WO2014077291A1 - 着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物 - Google Patents
着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物 Download PDFInfo
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- WO2014077291A1 WO2014077291A1 PCT/JP2013/080720 JP2013080720W WO2014077291A1 WO 2014077291 A1 WO2014077291 A1 WO 2014077291A1 JP 2013080720 W JP2013080720 W JP 2013080720W WO 2014077291 A1 WO2014077291 A1 WO 2014077291A1
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Classifications
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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
- 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
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0678—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having-COOH or -SO3H radicals or derivatives thereof directly linked to the skeleton
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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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/073—Preparation from isoindolenines, e.g. pyrrolenines
-
- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/20—Obtaining compounds having sulfur atoms directly bound to the phthalocyanine skeleton
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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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures of phthalocyanines
Definitions
- the present invention provides a coloring composition that is excellent in ozone resistance, has a suppressed bronze gloss, and can obtain a neutral gray or black hue when a composite gray or black is prepared together with other yellow and magenta.
- the present invention relates to an inkjet recording ink, an inkjet recording method, an inkjet printer cartridge, and an inkjet recorded matter.
- 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 in an imaging device such as a CCD in a photographing apparatus and in an LCD or PDP in a display.
- the ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
- Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals.
- ink for ink jet recording water-based ink, oil-based ink, or solid (melting type) ink is used.
- the solvent has good solubility or dispersibility, high-density recording is possible, hue is good, light, heat, in the environment Fast against active gases (NOx, ozone and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image-receiving materials, and low bleeding. It is required that the ink has excellent storability, has no toxicity, has high purity, and can be obtained at low cost.
- Patent Document 1 describes the use of a phosphonate additive as a compound that can prevent the occurrence of kogation against the heat of a recording liquid such as ink for inkjet recording.
- Cyan dye skeletons used in ink jet recording inks include phthalocyanine, anthraquinone, and triphenylmethane, which use phthalocyanine compounds with excellent hue and light fastness. In particular, since it does not have sufficient fastness to ozone and ink stability cannot be satisfied, improvement is desired.
- Phthalocyanine dyes represented by Direct Blue 87 or Direct Blue 199 which are currently widely used, and also described in the above publications, etc., are characterized by their excellent light resistance compared to magenta and yellow, but are soluble in dyes. In many cases, for example, a dissolution failure occurs at the time of manufacturing, resulting in a manufacturing trouble, or an insoluble material precipitates during product storage or use. In particular, the above-described ink jet recording has problems such as clogging of the print head and ejection failure due to poor ink storage stability such as precipitation of dye, leading to significant deterioration of the printed image.
- Patent Document 2 a phthalocyanine dye having a specific sulfonyl group or sulfinyl group has been described in Patent Document 2 as a phthalocyanine dye having both hue, light and ozone fastness, and an azaphthalocyanine dye having a sulfo group and a substituted sulfamoyl group has been patented. It is described in Document 3.
- the substitution position of the substituent is a ⁇ -position substitution type (the following general formula (the following general formula (1)) rather than the ⁇ , ⁇ -position mixed type (one having no regularity in the substitution position of the substitution group).
- R 1 to R 16 are in the 1st to 16th positions, respectively, they are specified as the 2nd and / or 3rd position, 6th and / or 7th position, 10th and / or 11th position, 14th and / or 15th position
- R 1 to R 16 are in the 1st to 16th positions, respectively, they are specified as the 2nd and / or 3rd position, 6th and / or 7th position, 10th and / or 11th position, 14th and / or 15th position
- a sulfonyl group or a sulfinyl group are excellent in hue, light and ozone fastness.
- the present invention has been made in view of such circumstances.
- the composite gray or black is produced together with other yellow and magenta, the neutral gray or black has excellent ozone resistance and the bronze gloss is suppressed. It is an object of the present invention to provide a coloring composition, an ink for ink jet recording, an ink jet recording method, an ink jet printer cartridge, and an ink jet recorded product capable of obtaining the hue of the above.
- the inventors of the present invention have a weak association property, a first dye having excellent print density, a second dye property having a strong association property and excellent fastness, a strong association property, excellent fastness, and a second dye property. It has been found that a coloring composition containing a third dye having a lower saturation than that of the coloring material can solve the above-mentioned problems. Generally, cyan dyes with high saturation are advantageous from the viewpoint of color reproducibility, but on the other hand, when printing composite blacks made with yellow, magenta and cyan colorants, the hue point is high. Is disadvantageous.
- the present invention by combining the first and second dyes having high saturation and the third dye having low saturation, while ensuring a color reproduction range having no practical problem, other yellow and Even when a composite black is produced together with magenta, a neutral gray or black image can be obtained, and the conflicting effects can be achieved.
- the effects obtained by using the first to third dyes could not be predicted from the respective single spectral spectra, and the mechanism of action is unknown, but the effects of the first and second dyes and the first dye are the same. It is considered that some interaction and synergistic effect are working by using together with the dye of No. 3.
- the object of the present invention has been achieved by the following method.
- the phthalocyanine dye represented by the following general formula (1) the phthalocyanine dye represented by the following general formula (2), the azaphthalocyanine dye represented by the following general formula (12), and the following general formula (22) And a phthalocyanine dye, and at least one dye selected from Direct Blue 199.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryl
- Z 1 , Z 2 , Z 3 and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
- M 1 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group
- Z 5 , Z 6 , Z 7 and Z 8 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z 5 , Z 6 , Z 7 , and Z 8 has an ionic hydrophilic group as a substituent.
- M 2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- Each P independently represents a nitrogen atom or CH, and at least one P represents a nitrogen atom. However, in each of the four rings containing P, P representing a nitrogen atom is 2 or less.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- R 24 represents a substituted or unsubstituted hydrocarbon group.
- R 23 and R 24 may be bonded together with a nitrogen atom to form a substituted or unsubstituted heterocycle.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- R 17 and R 18 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted.
- An aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 17 , R 18 , and A are connected to each other to form a ring;
- Y and Z each independently represent a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, or a substituted group.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 in the phthalocyanine dye represented by the general formula (1) are hydrogen atoms.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 in the phthalocyanine dye represented by the general formula (2) are hydrogen atoms [1] or The coloring composition as described in [2].
- Z 1 , Z 2 , Z 3 and Z 4 in the phthalocyanine dye represented by the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group.
- Z 5 , Z 6 , Z 7 and Z 8 in the phthalocyanine dye represented by the general formula (2) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group.
- the colored composition according to any one of [1] to [4], wherein the colored composition represents a substituted heterocyclic group.
- Z 5 , Z 6 , Z 7 , and Z 8 represent a substituted alkyl group, and at least one of the substituents of the alkyl group is a —SO 2 NHR group (provided that R Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group), [1] to [5].
- the coloring composition according to item. In general formula (13-1) and general formula (13-2), Each P independently represents a nitrogen atom or CH, and at least one P represents a nitrogen atom.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
- R 24 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- R 23 represents a hydrogen atom
- R 24 is substituted with a substituent represented by the following general formula (T1).
- T1 The colored composition according to any one of [1] to [13], which is a substituted alkyl group.
- L represents a single bond or a substituted or unsubstituted alkylene group.
- X represents independently a substituent selected from —OR 25 , —SR 25 , and —NR 25 R 26 , and R 25 and R 26 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted group Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and at least one of R 25 and R 26 has an ionic hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- L represents a single bond or a substituted or unsubstituted alkylene group.
- R 29 , R 210 , and R 211 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and is ionic It has at least one hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- each of R 27 and R 28 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 27 , R 28 , and A are linked to each other; To form a ring.
- R 29 , R 210 , and R 211 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group.
- m and n are 1 to 3, and the sum of m and n is 2 to 4.
- [19] [17] An ink cartridge filled with the ink for ink jet recording described in [17]. [20] [17] An ink jet recorded matter in which a colored image is formed on a recording material using the ink for ink jet recording described in [17].
- the ozone resistance is excellent, the bronze gloss is suppressed, and when a composite gray or black is prepared together with other yellow and magenta, a neutral gray or black hue can be obtained.
- Compositions, inkjet recording inks, inkjet recording methods, inkjet printer cartridges, and inkjet recordings are provided.
- Halogen atom for example, chlorine atom, bromine atom
- Specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl
- aryl group for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl
- heteroatom for example, phenyl
- the coloring composition of the present invention includes a phthalocyanine dye represented by the following general formula (1), a phthalocyanine dye represented by the following general formula (2), an azaphthalocyanine dye represented by the following general formula (12), A phthalocyanine dye represented by the following general formula (22), and at least one dye selected from Direct Blue 199.
- the coloring composition comprises a phthalocyanine dye represented by the general formula (1), a phthalocyanine dye represented by the general formula (2), and an azaphthalocyanine dye represented by the general formula (12) as a third dye.
- some interaction works, ozone resistance is improved, and bronze gloss is suppressed.
- a composite gray or black is produced together with other yellow and magenta, it is considered that there is an effect that a neutral gray or black hue can be obtained.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryl
- Z 1 , Z 2 , Z 3 and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
- M 1 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an alkenyl.
- Examples of the halogen atom represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 include a fluorine atom, a chlorine atom and a bromine atom.
- the alkyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkyl group having a substituent and an unsubstituted alkyl group.
- an alkyl group having 1 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group.
- alkyl group examples include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.
- the cycloalkyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
- the cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.
- the alkenyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkenyl group having a substituent and an unsubstituted alkenyl group.
- an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Examples of the alkenyl group include a vinyl group and an allyl group.
- the aralkyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aralkyl group having a substituent and an unsubstituted aralkyl group.
- an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- the aralkyl group include a benzyl group and a 2-phenethyl group.
- the aryl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryl group having a substituent and an unsubstituted aryl group.
- the aryl group is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed.
- the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group.
- Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.
- the heterocyclic group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group.
- the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
- the substituent include an ionic hydrophilic group.
- Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group and a 2-furyl group.
- the alkylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkylamino group having a substituent and an unsubstituted alkylamino group.
- the alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
- the alkoxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkoxy group having a substituent and an unsubstituted alkoxy group.
- the alkoxy group excluding the substituent is preferably an alkoxy group having 1 to 12 carbon atoms.
- Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.
- the aryloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryloxy group having a substituent and an unsubstituted aryloxy group.
- the aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed.
- the substituent include an alkoxy group and an ionic hydrophilic group.
- Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.
- the amide group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an amide group having a substituent and an unsubstituted amide group.
- the amide group is preferably an amide group having 2 to 12 carbon atoms when a substituent is removed.
- the substituent include an ionic hydrophilic group.
- Examples of the amide group include an acetamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.
- the arylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an arylamino group having a substituent and an unsubstituted arylamino group.
- the arylamino group is preferably an arylamino group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.
- the ureido group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a ureido group having a substituent and an unsubstituted ureido group.
- the ureido group is preferably a ureido group having 1 to 12 carbon atoms when a substituent is removed.
- the substituent include an alkyl group and an aryl group.
- Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.
- the sulfamoylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group.
- a group is included.
- the substituent include an alkyl group.
- Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.
- the alkylthio group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkylthio group having a substituent and an unsubstituted alkylthio group.
- the alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.
- the arylthio group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an arylthio group having a substituent and an unsubstituted arylthio group.
- the arylthio group is preferably an arylthio group having 6 to 12 carbon atoms when a substituent is removed.
- the substituent include an alkyl group and an ionic hydrophilic group.
- Examples of the arylthio group include a phenylthio group and a p-tolylthio group.
- the alkoxycarbonylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. It is.
- the alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.
- the sulfonamide group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group.
- the sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.
- the carbamoyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group.
- the substituent include an alkyl group.
- the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
- the sulfamoyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group.
- the substituent include an alkyl group and an aryl group.
- the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.
- the alkoxycarbonyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group.
- the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
- the heterocyclic oxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. It is.
- the heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered heterocyclic ring.
- the substituent include a hydroxyl group and an ionic hydrophilic group.
- Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.
- the azo group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an azo group having a substituent and an unsubstituted azo group.
- Examples of the azo group include a p-nitrophenylazo group.
- the acyloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an acyloxy group having a substituent and an unsubstituted acyloxy group.
- the acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
- the carbamoyloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group.
- the substituent include an alkyl group.
- the carbamoyloxy group include an N-methylcarbamoyloxy group.
- the silyloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a silyloxy group having a substituent and an unsubstituted silyloxy group.
- the substituent include an alkyl group.
- the silyloxy group include a trimethylsilyloxy group.
- the aryloxycarbonyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. It is.
- the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
- the aryloxycarbonylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino A group is included.
- the aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.
- the imide group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an imide group having a substituent and an unsubstituted imide group.
- Examples of the imide group include an N-phthalimide group and an N-succinimide group.
- the heterocyclic thio group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. It is.
- the heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.
- the phosphoryl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group.
- Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.
- the acyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an acyl group having a substituent and an unsubstituted acyl group.
- the acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.
- the ionic hydrophilic group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like.
- a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido, among others Group, sulfonamido group, carbamoyl group, sulfamoyl group and alkoxycarbonyl group are preferable, hydrogen atom, halogen atom and cyano group are particularly preferable, and hydrogen atom is most preferable.
- Z 1 , Z 2 , Z 3 , and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, It represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
- at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent. Examples of the substituent include the substituents described in the above substituent group A.
- the alkyl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes an alkyl group having a substituent and an unsubstituted alkyl group.
- the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms when a substituent is removed.
- substituent group a hydroxyl group, an alkoxy group, a cyano group, an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), a sulfamoyl group (-SO 2 NHR, -SO 2 NRR ') Sulfonylamino group (—NHSO 2 R), —SONHR group, —SONRR ′ group, halogen atom and ionic hydrophilic group.
- R and R ′ represent an alkyl group and a phenyl group, and these may further have a substituent.
- Examples of the substituent include an alkylamino group, a hydroxyl group, and an ionic hydrophilic group. R and R ′ may form a ring by a chemical bond.
- Examples of the alkyl group include methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trimethyl. Included are fluoromethyl, 3-sulfopropyl and 4-sulfobutyl.
- the cycloalkyl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
- the cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.
- the alkenyl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes an alkenyl group having a substituent and an unsubstituted alkenyl group.
- an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Examples of the alkenyl group include a vinyl group and an allyl group.
- the aralkyl group represented by Z 1 , Z 2 , Z 3 and Z 4 includes an aralkyl group having a substituent and an unsubstituted aralkyl group.
- an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- the aralkyl group include a benzyl group and a 2-phenethyl group.
- the aryl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes an aryl group having a substituent and an unsubstituted aryl group.
- the aryl group is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl.
- substituents examples include an alkyl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), a sulfamoyl group (—SO 2 NHR), A sulfonylamino group (—NHSO 2 R), a halogen atom, and an ionic hydrophilic group are included (wherein R and R ′ represent an alkyl group and a phenyl group, and these may have an ionic hydrophilic group). Good).
- the heterocyclic group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and may form a condensed ring with another ring.
- the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
- the heterocyclic group may form a condensed ring with another ring. Examples of the heterocyclic group include, but are not limited to, the substitution position of the heterocyclic ring.
- substituents examples include an alkyl group (R—), an aryl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), and a sulfamoyl group.
- R— alkyl group
- R— aryl group
- R— an alkoxy group
- RNH—, RR′N— an alkylamino group
- CONHR —CONHR
- sulfamoyl group —SO 2 NHR
- sulfonylamino group —NHSO 2 R
- sulfonyl group —SO 2 R
- acylamino group —NHCOR
- halogen atom, ionic hydrophilic group are included (note that R, R 'Represents an alkyl group or an aryl group, and these may have an ionic hydrophilic group or a substituent having an ionic hydrophil
- Z 1 , Z 2 , Z 3 and Z 4 are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group.
- a substituted heterocyclic group is more preferred, and a substituted alkyl group is still more preferred.
- At least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
- the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group.
- a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- alkali metal ions eg, sodium ion, potassium ion
- organic cations eg, tetramethylguanidinium ion.
- q 1 , q 2 , q 3 and q 4 each independently represent 1 or 2.
- M 1 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- M 1 is a metal element other than a hydrogen atom, such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru. Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable.
- Preferred examples of the metal oxide include VO and GeO.
- Si (OH) 2 , Cr (OH) 2 , Sn (OH) 2, etc. are mentioned preferably.
- the metal halide AlCl, SiCl 2, VCl, VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently R 2 , R 3 , R 6 , R 7 , R in the general formula (1).
- 10 , R 11 , R 14 and R 15 are synonymous with each other.
- Z 5 , Z 6 , Z 7 , and Z 8 are each independently synonymous with Z 1 , Z 2 , Z 3 , and Z 4 in the general formula (1).
- t, u, v, w, q 5 , q 6 , q 7 and q 8 each independently represent 1 or 2.
- M 2 has the same meaning as M 1 in the general formula (1).
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently R 2 , R 3 , R 6 , R 7 , R in the general formula (1).
- 10 , R 11 , R 14, and R 15 each having the same meaning, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and
- An alkoxycarbonyl group is preferable, a hydrogen atom, a halogen atom, or a cyano group is particularly preferable, and a hydrogen atom is most preferable.
- These groups may further have a substituent. Examples of the substituent include the substituents described in the above substituent group A.
- Z 5 , Z 6 , Z 7 , and Z 8 are each independently synonymous with Z 1 , Z 2 , Z 3 , and Z 4 in the general formula (1).
- Z 5 , Z 6 , Z 7 and Z 8 are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group.
- a substituted heterocyclic group is more preferred, and a substituted alkyl group is still more preferred.
- At least one of the substituents of the substituted alkyl group is a —SO 2 NHR group (where R is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group). Represents a phenyl group).
- the ionic hydrophilic group which at least one of Z 5 , Z 6 , Z 7 and Z 8 has as a substituent is substituted by Z 1 , Z 2 , Z 3 and Z 4 in the general formula (1). It is synonymous with the ionic hydrophilic group which has as a group, and its preferable example is also the same.
- q 5 , q 6 , q 7 and q 8 each independently represent 1 or 2.
- M 2 has the same meaning as M 1 in the general formula (1), and preferred examples thereof are also the same.
- phthalocyanine dyes examples include “Phthalocyanine—Chemistry and Function” (P. 1 to 62) published by K. Shirai and Kobayashi, Inc. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (P. 1 to 54), etc., can be synthesized by combining quoted or similar methods.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are hydrogen, q 5 , q 6 , q 7.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently R 2 , R 3 , R 6 , R 7 , R in the general formula (1).
- 10 , R 11 , R 14 and R 15 are synonymous with each other.
- Z 5 , Z 6 , Z 7 , and Z 8 are each independently synonymous with Z 1 , Z 2 , Z 3 , and Z 4 in the general formula (1).
- t, u, v, w, q 5 , q 6 , q 7 and q 8 each independently represent 1 or 2.
- x is synonymous with t, u, v, and w in general formula (2).
- Z represents a substituent corresponding to Z 5 , Z 6 , Z 7 , and Z 8 .
- Y represents a monovalent or divalent ligand such as a halogen atom, acetate anion, acetylacetonate or oxygen, and d is an integer of 1 to 4.
- Examples of the metal derivative represented by M- (Y) d include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, and Pb. Halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes, and the like. Specific examples include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, acetic acid.
- Examples include zinc, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.
- the amount of the metal derivative and the phthalonitrile compound represented by the general formula (V) is preferably 1: 3 to 1: 6 in terms of molar ratio.
- the amount of the metal derivative and the diiminoisoindoline derivative represented by the general formula (VI) is preferably 1: 3 to 1: 6 in terms of molar ratio.
- the reaction is usually performed in the presence of a solvent.
- a solvent an organic solvent having a boiling point of 80 ° C. or higher, preferably 130 ° C. or higher is used.
- the amount of the solvent used is 1 to 100 times, preferably 5 to 20 times, that of the phthalonitrile compound.
- 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or ammonium molybdate may be added as a catalyst.
- the addition amount is 0.1 to 10 times mol, preferably 0.5 to 2 times mol for 1 mol of the phthalonitrile compound and / or diiminoisoindoline derivative.
- the reaction temperature is preferably 80 to 300 ° C., preferably 100 to 250 ° C., and particularly preferably 130 to 230 ° C. Below 80 ° C, the reaction rate is extremely slow. If it exceeds 300 ° C, the phthalocyanine compound may be decomposed.
- the reaction time is 2 to 20 hours, preferably 5 to 15 hours, more preferably 5 to 10 hours. If it is less than 2 hours, there are many unreacted raw materials, and if it exceeds 20 hours, decomposition of the phthalocyanine compound may occur.
- the product obtained by these reactions is treated as a product after being treated according to a post-treatment method of a normal organic synthesis reaction and then purified or not purified. That is, for example, those which are liberated from the reaction system are not purified, or operations for purification by recrystallization or column chromatography (for example, gel permeation chromatography (SEPHADEX TM LH-20: manufactured by Pharmacia) etc. are used alone or in combination.
- the reaction solvent is distilled off or is poured into water or ice without being distilled off, and is neutralized or liberated without being neutralized.
- the product can be provided as a product after it has been purified by recrystallization, column chromatography, etc. alone or in combination.
- the product can be provided as a product after it has been purified alone or in combination without being purified, or purified by crystallization or column chromatography.
- the compounds represented by the above general formulas (a) -1 to (a) -4 have ⁇ -position substitution type (R 1 to R 16 in the following general formula (IV) are respectively in the 1st to 16th positions.
- Phthalocyanine compounds having specific substituents at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position).
- the phthalocyanine dye represented by the general formula (1) of the present invention is ⁇ -position substituted type (1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position).
- the phthalocyanine dye represented by the general formula (2) is ⁇ -position substituted type (2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, Phthalocyanine compound having a specific substituent at positions 14 and / or 15).
- any substitution type having a specific substituent represented by —SO—Z and / or —SO 2 —Z is important for good robustness.
- phthalocyanine dye represented by the general formula (1) or (2) are shown below using the following general formula (IV), but the phthalocyanine dye used in the present invention is limited to the following examples. Is not to be done.
- the colored composition of the present invention includes an aza represented by the following general formula (12). It contains at least one dye selected from phthalocyanine dyes, phthalocyanine dyes represented by the following general formula (22), and direct blue 199.
- the azaphthalocyanine dye represented by the general formula (12) will be described in detail.
- Each P independently represents a nitrogen atom or CH, and at least one P represents a nitrogen atom. However, in each of the four rings containing P, P representing a nitrogen atom is 2 or less.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- R 24 represents a substituted or unsubstituted hydrocarbon group.
- R 23 and R 24 may be bonded together with a nitrogen atom to form a substituted or unsubstituted heterocycle.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- the azaphthalocyanine dye represented by the general formula (12) is preferably an azaphthalocyanine dye represented by the following general formula (13-1) or general formula (13-2).
- Each P independently represents a nitrogen atom or CH, and at least one P represents a nitrogen atom.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- R 24 represents a substituted or unsubstituted hydrocarbon group.
- R 23 and R 24 may be bonded together with a nitrogen atom to form a substituted or unsubstituted heterocycle.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- the substituted or unsubstituted alkyl group represented by R 21 and R 22 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 1 to More preferred is an alkyl group of 4.
- Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable.
- the alkyl group is preferably methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl, more preferably methyl or n-propyl, and still more preferably n-propyl.
- R 21 preferably represents a methyl group or a hydrogen atom, and more preferably represents a hydrogen atom.
- R 22 preferably represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and when it has a substituent, the substituent is preferably a hydroxyl group, n-propyl or a hydrogen atom Is more preferable, and a hydrogen atom is more preferable.
- the substituted or unsubstituted hydrocarbon group represented by R 23 and R 24 is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group.
- the substituted or unsubstituted alkyl group represented by R 23 and R 24 is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms when the substituent is removed. Further, an alkyl group having 1 to 4 carbon atoms is more preferable.
- Substituent group A is mentioned as a substituent.
- the alkyl group methyl, ethyl, butyl, isopropyl and t-butyl are preferable.
- the substituted or unsubstituted heterocyclic group represented by R 23 and R 24 is preferably a 5-membered or 6-membered heterocyclic group.
- Substituent group A is mentioned as a substituent, and an ionic hydrophilic group is contained.
- the heterocyclic group a 2-pyridyl group, a 2-thienyl group and a 2-furyl group are preferable.
- the substituted or unsubstituted aryl group represented by R 23 and R 24 is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed.
- substituent group A examples include substituent group A, and an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group are preferable.
- aryl group phenyl or naphthyl is preferable.
- R 23 preferably represents a methyl group or a hydrogen atom, and more preferably represents a hydrogen atom.
- R 24 is preferably a substituent represented by the following general formula (T1).
- R 23 represents a hydrogen atom
- R 24 is a substituent represented by the following general formula (T1). preferable.
- L represents a single bond or a substituted or unsubstituted alkylene group.
- X represents independently a substituent selected from —OR 25 , —SR 25 , and —NR 25 R 26 , and R 25 and R 26 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted group Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and at least one of R 25 and R 26 has an ionic hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- the substituted or unsubstituted alkylene group represented by L is preferably an alkylene group having 1 to 12 carbon atoms when the substituent is removed, more preferably an alkylene group having 1 to 8 carbon atoms, Is more preferably an alkylene group of 1 to 4.
- Substituent group A is mentioned as a substituent.
- the alkylene group methylene, ethylene, butylene, isopropylene and t-butylene are preferable.
- X is preferably —NR 25 R 26 .
- R 27 is preferably an alkyl group having 1 to 12 carbon atoms when the substituent is removed, more preferably an alkyl group having 1 to 8 carbon atoms, More preferred are alkyl groups having 1 to 4 numbers.
- R 27 preferably represents a methyl group or a hydrogen atom, and more preferably represents a hydrogen atom.
- the substituent represented by the general formula (T1) is a substituent represented by the following general formula (T2).
- L represents a single bond or a substituted or unsubstituted alkylene group.
- R 29 , R 210 , and R 211 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and is ionic It has at least one hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- L and R 27 are synonymous with L and R 27 in formula (T1), and preferred ones are also the same.
- the substituted or unsubstituted alkyl group represented by R 29 , R 210 , and R 211 has the same meaning as that described for R 27 in General Formula (T1), and preferred examples thereof are also the same.
- R 27 , R 29 , R 210 , and R 211 preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.
- R 212 preferably represents a substituted aryl group, and examples of the substituent include Substituent Group A, which has at least one ionic hydrophilic group as a substituent.
- the substituent is preferably an ionic hydrophilic group, preferably a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group, more preferably a carboxyl group and a sulfo group.
- a sulfo group is more preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- R 212 is preferably an aryl group substituted with 1 to 3 ionic hydrophilic groups, preferably an aryl group substituted with 2 ionic hydrophilic groups (preferably a carboxyl group or a sulfo group). It is more preferable.
- the azaphthalocyanine compound represented by the general formula (12) according to the present invention can be synthesized by the method described in International Publication No. 2010/020802.
- R 17 and R 18 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted.
- An aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 17 , R 18 , and A are connected to each other to form a ring;
- Y and Z each independently represent a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, or a substituted group.
- the substituted or unsubstituted alkyl group represented by R 17 and R 18 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 1 to More preferred is an alkyl group of 4.
- Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable.
- the alkyl group is preferably methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl, more preferably methyl or n-propyl, and still more preferably n-propyl.
- R 27 and R 28 preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.
- the cycloalkyl group represented by R 17 and R 18 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
- the cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group.
- a cyclohexyl group is preferred as an example of a cycloalkyl group.
- Examples of the aralkyl group represented by R 17 and R 18 include a substituted aralkyl group and an unsubstituted aralkyl group.
- an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Examples of the aralkyl group are preferably a benzyl group and a 2-phenethyl group.
- the substituted or unsubstituted aryl group represented by R 17 and R 18 is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed.
- substituent group A examples include substituent group A, and an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group are preferable.
- aryl group phenyl or naphthyl is preferable.
- the substituted or unsubstituted heterocyclic group represented by R 17 and R 18 is preferably a 5-membered or 6-membered heterocyclic group.
- Substituent group A is mentioned as a substituent, and an ionic hydrophilic group is contained.
- the heterocyclic group a 2-pyridyl group, a 2-thienyl group and a 2-furyl group are preferable.
- the alkenyl group represented by R 17 and R 18 includes an alkenyl group having a substituent and an unsubstituted alkenyl group.
- an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Preferred examples of the alkenyl group include a vinyl group and an allyl group.
- the aryloxy group represented by R 17 and R 18 includes an aryloxy group having a substituent and an unsubstituted aryloxy group.
- the aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed.
- Examples of the substituent include an alkoxy group and an ionic hydrophilic group.
- Examples of the aryloxy group are preferably a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.
- a halogen atom represented by Y and Z a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted Aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group Substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkylthio group, substituted
- the divalent linking group represented by A includes an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SOn- (n is 0, 1, 2), -NR- (R is a hydrogen atom, an alkyl group, Represents an aryl group), -O-, and a divalent group obtained by combining these linking groups, and further include an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, a halogen atom, You may have substituents, such as a hydroxyl group, a carboxyl group, a sulfamoyl group, a carbamoyl group, and a sulfonamide group.
- An alkylene group is preferred, and an ethylene group and an n-propylene group are preferred.
- the phthalocyanine dye represented by the general formula (22) is preferably a phthalocyanine dye represented by the following general formula (22-1).
- each of R 27 and R 28 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 27 , R 28 , and A are linked to each other; To form a ring.
- R 29 , R 210 , and R 211 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group.
- m and n are 1 to 3, and the sum of m and n is 2 to 4.
- R 27 and R 28 have the same meanings as A, R 17 and R 18 in formula (21), and preferred ones are also the same.
- the substituted or unsubstituted alkyl group represented by R 29 , R 210 and R 211 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, More preferred are alkyl groups having 1 to 4 numbers.
- Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable.
- the alkyl group is preferably methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl, more preferably methyl or n-propyl, and still more preferably n-propyl.
- R 27 and R 28 preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.
- R 212 preferably represents a substituted aryl group, and examples of the substituent include Substituent Group A, which has at least one ionic hydrophilic group as a substituent.
- the substituent is preferably an ionic hydrophilic group, preferably a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group, more preferably a carboxyl group and a sulfo group.
- a sulfo group is more preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- alkali metal ions eg, sodium ion, potassium ion
- organic cations eg, tetramethylguanidinium ion.
- R 212 represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and more preferably a substituted alkyl group or a substituted aryl group.
- R 212 is preferably an aryl group substituted with 1 to 3 ionic hydrophilic groups, preferably an aryl group substituted with 2 ionic hydrophilic groups (preferably a carboxyl group or a sulfo group). It is more preferable.
- phthalocyanine dye represented by the general formula (22) Specific examples of the phthalocyanine dye represented by the general formula (22) are shown below, but the phthalocyanine dye used in the present invention is not limited to the following examples.
- the phthalocyanine derivative represented by the general formula (22) can be synthesized, for example, by the method described in JP-A-2004-329677.
- Direct Blue 199 that can be used in the present invention can be easily obtained as a commercial product.
- the coloring composition according to the present invention is represented by the general formula (12) in addition to the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2).
- the coloring composition of the present invention includes a phthalocyanine dye represented by the general formula (1), a phthalocyanine dye represented by the general formula (2), an azaphthalocyanine dye represented by the general formula (12), A phthalocyanine dye represented by the general formula (22) and at least one dye selected from Direct Blue 199.
- the coloring composition contains a phthalocyanine dye represented by the general formula (1) and a phthalocyanine dye represented by the general formula (2), and is represented by the general formula (12) as a third dye.
- the colored composition of the present invention can be preferably used as a colored composition for image formation.
- Applications of the colored composition of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal transfer type images including ink jet recording materials described in detail below.
- Recording materials pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, thermal transfer type image recording materials, electrophotographic methods
- an ink jet recording material is preferable. It can also be applied to dyeing solutions for dyeing various fibers of color filters used in solid-state imaging devices such as LCDs and CCDs described in US Pat. No. 4,808,501 and JP-A-6-35182. .
- the phthalocyanine dye used in the present invention is used by adjusting physical properties such as solubility and heat transfer properties suitable for the intended use with a substituent.
- the phthalocyanine dye used in the present invention can be used in a uniform dissolved state or a dispersed dissolved state such as an emulsified dispersion depending on the system used.
- the mass ratio of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is preferably 50/50 to 10/90, ⁇ 20/80 is more preferred.
- the colored composition is excellent in stability over time (viscosity change, precipitation, etc.) at a high concentration, and is excellent in ozone fastness of a print sample using the colored composition. Further, it is possible to obtain a feature that the print density is excellent.
- the content of the phthalocyanine dye represented by the general formula (1) in the coloring composition is preferably 0.1 to 20% by mass.
- the amount is less than 0.1% by mass, the color composition is deteriorated in stability over time at a high concentration and the print density, and when it exceeds 20% by mass, the ozone fastness of the print sample is deteriorated.
- the ink for inkjet recording of the present invention contains the above colored composition.
- the ink for inkjet recording can be produced by dissolving and / or dispersing the phthalocyanine compound in an oleophilic medium or an aqueous medium.
- the ink uses an aqueous medium. If necessary, other additives are contained 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, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.
- the anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.
- a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
- Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin.
- Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives.
- lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl)
- polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
- said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.
- the penetration accelerator is preferably used for the purpose of allowing the ink for inkjet to penetrate better into the paper.
- penetration enhancers alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants, etc. can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in an additive amount range that does not cause printing bleeding or paper loss (print-through).
- UV absorbers are used for the purpose of improving image storage stability.
- examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like.
- the anti-fading agent is used for the purpose of improving image storage stability.
- various organic and metal complex anti-fading agents can be used.
- Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid.
- the compounds described in the patent cited in Japanese Patent No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.
- antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in an amount of 0.02 to 1.00% by mass in the ink.
- the neutralizing agent organic base, inorganic alkali
- the pH adjuster is preferably added so that the ink for ink jet recording has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. preferable.
- the surface tension adjusting agent includes nonionic, cationic or anionic surfactants.
- the surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m. Further, 25 to 60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa ⁇ s or less. Furthermore, it is more preferable to adjust to 20 mPa ⁇ s or less.
- surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates.
- Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester
- Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred.
- SURFYNOLS Air Products & Chemicals
- An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred.
- pages (37) to (38) of JP-A-59-157,636, Research, Disclosure No. The surfactants described in 308119 (1989) can also be used.
- fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.
- the phthalocyanine compound and azaphthalocyanine compound of the present invention are dispersed in an aqueous medium, they are described in JP-A Nos. 11-286637, 2000-78491, 2000-80259, 2000-62370, etc.
- colored fine particles containing a pigment and an oil-soluble polymer are dispersed in an aqueous medium, and each specification of Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 2000-203857 is disclosed. It is preferable to disperse the compound of the present invention dissolved in a high-boiling organic solvent in an aqueous medium as described.
- the specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications. be able to.
- the phthalocyanine compound may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used.
- Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer)
- mill method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- high pressure homogenizer high pressure homogenizer
- Specific examples of commercially available devices include gorin homogenizers, microfluid
- the ink jet recording ink preparation method described above is disclosed in JP-A-5-148436, JP-A-5-295212, JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.
- a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used.
- the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene
- the inkjet recording ink of the present invention 0.2 parts by mass in total of the phthalocyanine compound represented by the general formulas (1), (2), (12) and (22) and Direct Blue 199 It is preferably contained in an amount of 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, still more preferably 3 parts by mass or more and 5 parts by mass or less, and more preferably 3.5 parts by mass or more and 5 parts by mass. What is contained below is most preferable.
- the inkjet ink of the present invention may be used in combination with other dyes together with the phthalocyanine compounds represented by the general formulas (1), (2), (12) and (22), and Direct Blue 199. Good. When other pigments are used in combination, the total pigment content is preferably within the above range.
- the ratio of the dye represented by the general formula (1) to the dye represented by the general formula (2) and the dye represented by the general formula (12) is 5 to 30/5 to 70/5 to 80, more preferably 10 to 30/10 to 40/40 to 80.
- the preferred ratio of the dye represented by the general formula (1), the dye represented by the general formula (2) and the dye represented by the general formula (22) is 5 to 30/40 to 70. / 5 to 40, more preferably 10 to 20/50 to 60/20 to 30.
- the preferred ratio of the dye represented by the general formula (1), the dye represented by the general formula (2) and direct blue 199 is 5 to 30/40 to 80/5 to 40. More preferably, it is 20 to 30/50 to 60/10 to 30.
- the ink for ink jet recording of the present invention preferably has a viscosity of 40 cp or less.
- the surface tension is preferably 20 mN / m or more and 70 mN / m or less.
- Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.
- the ink for inkjet recording of the present invention 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.
- Any applicable yellow dye can be used.
- coupler components as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain type active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro, nitroso dyes, acridine dyes, acridinone dyes, and the like.
- magenta dye Any applicable magenta dye can be used.
- aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc.
- coupler components for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.
- cyan dye can be used.
- aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo and thioindigo dyes.
- each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated.
- the counter cation is an alkali metal or an inorganic cation such as ammonium.
- it may be an organic cation such as pyridinium or a quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
- Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.
- the present invention also relates to an ink jet recording method using the ink for ink jet recording according to the present invention.
- energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153789, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc.
- a known image receiving material that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153789,
- the ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element.
- Pulse method acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink
- thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems.
- Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.
- a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance.
- the timing of applying the polymer latex to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition place may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone.
- the method described in the specification can be preferably used.
- the ink cartridge for ink jet recording of the present invention is filled with the ink for ink jet recording of the present invention described above. Further, the ink-jet recorded matter of the present invention is obtained by forming a colored image on a recording material using the above-described ink for ink-jet recording of the present invention.
- the support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP.
- Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there.
- either synthetic paper or plastic film sheets may be used.
- the thickness of the support is preferably 10 to 250 ⁇ m and the basis weight is preferably 10 to 250 g / m 2.
- the support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided.
- the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
- paper and plastic films laminated on both sides with polyolefin for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof
- a white pigment for example, titanium oxide or zinc oxide
- a coloring dye for example, cobalt blue, ultramarine blue, or neodymium oxide
- the ink receiving layer provided on the support contains a pigment and an aqueous binder.
- a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins.
- porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable.
- synthetic amorphous silica either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.
- aqueous binder contained in the ink receiving layer examples include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like.
- Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more.
- polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
- the ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.
- the mordant added to the ink receiving layer is preferably immobilized.
- a polymer mordant is preferably used.
- the polymer mordant JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, 60-23852, 60-23835, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos.
- the water-proofing agent is effective for making the image water-resistant.
- cationic resins are particularly desirable.
- examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc.
- polyamide polyamine epichlorohydrin is particularly preferable. is there.
- the content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.
- the light resistance improver examples include zinc sulfate, zinc oxide, hindered amine antioxidants, benzotriazole ultraviolet absorbers such as benzophenone, and the like. Of these, zinc sulfate is particularly preferred.
- the surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent.
- Surfactants are described in JP-A Nos. 62-173463 and 62-183457.
- An organic fluoro compound may be used in place of the surfactant.
- the organic fluoro compound is preferably hydrophobic.
- Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin).
- the organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-2994 and JP-A-62-135826.
- the ink receiving layer may be one layer or two layers.
- Recording paper and recording film can be provided with a backcoat layer, and examples of components that can be added to this layer include white pigments, aqueous binders, and other components.
- white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate.
- White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide
- organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.
- aqueous binder contained in the backcoat layer As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.
- Polymer latex may be added to the constituent layers (including the backcoat layer) of the inkjet recording paper and recording film.
- the polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention.
- the polymer latex is described in JP-A Nos. 62-245258, 62-1316648, and 62-110066.
- a polymer latex having a low glass transition temperature 40 ° C. or lower
- cracking and curling of the layer can be prevented.
- curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.
- the phthalocyanine compound of the present invention can be derived from, for example, the following synthetic route.
- ⁇ max is the absorption maximum wavelength
- ⁇ max is the molar extinction coefficient at the absorption maximum wavelength.
- Synthesis Example 1 Synthesis of Compound (A)
- 26.0 g of 4-nitrophthalonitrile (Tokyo Kasei) was dissolved in 200 mL of DMSO (dimethyl sulfoxide) and stirred at an internal temperature of 20 ° C.
- 30.3 g of sodium 3-mercapto-propane-sulfonate (Aldrich) was added.
- 24.4 g of anhydrous sodium carbonate was gradually added to the mixture being stirred at an internal temperature of 20 ° C. While stirring the reaction solution, it was heated to 30 ° C. and stirred at the same temperature for 1 hour.
- the reaction solution is filtered with Nutsche, and the filtrate is poured into 15000 mL of ethyl acetate for crystallization, followed by stirring at room temperature for 30 minutes, and the precipitated crude crystals are filtered with Nutsche, and ethyl acetate is added. Washed with and dried. The obtained crude crystals were recrystallized from methanol / ethyl acetate to obtain 42.5 g of Compound A.
- Synthesis Example 2 Synthesis The compounds of 42.0g of compound (B) (A) was dissolved in acetic acid 300 mL, the resultant mixture was stirred at an internal temperature of 20 ° C., 2.5 g of Na 2 WO 4 ⁇ 2H 2 O Then, the mixture was cooled to an internal temperature of 10 ° C. in an ice bath. Subsequently, 32 mL of hydrogen peroxide (30%) was gradually added dropwise while paying attention to heat generation. After stirring at an internal temperature of 15 to 20 ° C. for 30 minutes, the reaction solution was heated to an internal temperature of 60 ° C. and stirred at the same temperature for 1 hour.
- Synthesis Example 3 Synthesis of Exemplified Compound 102 ⁇ (Dye 1A of General Formula (1)) To a three-necked flask equipped with a cooling tube, 70 mL of n-amyl alcohol was added, and 6.7 g of compound B, copper (II) chloride 1 was added thereto. 0.0 g was added, and 7.0 mL of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise at room temperature with stirring. Subsequently, the reaction solution was heated to an internal temperature of 100 ° C. and stirred at the same temperature for 10 hours. After cooling to 40 ° C., 250 mL of heated methanol at 50 ° C.
- DBU 1,8-diazabicyclo [5.4.0] -7-undecene
- the phthalocyanine copper (II) -substitution position defined in this specification is ⁇ -position substituted type ⁇ in each (2 or 3 position), (6 or 7 position), (10 or 11 position), (14 or 15 position) of each benzene nucleus- ⁇ SO 2- (CH 2 ) 3 one of -SO 3 Na ⁇ group, copper phthalocyanine per molecule - a (CH 2) 3 -SO 3 Na ⁇ group confirmed that the a total of four to chromatic ⁇ - ⁇ SO 2.
- Example 1 Deionized water was added to the following ingredients to make 100 g, followed by stirring for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with NaOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m to prepare an ink solution for cyan.
- Example 2 to 41, Comparative Examples 1 to 14 Examples 2 to 41 and Comparative Examples were the same as the preparation of the ink liquid of Example 1, except that the type and addition amount of phthalocyanine dye and the addition amount of Direct Blue 199 were changed as shown in Tables 31 to 33 below. Ink liquids 1 to 14 were prepared.
- the photo glossy paper on which the image has been formed is left in a box set at an ozone gas concentration of 0.5 ⁇ 0.1 ppm, room temperature and dark place for 7 days, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X -Rite310TR) and evaluated as the residual ratio of the dye. The reflection density was measured at three points of 1, 1.5 and 2.0.
- the ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
- AA when the dye residual ratio is 75% or more at any concentration A when the dye residual ratio is 70% or more and less than 75% at any concentration, A, 1 or 2 points less than 70% B, all the concentrations The case of less than 70% was evaluated as C and evaluated in three stages.
- the ink for inkjet recording of the present invention is superior in ozone resistance to the ink of the comparative example, has a suppressed bronze gloss, and can obtain a neutral gray or black hue with other yellow and magenta. I understood that I can do it.
- the ozone resistance is excellent, the bronze gloss is suppressed, and when a composite gray or black is prepared together with other yellow and magenta, a neutral gray or black hue can be obtained.
- Compositions, inkjet recording inks, inkjet recording methods, inkjet printer cartridges, and inkjet recordings are provided.
Abstract
Description
更に、上述した従来のインクでは、ブロンズ光沢を十分に抑制することができず、また、他の染料と共に作成したグレー及びブラックにおいて、ニュートラルな色相を得ることが困難であった。
本発明においては、彩度が高い第1及び第2の染料と、彩度が低い第3の染料とを併用することにより、実用上問題のない色再現域を確保しつつ、他のイエロー及びマゼンタと共にコンポジットブラックを作成した場合においても、ニュートラルなグレー又はブラックの画像を得ることができ、相反する作用を両立することができる。第1~第3の染料を使用することにより得られる効果は、それぞれの単独の分光スペクトルからは予測できなかったものであり、作用機構は不明であるが、第1及び第2の染料と第3の染料とを併用することにより、何らかの相互作用、相乗効果が働いているものと考えられる。
下記一般式(1)で表されるフタロシアニン染料と、下記一般式(2)で表されるフタロシアニン染料と、下記一般式(12)で表されるアザフタロシアニン染料、下記一般式(22)で表されるフタロシアニン染料、及びダイレクトブルー199から選択される少なくとも1種の染料と、を含むことを特徴とする着色組成物。
一般式(1)中、
R2、R3、R6、R7、R10、R11、R14及びR15は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z1、Z2、Z3、及びZ4は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z1、Z2、Z3、及びZ4のうち少なくとも1つは、イオン性親水性基を置換基として有する。
l、m、n、p、q1、q2、q3及びq4は、それぞれ独立に、1又は2を表す。
M1は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
一般式(2):
一般式(2)中、
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z5、Z6、Z7、及びZ8のうち少なくとも1つは、イオン性親水性基を置換基として有する。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M2は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。ただし、Pを含む4つの環において、それぞれ、窒素原子を表すPは2以下である。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
(一般式(22)中、R17及びR18はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR17、R18、及びAは互いに連結して環を形成しても良い。Y及びZは、それぞれ独立してハロゲン原子、水酸基、スルホン酸基、カルボキシル基、アミノ基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のシクロアルキルオキシ基、置換若しくは無置換のアリロキシ基、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアラルキルオキシ基、置換若しくは無置換のアルケニルオキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のシクロアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテロ環アミノ基、置換若しくは無置換のアラルキルアミノ基、置換若しくは無置換のアルケニルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロ環チオ基、置換若しくは無置換のアラルキルチオ基、置換若しくは無置換のアルケニルチオ基を表す。但し、Y、Zのうち少なくとも1つは、スルホン酸基、カルボキシル基、又はイオン性親水性基を置換基として有する基である。m、及びnは1から3であり、かつmとnの和は2から4である。)
〔2〕
一般式(1)で表されるフタロシアニン染料におけるR2、R3、R6、R7、R10、R11、R14及びR15が、水素原子であることを特徴とする〔1〕に記載の着色組成物。
〔3〕
一般式(2)で表されるフタロシアニン染料におけるR1、R4、R5、R8、R9、R12、R13及びR16が、水素原子であることを特徴とする〔1〕又は〔2〕に記載の着色組成物。
〔4〕
一般式(1)で表されるフタロシアニン染料におけるZ1、Z2、Z3、及びZ4が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする〔1〕~〔3〕のいずれか1項に記載の着色組成物。
〔5〕
一般式(2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする〔1〕~〔4〕のいずれか1項に記載の着色組成物。
〔6〕
一般式(2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、置換アルキル基を表し、アルキル基が有する置換基の少なくとも一つが-SO2NHR基(但しRは置換若しくは無置換のアルキル基、又は置換若しくは無置換のフェニル基を表す)である〔1〕~〔5〕のいずれか1項に記載の着色組成物。
〔7〕
一般式(1)で表されるフタロシアニン染料におけるl、m、n及びpが1である〔1〕~〔6〕のいずれか1項に記載の着色組成物。
〔8〕
一般式(2)で表されるフタロシアニン染料におけるt、u、v及びwが1である〔1〕~〔7〕のいずれか1項に記載の着色組成物。
〔9〕
一般式(1)で表されるフタロシアニン染料におけるq1、q2、q3及びq4が2である〔1〕~〔8〕のいずれか1項に記載の着色組成物。
〔10〕
一般式(2)で表されるフタロシアニン染料におけるq5、q6、q7及びq8が2である〔1〕~〔9〕のいずれか1項に記載の着色組成物。
〔11〕
一般式(1)で表されるフタロシアニン染料と、一般式(2)で表されるフタロシアニン染料との質量比が50/50~10/90である〔1〕~〔10〕のいずれか1項に記載の着色組成物。
〔12〕
一般式(1)で表されるフタロシアニン染料の含有量が1~20質量%である〔1〕~〔11〕のいずれか1項に記載の着色組成物。
〔13〕
一般式(12)で表されるアザフタロシアニン染料が、下記一般式(13-1)又は一般式(13-2)で表されるアザフタロシアニン染料である〔1〕~〔12〕のいずれか1項に記載の着色組成物。
(一般式(13-1)及び一般式(13-2)中、
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基を表す。
R24は置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基を表す。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
〔14〕
前記一般式(12)、一般式(13-1)又は一般式(13-2)における、R23が水素原子を表し、R24が下記一般式(T1)で表される置換基で置換された置換アルキル基である〔1〕~〔13〕のいずれか1項に記載の着色組成物。
(一般式(T1)中、
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
Xはそれぞれ独立に-OR25、-SR25、及び-NR25R26より選択される置換基を表し、R25及びR26はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表し、R25及びR26の少なくとも一つはイオン性親水性基を置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
〔15〕
前記一般式(T1)で表される置換基が、下記一般式(T2)で表される置換基である〔14〕に記載の着色組成物。
(一般式(T2)中、
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
〔16〕
前記一般式(22)で表されるフタロシアニン染料が、一般式(22-1)で表されるフタロシアニン染料である〔1〕~〔15〕のいずれか1項に記載の着色組成物。
(一般式(22-1)中、R27及びR28はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR27、R28、及びAは互いに連結して環を形成しても良い。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。m、及びnは1から3であり、かつmとnの和は2から4である。)
〔17〕
〔1〕~〔16〕のいずれか1項に記載の着色組成物を含むインクジェット記録用インク。
〔18〕
〔17〕に記載のインクジェット記録用インクを用いるインクジェット記録方法。
〔19〕
〔17〕に記載のインクジェット記録用インクを充填したインクカートリッジ。
〔20〕
〔17〕に記載のインクジェット記録用インクを用いて、被記録材に着色画像を形成したインクジェット記録物。
ハロゲン原子(例えば、塩素原子、臭素原子);炭素数1~12の直鎖状又は分岐状鎖アルキル基、炭素数7~18のアラルキル基、炭素数2~12のアルケニル基、炭素数2~12の直鎖状又は分岐鎖状アルキニル基、側鎖を有していてもよい炭素数3~12のシクロアルキル基、側鎖を有していてもよい炭素数3~12のシクロアルケニル基(上記基の具体的例として、例えばメチル、エチル、プロピル、イソプロピル、t-ブチル、2-メタンスルホニルエチル、3-フェノキシプロピル、トリフルオロメチル、シクロペンチル):アリール基(例えば、フェニル、4-t-ブチルフェニル、2,4-ジ-t-アミルフェニル);ヘテロ環基(例えば、イミダゾリル、ピラゾリル、トリアゾリル、2-フリル、2-チエニル、2-ピリミジニル、2-ベンゾチアゾリル);アルキルオキシ基(例えば、メトキシ、エトキシ、2-メトキシエトキシ、2-メタンスルホニルエトキシ);アリールオキシ基(例えば、フェノキシ、2-メチルフェノキシ、4-t-ブチルフェノキシ、3-ニトロフェノキシ、3-t-ブチルオキシカルバモイルフェノキシ、3-メトキシカルバモイル);アシルアミノ基(例えば、アセトアミド、ベンズアミド、4-(3-t-ブチル-4-ヒドロキシフェノキシ)ブタンアミド);アルキルアミノ基(例えば、メチルアミノ、ブチルアミノ、ジエチルアミノ、メチルブチルアミノ);アニリノ基(例えば、フェニルアミノ、2-クロロアニリノ;ウレイド基(例えば、フェニルウレイド、メチルウレイド、N,N-ジブチルウレイド);スルファモイルアミノ基(例えば、N,N-ジプロピルスルファモイルアミノ);アルキルチオ基(例えば、メチルチオ、オクチルチオ、2-フェノキシエチルチオ);アリールチオ基(例えば、フェニルチオ、2-ブトキシ-5-t-オクチルフェニルチオ、2-カルボキシフェニルチオ);アルキルオキシカルボニルアミノ基(例えば、メトキシカルボニルアミノ);スルホンアミド基(例えば、メタンスルホンアミド、ベンゼンスルホンアミド、p-トルエンスルホンアミド、オクタデカン);カルバモイル基(例えば、N-エチルカルバモイル、N,N-ジブチルカルバモイル);スルファモイル基(例えば、N-エチルスルファモイル、N,N-ジプロピルスルファモイル、N,N-ジエチルスルファモイル);スルホニル基(例えば、メタンスルホニル、オクタンスルホニル、ベンゼンスルホニル、トルエンスルホニル);アルキルオキシカルボニル基(例えば、メトキシカルボニル、ブチルオキシカルボニル);ヘテロ環オキシ基(例えば、1-フェニルテトラゾール-5-オキシ、2-テトラヒドロピラニルオキシ);アゾ基(例えば、フェニルアゾ、4-メトキシフェニルアゾ、4-ピバロイルアミノフェニルアゾ、2-ヒドロキシ-4-プロパノイルフェニルアゾ);アシルオキシ基(例えば、アセトキシ);カルバモイルオキシ基(例えば、N-メチルカルバモイルオキシ、N-フェニルカルバモイルオキシ);シリルオキシ基(例えば、トリメチルシリルオキシ、ジブチルメチルシリルオキシ);アリールオキシカルボニルアミノ基(例えば、フェノキシカルボニルアミノ);イミド基(例えば、N-スクシンイミド、N-フタルイミ);ヘテロ環チオ基(例えば、2-ベンゾチアゾリルチオ、2,4-ジ-フェノキシ-1,3,5-トリアゾール-6-チオ、2-ピリジルチオ);スルフィニル基(例えば、3-フェノキシプロピルスルフィニル);ホスホニル基(例えば、フェノキシホスホニル、オクチルオキシホスホニル、フェニルホスホニル);アリールオキシカルボニル基(例えば、フェノキシカルボニル);アシル基(例えば、アセチル、3-フェニルプロパノイル、ベンゾイル);イオン性親水性基(例えば、カルボキシル基、スルホ基、及び4級アンモニウム基);その他シアノ基、ヒドロキシル基、ニトロ基、アミノ基。
まず、一般式(1)で表されるフタロシアニン染料について詳細に説明する。
R2、R3、R6、R7、R10、R11、R14及びR15は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z1、Z2、Z3、及びZ4は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z1、Z2、Z3、及びZ4のうち少なくとも1つは、イオン性親水性基を置換基として有する。
l、m、n、p、q1、q2、q3及びq4は、それぞれ独立に、1又は2を表す。
M1は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
次に、一般式(2)で表されるフタロシアニン染料について詳細に説明する。
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、前記一般式(1)中のR2、R3、R6、R7、R10、R11、R14及びR15と各々同義である。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、前記一般式(1)中のZ1、Z2、Z3、及びZ4と各々同義である。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M2は、前記一般式(1)中のM1と同義である。
これらの基は、更に置換基を有していてもよい。置換基としては、上記置換基群Aに記載の置換基が挙げられる。
Z5、Z6、Z7、及びZ8は、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基が好ましく、置換のアルキル基、置換のアリール基、置換のヘテロ環基がより好ましく、置換のアルキル基であることが更に好ましい。また、置換のアルキル基が有する置換基の少なくとも一つが、-SO2NHR基であることがオゾン堅牢性の観点から最も好ましい(但しRは置換若しくは無置換のアルキル基、又は置換若しくは無置換のフェニル基を表す)。
Z5、Z6、Z7、及びZ8のうち少なくとも1つが置換基として有するイオン性親水性基は、前記一般式(1)中のZ1、Z2、Z3、及びZ4が置換基として有するイオン性親水性基と同義であり、好ましい例も同様である。
本発明に用いられるフタロシアニン誘導体は、例えば白井-小林共著、(株)アイピーシー発行「フタロシアニン-化学と機能-」(P.1~62)、C.C.Leznoff-A.B.P.Lever共著、VCH発行‘Phthalocyanines-Properties and Applications’(P.1~54)等に記載、引用若しくはこれらに類似の方法を組み合わせて合成することができる。
本発明の一般式(2)で表されるフタロシアニン染料のうちR1、R4、R5、R8、R9、R12、R13及びR16が水素、q5、q6、q7及びq8が2である化合物は、例えば下記一般式(V)で表されるフタロニトリル誘導体及び/又は下記一般式(VI)で表されるジイミノイソインドリン誘導体と下記M-(Y)dで表される金属誘導体を反応させることにより合成される。
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、前記一般式(1)中のR2、R3、R6、R7、R10、R11、R14及びR15と各々同義である。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、前記一般式(1)中のZ1、Z2、Z3、及びZ4と各々同義である。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M及びM2は、前記一般式(1)中のM1と同義であり、M=M2である。
Yはハロゲン原子、酢酸陰イオン、アセチルアセトネート、酸素などの1価又は2価の配位子を示し、dは1~4の整数である。
本発明の着色組成物は、上記一般式(1)で表されるフタロシアニン染料と、上記一般式(2)で表されるフタロシアニン染料との他に、下記一般式(12)で表されるアザフタロシアニン染料、下記一般式(22)で表されるフタロシアニン染料、及びダイレクトブルー199から選択される少なくとも1種の染料を含有する。次に、一般式(12)で表されるアザフタロシアニン染料について詳細に説明する。
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。ただし、Pを含む4つの環において、それぞれ、窒素原子を表すPは2以下である。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
R21はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R22は水素原子又は置換若しくは無置換の炭素原子数が1~4のアルキル基を表すことが好ましく、置換基を有する場合の置換基はヒドロキシル基であることが好ましく、n-プロピル又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R24は下記一般式(T1)で表される置換基であることが好ましい。
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
Xはそれぞれ独立に-OR25、-SR25、及び-NR25R26より選択される置換基を表し、R25及びR26はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表し、R25及びR26の少なくとも一つはイオン性親水性基を置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
R25及びR26が表す置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基としては、R23及びR24が表すものと同様の基が挙げられる。
R27が表す置換若しくは無置換のアルキル基としては、置換基を除いたときの炭素原子数が1~12のアルキル基が好ましく、炭素原子数が1~8のアルキル基がより好ましく、炭素原子数が1~4のアルキル基が更に好ましい。アルキル基としては、メチル、エチル、ブチル、イソプロピル、t-ブチルが好ましい。置換基としては、置換基群Aが挙げられる。
R27はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
R29、R210、及びR211が表す置換若しくは無置換のアルキル基としては、一般式(T1)におけるR27で挙げたものと同義であり好ましいものも同様である。
R27、R29、R210、及びR211はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R212は1~3個のイオン性親水性基で置換されたアリール基であることが好ましく、2個のイオン性親水性基(好ましくはカルボキシル基又はスルホ基)で置換されたアリール基であることがより好ましい。
更に、一般式(22)で表されるフタロシアニン染料について詳細に説明する。
R27及びR28はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R17及びR18が表すアラルキル基としては、置換基を有するアラルキル基及び無置換のアラルキル基が挙げられる。アラルキル基としては、置換基を除いたときの炭素原子数が7~12のアラルキル基が好ましい。置換基の例には、イオン性親水性基が挙げられる。アラルキル基の例には、ベンジル基、及び2-フェネチル基が好ましい。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。スルホン酸基、カルボキシル基、又はイオン性親水性基を置換基として有する基である。m、及びnは1から3であり、かつmとnの和は2から4である。)
R29、R210、及びR211が表す置換若しくは無置換のアルキル基としては、炭素原子数が1~12のアルキル基が好ましく、炭素原子数が1~8のアルキル基がより好ましく、炭素原子数が1~4のアルキル基が更に好ましい。置換基としては、置換基群Aが挙げられ、ヒドロキシル基、アルコキシ基、シアノ基、ハロゲン原子及びイオン性親水性基が好ましく、ヒドロキシル基又はイオン性親水性基がより好ましい。アルキル基としては、メチル、エチル、ブチル、イソプロピル、n-プロピル、又はt-ブチルが好ましく、メチル、又はn-プロピルがより好ましく、n-プロピルが更に好ましい。
R27及びR28メチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R212は1~3個のイオン性親水性基で置換されたアリール基であることが好ましく、2個のイオン性親水性基(好ましくはカルボキシル基又はスルホ基)で置換されたアリール基であることがより好ましい。
一般式(22)で表されるフタロシアニン誘導体は、例えば特開2004-329677号公報に記載の方法により合成することができる。
本発明で使用することができるダイレクトブルー199は、市販品として容易に入手することが可能である。
本発明の着色組成物は、上記一般式(1)で表されるフタロシアニン染料と、上記一般式(2)で表されるフタロシアニン染料と、上記一般式(12)で表されるアザフタロシアニン染料、上記一般式(22)で表されるフタロシアニン染料、及びダイレクトブルー199から選択される少なくとも1種の染料と、を含有する。着色組成物が、一般式(1)で表されるフタロシアニン染料と、一般式(2)で表されるフタロシアニン染料とを含有し、更に第3の染料として、一般式(12)で表されるアザフタロシアニン染料、一般式(22)で表されるフタロシアニン染料、及びダイレクトブルー199から選択される少なくとも1種の染料を含有することにより、耐オゾン性が向上し、ブロンズ光沢が抑制され、他のイエロー、マゼンタと共にコンポジットグレー又はブラックを作成した場合に、ニュートラルなグレー又はブラックの色相を得ることができる。
本発明の着色組成物は、好ましくは画像形成用着色組成物として用いることができる。本発明の着色組成物の用途としては、画像、特にカラー画像を形成するための画像記録材料が挙げられ、具体的には、以下に詳述するインクジェット方式記録材料を始めとして、感熱転写型画像記録材料、感圧記録材料、電子写真方式を用いる記録材料、転写式ハロゲン化銀感光材料、印刷インク、記録ペン等であり、好ましくはインクジェット方式記録材料、感熱転写型画像記録材料、電子写真方式を用いる記録材料であり、更に好ましくはインクジェット方式記録材料である。また、米国特許4808501号明細書、特開平6-35182号公報などに記載されているLCDやCCDなどの固体撮像素子で用いられているカラーフィルター各種繊維の染色のための染色液にも適用できる。本発明に用いるフタロシアニン染料は、その用途に適した溶解性、熱移動性などの物性を、置換基により調整して使用する。また、本発明に用いるフタロシアニン染料は、用いられる系に応じて均一な溶解状態、乳化分散のような分散された溶解状態で使用する事が出来る。
次に本発明のインクジェット記録用インクについて説明する。本発明のインクジェット記録用インクは、上記着色組成物を含む。インクジェット記録用インクは、親油性媒体や水性媒体中に前記フタロシアニン化合物を溶解及び/又は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、水性媒体を用いたインクである。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される。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。油溶性染料を分散物の形で用いる場合には、染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。
また別の好ましい形態は、一般式(1)で表される染料、一般式(2)で表される染料及び一般式(22)で表される染料の好ましい比率が5~30/40~70/5~40であり、より好ましくは10~20/50~60/20~30である。
更に別の好ましい形態は、一般式(1)で表される染料、一般式(2)で表される染料及びダイレクトブルー199の好ましい比率が、5~30/40~80/5~40であり、より好ましくは20~30/50~60/10~30である。
本発明は、本発明に係るインクジェット記録用インクを用いるインクジェット記録方法にも関する。本発明のインクジェット記録方法は、前記インクジェット記録用インクにエネルギーを供与して、公知の受像材料、即ち普通紙、樹脂コート紙、例えば特開平8-169172号公報、同8-27693号公報、同2-276670号公報、同7-276789号公報、同9-323475号公報、特開昭62-238783号公報、特開平10-153989号公報、同10-217473号公報、同10-235995号公報、同10-337947号公報、同10-217597号公報、同10-337947号公報等に記載されているインクジェット専用紙、フィルム、電子写真共用紙、布帛、ガラス、金属、陶磁器等に画像を形成する。
本発明のインクジェット記録用インクカートリッジは、上記した本発明のインクジェット記録用インクを充填したものである。また、本発明のインクジェット記録物は、上記した本発明のインクジェット記録用インクを用いて、被記録材に着色画像を形成したものである。
以下、実施例に本発明のフタロシアニン系色素誘導体の合成法を詳しく説明するが、出発物質、色素中間体及び合成ル-トについて限定されるものでない。
窒素気流下、4-ニトロフタロニトリル(東京化成)26.0gを200mLのDMSO(ジメチルスルホキシド)に溶解し、内温20℃で攪拌しているところへ、30.3gの3-メルカプト-プロパン-スルホン酸ナトリウム(アルドリッチ)を添加した。続いて、内温20℃で攪拌しているところへ、24.4gの無水炭酸ナトリウムを徐々に加えた。反応液を攪拌しながら、30℃まで加温し、同温度で1時間撹拌した。20℃まで冷却した後、反応液をヌッチェでろ過し、ろ液を15000mLの酢酸エチルにあけて晶析し、引き続き室温で30分間撹拌して、析出した粗結晶をヌッチェでろ過し、酢酸エチルで洗浄し、乾燥した。得られた粗結晶を、メタノール/酢酸エチルから再結晶して、42.5gの化合物Aを得た。1H-NMR(DMSO-d6),δ値TMS基準:1.9~2.0(2H,t);2.5~2.6(2H,m);3.2~3.3(2H,t);7.75~7.85(1H,d);7.93~8.03(1H,d);8.05~8.13(1H,s)
42.0gの化合物(A)を300mLの酢酸に溶解し、内温20℃で攪拌しているところへ、2.5gのNa2WO4・2H2Oを添加した後、氷浴中、内温10℃まで冷却した。引き続き、32mLの過酸化水素水(30%)を発熱に注意しながら徐々に滴下した。内温15~20℃で30分間撹拌した後に、反応液を内温60℃まで加温して、同温度で1時間撹拌した。20℃まで冷却した後、反応液に1500mLの酢酸エチルを注入し、引き続き同温度にて30分間撹拌した後に、析出した粗結晶をヌッチェでろ過し、200mLの酢酸エチルで洗浄し、乾燥した。得られた粗結晶を、メタノール/酢酸エチルを用いて加熱洗浄して精製して、40.0gの化合物Bを得た。1H-NMR(DMSO-d6),δ値TMS基準:1.8~1.9(2H,t);2.4~2.5(2H,m);3.6~3.7(2H,t);8.3~8.4(1H,d);8.4~8.5(1H,d);8.6~8.7(1H,s)
冷却管の付いた三つ口フラスコに、n-アミルアルコール70mL加え、そこに化合物B6.7g、塩化銅(II)1.0gを加え、攪拌しながら室温で7.0mLの1,8-ジアザビシクロ[5.4.0]-7-ウンデセン(DBU)を滴下した。引き続き、反応液を内温100℃まで加温して、同温度で10時間撹拌した。40℃まで冷却した後、50℃の加温したメタノ-ル250mLを注入して、還流下で1時間攪拌した。次に、反応液を室温まで冷却した後、得られた固体をヌッチェでろ過し、200mLのメタノールで洗浄した。続いて得られた固体を塩化ナトリウムで飽和した100mLの1M塩酸水溶液に加え、未反応の銅塩を溶かし出した。不溶物をろ過した後、ろ液に300mLのメタノールを滴下して晶析した後、得られた粗結晶をヌッチェでろ過し、200mLのメタノールで洗浄した。粗結晶を、50mLの水に溶解させた後、水溶液を攪拌しながら酢酸ナトリウムの飽和メタノール溶液100mLを徐々に添加して造塩した。更に、攪拌しながら還流温度まで加温し、同温度で1時間撹拌した。室温まで冷却した後、析出した結晶をろ過し、メタノールで洗浄した。引き続き、80%メタノール100mLに得られた結晶を加え、1時間還流下撹拌し、室温まで冷却した後、析出した結晶をろ過し、更に、70%メタノール水溶液100mLに得られた結晶を加え、1時間還流撹拌し、室温まで冷却した後、析出した結晶をろ過し、メタノ-ル100mLで洗浄後乾燥して、3.8gの例示化合物102βを青色結晶として得た。
λmax(吸収極大波長):629.1nm;εmax(吸収極大波長におけるモル吸光係数)=6.19×104(水溶液中)。得られた化合物を分析(質量分析法:ESI-MS、元素分析、中和滴定等種々の機器解析方法により測定)した結果、本明細書中で定義したフタロシアニン銅(II)-置換位置が、β-位置換型{それぞれの各ベンゼン核の(2又は3位)、(6又は7位)、(10又は11位)、(14又は15位)に-{SO2-(CH2)3-SO3Na}基を1個、銅フタロシアニン一分子中-{SO2-(CH2)3-SO3Na}基を合計4個有する}であることが確認できた。
下記の成分に脱イオン水を加え100gとした後、30~40℃で加熱しながら1時間撹拌した。その後NaOH10mol/LにてpH=9に調製し、平均孔径0.25μmのミクロフィルターで減圧濾過しシアン用インク液を調製した。
第2の染料 (化合物2B) 1g
第3の染料 (化合物3A) 3g
ジエチレングリコール 2g
グリセリン 12g
ジエチレングリコールモノブチルエーテル 23g
2-ピロリドン 8g
トリエタノールアミン 1.79g
ベンゾトリアゾール 0.006g
サーフィノールTG 0.85g
PROXEL XL2 0.18g
フタロシアニン染料の種類と添加量、ダイレクトブルー199の添加量を下記表31~33に示すように変更した以外は、実施例1のインク液の調製と同様にして、実施例2~41及び比較例1~14のインク液を調製した。
以上の各実施例(実施例1~41)及び比較例(比較例1~14)のインクジェット用シアンインクについて、下記評価を行った。その結果を表34及び35に示した。なお、画像記録は、各インクジェット用インクを、インクジェットプリンター(EPSON(株)社製;PM-700C)のインクカートリッジ(PMIC1C(EPSON(株)製、商品名)シアンカートリッジの部分に入れ替えて、イエロー及びマゼンタはそのまま使用して、フォト光沢紙(PT-101、Canon)、及び普通紙(GF500、Canon)に画像を記録した。
前記画像を形成したフォト光沢紙を、オゾンガス濃度が0.5±0.1ppm、室温、暗所に設定されたボックス内に7日間放置し、オゾンガス下放置前後の画像濃度を反射濃度計(X-Rite310TR)を用いて測定し、色素残存率として評価した。なお、前記反射濃度は、1、1.5及び2.0の3点で測定した。ボックス内のオゾンガス濃度は、APPLICS製オゾンガスモニター(モデル:OZG-EM-01)を用いて設定した。何れの濃度でも色素残存率が75%以上の場合をAA、何れの濃度でも色素残存率が70%以上75%未満の場合をA、1又は2点が70%未満をB、全ての濃度で70%未満の場合をCとして、三段階で評価した。
印画したサンプルの最高濃度部分を白色蛍光灯下で目視で観測し、赤銅がかった光沢が観測されない場合をA、うっすらと観測される場合をB、明らかに観測される場合をCの三段階で評価した。
印画したサンプルを目視で観測し、純色のシアンである場合をA、やや赤みががった青色に近いシアンをB、明らかに青色の場合をCの三段階で評価した。
Photoshop(Adobe社製)を用いて、(R,G,B)=(25,25,25)、(125,125,125)及び(255,255,255)の3つのベタパターンの画像を作成し、上述のシアンインク及びPMIC1C(商品名、EPSON社製)のマゼンタインク、イエローインクを用いて印画した画像を目視にて観測し、ニュートラルなグレー及びブラックである場合をA、やや緑み若しくは赤みがかったグレイである場合をB、明らかにカラーバランスが崩れている場合をCの三段階で評価した。
本出願は、2012年11月15日出願の日本特許出願(特願2012-251692)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 (20)
- 下記一般式(1)で表されるフタロシアニン染料と、下記一般式(2)で表されるフタロシアニン染料と、下記一般式(12)で表されるアザフタロシアニン染料、下記一般式(22)で表されるフタロシアニン染料、及びダイレクトブルー199から選択される少なくとも1種の染料と、を含むことを特徴とする着色組成物。
一般式(1)中、
R2、R3、R6、R7、R10、R11、R14及びR15は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z1、Z2、Z3、及びZ4は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z1、Z2、Z3、及びZ4のうち少なくとも1つは、イオン性親水性基を置換基として有する。
l、m、n、p、q1、q2、q3及びq4は、それぞれ独立に、1又は2を表す。
M1は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
一般式(2):
一般式(2)中、
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z5、Z6、Z7、及びZ8のうち少なくとも1つは、イオン性親水性基を置換基として有する。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M2は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
(一般式(12)中、
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。ただし、Pを含む4つの環において、それぞれ、窒素原子を表すPは2以下である。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
(一般式(22)中、R17及びR18はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR17、R18、及びAは互いに連結して環を形成しても良い。Y及びZは、それぞれ独立してハロゲン原子、水酸基、スルホン酸基、カルボキシル基、アミノ基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のシクロアルキルオキシ基、置換若しくは無置換のアリロキシ基、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアラルキルオキシ基、置換若しくは無置換のアルケニルオキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のシクロアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテロ環アミノ基、置換若しくは無置換のアラルキルアミノ基、置換若しくは無置換のアルケニルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロ環チオ基、置換若しくは無置換のアラルキルチオ基、置換若しくは無置換のアルケニルチオ基を表す。但し、Y、Zのうち少なくとも1つは、スルホン酸基、カルボキシル基、又はイオン性親水性基を置換基として有する基である。m、及びnは1から3であり、かつmとnの和は2から4である。) - 一般式(1)で表されるフタロシアニン染料におけるR2、R3、R6、R7、R10、R11、R14及びR15が、水素原子であることを特徴とする請求項1に記載の着色組成物。
- 一般式(2)で表されるフタロシアニン染料におけるR1、R4、R5、R8、R9、R12、R13及びR16が、水素原子であることを特徴とする請求項1又は2に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料におけるZ1、Z2、Z3、及びZ4が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする請求項1~3のいずれか1項に記載の着色組成物。
- 一般式(2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする請求項1~4のいずれか1項に記載の着色組成物。
- 一般式(2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、置換アルキル基を表し、アルキル基が有する置換基の少なくとも一つが-SO2NHR基(但しRは置換若しくは無置換のアルキル基、又は置換若しくは無置換のフェニル基を表す)である請求項1~5のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料におけるl、m、n及びpが1である請求項1~6のいずれか1項に記載の着色組成物。
- 一般式(2)で表されるフタロシアニン染料におけるt、u、v及びwが1である請求項1~7のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料におけるq1、q2、q3及びq4が2である請求項1~8のいずれか1項に記載の着色組成物。
- 一般式(2)で表されるフタロシアニン染料におけるq5、q6、q7及びq8が2である請求項1~9のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料と、一般式(2)で表されるフタロシアニン染料との質量比が50/50~10/90である請求項1~10のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料の含有量が1~20質量%である請求項1~11のいずれか1項に記載の着色組成物。
- 一般式(12)で表されるアザフタロシアニン染料が、下記一般式(13-1)又は一般式(13-2)で表されるアザフタロシアニン染料である請求項1~12のいずれか1項に記載の着色組成物。
(一般式(13-1)及び一般式(13-2)中、
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基を表す。
R24は置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基を表す。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。) - 前記一般式(12)、一般式(13-1)又は一般式(13-2)における、R23が水素原子を表し、R24が下記一般式(T1)で表される置換基で置換された置換アルキル基である請求項1~13のいずれか1項に記載の着色組成物。
(一般式(T1)中、
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
Xはそれぞれ独立に-OR25、-SR25、及び-NR25R26より選択される置換基を表し、R25及びR26はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表し、R25及びR26の少なくとも一つはイオン性親水性基を置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。) - 前記一般式(22)で表されるフタロシアニン染料が、一般式(22-1)で表されるフタロシアニン染料である請求項1~15のいずれか1項に記載の着色組成物。
(一般式(22-1)中、R27及びR28はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR27、R28、及びAは互いに連結して環を形成しても良い。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。m、及びnは1から3であり、かつmとnの和は2から4である。) - 請求項1~16のいずれか1項に記載の着色組成物を含むインクジェット記録用インク。
- 請求項17に記載のインクジェット記録用インクを用いるインクジェット記録方法。
- 請求項17に記載のインクジェット記録用インクを充填したインクカートリッジ。
- 請求項17に記載のインクジェット記録用インクを用いて、被記録材に着色画像を形成したインクジェット記録物。
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Publication number | Priority date | Publication date | Assignee | Title |
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (94)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2484430A (en) | 1946-12-31 | 1949-10-11 | Eastman Kodak Co | Quaternary salts of polyvinyl pyridine and polyvinyl quinoline |
US2548564A (en) | 1946-12-31 | 1951-04-10 | Eastman Kodak Co | Photographic silver halide element with mordanted dye layer |
US3148061A (en) | 1960-08-22 | 1964-09-08 | Polaroid Corp | Photographic diffusion transfer processes employing image receiving layers containing poly-4-vinylpyridine |
US3214463A (en) | 1960-05-12 | 1965-10-26 | Du Pont | Uv-absorbing sulfonated benzophenone derivatives |
US3309690A (en) | 1966-05-19 | 1967-03-14 | Melville M Moffitt | Helmet with detecting circuit mounted thereon for indicating approach to an energized powerline |
JPS462784A (ja) | 1971-03-11 | 1971-10-21 | ||
JPS4828325A (ja) | 1971-08-20 | 1973-04-14 | ||
JPS4830492A (ja) | 1971-08-19 | 1973-04-21 | ||
US4115124A (en) | 1974-09-06 | 1978-09-19 | Eastman Kodak Company | Method of immobilizing optical brighteners |
US4124386A (en) | 1973-10-24 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Color diffusion transfer receiving layer comprising polymeric quaternary n-heterocyclic mordant |
JPS5474430A (en) | 1977-10-24 | 1979-06-14 | Konishiroku Photo Ind Co Ltd | Photographic element for color diffusion transfer |
JPS54124726A (en) | 1978-03-20 | 1979-09-27 | Konishiroku Photo Ind Co Ltd | Photographic material for color diffusion transfer method |
JPS5522766A (en) | 1978-08-08 | 1980-02-18 | Konishiroku Photo Ind Co Ltd | Photographic element |
US4193800A (en) | 1977-10-24 | 1980-03-18 | Konishiroku Photo Industry Co., Ltd. | Photographic dye mordant |
JPS55142339A (en) | 1979-04-23 | 1980-11-06 | Konishiroku Photo Ind Co Ltd | Photographic element |
JPS5621141A (en) | 1979-07-30 | 1981-02-27 | Sharp Corp | Copying machine with timer |
US4273853A (en) | 1979-03-30 | 1981-06-16 | Eastman Kodak Company | Metal complexes of copolymers comprising vinylimidazole and their use in photographic elements |
US4282305A (en) | 1979-01-15 | 1981-08-04 | Eastman Kodak Company | Receiving elements for image transfer film units |
JPS579053A (en) | 1980-06-18 | 1982-01-18 | Mitsubishi Electric Corp | Cathode ray tube |
JPS58185677A (ja) | 1982-04-22 | 1983-10-29 | Konishiroku Photo Ind Co Ltd | 紫外線吸収剤 |
US4450224A (en) | 1983-07-06 | 1984-05-22 | Eastman Kodak Company | Polymeric mordants |
JPS59157636A (ja) | 1983-02-25 | 1984-09-07 | Fuji Photo Film Co Ltd | カラ−画像形成方法 |
JPS6023852A (ja) | 1983-07-19 | 1985-02-06 | Konishiroku Photo Ind Co Ltd | 写真要素 |
JPS6023851A (ja) | 1983-07-19 | 1985-02-06 | Konishiroku Photo Ind Co Ltd | 写真要素 |
JPS6023850A (ja) | 1983-07-20 | 1985-02-06 | Fuji Photo Film Co Ltd | 新規な電子伝達剤及びそれを含有するカラ−写真感光材料 |
JPS6023853A (ja) | 1983-07-19 | 1985-02-06 | Konishiroku Photo Ind Co Ltd | 写真要素 |
JPS6057836A (ja) | 1983-09-09 | 1985-04-03 | Fuji Photo Film Co Ltd | 写真要素 |
JPS6060643A (ja) | 1983-09-13 | 1985-04-08 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60118834A (ja) | 1983-11-30 | 1985-06-26 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60122942A (ja) | 1983-12-08 | 1985-07-01 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60122940A (ja) | 1983-12-08 | 1985-07-01 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60122941A (ja) | 1983-12-08 | 1985-07-01 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60235134A (ja) | 1984-05-08 | 1985-11-21 | Fuji Photo Film Co Ltd | 写真要素 |
JPS6120994A (ja) | 1984-07-10 | 1986-01-29 | 松下電器産業株式会社 | カラオケ練習装置 |
JPS61190537A (ja) | 1985-01-22 | 1986-08-25 | チバーガイギー アクチエンゲゼルシヤフト | 2―(2―ヒドロキシ―3―分枝アルキル―5―メチルフェニル)―2h―ベンゾトリアゾール混合物,該混合物の製造法,および該混合物からなる安定剤 |
JPS62110066A (ja) | 1985-11-07 | 1987-05-21 | Aisin Seiki Co Ltd | 変速機 |
JPS62135826A (ja) | 1985-12-09 | 1987-06-18 | Konishiroku Photo Ind Co Ltd | 熱現像感光材料 |
JPS62136648A (ja) | 1985-12-11 | 1987-06-19 | Konishiroku Photo Ind Co Ltd | 熱現像カラ−感光材料 |
JPS62183457A (ja) | 1986-02-07 | 1987-08-11 | Fuji Photo Film Co Ltd | 画像形成方法 |
JPS62215272A (ja) | 1986-02-17 | 1987-09-21 | Fuji Photo Film Co Ltd | カラ−画像形成方法 |
JPS62238783A (ja) | 1986-04-10 | 1987-10-19 | Nitto Boseki Co Ltd | インクジエツト記録用紙 |
JPS62245258A (ja) | 1986-04-18 | 1987-10-26 | Fuji Photo Film Co Ltd | 画像形成方法 |
US4808501A (en) | 1985-10-15 | 1989-02-28 | Polaroid Corporation, Patent Dept. | Method for manufacturing an optical filter |
JPH01161236A (ja) | 1987-12-17 | 1989-06-23 | Fuji Photo Film Co Ltd | 画像形成方法 |
JPH02782A (ja) | 1987-12-28 | 1990-01-05 | Ciba Geigy Ag | 新規な2―(2―ヒドロキシフェニル)ベンゾトリアゾール誘導体 |
JPH02276670A (ja) | 1988-12-16 | 1990-11-13 | Asahi Glass Co Ltd | 記録用シート |
JPH04298503A (ja) | 1990-05-10 | 1992-10-22 | Ciba Geigy Ag | 輻射線硬化性、光安定化組成物 |
JPH05148436A (ja) | 1991-11-26 | 1993-06-15 | Canon Inc | インクジエツト記録液、その製造方法およびこれを用いるインクジエツト記録方法 |
JPH05194483A (ja) | 1991-07-03 | 1993-08-03 | Ciba Geigy Ag | フェニルチオフェニルケトン |
JPH05197075A (ja) | 1991-09-05 | 1993-08-06 | Ciba Geigy Ag | 紫外線吸収剤を含有する写真フィルム材料 |
JPH05295312A (ja) | 1992-04-17 | 1993-11-09 | Canon Inc | インク、これを用いたインクジェット記録方法及びかかるインクを用いた機器 |
JPH0635182A (ja) | 1992-07-20 | 1994-02-10 | Sumitomo Chem Co Ltd | ポジ型レジスト組成物及びそれを用いるカラーフィルターの製造方法 |
JPH0782515A (ja) | 1993-06-25 | 1995-03-28 | Fuji Xerox Co Ltd | インクジェット記録用インク、インクジェット記録装置およびその方法 |
JPH0797541A (ja) | 1992-11-09 | 1995-04-11 | Seiko Epson Corp | 黒色再現性に優れた黒色インク組成物 |
JPH07118584A (ja) | 1993-10-20 | 1995-05-09 | Seiko Epson Corp | インクジェット記録用インク |
JPH07276789A (ja) | 1994-04-05 | 1995-10-24 | Fuji Photo Film Co Ltd | 記録用シート |
JPH0827693A (ja) | 1994-07-12 | 1996-01-30 | Mitsubishi Paper Mills Ltd | 記録用紙及び塗工用原紙 |
JPH08501291A (ja) | 1992-09-07 | 1996-02-13 | チバ−ガイギー アクチエンゲゼルシャフト | ヒドロキシフェニル−s−トリアジン |
JPH0853427A (ja) | 1994-07-27 | 1996-02-27 | Ciba Geigy Ag | 赤色側にシフトされたトリス−アリール−s−トリアジンおよびそれらにより安定化された組成物 |
JPH08169172A (ja) | 1994-12-20 | 1996-07-02 | Mitsubishi Paper Mills Ltd | インクジェット記録シート |
JPH08239368A (ja) | 1994-10-10 | 1996-09-17 | Ciba Geigy Ag | ビスレゾルシニルトリアジン |
JPH0934057A (ja) | 1995-06-19 | 1997-02-07 | Eastman Kodak Co | 特定の置換基を有し、2′−ヒドロキシフェニルベンズトリアゾールを基にした紫外線吸収ポリマーおよびそれを含有する写真要素 |
JPH09323475A (ja) | 1996-06-06 | 1997-12-16 | Konica Corp | インクジェット記録用紙およびこれを用いた記録方法 |
JPH1088106A (ja) | 1996-08-16 | 1998-04-07 | Eastman Kodak Co | 紫外線吸収性ポリマー粒子 |
JPH10153989A (ja) | 1996-11-22 | 1998-06-09 | Nec Home Electron Ltd | ドットクロック回路 |
JPH10182621A (ja) | 1996-11-20 | 1998-07-07 | Ciba Specialty Chem Holding Inc | ヒドロキシフェニルトリアジン |
JPH10217473A (ja) | 1996-10-14 | 1998-08-18 | Canon Inc | 液体噴射記録ヘッドおよびその製造方法 |
JPH10217597A (ja) | 1997-02-10 | 1998-08-18 | Fuji Photo Film Co Ltd | 画像形成方法 |
JPH10235995A (ja) | 1996-12-26 | 1998-09-08 | Fuji Photo Film Co Ltd | 画像記録媒体および画像記録方法 |
JPH10337947A (ja) | 1997-06-04 | 1998-12-22 | Fuji Photo Film Co Ltd | 画像記録媒体 |
JPH11286637A (ja) | 1998-02-03 | 1999-10-19 | Agfa Gevaert Ag | インキジエツトインキ |
JP2000062370A (ja) | 1998-08-17 | 2000-02-29 | Kenji Yokoyama | シート保持具 |
JP2000078491A (ja) | 1998-09-02 | 2000-03-14 | Matsushita Electric Ind Co Ltd | デジタル放送受信装置の制御プログラム書き換え方法及びデジタル放送受信装置 |
JP2000078454A (ja) | 1998-09-01 | 2000-03-14 | Matsushita Electric Ind Co Ltd | 監視用プリセット型ズームレンズ装置 |
JP2000080259A (ja) | 1998-09-03 | 2000-03-21 | Showa Denko Kk | 脂肪族系ポリエステル組成物 |
JP2000087539A (ja) | 1998-09-09 | 2000-03-28 | Yamaha Ribingutetsuku Kk | 床ユニット及び床暖房装置 |
JP2000203856A (ja) | 1999-01-12 | 2000-07-25 | Sumitomo Electric Ind Ltd | 石英ガラス物品及びその製造方法 |
JP2000203857A (ja) | 1999-01-08 | 2000-07-25 | Nippon Sheet Glass Co Ltd | ガラススペ―サの製造方法 |
JP2000268952A (ja) | 1999-03-16 | 2000-09-29 | Fuji Xerox Co Ltd | 加熱装置及び画像形成装置 |
JP2000297365A (ja) | 1999-04-14 | 2000-10-24 | Agency Of Ind Science & Technol | AlTi系合金スパッタリングターゲット及び耐摩耗性AlTi系合金硬質皮膜並びに同皮膜の形成方法 |
JP2000299465A (ja) | 1999-04-15 | 2000-10-24 | Sony Corp | 薄膜トランジスタ及びその製造方法と表示装置 |
JP2000315231A (ja) | 1999-04-30 | 2000-11-14 | Sanpurasu:Kk | クレジットカード番号を使用したパスワード認証システム |
JP2000343944A (ja) | 1999-06-03 | 2000-12-12 | Fujio Amari | 開閉、調光可能な乗用車用、防眩用半透明板 |
JP2000354380A (ja) | 1999-06-08 | 2000-12-19 | Hitachi Ltd | モータ制御装置 |
JP2002249677A (ja) | 2001-02-22 | 2002-09-06 | Fuji Photo Film Co Ltd | フタロシアニン化合物、着色組成物、インクジェット記録用インク及びインクジェット記録方法 |
JP2002317136A (ja) | 2001-02-12 | 2002-10-31 | Hewlett Packard Co <Hp> | コゲーション低減インク |
JP2004329677A (ja) | 2003-05-09 | 2004-11-25 | Ykk Corp | スライドファスナーエレメント列の噛合状態検出装置 |
JP2005075778A (ja) * | 2003-09-01 | 2005-03-24 | Fuji Photo Film Co Ltd | 水溶性フタロシアニン化合物の製造方法及びその合成中間体 |
JP2007065355A (ja) * | 2005-08-31 | 2007-03-15 | Fujifilm Holdings Corp | 熱現像感光材料 |
JP2009132891A (ja) * | 2007-10-31 | 2009-06-18 | Fujifilm Corp | インクセット、インクジェット記録方法、及び記録物 |
JP2010037504A (ja) * | 2008-08-08 | 2010-02-18 | Canon Inc | インクセット、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置 |
WO2010020802A2 (en) | 2008-08-22 | 2010-02-25 | Fujifilm Imaging Colorants Limited | Phthalocyanines and their use in ink-jet printing |
JP2011111604A (ja) * | 2009-11-30 | 2011-06-09 | Brother Industries Ltd | インクジェット記録用水性インク、インクカートリッジおよびインクジェット記録装置 |
WO2013069667A1 (ja) * | 2011-11-08 | 2013-05-16 | 富士フイルム株式会社 | 着色組成物及びインクジェット記録用インク |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4383007B2 (ja) * | 2001-06-22 | 2009-12-16 | 富士フイルム株式会社 | フタロシアニン化合物、それを含む着色画像形成組成物、インク、インクジェット用インク、インクジェット記録方法及びオゾンガス褪色耐性の改良方法 |
JP4420267B2 (ja) * | 2003-04-23 | 2010-02-24 | 日本化薬株式会社 | 色素混合物、インク、インクセット、このインク又はインクセットを用いたインクジェット記録方法、着色体、及び製造方法 |
CN101580646B (zh) * | 2008-05-13 | 2012-07-04 | 珠海纳思达企业管理有限公司 | 耐候染料及其用途 |
JP2010106066A (ja) * | 2008-10-28 | 2010-05-13 | Canon Inc | インクジェット用インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置 |
CN102558948B (zh) * | 2010-12-10 | 2016-02-10 | 精工爱普生株式会社 | 油墨组合物、使用其的喷墨记录方法以及记录物 |
JP5826004B2 (ja) * | 2011-11-30 | 2015-12-02 | 富士フイルム株式会社 | 着色組成物及びインクジェット記録用インク |
JP5826003B2 (ja) * | 2011-11-30 | 2015-12-02 | 富士フイルム株式会社 | 着色組成物及びインクジェット記録用インク |
JP5826134B2 (ja) * | 2011-11-08 | 2015-12-02 | 富士フイルム株式会社 | 着色組成物及びインクジェット記録用インク |
JP2014098120A (ja) * | 2012-11-15 | 2014-05-29 | Fujifilm Corp | 着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物 |
-
2013
- 2013-11-13 EP EP13855644.4A patent/EP2921531A1/en not_active Withdrawn
- 2013-11-13 JP JP2014547011A patent/JPWO2014077291A1/ja active Pending
- 2013-11-13 KR KR1020157011913A patent/KR20150075093A/ko not_active Application Discontinuation
- 2013-11-13 CN CN201380059721.3A patent/CN104797658A/zh active Pending
- 2013-11-13 WO PCT/JP2013/080720 patent/WO2014077291A1/ja active Application Filing
- 2013-11-15 TW TW102141556A patent/TW201435016A/zh unknown
-
2015
- 2015-05-14 US US14/712,161 patent/US20150240096A1/en not_active Abandoned
Patent Citations (94)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2484430A (en) | 1946-12-31 | 1949-10-11 | Eastman Kodak Co | Quaternary salts of polyvinyl pyridine and polyvinyl quinoline |
US2548564A (en) | 1946-12-31 | 1951-04-10 | Eastman Kodak Co | Photographic silver halide element with mordanted dye layer |
US3214463A (en) | 1960-05-12 | 1965-10-26 | Du Pont | Uv-absorbing sulfonated benzophenone derivatives |
US3148061A (en) | 1960-08-22 | 1964-09-08 | Polaroid Corp | Photographic diffusion transfer processes employing image receiving layers containing poly-4-vinylpyridine |
US3309690A (en) | 1966-05-19 | 1967-03-14 | Melville M Moffitt | Helmet with detecting circuit mounted thereon for indicating approach to an energized powerline |
JPS462784A (ja) | 1971-03-11 | 1971-10-21 | ||
JPS4830492A (ja) | 1971-08-19 | 1973-04-21 | ||
JPS4828325A (ja) | 1971-08-20 | 1973-04-14 | ||
US4124386A (en) | 1973-10-24 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Color diffusion transfer receiving layer comprising polymeric quaternary n-heterocyclic mordant |
US4115124A (en) | 1974-09-06 | 1978-09-19 | Eastman Kodak Company | Method of immobilizing optical brighteners |
JPS5474430A (en) | 1977-10-24 | 1979-06-14 | Konishiroku Photo Ind Co Ltd | Photographic element for color diffusion transfer |
US4193800A (en) | 1977-10-24 | 1980-03-18 | Konishiroku Photo Industry Co., Ltd. | Photographic dye mordant |
JPS54124726A (en) | 1978-03-20 | 1979-09-27 | Konishiroku Photo Ind Co Ltd | Photographic material for color diffusion transfer method |
JPS5522766A (en) | 1978-08-08 | 1980-02-18 | Konishiroku Photo Ind Co Ltd | Photographic element |
US4282305A (en) | 1979-01-15 | 1981-08-04 | Eastman Kodak Company | Receiving elements for image transfer film units |
US4273853A (en) | 1979-03-30 | 1981-06-16 | Eastman Kodak Company | Metal complexes of copolymers comprising vinylimidazole and their use in photographic elements |
JPS55142339A (en) | 1979-04-23 | 1980-11-06 | Konishiroku Photo Ind Co Ltd | Photographic element |
JPS5621141A (en) | 1979-07-30 | 1981-02-27 | Sharp Corp | Copying machine with timer |
JPS579053A (en) | 1980-06-18 | 1982-01-18 | Mitsubishi Electric Corp | Cathode ray tube |
JPS58185677A (ja) | 1982-04-22 | 1983-10-29 | Konishiroku Photo Ind Co Ltd | 紫外線吸収剤 |
JPS59157636A (ja) | 1983-02-25 | 1984-09-07 | Fuji Photo Film Co Ltd | カラ−画像形成方法 |
US4450224A (en) | 1983-07-06 | 1984-05-22 | Eastman Kodak Company | Polymeric mordants |
JPS6023852A (ja) | 1983-07-19 | 1985-02-06 | Konishiroku Photo Ind Co Ltd | 写真要素 |
JPS6023851A (ja) | 1983-07-19 | 1985-02-06 | Konishiroku Photo Ind Co Ltd | 写真要素 |
JPS6023853A (ja) | 1983-07-19 | 1985-02-06 | Konishiroku Photo Ind Co Ltd | 写真要素 |
JPS6023850A (ja) | 1983-07-20 | 1985-02-06 | Fuji Photo Film Co Ltd | 新規な電子伝達剤及びそれを含有するカラ−写真感光材料 |
JPS6057836A (ja) | 1983-09-09 | 1985-04-03 | Fuji Photo Film Co Ltd | 写真要素 |
JPS6060643A (ja) | 1983-09-13 | 1985-04-08 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60118834A (ja) | 1983-11-30 | 1985-06-26 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60122942A (ja) | 1983-12-08 | 1985-07-01 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60122940A (ja) | 1983-12-08 | 1985-07-01 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60122941A (ja) | 1983-12-08 | 1985-07-01 | Fuji Photo Film Co Ltd | 写真要素 |
JPS60235134A (ja) | 1984-05-08 | 1985-11-21 | Fuji Photo Film Co Ltd | 写真要素 |
JPS6120994A (ja) | 1984-07-10 | 1986-01-29 | 松下電器産業株式会社 | カラオケ練習装置 |
JPS61190537A (ja) | 1985-01-22 | 1986-08-25 | チバーガイギー アクチエンゲゼルシヤフト | 2―(2―ヒドロキシ―3―分枝アルキル―5―メチルフェニル)―2h―ベンゾトリアゾール混合物,該混合物の製造法,および該混合物からなる安定剤 |
US4808501A (en) | 1985-10-15 | 1989-02-28 | Polaroid Corporation, Patent Dept. | Method for manufacturing an optical filter |
JPS62110066A (ja) | 1985-11-07 | 1987-05-21 | Aisin Seiki Co Ltd | 変速機 |
JPS62135826A (ja) | 1985-12-09 | 1987-06-18 | Konishiroku Photo Ind Co Ltd | 熱現像感光材料 |
JPS62136648A (ja) | 1985-12-11 | 1987-06-19 | Konishiroku Photo Ind Co Ltd | 熱現像カラ−感光材料 |
JPS62183457A (ja) | 1986-02-07 | 1987-08-11 | Fuji Photo Film Co Ltd | 画像形成方法 |
JPS62215272A (ja) | 1986-02-17 | 1987-09-21 | Fuji Photo Film Co Ltd | カラ−画像形成方法 |
JPS62238783A (ja) | 1986-04-10 | 1987-10-19 | Nitto Boseki Co Ltd | インクジエツト記録用紙 |
JPS62245258A (ja) | 1986-04-18 | 1987-10-26 | Fuji Photo Film Co Ltd | 画像形成方法 |
JPH01161236A (ja) | 1987-12-17 | 1989-06-23 | Fuji Photo Film Co Ltd | 画像形成方法 |
JPH02782A (ja) | 1987-12-28 | 1990-01-05 | Ciba Geigy Ag | 新規な2―(2―ヒドロキシフェニル)ベンゾトリアゾール誘導体 |
JPH02276670A (ja) | 1988-12-16 | 1990-11-13 | Asahi Glass Co Ltd | 記録用シート |
JPH04298503A (ja) | 1990-05-10 | 1992-10-22 | Ciba Geigy Ag | 輻射線硬化性、光安定化組成物 |
JPH05194483A (ja) | 1991-07-03 | 1993-08-03 | Ciba Geigy Ag | フェニルチオフェニルケトン |
JPH05197075A (ja) | 1991-09-05 | 1993-08-06 | Ciba Geigy Ag | 紫外線吸収剤を含有する写真フィルム材料 |
JPH05148436A (ja) | 1991-11-26 | 1993-06-15 | Canon Inc | インクジエツト記録液、その製造方法およびこれを用いるインクジエツト記録方法 |
JPH05295312A (ja) | 1992-04-17 | 1993-11-09 | Canon Inc | インク、これを用いたインクジェット記録方法及びかかるインクを用いた機器 |
JPH0635182A (ja) | 1992-07-20 | 1994-02-10 | Sumitomo Chem Co Ltd | ポジ型レジスト組成物及びそれを用いるカラーフィルターの製造方法 |
JPH08501291A (ja) | 1992-09-07 | 1996-02-13 | チバ−ガイギー アクチエンゲゼルシャフト | ヒドロキシフェニル−s−トリアジン |
JPH0797541A (ja) | 1992-11-09 | 1995-04-11 | Seiko Epson Corp | 黒色再現性に優れた黒色インク組成物 |
JPH0782515A (ja) | 1993-06-25 | 1995-03-28 | Fuji Xerox Co Ltd | インクジェット記録用インク、インクジェット記録装置およびその方法 |
JPH07118584A (ja) | 1993-10-20 | 1995-05-09 | Seiko Epson Corp | インクジェット記録用インク |
JPH07276789A (ja) | 1994-04-05 | 1995-10-24 | Fuji Photo Film Co Ltd | 記録用シート |
JPH0827693A (ja) | 1994-07-12 | 1996-01-30 | Mitsubishi Paper Mills Ltd | 記録用紙及び塗工用原紙 |
JPH0853427A (ja) | 1994-07-27 | 1996-02-27 | Ciba Geigy Ag | 赤色側にシフトされたトリス−アリール−s−トリアジンおよびそれらにより安定化された組成物 |
JPH08239368A (ja) | 1994-10-10 | 1996-09-17 | Ciba Geigy Ag | ビスレゾルシニルトリアジン |
JPH08169172A (ja) | 1994-12-20 | 1996-07-02 | Mitsubishi Paper Mills Ltd | インクジェット記録シート |
JPH0934057A (ja) | 1995-06-19 | 1997-02-07 | Eastman Kodak Co | 特定の置換基を有し、2′−ヒドロキシフェニルベンズトリアゾールを基にした紫外線吸収ポリマーおよびそれを含有する写真要素 |
JPH09323475A (ja) | 1996-06-06 | 1997-12-16 | Konica Corp | インクジェット記録用紙およびこれを用いた記録方法 |
JPH1088106A (ja) | 1996-08-16 | 1998-04-07 | Eastman Kodak Co | 紫外線吸収性ポリマー粒子 |
JPH10217473A (ja) | 1996-10-14 | 1998-08-18 | Canon Inc | 液体噴射記録ヘッドおよびその製造方法 |
JPH10182621A (ja) | 1996-11-20 | 1998-07-07 | Ciba Specialty Chem Holding Inc | ヒドロキシフェニルトリアジン |
JPH10153989A (ja) | 1996-11-22 | 1998-06-09 | Nec Home Electron Ltd | ドットクロック回路 |
JPH10235995A (ja) | 1996-12-26 | 1998-09-08 | Fuji Photo Film Co Ltd | 画像記録媒体および画像記録方法 |
JPH10217597A (ja) | 1997-02-10 | 1998-08-18 | Fuji Photo Film Co Ltd | 画像形成方法 |
JPH10337947A (ja) | 1997-06-04 | 1998-12-22 | Fuji Photo Film Co Ltd | 画像記録媒体 |
JPH11286637A (ja) | 1998-02-03 | 1999-10-19 | Agfa Gevaert Ag | インキジエツトインキ |
JP2000062370A (ja) | 1998-08-17 | 2000-02-29 | Kenji Yokoyama | シート保持具 |
JP2000078454A (ja) | 1998-09-01 | 2000-03-14 | Matsushita Electric Ind Co Ltd | 監視用プリセット型ズームレンズ装置 |
JP2000078491A (ja) | 1998-09-02 | 2000-03-14 | Matsushita Electric Ind Co Ltd | デジタル放送受信装置の制御プログラム書き換え方法及びデジタル放送受信装置 |
JP2000080259A (ja) | 1998-09-03 | 2000-03-21 | Showa Denko Kk | 脂肪族系ポリエステル組成物 |
JP2000087539A (ja) | 1998-09-09 | 2000-03-28 | Yamaha Ribingutetsuku Kk | 床ユニット及び床暖房装置 |
JP2000203857A (ja) | 1999-01-08 | 2000-07-25 | Nippon Sheet Glass Co Ltd | ガラススペ―サの製造方法 |
JP2000203856A (ja) | 1999-01-12 | 2000-07-25 | Sumitomo Electric Ind Ltd | 石英ガラス物品及びその製造方法 |
JP2000268952A (ja) | 1999-03-16 | 2000-09-29 | Fuji Xerox Co Ltd | 加熱装置及び画像形成装置 |
JP2000297365A (ja) | 1999-04-14 | 2000-10-24 | Agency Of Ind Science & Technol | AlTi系合金スパッタリングターゲット及び耐摩耗性AlTi系合金硬質皮膜並びに同皮膜の形成方法 |
JP2000299465A (ja) | 1999-04-15 | 2000-10-24 | Sony Corp | 薄膜トランジスタ及びその製造方法と表示装置 |
JP2000315231A (ja) | 1999-04-30 | 2000-11-14 | Sanpurasu:Kk | クレジットカード番号を使用したパスワード認証システム |
JP2000343944A (ja) | 1999-06-03 | 2000-12-12 | Fujio Amari | 開閉、調光可能な乗用車用、防眩用半透明板 |
JP2000354380A (ja) | 1999-06-08 | 2000-12-19 | Hitachi Ltd | モータ制御装置 |
JP2002317136A (ja) | 2001-02-12 | 2002-10-31 | Hewlett Packard Co <Hp> | コゲーション低減インク |
JP2002249677A (ja) | 2001-02-22 | 2002-09-06 | Fuji Photo Film Co Ltd | フタロシアニン化合物、着色組成物、インクジェット記録用インク及びインクジェット記録方法 |
JP2004329677A (ja) | 2003-05-09 | 2004-11-25 | Ykk Corp | スライドファスナーエレメント列の噛合状態検出装置 |
JP2005075778A (ja) * | 2003-09-01 | 2005-03-24 | Fuji Photo Film Co Ltd | 水溶性フタロシアニン化合物の製造方法及びその合成中間体 |
JP2007065355A (ja) * | 2005-08-31 | 2007-03-15 | Fujifilm Holdings Corp | 熱現像感光材料 |
JP2009132891A (ja) * | 2007-10-31 | 2009-06-18 | Fujifilm Corp | インクセット、インクジェット記録方法、及び記録物 |
JP2010037504A (ja) * | 2008-08-08 | 2010-02-18 | Canon Inc | インクセット、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置 |
WO2010020802A2 (en) | 2008-08-22 | 2010-02-25 | Fujifilm Imaging Colorants Limited | Phthalocyanines and their use in ink-jet printing |
JP2011111604A (ja) * | 2009-11-30 | 2011-06-09 | Brother Industries Ltd | インクジェット記録用水性インク、インクカートリッジおよびインクジェット記録装置 |
WO2013069667A1 (ja) * | 2011-11-08 | 2013-05-16 | 富士フイルム株式会社 | 着色組成物及びインクジェット記録用インク |
Non-Patent Citations (7)
Title |
---|
"Research Disclosure No. 17643" |
C.C. LEZNOFF; A. B. P. LEVER: "Phthalocyanines Properties and Applications", VCH, pages: 1 - 54 |
RESEARCH DISCLOSURE NO. 18716, pages 650 |
RESEARCH DISCLOSURE NO. 307105, pages 872 |
RESEARCH DISCLOSURE NO. 308119, 1989 |
RESEARCH DISCLOSURE NO. 36544, pages 527 |
SHIRAI KOBAYASHI ET AL.: "Phthalocyanine - Chemistry and Function", IPC CO., LTD., pages: 1 - 62 |
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CN104797658A (zh) | 2015-07-22 |
TW201435016A (zh) | 2014-09-16 |
US20150240096A1 (en) | 2015-08-27 |
JPWO2014077291A1 (ja) | 2017-01-05 |
EP2921531A1 (en) | 2015-09-23 |
KR20150075093A (ko) | 2015-07-02 |
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