersion 13 2.5 parts of ⁇ -type crystal form azo pigment (1) -11 synthesized in Synthesis Example 1-11, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 13 (volume average particle size; Mv ⁇ 87.3 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 14 Preparation of Pigment Dispersion 14 2.5 parts of ⁇ -type crystal form azo pigment (1) -11 synthesized in Synthesis Example 1-11, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed at 300 rpm for 2 hours using a planetary ball mill together with 100 parts of zirconia beads having a diameter of 0.1 mm. After completion of the dispersion, zirconia beads were separated to obtain a yellow pigment dispersion 14 (volume average particle size; Mv ⁇ 67.9 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 15 Preparation of pigment dispersion 15 2.5 parts of the crude pigment (1-2) synthesized in Synthesis Example 1-1, 0.5 part of sodium oleate, 5 parts of glycerin and 42 parts of water were mixed. Using a planetary ball mill together with 100 parts of zirconia beads having a diameter of 0.1 mm, dispersion was performed at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 15 (volume average particle diameter; Mv ⁇ 79.2 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 16 Preparation of Pigment Dispersion 16 2.5 parts of ⁇ -type crystal form azo pigment (1) -12 synthesized in Synthesis Example 1-12, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed with 100 parts of zirconia beads having a diameter of 0.1 mm using a planetary ball mill at 300 rpm for 1 hour and 30 minutes. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 16 (volume average particle diameter; Mv ⁇ 122.9 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Example 17 Preparation of Pigment Dispersion 17 2.5 parts of ⁇ -type crystal form azo pigment (1) -12 synthesized in Synthesis Example 1-12, 0.5 part of sodium oleate, 5 parts of glycerin, water 42 The parts were mixed and dispersed at 300 rpm for 2 hours using a planetary ball mill together with 100 parts of zirconia beads having a diameter of 0.1 mm. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 17 (volume average particle diameter; Mv ⁇ 64.0 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).
- Mv ⁇ 64.0 nm measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.
- Comparative Example 1 Preparation of Comparative Pigment Dispersion 1 In place of the ⁇ -type crystal form azo pigment composition (1) -1 used in Example 1, C.I. I. A yellow comparative pigment dispersion 1 was obtained in the same manner as in Example 1 except that CI Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) was used.
- Comparative Example 2 Preparation of Comparative Pigment Dispersion 2 In place of ⁇ -type crystal form azo pigment composition (1) -1 used in Example 1, C.I. I. A yellow comparative pigment dispersion 2 was obtained in the same manner as in Example 1 except that CI Pigment Yellow 155 (INKJET YELLOW 4G VP2532 manufactured by Clariant) was used.
- Comparative Example 3 Preparation of Comparative Dispersion 3 Example 1 except that the ⁇ -type crystal form azo pigment (1) -1 used in Example 1 was replaced by the following compound (DYE-1). Dispersion was attempted in the same manner as in Example 1, but it was dissolved and could not be dispersed.
- ⁇ the case where coarse particles of 200 nm or more were hardly confirmed was marked with ⁇ , and the case where the dispersion could not be dispersed due to dissolution in an aqueous solvent or gelation of the dispersion was marked with x.
- ⁇ is defined as Pigment Dispersion 3, Pigment Dispersion 13, Pigment Dispersion 16, Comparative Pigment Dispersion 1, Comparative Pigment Dispersion 2, and Comparative Dye Dispersion 3. evaluated. The results are shown in Table 3.
- Example 3 ⁇ Evaluation of coloring power>
- the image density of the obtained coating was measured using a reflection densitometer (X-Rite 938 manufactured by X-Rite), and “Color Density (OD: Optical Density)” was evaluated according to the following criteria. A case where the OD was 1.4 or more was evaluated as “ ⁇ ”, a case where the OD was 1.2 or more and less than 1.4 was evaluated as “ ⁇ ”, and a case where it was less than 1.2 was evaluated as “X”. The results are shown in Table 3.
- an azo pigment that is excellent in color characteristics such as coloring power, is stable in pigment particle diameter over time, and is excellent in pigment dispersion stability and ink liquid stability.
- a pigment dispersion having excellent color characteristics, dispersion stability and ink liquid stability can be obtained.
- the pigment dispersion can be used, for example, in printing inks such as inkjet, color toners for electrophotography, displays such as LCDs and PDPs, color filters used in image sensors such as CCDs, paints, and colored plastics. it can.
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Abstract
Description
また、顔料を使用するにあたっては、他にも、所望の透明性を発現させるために必要な粒子径及び粒子形を有すること、使用される環境条件下における堅牢性、例えば耐光性、耐熱性、オゾンなどの酸化性ガスに対する耐性、その他有機溶剤や亜硫酸ガスなどへの耐薬品堅牢性が良好であること、使用される媒体中において微小粒子まで分散し、かつ、その分散状態が安定であること、等の性質も必要となる。
有機顔料には、例えばアゾ顔料のように、合成時に適切な反応条件を選択することにより、微細で整粒された粒子を得ることができるものもあり、銅フタロシアニングリーン顔料のように、合成時に生成する極めて微細で凝集した粒子を、後工程で粒子成長、整粒させることにより顔料化するもの、銅フタロシアニンブルー顔料のように、合成時に生成する粗大で不揃いな粒子を後工程で微細化し、整粒させることにより顔料化を行うものもある。例えば、ジケトピロロピロール顔料は、一般的には、琥珀酸ジエステルと芳香族ニトリルとを有機溶媒中で反応させて合成される(例えば、特許文献1参照)。そして、粗製ジケトピロロピロール顔料は、水又は有機溶剤中で熱処理し、次に湿式摩砕のごとき粉末化を行うことにより、使用に適する形態にされる(例えば、特許文献2参照)。C.I.ピグメントレッド254には、α型とβ型の結晶形態が知られている(例えば、特許文献3参照)。また、アゾ顔料であるC.I.ピグメントイエロー181は、数種の結晶形態が知られている(例えば、特許文献4参照)。
本発明の態様において、本発明は、色再現性、分散性及び顔料分散物安定性が極めて良好であり、優れた色相及び着色力を有するアゾ顔料を提供することを目的とするものである。
好ましくは透過型顕微鏡で観察した際の長軸方向の長さが0.01μm~10μmであるアゾ顔料を提供することを目的とするものである。
更に本発明は、該アゾ顔料を含有する着色組成物を提供することを目的とするものである。
そして本発明は、特定の構造異性及び結晶多型に制御しながら再現性よく高効率に製造することのできるアゾ顔料の製造方法を提供することを目的とするものである。
更に、該アゾ顔料の分散物を含む着色組成物を提供することを目的とするものである。
更に、特定の構造異性及び結晶多型に制御しながら再現性よく高効率にアゾ顔料を製造することのできるアゾ顔料の製造方法を見出し、本発明を完成するに至った。
〔1〕
CuKα特性X線回折におけるブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的X線回折ピークを有する下記式(1)で表されるアゾ顔料、又はその互変異性体。
下記式(2)で表されるヘテロ環アミンから誘導したジアゾニウム塩と、下記式(3)で表される化合物とをアゾカップリング反応させる工程を含むことを特徴とする、下記式(1)で表されるアゾ顔料又はその互変異性体の製造方法。
更に後処理を行う工程を含むことを特徴とする〔2〕に記載の製造方法。
〔4〕
上記〔2〕に記載の製造方法で得たアゾ顔料を単離することなく、引き続き後処理を行う工程を含むことを特徴とする〔2〕に記載の製造方法。
〔5〕
〔2〕、〔3〕又は〔4〕に記載の製造方法で製造されたことを特徴とする〔1〕に記載のアゾ顔料。
〔6〕
〔1〕又は〔5〕に記載のアゾ顔料を含有することを特徴とする顔料分散物。
〔7〕
顔料分散物中の顔料粒子の体積平均粒子径が0.01μm~0.15μmであることを特徴とする〔6〕に記載の顔料分散物。
〔8〕
〔1〕若しくは〔5〕に記載のアゾ顔料又は〔6〕若しくは〔7〕に記載の顔料分散物を含有することを特徴とする着色組成物。
本発明のアゾ顔料、又はその互変異性体は、それらの水和物、あるいは溶媒和物、あるいは塩であっても良い。
7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを有する結晶形態は、更に、7.2°、13.4°、15.0°、19.8°、及び25.9°に顕著なX線回折線を有するX線回折パターンを示す結晶形態がより好ましい。その中でも、7.2°、8.2°、10.0°、13.4°、15.0°、19.8°、及び25.9°に顕著なX線回折線を有するX線回折パターンを示す結晶形態が最も好ましい。
本発明の製造方法は下記式(2)で表されるヘテロ環アミンから誘導したジアゾニウム塩と、下記式(3)で表される化合物とをアゾカップリング反応させる工程を含む。
カップリング反応する工程は、酸性反応媒質中~塩基性反応媒質中で実施することができるが、本発明のアゾ顔料は酸性~中性反応媒質中で実施することが好ましく、特に酸性反応媒質中で実施することがジアゾニウム塩の分解を抑制し効率良くアゾ顔料に誘導することができる。
本発明は上記製造方法で製造されたα型結晶形態アゾ顔料にも関する。
本発明の製造方法においては、後処理を行う工程を含むことが好ましい。本発明において後処理工程とは、溶媒加熱処理による顔料粒子制御を指す。この後処理により、結晶形態、粒子の大きさや形等を整えることができる。
また、本発明の製造方法においては、得られたアゾ顔料を単離することなく、引き続き後処理を行う工程を含むことが好ましい。本発明の製造方法は高収率でかつ高品質なアゾ顔料が得られるため、引き続き後処理に供することができ工程数を削減することができる。
溶媒加熱処理の温度は所望する顔料の一次粒子径の大きさによって異なるが、40~150℃が好ましく、60~100℃が更に好ましい。また、処理時間は、30分~24時間が好ましい。
本発明の顔料分散物は、本発明のアゾ顔料を少なくとも1種を含むことを特徴とする。これにより、色彩的特性、耐久性及び分散安定性に優れた顔料分散物とすることができる。
顔料分散物中の顔料粒子の体積平均粒子径が0.01μm以上である場合には、分散物の経時安定性が増し、凝集し難く好ましい。また、粒子の体積平均粒子径が0.15μm以下である場合には、光学濃度が高くなり印画物の濃度が濃くなり、赤や緑などの混色部の色再現性が向上し、透明性が高くなり、インクジェット等で印画する際に、ノズルの目詰まりが起こりにくくなるため好ましい。
本発明の着色組成物は、少なくとも一種の本発明のアゾ顔料を含有する着色組成物を意味する。本発明の着色組成物は、媒体を含有させることができるが、媒体として溶媒を用いた場合は特にインクジェット記録用インクとして好適である。本発明の着色組成物は、媒体として、親油性媒体や水性媒体を用いて、それらの中に、本発明のアゾ顔料を分散させることによって作製することができる。好ましくは、水性媒体を用いる場合である。本発明の着色組成物には、媒体を除いたインク用組成物も含まれる。本発明の着色組成物は、必要に応じてその他の添加剤を、本発明の効果を害しない範囲内において含有しうる。その他の添加剤としては、例えば、乾燥防止剤(湿潤剤)、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤、pH調整剤、表面張力調整剤、消泡剤、粘度調整剤、分散剤、分散安定剤、防錆剤、キレート剤等の公知の添加剤(特開2003-306623号公報に記載)が挙げられる。これらの各種添加剤は、水溶性インクの場合にはインク液に直接添加する。油溶性インクの場合には、アゾ顔料分散物の調製後分散物に添加するのが一般的であるが、調製時に油相又は水相に添加してもよい。
次に、インクについて説明する。
本発明においてインクは、上記で説明した顔料分散物を用いることができる。好ましくは、水溶性溶媒、水等を混合して調製される。ただし、特に問題がない場合は、前記本発明の顔料分散物をそのまま用いてもよい。
また、本発明の顔料を含有する着色組成物はインクジェット記録用インクとして好ましく用いることができる。
次に、インクジェット記録用インクについて説明する。
インクジェット記録方法は、インクジェット記録用インクを用い、記録信号に応じて記録ヘッドから記録媒体表面にインクを吐出して、記録媒体表面に画像を形成する方法である。
また、インクジェット記録装置は、インクジェット記録用インクを用い、インク(必要により処理液)を記録媒体表面に吐出する記録ヘッドを備え、記録媒体表面に前記インクを記録ヘッドから吐出することにより、画像を形成する装置である。なお、インクジェット記録装置は、記録ヘッドに、インクを供給することができ、かつ、インクジェット記録装置本体に対して脱着可能なインクジェット記録用インクタンク(以下、「インクタンク」と称す場合がある)を備えていてもよい。この場合、このインクジェット記録用インクタンクには、インクが収納される。
また、インクジェット記録用インクタンクは、記録ヘッドを備えたインクジェット記録装置に対して脱着可能であり、インクジェット記録装置に装着した状態で、記録ヘッドにインクを供給できる構成を有するものであれば、従来公知のインクタンクが利用できる。
カラートナー100質量部中のアゾ顔料の含有量は特に制限がないが、0.1質量部以上含有するのが好ましく、1~20質量部がより好ましく、2~10質量部含有するのが最も好ましい。アゾ顔料を導入するカラートナー用バインダー樹脂としては一般に使用される全てのバインダーが使用出来る。例えば、スチレン系樹脂・アクリル系樹脂・スチレン/アクリル系樹脂・ポリエステル樹脂等が挙げられる。
トナーに対して流動性向上、帯電制御等を目的として無機微粉末、有機微粒子を外部添加しても良い。表面をアルキル基含有のカップリング剤等で処理したシリカ微粒子、チタニア微粒子が好ましく用いられる。なお、これらは数平均一次粒子径が10~500nmのものが好ましく、更にはトナー中に0.1~20質量%添加するのが好ましい。
感熱記録材料は、支持体上に本発明のアゾ顔料をバインダーとともに塗設したインクシート、及び画像記録信号に従ってサーマルヘッドから加えられた熱エネルギーに対応して移行してきた顔料を固定する受像シートから構成される。インクシートは、本発明のアゾ顔料をバインダーと共に溶媒中に微粒子状に分散させることによってインク液を調製し、該インクを支持体上に塗布して適宜に乾燥することにより形成することができる。支持体上のインクの塗布量は特に制限するものではないが、好ましくは30~1000mg/m2である。好ましいバインダー樹脂、インク溶媒、支持体、更には受像シートについては、特開平7-137466号に記載されたものを好ましく用いることができる。
カラーフィルターの形成方法としては、初めにフォトレジストによりパターンを形成し、次いで染色する方法、或いは特開平4-163552号、特開平4-128703号、特開平4-175753号公報で開示されているように色素を添加したフォトレジストによりパターンを形成する方法がある。本発明の色素をカラーフィルターに導入する場合に用いられる方法としては、これらのいずれの方法を用いても良いが、好ましい方法としては、特開平4-175753号や特開平6-35182号に記載されたところの、熱硬化性樹脂、キノンジアジド化合物、架橋剤、色素及び溶剤を含有してなるポジ型レジスト組成物、並びに、それを基体上に塗布後、マスクを通して露光し、該露光部を現像してポジ型レジストパターンを形成させ、上記ポジ型レジストパターンを全面露光し、次いで露光後のポジ型レジストパターンを硬化させることからなるカラーフィルターの形成方法を挙げる事ができる。又、常法に従いブラックマトリックスを形成させ、RGB原色系あるいはY、M、C補色系カラーフィルターを得ることができる。カラーフィルターの場合も本発明のアゾ顔料の使用量の制限はないが0.1~50質量%が好ましい。
X線管球:Cu
管電圧:55KV
管電流:280mA
スキャン方法:2θ/θスキャン
スキャン速度:6deg./min
サンプリング間隔:0.100deg.
スタート角度(2θ):5deg.
ストップ角度(2θ):55deg.
ダイバージェンススリット:2deg.
スキャッタリングスリット:2deg.
レシービングスリット:0.6mm
縦型ゴニオメータ使用
α型結晶形態アゾ顔料(1)-1~(1)-12の合成スキームを下記に示す。
シアノ酢酸メチル29.7g(0.3モル)にオルトギ酸トリメチル42.4g(0.4モル)、無水酢酸20.4g(0.2モル)、p-トルエンスルホン酸0.5gを加えて110℃(外温)に加熱し、反応系から生じる低沸点成分を留去しながら20時間攪拌した。この反応液を減圧濃縮した後、シリカゲルカラム精製を行い前記中間体(a)を14.1g(黄色粉末、収率30%)で得た。得られた中間体(a)のNMR測定結果は以下の通りである。
1H-NMR(300MHz、CDCl3)7.96(s,1H),4.15(s,3H),3.81(s,3H)
メチルヒドラジン7.4mL(141ミリモル)にイソプロパノール150mLを加えて15℃(内温)に冷却し、この混合液に中間体(a)7.0g(49.6ミリモル)を徐々に添加した後、50℃に加熱して1時間40分攪拌した。この反応液を減圧濃縮した後、シリカゲルカラム精製を行い前記中間体(b)を10.5g(白色粉末、収率50%)で得た。得られた中間体(b)のNMR測定結果は以下の通りである。
1H-NMR(300MHz、CDCl3)7.60(s,1H),4.95(brs,2H),3.80(s,3H),3.60(s,3H)
メタノール1.1Lに水136mLを加えて、炭酸水素ナトリウム182g(2.17モル)を添加し、室温にて攪拌した。同温度にて塩化シアヌル200g(1.08モル)を分割添加した。添加終了後、内温を30℃まで昇温した。同温度にて30分間攪拌した後、水500mLを加え、析出した固体を濾別し、水500mL、メタノール300mLでかけ洗い後、乾燥を行い、前記中間体(c)を168g(白色粉末、収率86.2%)で得た。得られた中間体(c)のNMR測定結果は以下の通りである。
1H-NMR(300MHz、CDCl3)4.14(s,3H)
ヒドラジン1水和物363mL(7.46モル)に水673mLを加えて10℃(内温)に冷却し、この混合液に中間体(c)168g(934ミリモル)を徐々に添加(内温20℃以下)した後、氷浴をはずし、室温まで昇温し、同温度にて30分攪拌した。反応液から析出した結晶をろ取、水700mL、アセトニトリル1Lでかけ洗い後、乾燥を行い前記中間体(d)の疎精製物(白色粉末)を得た。
中間体(d)の疎精製物に、エチレングリコール480mLを加えて室温で攪拌した。この懸濁液にピバロイルアセトニトリル257g(2.06モル)を加え、内温が50℃になるまで加熱した。同温度にて12M塩酸水をpH3になるように滴下した後、内温が80℃になるまで加熱して3時間攪拌した。反応終了後、氷冷し内温が8℃になるまで冷却し、析出した結晶をろ取、水でかけ洗い後、シリカゲルカラム精製を行い、前記中間体(e)を105g(白色粉末、2工程収率29.2%)で得た。得られた中間体(e)のNMR測定結果は以下の通りである。
1H-NMR(300MHz、d-DMSO)7.00(s,4H),5.35(s,2H),4.05(s,3H),5.35(s,2H),1.22(s,18H)
酢酸20.5mLを氷冷し、内温10℃にした。内温15℃以下になるようにニトロシル硫酸16.8gを添加し、続いて内温15℃以下になるように中間体(b)9.5gを分割添加した。内温15℃にて15分間攪拌した後、15分かけて内温25℃に昇温した。同温度にて90分間攪拌した後、同温度にて尿素0.4gを分割添加し、同温度にて15分間攪拌し、ジアゾニウム塩溶液を得た。
別に、中間体(e)11.6gをメタノール405mLに室温にて完溶させ、氷冷して内温を-3℃に冷却した。同温にて、上述のジアゾニウム塩溶液を内温が3℃以下になるように分割添加し、添加終了後2時間攪拌し、アゾ化合物反応液を得た。別に水810mLを用意し、アゾ化合物反応液を添加した。室温にて30分間攪拌し、析出した結晶を濾別し、メタノール150mLでかけ洗いし、更に水100mLでかけ洗いした。得られた結晶を乾燥せずに水750mLに懸濁させ、8規定の水酸化カリウム水溶液を添加して、pHを5.7にした。室温にて20分間攪拌した後、得られた結晶を濾別し、水で十分にかけ洗いしたのち、メタノール80mLでかけ洗いして、粗顔料(1-1)を得た。得られた粗顔料(1-1)を室温にて、12時間乾燥させ、粗顔料(1-2)を得た。
得られた粗顔料(1-2)を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約40~500nmであった。
粗顔料(1-2)のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図1に示す。
得られたα型結晶形態アゾ顔料(1)-1を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約40~180nmであった。
α型結晶形態顔料(1)-1のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図2に示す。
合成例1-1で得た粗顔料(1-2)10gを2-プロパノール50mL、水50mLの混合溶媒に懸濁させた後、内温78°にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-2を9.5g(収率95.0%)得た。
得られたα型結晶形態アゾ顔料(1)-2を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約40~160nmであった。
α型結晶形態顔料(1)-3のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図3に示す。
合成例1-1で得た粗顔料(1-2)10gを2-メチル-1-プロパノール200mLに懸濁させた後、内温80℃にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-3を9.3g(収率93.0%)得た。
得られたα型結晶形態アゾ顔料(1)-3を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約30~140nmであった。
α型結晶形態顔料(1)-3のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図4に示す。
合成例1-1で得た粗顔料(1-2)10gを2-メチル-1-プロパノール50mL、水50mLに懸濁させた後、内温80℃にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-4を9.3g(収率93.0%)得た。
得られたα型結晶形態アゾ顔料(1)-4を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約40~120nmであった。
α型結晶形態顔料(1)-4のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図5に示す。
合成例1-1で得た粗顔料(1-2)10gを2-メチル-1-プロパノール25mL、水75mLに懸濁させた後、内温80℃にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-5を9.3g(収率93.0%)得た。
得られたα型結晶形態アゾ顔料(1)-5を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約30~110nmであった。
α型結晶形態顔料(1)-5のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図6に示す。
合成例1-1で得た粗顔料(1-2)10gを水200mLに懸濁させた後、80℃にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-6を9.6g(収率96.0%)得た。
得られたα型結晶形態アゾ顔料(1)-6を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約30~150nmであった。
α型結晶形態顔料(1)-6のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図7に示す。
合成例1-1で得た粗顔料(1-2)10gをアセトン200mLに懸濁させた後、還流下2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-7を8.5g(収率85.0%)得た。
得られたα型結晶形態アゾ顔料(1)-7を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約60~190nmであった。
α型結晶形態顔料(1)-7のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図8に示す。
合成例1-1で得た粗顔料(1-2)10gをアセトン100mL、水100mLの混合溶媒に懸濁させた後、内温60℃にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-8を9.0g(収率90.0%)得た。
得られたα型結晶形態アゾ顔料(1)-8を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約50~160nmであった。
α型結晶形態顔料(1)-8のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図9に示す。
合成例1-1で得た粗顔料(1-2)10gをメタノール100mLに懸濁させた後、還流下2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-9を9.2g(収率92.0%)得た。
得られたα型結晶形態アゾ顔料(1)-9を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約50~140nmであった。
α型結晶形態顔料(1)-9のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図10に示す。
合成例1-1で得た粗顔料(1-2)10gをメタノール100mL、水100mLの混合溶媒に懸濁させた後、内温70℃にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-10を9.4g(収率94.0%)得た。
得られたα型結晶形態アゾ顔料(1)-10を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約40~130nmであった。
α型結晶形態顔料(1)-10のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図11に示す。
43%ニトロシル硫酸43.3gを氷冷し、内温を10℃まで冷却した。内温15℃以下になるように酢酸60mLを添加し、続いて、内温15℃以下になるように中間体(b)25gを分割添加した。内温15℃にて15分間攪拌した後、内温25℃に昇温し、同温度にて90分間攪拌した。その後、同温度にて尿素0.9gを分割添加し、同温度にて15分間攪拌し、ジアゾニウム塩溶液を得た。別に、中間体(e)30.3gをメタノール518mLに室温にて懸濁させ、内温を15℃に冷却した。同温度にて、上述のジアゾニウム塩溶液を内温が30℃以下になるように添加した。添加終了後、2時間攪拌し、アゾ化合物反応液を得た。別に水810mLを用意し、アゾ化合物反応液を添加した。室温にて30分間攪拌した後、8規定の水酸化ナトリウム水溶液を添加して、pHを6.0にした。その後、攪拌を止めて12時間静置し、上澄み液を除去し、除去した量と同量の水を加え、30分間攪拌した。この操作を3回繰り返し行った後、内温80℃に昇温し、同温度にて2時間攪拌した。その後、熱時にて濾過を行い、水1Lでかけ洗いをした後、減圧下室温にて、24時間乾燥させ、α型結晶形態アゾ顔料(1)-11を53.4g(収率97.1%)を得た。
得られたα型結晶形態アゾ顔料(1)-11を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約60~250nmであった。
α型結晶形態アゾ顔料(1)-11のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図12に示す。
合成例1-1で得た粗顔料(1-2)10gをN,N-ジメチルアセトアミド100mL、水100mLの混合溶媒に懸濁させた後、内温80℃にて2時間攪拌した。その後、得られた結晶を熱時にて濾別して室温にて12時間乾燥させ、本発明の結晶形を有する式(1)で表されるα型結晶形態アゾ顔料(1)-12を9.0g(収率90.0%)得た。
得られたα型結晶形態アゾ顔料(1)-12を透過型顕微鏡(日本電子(株)製:JEM-1010電子顕微鏡)で目視にて観察したところ、1次粒子の長軸方向の長さは、約60nm~2μmであった。
α型結晶形態顔料(1)-12のX線回折の測定を上記の条件により行ったところ、ブラッグ角(2θ±0.2°)が7.2°、13.4°、15.0°及び25.9°に特徴的なX線回折ピークを示した。
CuKα特性X線回折図を図13に示す。
合成例1-1で合成したα型結晶形態アゾ顔料(1)-1を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物1(体積平均粒子径;Mv≒90.3nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-6で合成したα型結晶形態アゾ顔料(1)-6を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物2(体積平均粒子径;Mv≒70.1nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-6で合成したα型結晶形態アゾ顔料(1)-6を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、3時間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物3(体積平均粒子径;Mv≒65.2nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-6で合成したα型結晶形態アゾ顔料(1)-6を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、4時間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物4(体積平均粒子径;Mv≒45.9nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-2で合成したα型結晶形態アゾ顔料(1)-2を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物5(体積平均粒子径;Mv≒71.3nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-3で合成したα型結晶形態アゾ顔料(1)-3を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物6(体積平均粒子径;Mv≒75.2m:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-4で合成したα型結晶形態アゾ顔料(1)-4を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物7(体積平均粒子径;Mv≒69.2nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-5で合成したα型結晶形態アゾ顔料(1)-5を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物8(体積平均粒子径;Mv≒62.8nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-7で合成したα型結晶形態アゾ顔料(1)-7を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物9(体積平均粒子径;Mv≒85.4nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-8で合成したα型結晶形態アゾ顔料(1)-8を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物10(体積平均粒子径;Mv≒78.8nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-9で合成したα型結晶形態アゾ顔料(1)-9を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物11(体積平均粒子径;Mv≒70.9nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-10で合成したα型結晶形態アゾ顔料(1)-10を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物12(体積平均粒子径;Mv≒64・7nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-11で合成したα型結晶形態アゾ顔料(1)-11を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物13(体積平均粒子径;Mv≒87.3nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-11で合成したα型結晶形態アゾ顔料(1)-11を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、2時間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物14(体積平均粒子径;Mv≒67.9nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-1で合成した粗顔料(1-2)を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物15(体積平均粒子径;Mv≒79.2nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-12で合成したα型結晶形態アゾ顔料(1)-12を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物16(体積平均粒子径;Mv≒122.9nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
合成例1-12で合成したα型結晶形態アゾ顔料(1)-12を2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、2時間分散を行った。分散終了後、ジルコニアビーズを分離し、黄色の顔料分散物17(体積平均粒子径;Mv≒64.0nm:日機装(株)製Nanotrac150(UPA-EX150)を用いて測定)を得た。
実施例1で用いたα型結晶形態アゾ顔料組成物(1)-1に替えてC.I.ピグメント・イエロー74(チバスペシャリティ社製Iralite YELLOW GO)を用いた以外は実施例1と同様にして黄色の比較顔料分散物1を得た。
実施例1で用いたα型結晶形態アゾ顔料組成物(1)-1に替えてC.I.ピグメント・イエロー155(クラリアント社製INKJET YELLOW 4G VP2532)を用いた以外は実施例1と同様にして黄色の比較顔料分散物2を得た。
実施例1で用いたα型結晶形態アゾ顔料(1)-1に替えて下記で表される化合物(DYE-1)を用いた以外は実施例1と同様に分散を試みたが、溶解してしまい、分散できなかった。
顔料2.5部、オレイン酸ナトリウム0.5部、グリセリン5部、水42部を混合し、直径0.1mmのジルコニアビーズ100部とともに遊星型ボールミルを用いて毎分300回転、1時間30分間分散を行った結果、200nm以上の粗大粒子がほとんど確認されないものを◎、水系溶剤に溶解した、又は分散物がゲル化した等により分散できなかったものを×とした。更に、1時間30分間分散を行った際には200nm以上の粗大粒子が確認されたが、4時間分散を行った際には200nm以上の粗大粒子がほとんど確認されないものを○、2時間分散を行っても200nm以上の粗大粒子が確認されるものを△として顔料分散物3、顔料分散物13、顔料分散物16、比較顔料分散物1、比較顔料分散物2、及び比較染料分散物3を評価した。結果を表3に示す。
上記実施例3、実施例13、実施例16、比較例1、2及び比較例3で得られた顔料分散物を室温にて3週間静置した。その結果、沈殿物が確認されるものを×、沈殿物が確認されなかったものを○とした。結果を表3に示す。
上記実施例3、実施例13、実施例16、比較例1、2及び比較例3で得られた顔料分散物をNo.3のバーコーターを用いてエプソン社製フォトマット紙に塗布した。得られた塗布物の画像濃度を反射濃度計(X-Rite社製X-Rite938)を用いて測定し、「着色力(OD:Optical Density)」を以下の基準で評価した。ODが1.4以上の場合を○、1.2以上で1.4未満の場合を△、1.2未満の場合を×とした。結果を表3に示す。
色相については、上記で得られた塗布物の色度を目視にて赤味が少なく鮮やかさが大きいものを○、どちらか一方が当てはまらないものを×(不良)として評価を行った。結果を表3に示す。
色相評価に用いた画像濃度1.0の塗布物を作成し、フェードメーターを用いてキセノン光(99000lux;TACフィルター存在下)を28日間照射し、キセノン照射前後の画像濃度を反射濃度計を用いて測定し、色素残存率[(照射後濃度/照射前濃度)×100%]が80%以上の場合を○、60%以上80%未満の場合を△、60%未満の場合を×として、顔料分散物3、顔料分散物13、顔料分散物16、比較顔料分散物1、比較顔料分散物2及び比較顔料分散物3を評価した。結果を表3に示す。
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
本出願は、2008年12月9日出願の日本特許出願(特願2008-313753)、2009年12月7日出願の日本特許出願(特願2009-278056)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (8)
- 更に後処理を行う工程を含むことを特徴とする請求項2に記載の製造方法。
- 上記請求項2に記載の製造方法で得たアゾ顔料を単離することなく、引き続き後処理を行う工程を含むことを特徴とする請求項2に記載の製造方法。
- 請求項2、3又は4に記載の製造方法で製造されたことを特徴とする請求項1に記載のアゾ顔料。
- 請求項1又は5に記載のアゾ顔料を含有することを特徴とする顔料分散物。
- 顔料分散物中の顔料粒子の体積平均粒子径が0.01μm~0.15μmであることを特徴とする請求項6に記載の顔料分散物。
- 請求項1若しくは5に記載のアゾ顔料又は請求項6若しくは7に記載の顔料分散物を含有することを特徴とする着色組成物。
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EP2230278A2 (en) * | 2009-03-11 | 2010-09-22 | FUJIFILM Corporation | Color composition for color filter, method for preparing it, and color filter |
CN103354828A (zh) * | 2011-02-04 | 2013-10-16 | 富士胶片株式会社 | 水系颜料分散物及其制造方法以及喷墨记录用墨水 |
EP2671926A4 (en) * | 2011-02-04 | 2015-07-22 | Fujifilm Corp | AQUEOUS PIGMENT DISPERSION AND MANUFACTURING METHOD AND INK FOR INKJET PRINTING |
CN103717680A (zh) * | 2011-07-29 | 2014-04-09 | 富士胶片株式会社 | 包括偶氮颜料、着色组合物、喷墨记录油墨的分散体和制备分散体的方法 |
US20140141249A1 (en) * | 2011-07-29 | 2014-05-22 | Fujifilm Corporation | Dispersion including azo pigment, coloring composition, inkjet recording ink and method for preparing dispersion |
US20140141250A1 (en) * | 2011-07-29 | 2014-05-22 | Fujifilm Corporation | Azo pigment, method for preparing azo pigment, dispersion including azo pigment, coloring composition, and inkjet recording ink |
EP2738223A1 (en) * | 2011-07-29 | 2014-06-04 | Fujifilm Corporation | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and inkjet recording ink |
EP2738223A4 (en) * | 2011-07-29 | 2015-01-21 | Fujifilm Corp | AZO PIGMENT, PROCESS FOR PRODUCING AZO PIGMENT, DISPERSION CONTAINING AZO PIGMENT, DYEING COMPOSITION AND INK FOR INKJET PRINTING |
US9359502B2 (en) * | 2011-07-29 | 2016-06-07 | Fujifilm Corporation | Dispersion including azo pigment, coloring composition, inkjet recording ink and method for preparing dispersion |
US9359503B2 (en) | 2011-07-29 | 2016-06-07 | Fujifilm Corporation | Azo pigment, method for preparing azo pigment, dispersion including azo pigment, coloring composition, and inkjet recording ink |
Also Published As
Publication number | Publication date |
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KR20110100270A (ko) | 2011-09-09 |
TW201033294A (en) | 2010-09-16 |
CN102307948B (zh) | 2013-07-24 |
US20110245475A1 (en) | 2011-10-06 |
JP5481177B2 (ja) | 2014-04-23 |
CN102307948A (zh) | 2012-01-04 |
EP2368943A1 (en) | 2011-09-28 |
CA2746036C (en) | 2016-05-17 |
AU2009325547B2 (en) | 2014-07-24 |
JP2010159405A (ja) | 2010-07-22 |
CA2746036A1 (en) | 2010-06-17 |
AU2009325547A1 (en) | 2011-07-07 |
TWI458782B (zh) | 2014-11-01 |
EP2368943B1 (en) | 2016-05-25 |
US8236065B2 (en) | 2012-08-07 |
EP2368943A4 (en) | 2014-01-01 |
KR101670772B1 (ko) | 2016-10-31 |
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